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Sample records for cathode catalyst layer

  1. Cathode catalyst layer using supported Pt catalyst on ordered mesoporous carbon for direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hee-Tak; Yoon, Hae-Kwon; Song, In-Seob [Samsung SDI Co. Ltd., 575 Shin-dong, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-391 (Korea); You, Dae Jong; Joo, Sang Hoon; Pak, Chanho; Chang, Hyuk [Samsung Advanced Institute of Technology, P.O. Box 111, Suwon 440-600 (Korea)

    2008-06-01

    The development of a cathode catalyst layer based on a supported Pt catalyst using an ordered mesoporous carbon (OMC) for direct methanol fuel cell is reported. An OMC with a mesopore structure between hexagonally arranged carbon nanorods is prepared using a template method. Platinum nanoparticles are supported on the OMC (Pt/OMC) with high metal loading of 60 wt.%. Compositional and morphological variations are made by varying the ionomer content and by compressing the catalyst layer to detect a parameter that determines the power performance. Increase in power density with decrease in the volume fraction of ionomer in the agglomerate comprising the Pt/OMC and the ionomer indicates that mass transport through the ionomer phase governs the kinetics of oxygen reduction. Impedance spectroscopic analysis suggests that a significant mass-transport limitation occurs at high ionomer content and in the compressed cathode. The power density of the optimum cathode layer, which employs a Pt/OMC catalyst with a Pt loading of 2 mg cm{sup -2}, is greater than that of a catalyst layer with 6 mg cm{sup -2} Pt-black catalyst at a voltage higher than 0.4 V. This would lead to a significant reduction in the cost of the membrane electrode assembly. (author)

  2. Partially Perfluorinated Hydrocarbon Ionomer for Cathode Catalyst Layer of Polymer Electrolyte Membrane Fuel Cell

    International Nuclear Information System (INIS)

    Hydrocarbon ionomers have not been successfully employed in the cathode of polymer electrolyte fuel cell (PEFC)s due to their low oxygen permeabilities. In this work, we propose a partially fluorinated aromatic polyether with sulfonic acid groups (s-PFPE) as an ionomer for the cathode catalyst layer. Compared to sulfonated poly(ether ether ketone) (s-PEEK), it exhibited more than 1.5 times higher oxygen permeability at RH 40% and 1.3 times higher at RH 100%. The catalyst layer based on s-PFPE showed higher power performance than that based on s-PEEK owing to enhanced oxygen transport and fast proton conduction through the s-PFPE ionomer phase covering the catalyst layer. We demonstrate that the introduction of the perfluorinated moieties to the hydrocarbon backbone is an effective strategy for the use of hydrocarbon ionomer in the cathode of PEMFCs

  3. Highly Durable Direct Methanol Fuel Cell with Double-Layered Catalyst Cathode

    Directory of Open Access Journals (Sweden)

    Jing Liu

    2015-01-01

    Full Text Available Polymer electrolyte membrane (PEM is one of the key components in direct methanol fuel cells. However, the PEM usually gets attacked by reactive oxygen species during the operation period, resulting in the loss of membrane integrity and formation of defects. Herein, a double-layered catalyst cathode electrode consisting of Pt/CeO2-C as inner catalyst and Pt/C as outer catalyst is fabricated to extend the lifetime and minimize the performance loss of DMFC. Although the maximum power density of membrane electrode assembly (MEA with catalyst cathode is slightly lower than that of the traditional one, its durability is significantly improved. No obvious degradation is evident in the MEA with double-layered catalyst cathode within durability testing. These results indicated that Pt/CeO2-C as inner cathode catalyst layer greatly improved the stability of MEA. The significant reason for the improved stability of MEA is the ability of CeO2 to act as free-radical scavengers.

  4. Composition optimization for cathode catalyst layer of PEM fuel cell based on percolation relations

    International Nuclear Information System (INIS)

    'Full text': The optimization of the cathode catalyst layer of polymer electrode membrane (PEM) fuel cell has been numerically discussed based on the available cathode catalyst layer model and percolation theory. One, two or all of the three design parameters, Pt loading, catalyst layer thickness and Nafion content, is/are respectively taken as the optimization variable(s) to conduct the corresponding optimization analysis. The optimization results of the case when only Pt loading is considered as the optimization parameter are compared with the experimental data carried out by C. C. Boyer et al at different cell potentials. Numerical optimization shows that when the optimization variables do not include both of the catalyst layer thickness and Pt loading, the optimum point lies in the interior of the feasible design region, but when the optimization variables do include both of the thickness and Pt loading, the optimum point occurs on the upper boundary of the thickness. Further analysis indicates that, when all of the three parameters are taken as optimization variables, the maximum current density is much better than that when one or two of the three parameters is/are taken as the optimization parameter(s). (author)

  5. Modelling cathode catalyst degradation in polymer electrolyte fuel cells

    OpenAIRE

    Rinaldo, Steven Giordano

    2013-01-01

    Nano-sized Pt particles in the cathode catalyst layer of a polymer electrolyte fuel cell afford a high initial electrochemically active surface-area. However, the gain in active surface area for desired surface reactions is offset in part by enhanced rates of degradation processes that cause losses in catalyst mass, catalyst surface-area, and electrocatalytic activity. The loss of electrochemically active surface-area of the catalyst causes severe performance degradation over relevant lifetim...

  6. Performance of practical-sized membrane-electrode assemblies using titanium nitride-supported platinum catalysts mixed with acetylene black as the cathode catalyst layer

    Science.gov (United States)

    Shintani, Haruhiko; Kakinuma, Katsuyoshi; Uchida, Hiroyuki; Watanabe, Masahiro; Uchida, Makoto

    2015-04-01

    The performance of practical-sized membrane-electrode assemblies (MEAs) using titanium nitride-supported platinum (Pt/TiN) as the cathode catalysts was evaluated with the use of a practical single cell designed for microscale combined heat and power (CHP) applications. The performance can be controlled by adding acetylene black (AB), with the behavior being dominated by the percolation law. The electrical resistance of the MEAs drastically decreased for AB contents greater than 37 vol%. The Pt utilization percentage was close to 100% for Pt/TiN with percolated AB networks. It was also found that the percolated AB networks supplied effective gas transport pathways, which were not flooded by generated water, thus enhancing the oxygen mass transport. The practical-sized MEA using Pt/TiN + 47 vol% AB showed 1.5 times greater mass activity and a comparable performance under a practical operating condition for micro-CHP applications, compared with the MEA using a commercial graphitized carbon black-supported platinum catalyst.

  7. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Science.gov (United States)

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  8. Catalysts, Protection Layers, and Semiconductors

    DEFF Research Database (Denmark)

    Chorkendorff, Ib

    2015-01-01

    Hydrogen is the simplest solar fuel to produce and in this presentation we shall give a short overview of the pros and cons of various tandem devices [1]. The large band gap semiconductor needs to be in front, but apart from that we can chose to have either the anode in front or back using either...... acid or alkaline conditions. Since most relevant semiconductors are very prone to corrosion the advantage of using buried junctions and using protection layers offering shall be discussed [2-4]. Next we shall discuss the availability of various catalysts for being coupled to these protections layers...... and how their stability may be evaluated [5, 6]. Examples of half-cell reaction using protection layers for both cathode and anode will be discussed though some of recent examples under both alkaline and acidic conditions. Si is a very good low band gap semiconductor and by using TiO2 as a protection...

  9. Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

    Science.gov (United States)

    Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

    2016-09-01

    The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

  10. Oxygen-reducing catalyst layer

    Science.gov (United States)

    O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; Yang, Ruizhi; Easton, E. Bradley; Dahn, Jeffrey R.; O'Neill, David G.

    2011-03-22

    An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  11. Novel anti-flooding poly(dimethylsiloxane) (PDMS) catalyst binder for microbial fuel cell cathodes

    KAUST Repository

    Zhang, Fang

    2012-11-01

    Poly(dimethylsiloxane) (PDMS) was investigated as an alternative to Nafion as an air cathode catalyst binder in microbial fuel cells (MFCs). Cathodes were constructed around either stainless steel (SS) mesh or copper mesh using PDMS as both catalyst binder and diffusion layer, and compared to cathodes of the same structure having a Nafion binder. With PDMS binder, copper mesh cathodes produced a maximum power of 1710 ± 1 mW m -2, while SS mesh had a slightly lower power of 1680 ± 12 mW m -2, with both values comparable to those obtained with Nafion binder. Cathodes with PDMS binder had stable power production of 1510 ± 22 mW m -2 (copper) and 1480 ± 56 mW m -2 (SS) over 15 days at cycle 15, compared to a 40% decrease in power with the Nafion binder. Cathodes with the PDMS binder had lower total cathode impedance than those with Nafion. This is due to a large decrease in diffusion resistance, because hydrophobic PDMS effectively prevented catalyst sites from filling up with water, improving oxygen mass transfer. The cost of PDMS is only 0.23% of that of Nafion. These results showed that PDMS is a very effective and low-cost alternative to Nafion binder that will be useful for large scale construction of these cathodes for MFC applications. © 2012 Elsevier B.V.

  12. Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

    Science.gov (United States)

    Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

    2016-09-01

    The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

  13. Impact of liquid water on oxygen reaction in cathode catalyst layer of proton exchange membrane fuel cell: A simple and physically sound model

    Science.gov (United States)

    Zhang, Xiaoxian; Gao, Yuan

    2016-06-01

    When cells work at high current density, liquid water accumulates in their catalyst layer (CL) and the gaseous oxygen could dissolve into the water and the ionomer film simultaneously; their associated dissolved concentrations in equilibrium with the gaseous oxygen are also different. Based on a CL acquired using tomography, we present new methods in this paper to derive agglomerate models for partly saturated CL by viewing the movement and reaction of the dissolved oxygen in the two liquids (water and ionomer) and the agglomerate as two independent random processes. Oxygen dissolved in the water moves differently from oxygen dissolved in the ionomer, and to make the analysis tractable, we use an average distribution function to describe the average movement of all dissolved oxygen. A formula is proposed to describe this average distribution function, which, in combination with the exponential distribution assumed in the literature for oxygen reaction, leads to a simple yet physically sound agglomerate model. The model has three parameters which can be directly calculated from CL structure rather than by calibration. We explain how to calculate these parameters under different water contents for a given CL structure, and analyse the impact of liquid water on cell performance.

  14. Enhanced stability of multilayer graphene-supported catalysts for polymer electrolyte membrane fuel cell cathodes

    Science.gov (United States)

    Marinkas, A.; Hempelmann, R.; Heinzel, A.; Peinecke, V.; Radev, I.; Natter, H.

    2015-11-01

    One of the biggest challenges in the field of polymer electrolyte membrane fuel cells (PEMFC) is to enhance the lifetime and the long-term stability of PEMFC electrodes, especially of cathodes, furthermore, to reduce their platinum loading, which could lead to a cost reduction for efficient PEMFCs. These demands could be achieved with a new catalyst support architecture consisting of a composite of carbon structures with significant different morphologies. A highly porous cathode catalyst support layer is prepared by addition of various carbon types (carbon black particles, multi-walled carbon nanotubes (MWCNT)) to multilayer graphene (MLG). The reported optimized cathodes shows extremely high durability and similar performance to commercial standard cathodes but with 89% lower Pt loading. The accelerated aging protocol (AAP) on the membrane electrode assemblies (MEA) shows that the presence of MLG increases drastically the durability and the Pt-extended electrochemical surface area (ECSA). In fact, after the AAP slightly enhanced performance can be observed for the MLG-containing cathodes instead of a performance loss, which is typical for the commercial carbon-based cathodes. Furthermore, the presence of MLG drastically decreases the ECSA loss rate. The MLG-containing cathodes show up to 6.8 times higher mass-normalized Pt-extended ECSA compared to the commercial standard systems.

  15. The coated cathode conductive layer chamber

    International Nuclear Information System (INIS)

    We describe a gaseous detector consisting of thin anode strips vacuum-evaporated on one side of a 100 μ thick plastic layer, alternating on the back side of the same foil with wider parallel cathode strips. Ionizatin released in a drift space on the anode side is amplified and detected much in the same way as in the microstrip gas chamber; in our detector however spontaenous breakdown due to surface currents is completely avoided by the presence of the insulating layer between anodes and cathodes. To reduce surface and volume charging up, we have used polymer foils with a moderate volume resistivity. The first results show good efficiency, good plateaux and time resolution in detecting low-rate minimum ionizing electrons. Although not suited for high rate or good energy resolution applications, this kind of detector seems rather promising for realizing cheaply large active surfaces. (orig.)

  16. Neutral hydrophilic cathode catalyst binders for microbial fuel cells

    KAUST Repository

    Saito, Tomonori

    2011-01-01

    Improving oxygen reduction in microbial fuel cell (MFC) cathodes requires a better understanding of the effects of the catalyst binder chemistry and properties on performance. A series of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) polymers with systematically varying hydrophilicity were designed to determine the effect of the hydrophilic character of the binder on cathode performance. Increasing the hydrophilicity of the PS-b-PEO binders enhanced the electrochemical response of the cathode and MFC power density by ∼15%, compared to the hydrophobic PS-OH binder. Increased cathode performance was likely a result of greater water uptake by the hydrophilic binder, which would increase the accessible surface area for oxygen reduction. Based on these results and due to the high cost of PS-b-PEO, the performance of an inexpensive hydrophilic neutral polymer, poly(bisphenol A-co-epichlorohydrin) (BAEH), was examined in MFCs and compared to a hydrophilic sulfonated binder (Nafion). MFCs with BAEH-based cathodes with two different Pt loadings initially (after 2 cycles) had lower MFC performance (1360 and 630 mW m-2 for 0.5 and 0.05 mg Pt cm-2) than Nafion cathodes (1980 and 1080 mW m -2 for 0.5 and 0.05 mg Pt cm-2). However, after long-term operation (22 cycles, 40 days), power production of each cell was similar (∼1200 and 700-800 mW m-2 for 0.5 and 0.05 mg Pt cm-2) likely due to cathode biofouling that could not be completely reversed through physical cleaning. While binder chemistry could improve initial electrochemical cathode performance, binder materials had less impact on overall long-term MFC performance. This observation suggests that long-term operation of MFCs will require better methods to avoid cathode biofouling. © 2011 The Royal Society of Chemistry.

  17. Diffusion layer characteristics for increasing the performance of activated carbon air cathodes in microbial fuel cells

    KAUST Repository

    Zhang, Xiaoyuan

    2016-01-01

    The characteristics of several different types of diffusion layers were systematically examined to improve the performance of activated carbon air cathodes used in microbial fuel cells (MFCs). A diffusion layer of carbon black and polytetrafluoroethylene (CB + PTFE) that was pressed onto a stainless steel mesh current collector achieved the highest cathode performance. This cathode also had a high oxygen mass transfer coefficient and high water pressure tolerance (>2 m), and it had the highest current densities in abiotic chronoamperometry tests compared to cathodes with other diffusion layers. In MFC tests, this cathode also produced maximum power densities (1610 ± 90 mW m−2) that were greater than those of cathodes with other diffusion layers, by 19% compared to Gore-Tex (1350 ± 20 mW m−2), 22% for a cloth wipe with PDMS (1320 ± 70 mW m−2), 45% with plain PTFE (1110 ± 20 mW m−2), and 19% higher than those of cathodes made with a Pt catalyst and a PTFE diffusion layer (1350 ± 50 mW m−2). The highly porous diffusion layer structure of the CB + PTFE had a relatively high oxygen mass transfer coefficient (1.07 × 10−3 cm s−1) which enhanced oxygen transport to the catalyst. The addition of CB enhanced cathode performance by increasing the conductivity of the diffusion layer. Oxygen mass transfer coefficient, water pressure tolerance, and the addition of conductive particles were therefore critical features for achieving higher performance AC air cathodes.

  18. A new dispenser cathode with dual-layer

    Science.gov (United States)

    Li, Yutao; Zhang, Honglai; Liu, Pukun; Zhang, Mingchen

    2005-09-01

    The emission and surface characteristics of the dispenser cathode coated with Os-W alloy and that coated with Os-W/Re are studied and compared. The dispenser cathode coated with Os-W/Re has been applied in electron gun measurement system for making measurement of higher emission current and life test. We called the cathode coated with Os-W/Re as the cathode with dual-layer. It is found that the dispenser cathode coated with dual-layer has higher current density than that coated only with Os-W alloy. After being activated, the cathode coated with dual-layer presents ternary composition on the surface of it. The W surface composition does not rise with time comparing with that of the cathode coated with Os-W alloy. In electron gun, the dispenser cathode coated with dual-layer has pulse current density of 30 A/cm 2 and life of more than 800 h.

  19. A new dispenser cathode with dual-layer

    International Nuclear Information System (INIS)

    The emission and surface characteristics of the dispenser cathode coated with Os-W alloy and that coated with Os-W/Re are studied and compared. The dispenser cathode coated with Os-W/Re has been applied in electron gun measurement system for making measurement of higher emission current and life test. We called the cathode coated with Os-W/Re as the cathode with dual-layer. It is found that the dispenser cathode coated with dual-layer has higher current density than that coated only with Os-W alloy. After being activated, the cathode coated with dual-layer presents ternary composition on the surface of it. The W surface composition does not rise with time comparing with that of the cathode coated with Os-W alloy. In electron gun, the dispenser cathode coated with dual-layer has pulse current density of 30 A/cm2 and life of more than 800 h

  20. Carbon xerogels as catalyst supports for PEM fuel cell cathode

    International Nuclear Information System (INIS)

    Carbon xerogels with various pore textures were prepared by evaporative drying and pyrolysis of resorcinol-formaldehyde gels, and used as supports for Pt catalysts in PEM fuel cell cathodes. The goal of this study was to determine whether carbon xerogels could replace the carbon aerogels which were previously used as Pt catalyst supports in the same electrochemical system, and to determine how the pore texture influences the cell performances. Pt catalysts were prepared by impregnation of carbon supports with aqueous H2PtCl6 solution followed by reduction in aqueous phase with NaBH4. Fuel cell measurements show that the metal surface actually available for the oxygen reduction reaction and the voltage losses due to diffusion phenomena strongly depend on the carbon pore texture. Finally, some carbon xerogels yield similar performance than carbon aerogels

  1. Power generation using carbon mesh cathodes with different diffusion layers in microbial fuel cells

    KAUST Repository

    Luo, Yong

    2011-11-01

    An inexpensive carbon material, carbon mesh, was examined to replace the more expensive carbon cloth usually used to make cathodes in air-cathode microbial fuel cells (MFCs). Three different diffusion layers were tested using carbon mesh: poly(dimethylsiloxane) (PDMS), polytetrafluoroethylene (PTFE), and Goretex cloth. Carbon mesh with a mixture of PDMS and carbon black as a diffusion layer produced a maximum power density of 1355 ± 62 mW m -2 (normalized to the projected cathode area), which was similar to that obtained with a carbon cloth cathode (1390 ± 72 mW m-2). Carbon mesh with a PTFE diffusion layer produced only a slightly lower (6.6%) maximum power density (1303 ± 48 mW m-2). The Coulombic efficiencies were a function of current density, with the highest value for the carbon mesh and PDMS (79%) larger than that for carbon cloth (63%). The cost of the carbon mesh cathode with PDMS/Carbon or PTFE (excluding catalyst and binder costs) is only 2.5% of the cost of the carbon cloth cathode. These results show that low cost carbon materials such as carbon mesh can be used as the cathode in an MFC without reducing the performance compared to more expensive carbon cloth. © 2011 Elsevier B.V.

  2. Lattice Boltzmann Pore-Scale Investigation of Coupled Physical-electrochemical Processes in C/Pt and Non-Precious Metal Cathode Catalyst Layers in Proton Exchange Membrane Fuel Cells

    International Nuclear Information System (INIS)

    Highlights: • Nanoscale structures of catalyst layer are reconstructed. • Pore-scale simulation is performed to predict macroscopic transport properties. • Reactive transport in catalyst layer with non-precious metal and Pt catalysts is studied. • Mesopores rather than micropores are required to enhance mass transport. - Abstract: High-resolution porous structures of catalyst layers (CLs) including non-precious metal catalysts (NPMCs) or Pt for proton exchange membrane fuel cells are reconstructed using the quartet structure generation set. The nanoscale structures are analyzed in terms of pore size distribution, specific surface area, and phase connectivity. Pore-scale simulation methods based on the lattice Boltzmann method are developed to predict the macroscopic transport properties in CLs. The non-uniform distribution of ionomer in CL generates more tortuous pathways for reactant transport, greatly reducing the effective diffusivity. The tortuosity of CLs is much higher than that adopted by the Bruggeman equation. Knudsen diffusion plays a significant role in oxygen diffusion and significantly reduces the effective diffusivity. Reactive transport inside the CLs is also investigated. Although the reactive surface area of the non-precious metal catalyst (NPMC) CL is much higher than that of the Pt CL, the oxygen reaction rate is lower in the NPMC CL due to the much lower reaction rate coefficient. Although pores of a few nanometers in size can increase the number of reactive sites in NPMC CLs, they contribute little to enhance the mass transport. Mesopores, which are a few tens of nanometers or larger in size, are shown to be required in order to increase the mass transport rate

  3. Polymer coatings as separator layers for microbial fuel cell cathodes

    Science.gov (United States)

    Watson, Valerie J.; Saito, Tomonori; Hickner, Michael A.; Logan, Bruce E.

    2011-03-01

    Membrane separators reduce oxygen flux from the cathode into the anolyte in microbial fuel cells (MFCs), but water accumulation and pH gradients between the separator and cathode reduces performance. Air cathodes were spray-coated (water-facing side) with anion exchange, cation exchange, and neutral polymer coatings of different thicknesses to incorporate the separator into the cathode. The anion exchange polymer coating resulted in greater power density (1167 ± 135 mW m-2) than a cation exchange coating (439 ± 2 mW m-2). This power output was similar to that produced by a Nafion-coated cathode (1114 ± 174 mW m-2), and slightly lower than the uncoated cathode (1384 ± 82 mW m-2). Thicker coatings reduced oxygen diffusion into the electrolyte and increased coulombic efficiency (CE = 56-64%) relative to an uncoated cathode (29 ± 8%), but decreased power production (255-574 mW m-2). Electrochemical characterization of the cathodes ex situ to the MFC showed that the cathodes with the lowest charge transfer resistance and the highest oxygen reduction activity produced the most power in MFC tests. The results on hydrophilic cathode separator layers revealed a trade off between power and CE. Cathodes coated with a thin coating of anion exchange polymer show promise for controlling oxygen transfer while minimally affecting power production.

  4. Polymer coatings as separator layers for microbial fuel cell cathodes

    KAUST Repository

    Watson, Valerie J.

    2011-03-01

    Membrane separators reduce oxygen flux from the cathode into the anolyte in microbial fuel cells (MFCs), but water accumulation and pH gradients between the separator and cathode reduces performance. Air cathodes were spray-coated (water-facing side) with anion exchange, cation exchange, and neutral polymer coatings of different thicknesses to incorporate the separator into the cathode. The anion exchange polymer coating resulted in greater power density (1167 ± 135 mW m-2) than a cation exchange coating (439 ± 2 mW m-2). This power output was similar to that produced by a Nafion-coated cathode (1114 ± 174 mW m-2), and slightly lower than the uncoated cathode (1384 ± 82 mW m-2). Thicker coatings reduced oxygen diffusion into the electrolyte and increased coulombic efficiency (CE = 56-64%) relative to an uncoated cathode (29 ± 8%), but decreased power production (255-574 mW m-2). Electrochemical characterization of the cathodes ex situ to the MFC showed that the cathodes with the lowest charge transfer resistance and the highest oxygen reduction activity produced the most power in MFC tests. The results on hydrophilic cathode separator layers revealed a trade off between power and CE. Cathodes coated with a thin coating of anion exchange polymer show promise for controlling oxygen transfer while minimally affecting power production. © 2010 Elsevier B.V. All rights reserved.

  5. Low platinum, high limiting current density of the PEMFC (proton exchange membrane fuel cell) based on multilayer cathode catalyst approach

    International Nuclear Information System (INIS)

    Novel multilayer cathode electrodes structures for PEMFC (proton exchange membrane fuel cell) based on sputtering technique were developed to provide high performance with low loading Pt of 0.05 mg/cm² compared to the standard MEA (membrane electrode assembly) cathode (∼0.2–0.3 mg/cm²). Different configurations of cathode catalyst layer were made by altering Pt and CN (Carbon–Nafion) ink carefully prepared on gas diffusion layer containing MPL (micro porous layer). The performances of PEMFC containing the multilayer electrodes were compared based on their measured polarization curves. Higher limiting current densities were achieved compared to standard MEA with platinum loading of 0.2 mg/cm² both at the cathode and the anode sides. Limiting current densities over 1.1 A/cm2, 1.2 A/cm2 and 1.4 A/cm2 were reached whereas maximum powers were in the range of 500 mW/cm² at 600 mW/cm². The good performances obtained can be due to the structural improvement which has contributed to a better catalyst utilization compared to conventional methods. A CN loading inferior to 0.24 mg/cm² between each layer is preferred for multilayer electrode. - Highlights: • Multilayer cathode of PEM fuel cell. • Enhanced performances with carbon–Nafion layer of PEM fuel cell. • Effect of the number of Pt sputtered layers on cell performance. • Increased power densities achieved. • Increased limiting current densities achieved

  6. Preparation, characterization and degradation investigations of cathode catalysts for automotive PEM fuel cells systems

    OpenAIRE

    Marcu, Alina

    2014-01-01

    This research was designed to meet Daimler systematic efforts to address future electromobility demands. The work focuses on developing potential cathode catalysts and tests procedures to be employed in prototype fuel cells. In order to achieve commercial cost-competitive polymer electrolyte membrane fuel cells (PEM FC), the following major challenges have to be addressed: i) The catalytic mass activity of the cathode catalysts has to be at least 0.44 A/mg Pt representing an increased factor ...

  7. Microbial Fuel Cell Cathodes With Poly(dimethylsiloxane) Diffusion Layers Constructed around Stainless Steel Mesh Current Collectors

    KAUST Repository

    Zhang, Fang

    2010-02-15

    A new and simplified approach for making cathodes for microbial fuel cells (MFCs) was developed by using metal meshcurrent collectorsandinexpensive polymer/carbon diffusion layers (DLs). Rather than adding a current collector to a cathode material such as carbon cloth, we constructed the cathode around the metal mesh itself, thereby avoiding the need for the carbon cloth or other supporting material. A base layer of poly(dimethylsiloxane) (PDMS) and carbon black was applied to the air-side of a stainless steel mesh, and Pt on carbon black with Nafion binder was applied to the solutionside as catalyst for oxygen reduction. The PDMS prevented water leakage and functioned as a DL by limiting oxygen transfer through the cathode and improving coulombic efficiency. PDMS is hydrophobic, stable, and less expensive than other DL materials, such as PTFE, that are commonly applied to air cathodes. Multiple PDMS/carbon layers were applied in order to optimize the performance of the cathode. Two PDMS/ carbon layers achieved the highest maximum power density of 1610 ± 56 mW/m 2 (normalized to cathode projected surface area; 47.0 ± 1.6 W/m3 based on liquid volume). This power output was comparable to the best result of 1635 ± 62 mW/m2 obtained using carbon cloth with three PDMS/carbon layers and a Pt catalyst. The coulombic efficiency of the mesh cathodes reached more than 80%, and was much higher than the maximum of 57% obtained with carbon cloth. These findings demonstrate that cathodes can be constructed around metal mesh materials such as stainless steel, and that an inexpensive coating of PDMS can prevent water leakage and lead to improved coulombic efficiencies. © 2010 American Chemical Society.

  8. Water Uptake in PEMFC Catalyst Layers

    Energy Technology Data Exchange (ETDEWEB)

    Gunterman, Haluna P.; Kwong, Anthony H.; Gostick, Jeffrey T.; Kusoglu, Ahmet; Weber, Adam Z.

    2011-07-01

    Water uptake profiles of proton-exchange-membrane fuel-cell catalyst layers are characterized in the form of capillary-pressure saturation (Pc-S) curves. The curves indicate that the catalyst layers tested are highly hydrophilic and require capillary pressures as low as -80 kPa to eject imbibed water. Comparison of materials made with and without Pt indicates a difference in water ejection and uptake phenomena due to the presence of Pt. The addition of Pt increases the tendency of the catalyst layer to retain water. Dynamic vapor sorption (DVS) is used to characterize the water-vapor sorption onto Nafion, Pt/C, and C surfaces. The DVS results align with the trends found from the Pc-S curves and show an increased propensity for water uptake in the presence of Pt. The effect of the ion in Nafion, sodium or protonated form, is also compared and demonstrates that although the protonation of the Nafion in the catalyst layer also increases hydrophilicity, the effect is not as great as that caused by Pt.

  9. Cathodes for lithium-air battery cells with acid electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Xing, Yangchuan; Huang, Kan; Li, Yunfeng

    2016-07-19

    In various embodiments, the present disclosure provides a layered metal-air cathode for a metal-air battery. Generally, the layered metal-air cathode comprises an active catalyst layer, a transition layer bonded to the active catalyst layer, and a backing layer bonded to the transition layer such that the transition layer is disposed between the active catalyst layer and the backing layer.

  10. Impact of salinity on cathode catalyst performance in microbial fuel cells (MFCs)

    KAUST Repository

    Wang, Xi

    2011-10-01

    Several alternative cathode catalysts have been proposed for microbial fuel cells (MFCs), but effects of salinity (sodium chloride) on catalyst performance, separate from those of conductivity on internal resistance, have not been previously examined. Three different types of cathode materials were tested here with increasingly saline solutions using single-chamber, air-cathode MFCs. The best MFC performance was obtained using a Co catalyst (cobalt tetramethoxyphenyl porphyrin; CoTMPP), with power increasing by 24 ± 1% to 1062 ± 9 mW/m2 (normalized to the projected cathode surface area) when 250 mM NaCl (final conductivity of 31.3 mS/cm) was added (initial conductivity of 7.5 mS/cm). This power density was 25 ± 1% higher than that achieved with Pt on carbon cloth, and 27 ± 1% more than that produced using an activated carbon/nickel mesh (AC) cathode in the highest salinity solution. Linear sweep voltammetry (LSV) was used to separate changes in performance due to solution conductivity from those produced by reductions in ohmic resistance with the higher conductivity solutions. The potential of the cathode with CoTMPP increased by 17-20 mV in LSVs when the NaCl addition was increased from 0 to 250 mM independent of solution conductivity changes. Increases in current were observed with salinity increases in LSVs for AC, but not for Pt cathodes. Cathodes with CoTMPP had increased catalytic activity at higher salt concentrations in cyclic voltammograms compared to Pt and AC. These results suggest that special consideration should be given to the type of catalyst used with more saline wastewaters. While Pt oxygen reduction activity is reduced, CoTMPP cathode performance will be improved at higher salt concentrations expected for wastewaters containing seawater. © 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  11. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk

    2014-12-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  12. Development of highly active and stable hybrid cathode catalyst for PEMFCs

    Science.gov (United States)

    Jung, Won Suk

    Polymer electrolyte membrane fuel cells (PEMFCs) are attractive power sources of the future for a variety of applications including portable electronics, stationary power, and automobile application. However, sluggish cathode kinetics, high Pt cost, and durability issues inhibit the commercialization of PEMFCs. To overcome these drawbacks, research has been focused on alloying Pt with transition metals since alloy catalysts show significantly improved catalytic properties like high activity, selectivity, and durability. However, Pt-alloy catalysts synthesized using the conventional impregnation method exhibit uneven particle size and poor particle distribution resulting in poor performance and/or durability in PEMFCs. In this dissertation, a novel catalyst synthesis methodology is developed and compared with catalysts prepared using impregnation method and commercial catalysts. Two approaches are investigated for the catalyst development. The catalyst durability was studied under U. S. DRIVE Fuel Cell Tech Team suggested protocols. In the first approach, the carbon composite catalyst (CCC) having active sites for oxygen reduction reaction (ORR) is employed as a support for the synthesis of Pt/CCC catalyst. The structural and electrochemical properties of Pt/CCC catalyst are investigated using high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, while RDE and fuel cell testing are carried out to study the electrochemical properties. The synergistic effect of CCC and Pt is confirmed by the observed high activity towards ORR for the Pt/CCC catalyst. The second approach is the synthesis of Co-doped hybrid cathode catalysts (Co-doped Pt/CCC) by diffusing the Co metal present within the CCC support into the Pt nanoparticles during heat-treatment. The optimized Co-doped Pt/CCC catalyst performed better than the commercial catalysts and the catalyst prepared using the impregnation method in PEMFCs and showed high

  13. Effect of catalyst layer defects on local membrane degradation in polymer electrolyte fuel cells

    Science.gov (United States)

    Tavassoli, Arash; Lim, Chan; Kolodziej, Joanna; Lauritzen, Michael; Knights, Shanna; Wang, G. Gary; Kjeang, Erik

    2016-08-01

    Aiming at durability issues of fuel cells, this research is dedicated to a novel experimental approach in the analysis of local membrane degradation phenomena in polymer electrolyte fuel cells, shedding light on the potential effects of manufacturing imperfections on this process. With a comprehensive review on historical failure analysis data from field operated fuel cells, local sources of iron oxide contaminants, catalyst layer cracks, and catalyst layer delamination are considered as potential candidates for initiating or accelerating the local membrane degradation phenomena. Customized membrane electrode assemblies with artificial defects are designed, fabricated, and subjected to membrane accelerated stress tests followed by extensive post-mortem analysis. The results reveal a significant accelerating effect of iron oxide contamination on the global chemical degradation of the membrane, but dismiss local traces of iron oxide as a potential stressor for local membrane degradation. Anode and cathode catalyst layer cracks are observed to have negligible impact on the membrane degradation phenomena. Notably however, distinct evidence is found that anode catalyst layer delamination can accelerate local membrane thinning, while cathode delamination has no apparent effect. Moreover, a substantial mitigating effect for platinum residuals on the site of delamination is observed.

  14. Hydrogen production with nickel powder cathode catalysts in microbial electrolysis cells

    KAUST Repository

    Selembo, Priscilla A.

    2010-01-01

    Although platinum is commonly used as catalyst on the cathode in microbial electrolysis cells (MEC), non-precious metal alternatives are needed to reduce costs. Cathodes were constructed using a nickel powder (0.5-1 μm) and their performance was compared to conventional electrodes containing Pt (0.002 μm) in MECs and electrochemical tests. The MEC performance in terms of coulombic efficiency, cathodic, hydrogen and energy recoveries were similar using Ni or Pt cathodes, although the maximum hydrogen production rate (Q) was slightly lower for Ni (Q = 1.2-1.3 m3 H2/m3/d; 0.6 V applied) than Pt (1.6 m3 H2/m3/d). Nickel dissolution was minimized by replacing medium in the reactor under anoxic conditions. The stability of the Ni particles was confirmed by examining the cathodes after 12 MEC cycles using scanning electron microscopy and linear sweep voltammetry. Analysis of the anodic communities in these reactors revealed dominant populations of Geobacter sulfurreduces and Pelobacter propionicus. These results demonstrate that nickel powder can be used as a viable alternative to Pt in MECs, allowing large scale production of cathodes with similar performance to systems that use precious metal catalysts. © 2009 Professor T. Nejat Veziroglu.

  15. Conducting polymer-doped polyprrrole as an effective cathode catalyst for Li-O2 batteries

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Doped polypyrrole as cathode catalysts for Li-O2 batteries. • Polypyrrole has an excellent redox capability to activate oxygen reduction. • Chloride doped polypyrrole demonstrated an improved catalytic performance in Li-O2 batteries. - Abstract: Polypyrrole conducting polymers with different dopants have been synthesized and applied as the cathode catalyst in Li-O2 batteries. Polypyrrole polymers exhibited an effective catalytic activity towards oxygen reduction in lithium oxygen batteries. It was discovered that dopant significantly influenced the electrochemical performance of polypyrrole. The polypyrrole doped with Cl− demonstrated higher capacity and more stable cyclability than that doped with ClO4−. Polypyrrole conducting polymers also exhibited higher capacity and better cycling performance than that of carbon black catalysts

  16. Effect of Particle Size and Operating Conditions on Pt3Co PEMFC Cathode Catalyst Durability

    Directory of Open Access Journals (Sweden)

    Mallika Gummalla

    2015-05-01

    Full Text Available The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC cathodes with Pt3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes with the smallest Pt3Co particle size was the highest and that of the largest Pt3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s, the relative improvement in performance of the cathode based on 8.1 nm Pt3Co over the 4.9 nm Pt3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA of the decayed membrane-electrode assembly (MEA showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.

  17. Modeling Low-Platinum-Loading Effects in Fuel-Cell Catalyst Layers

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Wonseok; Weber, Adam Z.

    2011-01-20

    The cathode catalyst layer within a proton-exchange-membrane fuel cell is the most complex and critical, yet least understood, layer within the cell. The exact method and equations for modeling this layer are still being revised and will be discussed in this paper, including a 0.8 reaction order, existence of Pt oxides, possible non-isopotential agglomerates, and the impact of a film resistance towards oxygen transport. While the former assumptions are relatively straightforward to understand and implement, the latter film resistance is shown to be critically important in explaining increased mass-transport limitations with low Pt-loading catalyst layers. Model results demonstrate agreement with experimental data that the increased oxygen flux and/or diffusion pathway through the film can substantially decrease performance. Also, some scale-up concepts from the agglomerate scale to the more macroscopic porous-electrode scale are discussed and the resulting optimization scenarios investigated.

  18. A SnO2-Based Cathode Catalyst for Lithium-Air Batteries.

    Science.gov (United States)

    Mei, Delong; Yuan, Xianxia; Ma, Zhong; Wei, Ping; Yu, Xuebin; Yang, Jun; Ma, Zi-Feng

    2016-05-25

    SnO2 and SnO2@C have been successfully synthesized with a simple hydrothermal procedure combined with heat treatment, and their performance as cathode catalysts of Li-air batteries has been comparatively evaluated and discussed. The results show that both SnO2 and SnO2@C are capable of catalyzing oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) at the cathode of Li-air batteries, but the battery with SnO2@C displays better performance due to its unique higher conductivity, larger surface area, complex pore distribution, and huge internal space. PMID:27152996

  19. Poly(vinylidene fluoride-co-hexafluoropropylene) phase inversion coating as a diffusion layer to enhance the cathode performance in microbial fuel cells

    KAUST Repository

    Yang, Wulin

    2014-12-01

    A low cost poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) phase inversion coating was developed as a cathode diffusion layer to enhance the performance of microbial fuel cells (MFCs). A maximum power density of 1430 ± 90 mW m-2 was achieved at a PVDF-HFP loading of 4.4 mg cm-2 (4:1 polymer:carbon black), with activated carbon as the oxygen reduction cathode catalyst. This power density was 31% higher than that obtained with a more conventional platinum (Pt) catalyst on carbon cloth (Pt/C) cathode with a poly(tetrafluoroethylene) (PTFE) diffusion layer (1090 ± 30 mW m-2). The improved performance was due in part to a larger oxygen mass transfer coefficient of 3 × 10-3 cm s-1 for the PVDF-HFP coated cathode, compared to 1.7 × 10-3 cm s -1 for the carbon cloth/PTFE-based cathode. The diffusion layer was resistant to electrolyte leakage up to water column heights of 41 ± 0.5 cm (4.4 mg cm-2 loading of 4:1 polymer:carbon black) to 70 ± 5 cm (8.8 mg cm-2 loading of 4:1 polymer:carbon black). This new type of PVDF-HFP/carbon black diffusion layer could reduce the cost of manufacturing cathodes for MFCs. © 2014 Elsevier B.V. All rights reserved.

  20. Fabrication of biofuel cell containing enzyme catalyst immobilized by layer-by-layer method

    Science.gov (United States)

    Hyun, Kyu Hwan; Han, Sang Won; Koh, Won-Gun; Kwon, Yongchai

    2015-07-01

    Enzymatic biofuel cell (EBC) employing a layer-by-layer (LbL) structure consisting of multiple layers of glucose oxidase (GOx) and poly(ethyleneimine) (PEI) at carbon nanotube (CNT) ([GOx/PEI]n/CNT) is fabricated. The [GOx/PEI]n/CNT serves as anode catalyst for promoting glucose reaction, while Pt is employed as cathode catalyst. To evaluate effect of [GOx/PEI]n/CNT on EBC performance and stability, several characterizations are conducted. The optimal GOx/PEI layer is determined electrochemically, and it turns out that [GOx/PEI]2/CNT is the best. Electron transfer rate constant of the optimal layer is 11.3 s-1, its glucose sensitivity is 83 μAmM-1cm-2, and maximum power density of EBC adopting [GOx/PEI]2/CNT is 1.34 mWcm-2. The values are superior to those of other reference structures, indicating that the [GOx/PEI]2/CNT can produce excellent reactivity, followed by improved EBC performance. In terms of redox reaction mechanism of flavin adenine dinucleotide (FAD) within [GOx/PEI]2/CNT, glucose does not affect the redox reaction of FAD, while oxygen serves as mediator in transferring electrons and protons produced by glucose oxidation into those for reduction reaction of FAD. It is also found that the [GOx/PEI]2/CNT is confined by surface reaction and the reaction is quasi-reversible. Regarding long-term stability, [GOx/PEI]2/CNT maintains ∼83% of initial activity even after two weeks.

  1. Effect of a cathode buffer layer on the stability of organic solar cells

    International Nuclear Information System (INIS)

    We present the effect of a cathode buffer layer on the performance and stability of organic photovoltaics (OPVs) based on a blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). Six kinds of cathode buffer layers, i.e. lithium fluoride, sodium chloride, NaCl/Mg, tris-(8-hydroxy-quinoline) aluminum, bathocuproine and 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene, were inserted between the photoactive layer and an Al cathode, which played a dominant role in the device’s performance. Devices with the cathode buffer layers above exhibited improved performance. The degradation of these devices with encapsulation was further investigated in an inert atmosphere. The results indicated that devices with inorganic cathode buffer layers exhibited better stability than those with organic cathode buffer layers. (paper)

  2. Mesoporous nitrogen-rich carbon materials as cathode catalysts in microbial fuel cells

    KAUST Repository

    Ahn, Yongtae

    2014-12-01

    The high cost of the catalyst material used for the oxygen reduction reaction in microbial fuel cell (MFC) cathodes is one of the factors limiting practical applications of this technology. Mesoporous nitrogen-rich carbon (MNC), prepared at different temperatures, was examined as an oxygen reduction catalyst, and compared in performance to Pt in MFCs and electrochemical cells. MNC calcined at 800 °C produced a maximum power density of 979 ± 131 mW m-2 in MFCs, which was 37% higher than that produced using MNC calined at 600 °C (715 ± 152 mW m-2), and only 14% lower than that obtained with Pt (1143 ± 54 mW m-2). The extent of COD removal and coulombic efficiencies were the same for all cathode materials. These results show that MNC could be used as an alternative to Pt in MFCs. © 2014 Elsevier B.V. All rights reserved.

  3. Load cycle durability of a graphitized carbon black-supported platinum catalyst in polymer electrolyte fuel cell cathodes

    Science.gov (United States)

    Takei, Chikara; Kakinuma, Katsuyoshi; Kawashima, Kazuhito; Tashiro, Keisuke; Watanabe, Masahiro; Uchida, Makoto

    2016-08-01

    We focus on Pt degradation occurring during fuel cell vehicle (FCV) combined drive cycles involving load and open circuit voltage (OCV) just after startup and during idling. Load cycle durability is evaluated as a function of OCV/load holding time, load rate and relative humidity (RH) with a graphitized carbon black-supported platinum catalyst (Pt/GCB) in the cathode. The degradation of Pt/GCB is suppressed for shorter OCV holding times, lower load rates and lower RH. Scanning ion microscopy (SIM) images of membrane cross-sections indicate that the amount of Pt deposited in the membrane decreases during drive cycles involving load with short OCV holding times. Investigations of the Pt distribution in the cathode catalyst layer (CL) by using scanning TEM-EDX show that the dissolution of Pt is suppressed on the membrane side in the CL. The Pt dissolution is accelerated by the high Pt oxidation due to the long OCV holding time. A load cycle with both long OCV holding time and low load inhibits the Pt2+ migration into the membrane but accelerates the Pt particle growth due to electrochemical Ostwald ripening; meanwhile, a load cycle with long OCV holding time at lower RH prevents both the Pt dissolution and particle growth.

  4. Nonactivated and Activated Biochar Derived from Bananas as Alternative Cathode Catalyst in Microbial Fuel Cells

    Directory of Open Access Journals (Sweden)

    Haoran Yuan

    2014-01-01

    Full Text Available Nonactivated and activated biochars have been successfully prepared by bananas at different thermotreatment temperatures. The activated biochar generated at 900°C (Biochar-act900 exhibited improved oxygen reduction reaction (ORR and oxygen evolution reaction (OER performances in alkaline media, in terms of the onset potential and generated current density. Rotating disk electron result shows that the average of 2.65 electrons per oxygen molecule was transferred during ORR of Biochar-act900. The highest power density of 528.2 mW/m2 and the maximum stable voltage of 0.47 V were obtained by employing Biochar-act900 as cathode catalyst, which is comparable to the Pt/C cathode. Owning to these advantages, it is expected that the banana-derived biochar cathode can find application in microbial fuel cell systems.

  5. Manganese Detection with a Metal Catalyst Free Carbon Nanotube Electrode: Anodic versus Cathodic Stripping Voltammetry

    OpenAIRE

    Yue, Wei; Bange, Adam; Riehl, Bill L.; Riehl, Bonnie D.; Johnson, Jay M.; Papautsky, Ian; Heineman, William R.

    2012-01-01

    Anodic stripping voltammetry (ASV) and cathodic stripping voltammetry (CSV) were used to determine Mn concentration using metal catalyst free carbon nanotube (MCFCNT) electrodes and square wave stripping voltammetry (SWSV). The MCFCNTs are synthesized using a Carbo Thermal Carbide Conversion method which results in a material that does not contain residual transition metals. Detection limits of 120 nM and 93 nM were achieved for ASV and CSV, respectively, with a deposition time of 60 s. CSV w...

  6. Effective reaction rates of a thin catalyst layer

    OpenAIRE

    Lenzinger, Michael; Schweizer, Ben

    2008-01-01

    The catalyst layer in a fuel cell can be described with the help of a system of reaction diffusion equations for the protonic overpotential and the oxygen concentration. The Tafel equation gives an exponential law for the reaction rate, the Tafel slope is a coefficient in this law. We present a rigorous thin layer analysis for two reaction regimes. In the case of thin catalyst layers, the original Tafel slope enters an effective boundary condition. In the case of large protonic overpotentials...

  7. Structure optimization of cathode microporous layer for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Highlights: • Pore-forming technology was introduced to optimize microporous layer microstructure. • The water removal and gas mass transfer property of diffusion layer were improved. • The optimum DMFC performance reached 292 mW cm−2 at 80 °C. - Abstract: To obtain the cathode microporous layer (CML) with high mass transfer performance and high electronic conductivity, a pore-forming technology was introduced to optimize CML microstructure for direct methanol fuel cells. In this paper, the effects of carbon material type, carbon material loading and pore-forming agent loading in CML on fuel cell performance were discussed systematically. The results indicated that the optimized CML consisted of carbon nanotubes and ammonium oxalate with the loading of 1.5 and 3.5 mg cm−2 respectively. The fuel cell performance was improved by 30.3%, from 224 to 292 mW cm−2 at 80 °C under 0.3 MPa O2. Carbon nanotube was found to be the most suitable carbon material for the CML due to its great specific surface area and small particle size, resulting in increasing the number of the hydrophobic sites and the contact area between the support and the catalyst layer. The carbon material and pore-forming agent loading directly influenced the pore distribution and the contact resistance of membrane electrode assembly. The water removal capacity and the gas mass transfer property of diffusion layer were improved by optimizing the amount of micropore and macropore structures

  8. Polyaromatic polymers as binders in PEMFC catalyst layers

    Energy Technology Data Exchange (ETDEWEB)

    Peron, J.M.; Edwards, D.; Le Marquand, P.; Shi, Z.; Holdcroft, S. [National Research Council of Canada, Vancouver, BC (Canada). Inst. for Fuel Cell Innovation

    2009-07-01

    The catalyst layers in proton exchange membrane (PEM) fuel cells are typically composed of platinum as the catalyst and carbon as the electron conductor. The binder that ensures the ionic pathway between catalyst particles and the electrolyte membrane is a perfluorinated polymer that brings the electrolyte, gaseous reactants, electrocatalyst and current collector into close contact within a confined spatial region known as the triple-phase-boundary. New non-fluorinated polymers have been developed in an effort to lower the cost and improve the stability of fuel cells. Although polyaromatic polymers have been extensively presented in the literature for membrane preparation, these new materials have been mainly characterized in presence of Nafion as a binder in the catalyst layer. This paper discussed the incorporation of polyaromatic polymers, such as sulfonated-PEEK (sPEEK), and its properties as a binder. sPEEK-based catalyst ink solutions, using different sPEEK/Pt ratios and preparation methods, have been deposited on membranes to form catalyst-coated-membranes (CCM). Initial catalyst ink were characterized using dynamic light scattering to determine agglomerate size. Catalyst layers were examined using SEM and TEM and their porosity was determined by Hg porosimetry. Various electrochemical techniques were used for in-situ characterization of prepared sPEEK CCMs.

  9. Scalable synthesis of palladium nanoparticle catalysts by atomic layer deposition

    International Nuclear Information System (INIS)

    Atomic layer deposition (ALD) was used to produce Pd/Al2O3 catalysts using sequential exposures of Pd(II) hexafluoroacetylacetonate and formalin at 200 °C in a fluidized bed reactor. The ALD-prepared Pd/alumina catalysts were characterized by various methods including hydrogen chemisorption, XPS, and TEM, and compared with a commercially available 1 wt% Pd/alumina catalyst, which was also characterized. The content of Pd on alumina support and the size of Pd nanoparticles can be controlled by the number of ALD-coating cycles and the dose time of the Pd precursor. One layer of organic component from the Pd precursor remained on the Pd particle surface. The ALD 0.9 wt% Pd/alumina had greater active metal surface area and percent metal dispersion than the commercial 1 wt% Pd/alumina catalyst. The ALD and commercial catalysts were subjected to catalytic testing to determine their relative activities for glucose oxidation to gluconic acid in aqueous solution. The ALD 0.9 wt% Pd/alumina catalyst had comparable activity as compared to the commercial 1 wt% Pd catalyst. No noticeable amount of Pd leaching was observed for the ALD-prepared catalysts during the vigorously stirred reaction.

  10. ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere

    International Nuclear Information System (INIS)

    There have been reports of challenges in designing platinum carbon (Pt/C) electrode catalysts for PEMFC. Pt/C electrode catalysts deactivate much faster on the cathode (in moisturized O2) than on the anode (in H2). To understand influences of moisture and oxygen on the deactivation of the Pt/C catalysts in proton-exchange-membrane fuel cells (PEMFCs), spherical-aberration-corrected environmental transmission electron microscopy (AC-ETEM) was applied with a high-speed CCD camera. Structural changes of the Pt/C electrode catalysts were dynamically recorded in moisturized nitrogen, oxygen and hydrogen. The mass spectrometry confirmed the moisture content (between 5 to 30 %) of nitrogen driving gas through a humidifier. Coalescence of platinum nanoparticles (D = 3.24 nm) was carefully evaluated in pure N2 and moisturized N2 atmosphere. The Pt/C showed considerable structural weakness in a moisturized N2 atmosphere. Comparable results obtained by AC-ETEM in different gas atmospheres also suggested ways to improve the oxygen reduction reaction (ORR). In this paper, the deactivation process due to moisture (hydroxylation) of carbon supports is discussed using for comparison the movement of platinum nanoparticles measured in moisturized nitrogen and pure nitrogen atmospheres

  11. Use of Pyrolyzed Iron Ethylenediaminetetraacetic Acid Modified Activated Carbon as Air–Cathode Catalyst in Microbial Fuel Cells

    KAUST Repository

    Xia, Xue

    2013-08-28

    Activated carbon (AC) is a cost-effective catalyst for the oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). To enhance the catalytic activity of AC cathodes, AC powders were pyrolyzed with iron ethylenediaminetetraacetic acid (FeEDTA) at a weight ratio of FeEDTA:AC = 0.2:1. MFCs with FeEDTA modified AC cathodes and a stainless steel mesh current collector produced a maximum power density of 1580 ± 80 mW/m2, which was 10% higher than that of plain AC cathodes (1440 ± 60 mW/m 2) and comparable to Pt cathodes (1550 ± 10 mW/m2). Further increases in the ratio of FeEDTA:AC resulted in a decrease in performance. The durability of AC-based cathodes was much better than Pt-catalyzed cathodes. After 4.5 months of operation, the maximum power density of Pt cathode MFCs was 50% lower than MFCs with the AC cathodes. Pyridinic nitrogen, quaternary nitrogen and iron species likely contributed to the increased activity of FeEDTA modified AC. These results show that pyrolyzing AC with FeEDTA is a cost-effective and durable way to increase the catalytic activity of AC. © 2013 American Chemical Society.

  12. Development of artificial surface layers for thin film cathode materials

    OpenAIRE

    Carrillo Solano, Mercedes Alicia

    2016-01-01

    The present work was based on the investigation of different thin film components of Li ion batteries. A first part was dedicated to the deposition of cathodes in thin film form of a known material, LiCoO2, and an alternative one, Li(NiMnCo)O2 employing physical vapor deposition (PVD) and chemical vapor deposition (CVD), respectively. A second part was focused on the cathode-electrolyte interface for three case studies: 1) as deposited LiCoO2 cathode thin film, 2) ZrO2 coated LiCoO2 thin...

  13. Investigation of Corrosion and Cathodic Protection in Reinforced Concrete. II: Properties of Steel Surface Layers

    NARCIS (Netherlands)

    Koleva, D.A.; De Wit, J.H.W.; Van Breugel, K.; Lodhi, Z.F.; Ye, G.

    2007-01-01

    The present study explores the formation of corrosion products on the steel surface (using as-received low carbon construction steel) in reinforced concrete in conditions of corrosion and subsequent transformation of these layers in conditions of cathodic protection (CP).

  14. Emission characteristics of dispenser cathodes with a fine-grained tungsten top layer

    Science.gov (United States)

    Kimura, S.; Higuchi, T.; Ouchi, Y.; Uda, E.; Nakamura, O.; Sudo, T.; Koyama, K.

    1997-02-01

    In order to improve the emission stability of the Ir-coated dispenser cathode under ion bombardment, a fine-grained tungsten top layer was applied on the substrate porous tungsten plug before Ir coating. The emission characteristics were studied after being assembled in a CRT gun. Cathode current was measured under pulse operation in a range of 0.1-9% duty. Remarkable anti-ion bombardment characteristics were observed over the range of 1-6% duty. The improved cathode showed 1.5 times higher emission current than that of a conventional Ir-coated dispenser cathode at 4% duty. AES analysis showed that the recovering rates of surface Ba and O atoms after ion bombardment were 2.5 times higher. From these results it is confirmed that the Ir coated cathode with a fine-grained tungsten top layer is provided with a good tolerance against the ion bombardment.

  15. Carbon nanotube forests growth using catalysts from atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Bingan; Zhang, Can; Esconjauregui, Santiago; Xie, Rongsi; Zhong, Guofang; Robertson, John [Department of Engineering, University of Cambridge, Cambridge CB3 0FA (United Kingdom); Bhardwaj, Sunil [Istituto Officina dei Materiali-CNR Laboratorio TASC, s.s. 14, km 163.4, I-34012 Trieste (Italy); Sincrotone Trieste S.C.p.A., s.s. 14, km 163.4, I-34149 Trieste (Italy); Cepek, Cinzia [Istituto Officina dei Materiali-CNR Laboratorio TASC, s.s. 14, km 163.4, I-34012 Trieste (Italy)

    2014-04-14

    We have grown carbon nanotubes using Fe and Ni catalyst films deposited by atomic layer deposition. Both metals lead to catalytically active nanoparticles for growing vertically aligned nanotube forests or carbon fibres, depending on the growth conditions and whether the substrate is alumina or silica. The resulting nanotubes have narrow diameter and wall number distributions that are as narrow as those grown from sputtered catalysts. The state of the catalyst is studied by in-situ and ex-situ X-ray photoemission spectroscopy. We demonstrate multi-directional nanotube growth on a porous alumina foam coated with Fe prepared by atomic layer deposition. This deposition technique can be useful for nanotube applications in microelectronics, filter technology, and energy storage.

  16. Cadmium ion adsorption on nickel surface Raney catalysts, and its effect on cathodic hydrogen evolution

    International Nuclear Information System (INIS)

    Cadmium adsorption was studied at nickel surface Raney catalysts (Ni /SUB src/ ) in CdSO4 solutions of different concentrations by recording potentiodynamic and polarization curves and adducing electron microscopy and X-ray spectrometry. It was shown that the main features of cadmium adsorption on Ni /SUB SRC/ are similar to those found at smooth and Raney nickel. It was concluded that irreversible desorption of hydrogen of high and intermediate bond strength from the electrode surfaces which occurs when cadmium is adsorbed on these sites is responsible for the enhanced catalytic activity exhibited in cathodic hydrogen evolution from alkaline solutions by electrodes based on Ni /SUB SRC/ when conditioned in solutions containing Cd2+ ions

  17. Fe-N-C catalyst modified graphene sponge as a cathode material for lithium-oxygen battery

    International Nuclear Information System (INIS)

    Highlights: • Hydrothermally-synthesized graphene sponge is excellent skeleton of Li-O2 cathode. • Fe-N-C catalyst loaded on GS was attained via pyrolysis of FePc and GS composites. • High capacity and good cyclability were achieved with Fe-N-GS air electrode. • The synergy of porous structure and catalytic activity leads to the high performance. - Abstract: The cathode of a lithium-oxygen battery needs the synergism of a porous conducting material and a catalyst to facilitate the formation and decomposition of lithium peroxide. Here we introduce a graphene sponge (GS) modified with Fe-N-C catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The porous, 3-dimensional conductive and free standing nature of the graphene sponge makes it become excellent skeleton of cathode for lithium-oxygen battery. The Fe-N-C catalyst nanoparticles dispersed uniformly on the graphene sheets show excellent catalytic reactivity in both discharge and charge processes. This kind of composite material greatly improves the capacity and cyclability of the lithium-oxygen battery. With dimethyl sulphoxide as electrolyte, the capacity reaches 6762 mAh g−1 which is twice of the pure graphene sponge. In addition, the cell containing Fe-N-GS air electrode exhibits stable cyclic performance and effective reduction of charge potential plateau, indicating that Fe-N-GS is promising as an OER catalyst in rechargeable lithium-air batteries

  18. Fe-N-C catalyst modified graphene sponge as a cathode material for lithium-oxygen battery

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Ling, E-mail: yulingcug@126.com; Shen, Yue, E-mail: shenyue1213@mail.hust.edu.cn; Huang, Yunhui, E-mail: huangyh@mail.hust.edu.cn

    2014-05-15

    Highlights: • Hydrothermally-synthesized graphene sponge is excellent skeleton of Li-O{sub 2} cathode. • Fe-N-C catalyst loaded on GS was attained via pyrolysis of FePc and GS composites. • High capacity and good cyclability were achieved with Fe-N-GS air electrode. • The synergy of porous structure and catalytic activity leads to the high performance. - Abstract: The cathode of a lithium-oxygen battery needs the synergism of a porous conducting material and a catalyst to facilitate the formation and decomposition of lithium peroxide. Here we introduce a graphene sponge (GS) modified with Fe-N-C catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The porous, 3-dimensional conductive and free standing nature of the graphene sponge makes it become excellent skeleton of cathode for lithium-oxygen battery. The Fe-N-C catalyst nanoparticles dispersed uniformly on the graphene sheets show excellent catalytic reactivity in both discharge and charge processes. This kind of composite material greatly improves the capacity and cyclability of the lithium-oxygen battery. With dimethyl sulphoxide as electrolyte, the capacity reaches 6762 mAh g{sup −1} which is twice of the pure graphene sponge. In addition, the cell containing Fe-N-GS air electrode exhibits stable cyclic performance and effective reduction of charge potential plateau, indicating that Fe-N-GS is promising as an OER catalyst in rechargeable lithium-air batteries.

  19. Alternative cathodes based on iron phthalocyanine catalysts for mini- or micro-DMFC working at room temperature

    International Nuclear Information System (INIS)

    Iron phthalocyanine based cathodes were prepared either by dispersion of FePc on carbon or by electropolymerization of aniline in presence of FeTsPc. The macrocycles based cathodes were compared to a classical commercial Pt/C cathode in a standard three-electrode electrochemical cell and under DMFC conditions at room temperature. It was shown that the molecular dispersion of FeTsPc into a PAni film greatly enhances the activity of the macrocycle catalyst towards oxygen reduction reaction (ORR). But, in the same time, the stability under DMFC conditions is drastically decreased compared to the stability obtained with a FePc/C electrode. It was suggested that this instability of the catalytic film was rather due to the release of the FeTsPc from the polymer than to the destruction of the macrocycle active centre. Even if iron phthalocyanine catalysts display total tolerance to methanol when the anode is fed with a 5 M methanol solution, the comparison between a PAni-FeTsPc/C cathode and a Pt/C cathode in DMFC working conditions is in favor of the Pt/C cathode, in term of maximum achieved power density. However, the ratio (platinum atoms per cm2/number of FeTsPc molecules per cm2) is close to 100, which allows to be optimistic for further enhancement of activity of polymer-FeTsPc electrodes. It was suggested that researches to develop new electron conductive polymers stable under oxidative environment and with a high doping capacity could be a direction to use platinum alternative cathode catalysts in DMFC technology

  20. Atomic Layer Deposited Catalysts for Fuel Cell Applications

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta

    techniques. Atomic layer deposition (ALD), on the other hand, is a highly suitable and still relatively unexplored approach for the synthesis of noble metal catalysts. It is a vapor phase growth method, primarily used to deposit thin lms. ALD is based on self-limiting chemical reactions of alternately...

  1. Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

    KAUST Repository

    Ou, Yiwei

    2011-11-01

    The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

  2. Protected Sulfur Cathode with Mixed Conductive Coating Layer for Lithium Sulfur Battery

    Science.gov (United States)

    Jin, Jun; Wen, Zhaoyin; Wang, Qingsong; Gu, Sui; Huang, Xiao; Chen, Chunhua

    2016-08-01

    A mixed conductive coating layer composed of lithium ion conductive ceramic powder, carbon and binder was introduced on the surface of a sulfur electrode. This coating layer is designed to suppress the migration of lithium polysulfides from the sulfur electrode, and improve the cycling capacity of a lithium sulfur battery. The protected sulfur cathode with a mixed conductive coating layer delivered an initial specific capacity of 1236 mAh g-1 at 0.5C and maintained a capacity of 842 mAh g-1 after 100 cycles. In particular, a soft package battery with protected cathode exhibits improved cycling capacity and excellent rate performance.

  3. Uncovering the role of cathode buffer layer in organic solar cells

    Science.gov (United States)

    Qi, Boyuan; Zhang, Zhi-Guo; Wang, Jizheng

    2015-01-01

    Organic solar cells (OSCs) as the third generation photovoltaic devices have drawn intense research, for their ability to be easily deposited by low-cost solution coating technologies. However the cathode in conventional OSCs, Ca, can be only deposited by thermal evaporation and is highly unstable in ambient. Therefore various solution processible cathode buffer layers (CBLs) are synthesized as substitute of Ca and show excellent effect in optimizing performance of OSCs. Yet, there is still no universal consensus on the mechanism that how CBL works, which is evidently a critical scientific issue that should be addressed. In this article detailed studies are targeted on the interfacial physics at the interface between active layer and cathode (with and without treatment of a polar CBL) by using ultraviolet photoelectron spectroscopy, capacitance-voltage measurement, and impedance spectroscopy. The experimental data demonstrate that CBL mainly takes effect in three ways: suppressing surface states at the surface of active layer, protecting the active layer from being damaged by thermally evaporated cathode, and changing the energy level alignment by forming dipole moments with active layer and/or cathode. Our findings here provide a comprehensive picture of interfacial physics in devices with and without CBL.

  4. Method for making oxygen-reducing catalyst layers

    Science.gov (United States)

    O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; O'Neill, David G.

    2010-06-22

    Methods are provided for making oxygen-reducing catalyst layers, which include simultaneous or sequential stops of physical vapor depositing an oxygen-reducing catalytic material onto a substrate, the catalytic material comprising a transition metal that is substantially free of platinum; and thermally treating the catalytic material. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  5. Modified Separator Using Thin Carbon Layer Obtained from Its Cathode for Advanced Lithium Sulfur Batteries.

    Science.gov (United States)

    Liu, Naiqiang; Huang, Bicheng; Wang, Weikun; Shao, Hongyuan; Li, Chengming; Zhang, Hao; Wang, Anbang; Yuan, Keguo; Huang, Yaqin

    2016-06-29

    The realization of a practical lithium sulfur battery system, despite its high theoretical specific capacity, is severely limited by fast capacity decay, which is mainly attributed to polysulfide dissolution and shuttle effect. To address this issue, we designed a thin cathode inactive material interlayer modified separator to block polysulfides. There are two advantages for this strategy. First, the coating material totally comes from the cathode, thus avoids the additional weights involved. Second, the cathode inactive material modified separator improve the reversible capacity and cycle performance by combining gelatin to chemically bond polysulfides and the carbon layer to physically block polysulfides. The research results confirm that with the cathode inactive material modified separator, the batteries retain a reversible capacity of 644 mAh g(-1) after 150 cycles, showing a low capacity decay of about 0.11% per circle at the rate of 0.5C. PMID:27267483

  6. Mechanical behaviour of PEM fuel cell catalyst layers during regular cell operation

    Energy Technology Data Exchange (ETDEWEB)

    Al-Baghdadi, Maher A.R. Sadiq [Fuel Cell Research Center, International Energy & Environment Foundation, Al-Najaf, P.O.Box 39 (Iraq)

    2010-07-01

    Damage mechanisms in a proton exchange membrane fuel cell are accelerated by mechanical stresses arising during fuel cell assembly (bolt assembling), and the stresses arise during fuel cell running, because it consists of the materials with different thermal expansion and swelling coefficients. Therefore, in order to acquire a complete understanding of the mechanical behaviour of the catalyst layers during regular cell operation, mechanical response under steady-state hygro-thermal stresses should be studied under real cell operating conditions and in real cell geometry (three-dimensional). In this work, full three-dimensional, non-isothermal computational fluid dynamics model of a PEM fuel cell has been developed to investigate the behaviour of the cathode and anode catalyst layers during the cell operation. A unique feature of the present model is to incorporate the effect of hygro and thermal stresses into actual three-dimensional fuel cell model. In addition, the temperature and humidity dependent material properties are utilize in the simulation for the membrane. The model is shown to be able to understand the many interacting, complex electrochemical, transport phenomena, and deformation that have limited experimental data.

  7. Mechanical behaviour of PEM fuel cell catalyst layers during regular cell operation

    Directory of Open Access Journals (Sweden)

    Maher A.R. Sadiq Al-Baghdadi

    2010-11-01

    Full Text Available Damage mechanisms in a proton exchange membrane fuel cell are accelerated by mechanical stresses arising during fuel cell assembly (bolt assembling, and the stresses arise during fuel cell running, because it consists of the materials with different thermal expansion and swelling coefficients. Therefore, in order to acquire a complete understanding of the mechanical behaviour of the catalyst layers during regular cell operation, mechanical response under steady-state hygro-thermal stresses should be studied under real cell operating conditions and in real cell geometry (three-dimensional. In this work, full three-dimensional, non-isothermal computational fluid dynamics model of a PEM fuel cell has been developed to investigate the behaviour of the cathode and anode catalyst layers during the cell operation. A unique feature of the present model is to incorporate the effect of hygro and thermal stresses into actual three-dimensional fuel cell model. In addition, the temperature and humidity dependent material properties are utilize in the simulation for the membrane. The model is shown to be able to understand the many interacting, complex electrochemical, transport phenomena, and deformation that have limited experimental data.

  8. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    OpenAIRE

    Kyu-Nam Jung; Soo Min Hwang; Min-Sik Park; Ki Jae Kim; Jae-Geun Kim; Shi Xue Dou; Jung Ho Kim; Jong-Won Lee

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanof...

  9. Optimization of Pt-Pd alloy catalyst and supporting materials for oxygen reduction in air-cathode Microbial Fuel Cells

    International Nuclear Information System (INIS)

    Highlights: • Pt-Pd alloy catalyst was fabricated on carbon paper via electro-deposition. • MFCs with Pt-Pd cathode of 15 deposition cycles generated a maximum power density. • Graphene decoration did not improve ORR activity of the Pt-Pd electrode. • CNT as the supporting material enhanced ORR activity of the Pt-Pd electrode. • CNT-Pt-Pd cathode demonstrates the potential of replacing Pt catalyst in MFCs. - ABSTRACT: In this study, Pt-Pd alloy catalyst was fabricated on carbon papers via electro-deposition as an alternative catalyst for oxygen reduction in air-cathode Microbial Fuel Cells (MFCs). Effects of electro-deposition cycles and supporting materials (graphene and carbon nanotubes (CNTs)) on oxygen reduction reaction (ORR) activity of the Pt-Pd electrode and power generation in MFCs were investigated. The structural and electrochemical properties of the Pt-Pd catalyst were characterized by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). Results showed that the Pt-Pd electrode showed a good ORR activity. A MFC with a Pt-Pd cathode of 15 deposition cycles produced a maximum power density of 1274 mWm−2, comparable to that with a conventional Pt/C cathode (0.5 mg Pt cm−2). CNT as the supporting material further increased ORR activity of the Pt-Pd electrode and power generation capacity in MFCs, while graphene as the supporting material did not produce positive effects. XRD results confirmed the presence of Pt/Pd elements on the electrode. SEM results showed that decoration using CNT reduced Pt-Pd particle size and promoted them even dispersion on the carbon paper. The Pt-Pd electrode attained a comparable performance to the Pt/C electrode when controlling an optimum deposition cycles and using CNT as the supporting materials, which demonstrates the potential of replacing Pt as an oxygen reduction catalyst in MFCs due to high oxygen reduction activity and relatively low cost

  10. Improving performance of inverted organic solar cells using ZTO nanoparticles as cathode buffer layer

    Science.gov (United States)

    Tsai, Meng-Yen; Cheng, Wen-Hui; Jeng, Jiann-Shing; Chen, Jen-Sue

    2016-06-01

    In this study, a low-temperature solution-processed zinc tin oxide (ZTO) films are successfully utilized as the cathode buffer layer in the inverted organic P3HT:PCBM bulk heterojunction solar cells. ZTO film cathode buffer layer with an appropriate Sn-doping concentration outperforms the zinc oxide (ZnO) film with an improved power conversion efficiency (1.96% (ZTO film) vs. 1.56% (ZnO film)). Furthermore, ZTO nanoparticles (NPs) are also synthesized via low-temperature solution route and the device with ZTO NPs buffer layer exhibits a significant improvement in device performance to reach a PCE of 2.60%. The crystallinity of the cathode buffer layer plays an influential factor in the performance. From impedance spectroscopy analysis, a correlation between short circuit current (Jsc), carrier life time (τavg) and, thus, PCE is observed. The interplay between composition and crystallinity of the cathode buffer layers is discussed to find their influences on the solar cell performance.

  11. Transparent organic light-emitting devices with CsCl capping layers on semitransparent Ca/Ag cathodes

    International Nuclear Information System (INIS)

    We have developed transparent organic light-emitting devices (TOLEDs) with CsCl capping layers deposited on top of semitransparent Ca/Ag cathodes. The CsCl layer was deposited by the thermal evaporation method which does not result in any damage to the underlying organic layers. The transmittance was enhanced by depositing the CsCl layer on the Ca/Ag cathode. The current efficiency measured at the cathode side increased by the enhanced transmittance of the cathode, whereas the anode-side current efficiency was determined by the reflectance of the cathode. In a TOLED with semitransparent Ca/Ag/CsCl layer, the microcavity effect was not profound so that the electroluminescence spectrum was not seriously changed by the CsCl capping layer.

  12. Different materials as a cathode modification layer on the impact of organic solar cells

    Science.gov (United States)

    Zhong, Jian; Huang, Qiuyan; Yu, Junsheng; Jiang, Yadong

    2010-10-01

    Organic thin film solar cells based on conjugated polymer or small molecules have showed an interesting approach to energy conversion since Tang reported a single donor-accepter hetero-junction solar cell. The power conversion efficiency of organic solar cells has increased steadily over last decade. Small-molecular weight organic double heterojunction donor-acceptor layer organic solar cells (OSC) with a structure of indium-tin-oxide (ITO)/CuPc(200Å)/C60(400Å)/x/Ag(1000Å), using CuPc(copper Phthalocyanine)as donor layer, and Alq3(8-Hydroxyquinoline aluminum salt), BCP(Bromocresol purple sodium salt) and Bphen(4'7-diphyenyl-1,10-phenanthroline) as cathode modification layer, respectively were fabricated. The performance of OSC was studied as a function of the different materials as an cathode modification layer to optimize the structure. The current-voltage characteristic of the solar cell under AM1.5 solar illumination at an intensity of 100 mw/cm2 showed that the power conversion efficiency (PCE) was dependent of the different materials of the cathode modification layer. the efficiency along with the different materials as an cathode modification layer will diminish under that standard solar illumination(AM1.5)was obtained. Using a double heterostructure of ITO/CuPc(200Å)/C60(400Å)/Alq3(60Å)/Ag(1000Å) with high-vacuum evaporation technology, the efficiency was 0.587%.the efficiency was 0.967% when the material of the cathode modification layer was BCP, with the structure of ITO/CuPc(200Å)/C60(400Å)/BCP(35Å)/Ag(1000Å), and the efficiency was 0.742% when the material of the cathode modification layer was Bphen, with the structure of ITO/CuPc(200Å)/C60(400Å)/ Bphen(50Å)/Ag(1000Å).Using different materials as a cathode modification layer, it can be seen that the material which matches the energy level could even eventually be able to improve the energy conversion efficiency more.

  13. Cathode-Electrolyte Interfaces with CGO Barrier Layers in SOFC

    DEFF Research Database (Denmark)

    Knibbe, Ruth; Hjelm, Johan; Menon, Mohan;

    2010-01-01

    10) barrier layer, the other had a barrier layer deposited by pulsed laser deposition (PLD) CGO10. Scanning electron microscopy, transmission electron microscopy (TEM), and electron backscattered diffraction (EBSD) investigations conclude that the major source of the cell performance difference is...... attributed to CGO–YSZ interdiffusion in the sprayed-cosintered barrier layer. From TEM and EBSD work, a dense CGO10 PLD layer is found to be deposited epitaxially on the 8YSZ electrolyte substrate—permitting a small amount of SrZrO3 formation and minimizing CGO–YSZ interdiffusion....

  14. Selective recovery of catalyst layer from supporting matrix of ceramic-honeycomb-type automobile catalyst.

    Science.gov (United States)

    Kim, Wantae; Kim, Boungyoung; Choi, Doyoung; Oki, Tatsuya; Kim, Sangbae

    2010-11-15

    Natural resources of platinum group metals (PGMs) are limited and their demand is increasing because of their extensive uses in industrial applications. The low rate of production of PGMs due to low concentration in the related natural ores and high cost of production have made the recovery of PGMs from previously discarded catalytic converters a viable proposition. The ceramic-honeycomb-type automobile catalytic converter contains appreciable amount of PGMs. These valuable substances, which are embedded in the catalyst layer and covered on the surface of the supporting matrix, were selectively recovered by attrition scrubbing. The attrition scrubbing was effective for the selective recovery of catalyst layer. The process was convinced as the comminution and separation process by physical impact and shearing action between particles in the scrubbing vessel. The catalyst layer was dislodged from the surface of the supporting matrix into fine particles by attrition scrubbing. The recovery of Al(2)O(3) and total PGMs in the fraction less than 300 μm increased with the residence time whereas their contents in the recovered materials slightly decreased. The interparticle scrubbing became favorable when the initial input size increased. However, the solid/liquid ratio in the mixing vessel was slightly affected by the low density of converter particles. PMID:20728274

  15. Catalyst layers for PEMFC manufactured by flexography printing process: performances and structure

    Energy Technology Data Exchange (ETDEWEB)

    Bois, C.; Blayo, A.; Chaussy, D. [Laboratory of Pulp and Paper Science and Graphic Arts (LGP2) (UMR 5518 CNRS-CTP-INPG), Grenoble Institute of Technology (INP Grenoble - PAGORA), St Martin d' Heres (France); Vincent, R.; Mercier, A.G.; Nayoze, C. [Commissariat a l' Energie Atomique et aux Energies Alternatives (CEA)/DRT/LITEN, Laboratoire des Composants Piles a Combustible, Electrolyse et Modelisation (LCPEM), Grenoble (France)

    2012-04-15

    This article focuses on the potential of a classic printing process, flexography, for manufacturing proton exchange membrane fuel cells (PEMFCs). Gas diffusion electrodes (GDEs) are produced by deposition of a water-based catalyst ink on a gas diffusion layer (GDL). The affinity between the ink and the GDL is quantified. Thus, the strong hydrophobic character of the GDL and the poor printability of the ink are demonstrated. However, the permeability of the GDL allows developing a multilayer protocol. The deposition by superimposition of ink layers allows control of the platinum amount and to obtain catalyst layers with a similar density of platinum nanoparticles to coated samples. At similar platinum loading, flexography and coating made catalyst layers offer similar performances, which confirm the relevance of flexography in catalyst layer manufacturing. Structural characterization shows that manufacturing protocol and process has an influence on catalyst layer microstructure. However, catalyst layer cracking and aggregation are increased with the catalyst layer thickness, diminishing the charge and gas diffusion into the catalyst layer resulting in performance degradation. Consequently, a catalyst layer with 0.46 mgPt cm{sup -2} reaches similar performances to catalyst layers with 1.77 and 2.01 times less platinum loading. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Iron-nitrogen-activated carbon as cathode catalyst to improve the power generation of single-chamber air-cathode microbial fuel cells.

    Science.gov (United States)

    Pan, Yajun; Mo, Xiaoping; Li, Kexun; Pu, Liangtao; Liu, Di; Yang, Tingting

    2016-04-01

    In order to improve the performance of microbial fuel cell (MFC), iron-nitrogen-activated carbon (Fe-N-C) as an excellent oxygen reduction reaction (ORR) catalyst was prepared here using commercial activated carbon (AC) as matrix and employed in single chamber MFC. In MFC, the maximum power density increased to 2437±55mWm(-2), which was 2 times of that with AC. The open circuit potential (OCP) of Fe-N-C cathode (0.47) was much higher than that of AC cathode (0.21V). The R0 of Fe-N-C decreased by 47% from 14.36Ω (AC) to 7.6Ω (Fe-N-C). From X-ray photoelectron spectroscopy (XPS), pyridinic nitrogen, quaternary nitrogen and iron species were present, which played an important role in the ORR performance of Fe-N-C. These results demonstrated that the as-prepared Fe-N-C material provided a potential alternative to Pt in AC air cathode MFC for relatively desirable energy generation and wastewater treatment. PMID:26898678

  17. Nitrogen-doped graphene/CoNi alloy encased within bamboo-like carbon nanotube hybrids as cathode catalysts in microbial fuel cells

    Science.gov (United States)

    Hou, Yang; Yuan, Heyang; Wen, Zhenhai; Cui, Shumao; Guo, Xiaoru; He, Zhen; Chen, Junhong

    2016-03-01

    Cost-effective catalysts are of key importance to the successful deployment of microbial fuel cells (MFCs) for electricity generation from organic wastes. Herein, a novel catalyst prepared by one-step synthesis strategy is reported. The catalyst features N-doped bamboo-like carbon nanotube (BCNT) in which CoNi-alloy is encapsulated at the end and/or the middle section of the tube with many graphene layers inside inner cavities of BCNT (N-G@CoNi/BCNT). The prepared N-G@CoNi/BCNT exhibits a high oxygen reduction reaction (ORR) activity with an early onset potential of 0.06 V vs. Ag/AgCl and a comparable exchange current density to that of commercial Pt/C. The excellent catalytic activity is further evidenced by a high electron transfer number of 3.63. When being applied in MFCs, the N-G@CoNi/BCNT yields an average current density of 6.7 A m-2, slightly lower than that of Pt/C but with a less mass transfer potential loss. The cost of the N-G@CoNi/BCNT for constructing a 1-m2 cathode electrode is 200 times lower than that of Pt/C. With such a competitive price and excellent electrocatalytic-activity resulting from its unique morphology, CoNi-alloy/nitrogen dopants, considerable specific surface area, and carbon-coated alloy/graphene hybridization, the present catalyst is a promising candidate for ORR catalysts in MFCs for energy recovery from wastes.

  18. Experimental analyses of low humidity operation properties of SiO2-containing catalyst layers for polymer electrolyte fuel cells

    International Nuclear Information System (INIS)

    Highlights: ► We examine SiO2-containing catalyst layers for PEFCs operated under low humidity. ► SiO2 addition led to decreased ohmic resistance due to increased water content. ► Pt utilization increased due to the increase in the σH in the electrolyte binder. ► The specific adsorption of sulfonate groups in the binder on Pt was suppressed. ► SiO2 addition promoted the back-diffusion of water generated at the cathode to anode. -- Abstract: Electrochemical operation properties of SiO2-containing catalyst layers (SiO2-CLs) under low humidity were clarified experimentally in a polymer electrolyte fuel cell (PEFC). The mass activities at 0.85 V and current densities at 0.7 V increased with increasing SiO2 content below 53% RH at 80 °C. The use of SiO2-CLs led to decreased ohmic resistance due to increased water content. It was found that such an increase in water content in the SiO2-CLs increased the electrochemically active surface area (ECA) of the Pt catalyst, due to enhancement of the proton-conducting network in the electrolyte binder, and suppressed the specific adsorption of sulfonate anions on the Pt surface. It was also clarified that the SiO2 addition in the CL promoted the back-diffusion of water generated at the cathode to the anode, resulting in an increased O2 gas diffusion rate to the cathode-CL/PEM interface, accompanied by an increased water content in the membrane. All of these factors greatly contributed to improve the cell performance under low humidity

  19. The function of microporous layers and the interaction between the anode and cathode in DMFCs

    DEFF Research Database (Denmark)

    Zhang, H. F.; Wang, SY; Pei, PC;

    2008-01-01

    A combined effect of microporous layers (MPLs) on direct methanol fuel cells (DMFCs) is investigated. From the distribution of the outstanding carbon loading combinations of the cathode MPL and anode MPL as well as the evolutions of polarization curves, a combined effect in which the contributions...... of the two MPLs interdepend is observed. A further discussion indicates that either MPL in DMFCs is of double roles: a side role of obstructing mass transfers and a main role of adjusting an interaction between the anode and cathode. It is inferred that it is the combination of the two roles that produces...

  20. Prediction of anisotropic transport in Nafion containing catalyst layers

    Energy Technology Data Exchange (ETDEWEB)

    Dorenbos, G.; Pomogaev, V.A.; Takigawa, M. [Knowledgenet Co., Lofty Chuo Bldg. (9F), 1-17-24, Shinkawa, Chuo-ku, Tokyo 104-0033 (Japan); Toyota Motor Co., Future Project Division, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan); Morohoshi, K. [Toyota Motor Co., Future Project Division, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan)

    2010-01-15

    Using dissipative particle dynamics we model phase separation within Nafion electrolytes of thickness between 5 and 10 nm containing 20 volume percent water, sandwiched between a carbon catalyst support (CCS) layer and air. The diffusion pathway for protons and water is probed by Monte Carlo trajectory calculations. While varying the interactions between CCS and water, diffusion parallel to the CCS is predicted to be highest and perpendicular diffusion to be lowest for a hydrophilic CCS. This is explained by variations in water density profiles along the perpendicular direction, which act as bottlenecks for diffusion. Increasing the hydrophobic character of the CCS lifts up these bottlenecks. (author)

  1. Highly Active and Durable Co-Doped Pt/CCC Cathode Catalyst for Polymer Electrolyte Membrane Fuel Cells

    International Nuclear Information System (INIS)

    Highlights: •Co-doped Pt core–shell type catalyst having 0.75 nm thick Pt shell is synthesized. •Co-doped Pt exhibited mass activity of 0.44 A mgPt−1 at 0.9 ViR-free. •Co-doped Pt cathode catalyst showed high stability under cycling conditions. •Co-doped Pt catalyst showed only 16% power density loss after 30,000 cycles. •The enhanced stability is due to the increase in onset potential for PtO2 formation. -- Abstract: Cathode catalyst based on Co-doped Pt deposited on carbon composite catalyst (CCC) support with high measured activity and stability under potential cycling conditions for polymer electrolyte membrane (PEM) fuel cells was developed in this study. The catalyst was synthesized through platinum deposition on Co-doped CCC support containing pyridinic-nitrogen active sites followed by controlled heat-treatment. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) studies confirmed uniform Pt deposition (Pt/CCC catalyst, dPt = 2 nm) and formation of Co-doped Pt/CCC catalyst (dPt = 5.4 nm) respectively. X-ray energy dispersive spectrometry (XEDS) line-scan studies showed the formation of Co-core Pt-shell type catalyst with a Pt-shell thickness of ∼0.75 nm. At 0.9 ViR-free, the Co-doped Pt/CCC catalyst showed initial mass activity of 0.44 A mgPt−1 and 0.25 A mgPt−1 after 30,000 potential cycles between 0.6 and 1.0 V corresponding to an overall measured activity loss of 42.8%. The commercial Pt-Co/C showed initial mass activity of 0.38 A mgPt−1 and ∼70% loss of activity after 30,000 cycles. The enhanced catalytic activity at high potentials and stability of mass activity for the Co-doped Pt/CCC catalyst are attributed to the formation of compressive Pt lattice catalyst due to Co doping. The Co-doped Pt/CCC showed stable open circuit potential close to 1.0 V under H2-air with an initial power density of 857 mW cm−2 and only 16% loss after 30,000 cycles. Catalyst durability studies performed between 0

  2. Dynamics of cathode spots in low-pressure arc plasma removing oxide layer on steel surfaces

    Science.gov (United States)

    Tang, Z. L.; Yang, K.; Liu, H. X.; Zhang, Y. C.; Li, H.; Zhu, X. D.

    2016-03-01

    The dynamics of cathode spots has been investigated in low-pressure arc plasma for removing oxide layer on low carbon steel surfaces. The motion of cathode spots was observed with a high speed camera, and the arc voltage was analyzed by fast Fourier transform. The spots move on clean steel surface as a random walk, and the low-frequency components dominated the voltage waveform. However, the spots on steel surfaces with oxide layer tend to burn on the rim of the eroded area formed in the previous arcing, and the low-frequency components decrease correspondingly. The "color" of the colored random noise for arc voltage varies from the approximate brown noise for clean steel surface to pink noise for thick oxide layer, where the edge effect of boundary is considered to play a significant role.

  3. Synthesis of carbon-supported titanium oxynitride nanoparticles as cathode catalyst for polymer electrolyte fuel cells

    International Nuclear Information System (INIS)

    Highlights: • A sol–gel route for the synthesis of rutile TiO2 was modified to synthesize TiOxNy-C. • N atoms were doped into TiOx nanoparticles solely by the heat-treatment under N2 gas. • The N2-treatment produced sites more active toward ORR compared with NH3-treatment. • TiOx doped with a small amount of N atoms are suggested to be responsible for ORR. -- Abstract: For use as the oxygen reduction reaction (ORR) catalyst in polymer electrolyte fuel cell cathodes, carbon-supported titanium oxynitride (TiOxNy-C) nanoparticles with a size of approximately 5 nm or less were synthesized without using NH3 gas. A sol–gel route developed for the synthesis of pure rutile TiO2 nanopowders was modified to prepare the carbon-supported titanium oxide nanoparticles (TiOx-C). For the first time, N atoms were doped into TiOx solely by heating TiOx-C under an inexpensive N2 atmosphere at 873 K for 3 h, which could be due to carbothermal reduction. The TiOx-C powder was also heated under NH3 gas at various temperatures (873–1273 K) and durations (3–30 h). This step resulted in the formation of a TiN phase irrespective of the heating conditions. Both N2- and NH3-treated TiOxNy-C did not crystallize well; however, the former showed a mass activity more than three times larger than that of the latter at 0.74 V versus the standard hydrogen electrode. Thus, titanium oxide nanoparticles doped with a small amount of N atoms are suggested to be responsible for catalyzing ORR in the case of N2-treated TiOxNy-C

  4. High catalytic activity and pollutants resistivity using Fe-AAPyr cathode catalyst for microbial fuel cell application

    Science.gov (United States)

    Santoro, Carlo; Serov, Alexey; Villarrubia, Claudia W. Narvaez; Stariha, Sarah; Babanova, Sofia; Artyushkova, Kateryna; Schuler, Andrew J.; Atanassov, Plamen

    2015-11-01

    For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm-2 and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm-2 by day 13, achieving similar values of an activated carbon based cathode. The presence of S2- and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater.

  5. Characterization of pore network structure in catalyst layers of polymer electrolyte fuel cells

    OpenAIRE

    El Hannach, Mohamed; Soboleva, Tatyana; Malek, Kourosh; Franco, Alejandro A.; Prat, Marc; Pauchet, Joël; Holdcroft, Steven

    2014-01-01

    International audience We model and validate the effect of ionomer content and Pt nanoparticles on nanoporous structure of catalyst layers in polymer electrolyte fuel cells. By employing Pore network modeling technique and analytical solutions, we analyze and reproduce experimental N2-adsorption isotherms of carbon, Pt/ carbon and catalyst layers with various ionomer contents. The porous catalyst layer structures comprise of Ketjen Black carbon, Pt and Nafion ionomer. The experimental pore...

  6. Layer Formation by Resputtering in Ti-Si-C Hard Coatings during Large Scale Cathodic Arc Deposition

    OpenAIRE

    Eriksson, Anders; Zhu, Jianqiang; Ghafoor, Naureen; Johansson, Mats; Sjölen, Jacob; Jensen, Jens; Odén, Magnus; Hultman, Lars; Rosén, Johanna

    2011-01-01

    This paper presents the physical mechanism behind the phenomenon of self-layering in thin films made by industrial scale cathodic arc deposition systems using compound cathodes and rotating substrate fixture. For Ti-Si-C films, electron microscopy and energy dispersive x-ray spectrometry reveals a trapezoid modulation in Si content in the substrate normal direction, with a period of 4 to 23 nm dependent on cathode configuration. This is caused by preferential resputtering of Si by the energet...

  7. Nanoscale Surface Modification of Lithium-Rich Layered-Oxide Composite Cathodes for Suppressing Voltage Fade.

    Science.gov (United States)

    Zheng, Fenghua; Yang, Chenghao; Xiong, Xunhui; Xiong, Jiawen; Hu, Renzong; Chen, Yu; Liu, Meilin

    2015-10-26

    Lithium-rich layered oxides are promising cathode materials for lithium-ion batteries and exhibit a high reversible capacity exceeding 250 mAh g(-1) . However, voltage fade is the major problem that needs to be overcome before they can find practical applications. Here, Li1.2 Mn0.54 Ni0.13 Co0.13 O2 (LLMO) oxides are subjected to nanoscale LiFePO4 (LFP) surface modification. The resulting materials combine the advantages of both bulk doping and surface coating as the LLMO crystal structure is stabilized through cationic doping, and the LLMO cathode materials are protected from corrosion induced by organic electrolytes. An LLMO cathode modified with 5 wt % LFP (LLMO-LFP5) demonstrated suppressed voltage fade and a discharge capacity of 282.8 mAh g(-1) at 0.1 C with a capacity retention of 98.1 % after 120 cycles. Moreover, the nanoscale LFP layers incorporated into the LLMO surfaces can effectively maintain the lithium-ion and charge transport channels, and the LLMO-LFP5 cathode demonstrated an excellent rate capacity. PMID:26335589

  8. Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

    Energy Technology Data Exchange (ETDEWEB)

    Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo; Aykol, Muratahan; Luo, Langli; Wu, Jinsong; Myers, Benjamin D.; Iddir, Hakim; Russell, John T.; Saldana, Spencer J.; Kumar, Rajan; Thackeray, Michael M.; Curtiss, Larry A.; Dravid, Vinayak P.; Wolverton, Christopher M.; Hersam, Mark C.

    2015-06-24

    Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.

  9. Cathodes incorporating thin fluoride layers for efficient injection in blue polymer light-emitting diodes

    Science.gov (United States)

    Brown, Thomas M.; Millard, Ian S.; Lacey, David; Burroughes, Jeremy H.; Friend, Richard H.; Cacialli, Franco

    2002-02-01

    Efficient blue Polymer Light-Emitting Diodes (PLEDs) were fabricated by evaporating thin LiF layers between Al or Ca cathodes. Electroabsorption measurements of the built-in potential across the diodes show that devices fabricated with LiF/Ca/Al cathodes exhibit the smallest average barrier height and operating voltage (compared to both Ca and LiF/Al currently amongst the most efficient electron injectors). The turn-on bias is essentially equivalent to the built-in potential (~2.7 V), indicating an effective minimisation of the barrier to electron injection. Results are also compared with devices incorporating CsF layers and are correlated with the electroluminescent characteristics of the LEDs. A very strong dependence (~ exponential) between the built-in potential and the current and luminance at a fixed electric field (0.5MV/cm) is observed and is explained with the reduction of the cathodic barrier height brought about by the different cathode multilayers.

  10. Layered cathode materials for lithium ion rechargeable batteries

    Science.gov (United States)

    Kang, Sun-Ho; Amine, Khalil

    2007-04-17

    A number of materials with the composition Li.sub.1+xNi.sub..alpha.Mn.sub..beta.Co.sub..gamma.M'.sub..delta.O.sub.2-- zF.sub.z (M'=Mg,Zn,Al,Ga,B,Zr,Ti) for use with rechargeable batteries, wherein x is between about 0 and 0.3, .alpha. is between about 0.2 and 0.6, .beta. is between about 0.2 and 0.6, .gamma. is between about 0 and 0.3, .delta. is between about 0 and 0.15, and z is between about 0 and 0.2. Adding the above metal and fluorine dopants affects capacity, impedance, and stability of the layered oxide structure during electrochemical cycling.

  11. Low cost fuel cell diffusion layer configured for optimized anode water management

    Science.gov (United States)

    Owejan, Jon P; Nicotera, Paul D; Mench, Matthew M; Evans, Robert E

    2013-08-27

    A fuel cell comprises a cathode gas diffusion layer, a cathode catalyst layer, an anode gas diffusion layer, an anode catalyst layer and an electrolyte. The diffusion resistance of the anode gas diffusion layer when operated with anode fuel is higher than the diffusion resistance of the cathode gas diffusion layer. The anode gas diffusion layer may comprise filler particles having in-plane platelet geometries and be made of lower cost materials and manufacturing processes than currently available commercial carbon fiber substrates. The diffusion resistance difference between the anode gas diffusion layer and the cathode gas diffusion layer may allow for passive water balance control.

  12. A sodium-ion battery exploiting layered oxide cathode, graphite anode and glyme-based electrolyte

    Science.gov (United States)

    Hasa, Ivana; Dou, Xinwei; Buchholz, Daniel; Shao-Horn, Yang; Hassoun, Jusef; Passerini, Stefano; Scrosati, Bruno

    2016-04-01

    Room-temperature rechargeable sodium-ion batteries (SIBs), in view of the large availability and low cost of sodium raw materials, represent an important class of electrochemical systems suitable for application in large-scale energy storage. In this work, we report a novel, high power SIB formed by coupling the layered P2-Na0.7CoO2 cathode with the graphite anode in an optimized ether-based electrolyte. The study firstly addresses the electrochemical optimization of the two electrode materials and then the realization and characterization of the novel SIB based on their combination. The cell represents an original sodium rocking chair battery obtained combining the intercalation/de-intercalation processes of sodium within the cathode and anode layers. We show herein that this battery, favored by suitable electrode/electrolyte combination, offers unique performance in terms of cycle life, efficiency and, especially, power capability.

  13. Investigation of platinum utilization and morphology in catalyst layer of polymer electrolyte fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Cheng Xiaoliang; Yi Baolian; Han Ming; Zhang Jingxin; Qiao Yaguang; Yu Jingrong (Chinese Academy of Sciences, Dalian (China). Inst. of Chemical Physics)

    1999-05-01

    Platinum utilization in the gas-diffusion catalyst layer and thin-film catalyst layer is investigated. The morphology of PTFE and Nafion in a simulated catalyst layer is examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the platinum utilization of the thin-film catalyst layer containing only Pt/C and Nafion is 45.4%. The low utilization is attributed to the fact that the electron conduction of many catalyst particles is impaired by some thick Nafion layers or clumps. For the gas-diffusion (E-TEK) electrode, the platinum utilization is mainly affected by the proton conduction provided by Nafion. The blocking effect of PTFE on the active sites is not serious. When the electrode is sufficiently impregnated with Nafion by an immersion method, the platinum utilization can reach 77.8%. Transmission electron micrographs reveal that although some thick Nafion layers and clumps are observed in the Pt/C+Nafion layer, the distribution of Nafion in the catalyst layer is basically uniform. The melted PTFE disperses in the catalyst layer very uniformly. No large PTFE clumps or wide net-like structure is observed. The reactant gas may have to diffuse evenly in the catalyst layer. (orig.)

  14. Atomic to Nanoscale Investigation of Functionalities of Al2O3 Coating Layer on Cathode for Enhanced Battery Performance

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Pengfei; Zheng, Jianming; Zhang, Xiaofeng; Xu, Rui; Amine, Khalil; Xiao, Jie; Zhang, Jiguang; Wang, Chong M.

    2016-01-06

    Surface coating of cathode has been identified as an effective approach for enhancing the capacity retention of layered structure cathode. However, the underlying operating mechanism of such a thin layer of coating, in terms of surface chemical functionality and capacity retention, remains unclear. In this work, we use aberration corrected scanning transmission electron microscopy and high efficient spectroscopy to probe the delicate functioning mechanism of Al2O3 coating layer on Li1.2Ni0.2Mn0.6O2 cathode. We discovered that in terms of surface chemical function, the Al2O3 coating suppresses the side reaction between cathode and the electrolyte upon the battery cycling. At the same time, the Al2O3 coating layer also eliminates the chemical reduction of Mn from the cathode particle surface, therefore avoiding the dissolution of the reduced Mn into the electrolyte. In terms of structural stability, we found that the Al2O3 coating layer can mitigate the layer to spinel phase transformation, which otherwise will initiate from the particle surface and propagate towards the interior of the particle with the progression of the battery cycling. The atomic to nanoscale effects of the coating layer observed here provide insight for optimized design of coating layer on cathode to enhance the battery properties.

  15. Ruthenium oxide modified titanium dioxide nanotube arrays as carbon and binder free lithium-air battery cathode catalyst

    Science.gov (United States)

    Zhao, Guangyu; Niu, Yanning; Zhang, Li; Sun, Kening

    2014-12-01

    RuO2 modified TiO2 nanotube arrays, growing on Ti foams, are used as carbon and binder free cathodes for Li-O2 batteries. The micrometer pores in Ti foams and nanometer pores in TiO2 nanotubes supply facilitated transport channels for oxygen diffusing into/out of the catalysts in discharge and charge processes. The RuO2 catalyst exhibits outstanding catalytic active toward oxygen evolution reaction (OER), which leads the charge voltage maintaining around 3.7 V all through the battery cycling. The stability of TiO2/Ti support, abundant oxygen transport path and favorable catalytic activity of RuO2 toward OER enable the Li-O2 batteries exhibiting 130 cycle discharge/charge.

  16. Contribution to mechanical and crystallographic analysis of molyledenum layers prepared by magnetron cathode sputtering

    International Nuclear Information System (INIS)

    Molybdenum coatings presenting different compression stresses are elaborated by magnetron cathode sputtering by varying the negative voltage of the substrate during deposition. Stress evolution is accompanied by crystal texture evolution and argon content incorporated in the layers. Crystallite orientation is explained by a phenomenon similar to canalisation observed in ion implantation. In a same deposit each component presents its own deformations different from neighbouring components

  17. Bifunctional Ag/Fe/N/C Catalysts for Enhancing Oxygen Reduction via Cathodic Biofilm Inhibition in Microbial Fuel Cells.

    Science.gov (United States)

    Dai, Ying; Chan, Yingzi; Jiang, Baojiang; Wang, Lei; Zou, Jinlong; Pan, Kai; Fu, Honggang

    2016-03-23

    Limitation of the oxygen reduction reaction (ORR) in single-chamber microbial fuel cells (SC-MFCs) is considered an important hurdle in achieving their practical application. The cathodic catalysts faced with a liquid phase are easily primed with the electrolyte, which provides more surface area for bacterial overgrowth, resulting in the difficulty in transporting protons to active sites. Ag/Fe/N/C composites prepared from Ag and Fe-chelated melamine are used as antibacterial ORR catalysts for SC-MFCs. The structure-activity correlations for Ag/Fe/N/C are investigated by tuning the carbonization temperature (600-900 °C) to clarify how the active-constituents of Ag/Fe and N-species influence the antibacterial and ORR activities. A maximum power density of 1791 mW m(-2) is obtained by Ag/Fe/N/C (630 °C), which is far higher than that of Pt/C (1192 mW m(-2)), only having a decline of 16.14% after 90 days of running. The Fe-bonded N and the cooperation of pyridinic N and pyrrolic N in Ag/Fe/N/C contribute equally to the highly catalytic activity toward ORR. The ·OH or O2(-) species originating from the catalysis of O2 can suppress the biofilm growth on Ag/Fe/N/C cathodes. The synergistic effects between the Ag/Fe heterojunction and N-species substantially contribute to the high power output and Coulombic efficiency of Ag/Fe/N/C catalysts. These new antibacterial ORR catalysts show promise for application in MFCs. PMID:26938657

  18. Impact of micro-porous layer on liquid water distribution at the catalyst layer interface and cell performance in a polymer electrolyte membrane fuel cell

    Science.gov (United States)

    Tabe, Yutaka; Aoyama, Yusuke; Kadowaki, Kazumasa; Suzuki, Kengo; Chikahisa, Takemi

    2015-08-01

    In polymer electrolyte membrane fuel cells, a gas diffusion layer (GDL) with a micro-porous layer (MPL) gives better anti-flooding performance than GDLs without an MPL. To investigate the function and mechanism of the MPL to suppress water flooding, the liquid water distribution at the cathode catalyst layer (CL) surface are observed by a freezing method; in the method liquid water is immobilized in ice form by rapid freezing, followed by disassembling the cell for observations. The ice covered area is quantified by image processing and cells with and without an MPL are compared. The results show that the MPL suppresses water accumulation at the interface due to smaller pore size and finer contact with the CL, and this results in less water flooding. Investigation of ice formed after -10 °C cold start shutdowns and the temporary performance deterioration at ordinary temperatures also indicates a significant influence of the liquid water accumulating at the interface. The importance of the fine contact between CL and MPL, the relative absence of gaps, is demonstrated by a gas diffusion electrode (GDE) which is directly coated with catalyst ink on the surface of the MPL achieving finer contact of the layers.

  19. Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries.

    Science.gov (United States)

    Wu, Feng; Li, Ning; Su, Yuefeng; Zhang, Linjing; Bao, Liying; Wang, Jing; Chen, Lai; Zheng, Yu; Dai, Liqin; Peng, Jingyuan; Chen, Shi

    2014-06-11

    Lack of high-performance cathode materials has become a technological bottleneck for the commercial development of advanced Li-ion batteries. We have proposed a biomimetic design and versatile synthesis of ultrathin spinel membrane-encapsulated layered lithium-rich cathode, a modification by nanocoating. The ultrathin spinel membrane is attributed to the superior high reversible capacity (over 290 mAh g(-1)), outstanding rate capability, and excellent cycling ability of this cathode, and even the stubborn illnesses of the layered lithium-rich cathode, such as voltage decay and thermal instability, are found to be relieved as well. This cathode is feasible to construct high-energy and high-power Li-ion batteries. PMID:24844948

  20. Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

    Science.gov (United States)

    Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

    2002-12-01

    There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

  1. An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

    Science.gov (United States)

    Hagh, Nader; Skandan, Ganesh

    2012-01-01

    At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation

  2. Transport parameters of thin, supported cathode layers in solid oxide fuel cells (SOFCs); Transportparameter duenner, getraegerter Kathodenschichten der oxidkeramischen Brennstoffzelle

    Energy Technology Data Exchange (ETDEWEB)

    Wedershoven, Christian

    2010-12-22

    The aim of this work was to determine the transport properties of thin cathode layers, which are part of the composite layer of a fabricated anode-supported solid oxide fuel cell (SOFC). The transport properties of the anode and cathode have a significant influence on the electrochemical performance of a fuel cell stack and therefore represent an important parameter when designing fuel cell stacks. In order to determine the transport parameters of the cathode layers in a fabricated SOFC, it is necessary to permeate the thin cathode layer deposited on the gas-tight electrolyte with a defined gas transport. These thin cathode layers cannot be fabricated as mechanically stable single layers and cannot therefore be investigated in the diffusion and permeation experiments usually used to determine transport parameters. The setup of these experiments - particularly the sample holder - was therefore altered in this work. The result of this altered setup was a three-dimensional flow configuration. Compared to the conventional setup, it was no longer possible to describe the gas transport in the experiments with an analytical one-dimensional solution. A numerical solution process had to be used to evaluate the measurements. The new setup permitted a sufficiently symmetrical gas distribution and thus allowed the description of the transport to be reduced to a two-dimensional description, which significantly reduced the computational effort required to evaluate the measurements. For pressure-induced transport, a parametrized coherent expression of transport could be derived. This expression is equivalent to the analytical description of the transport in conventional measurement setups, with the exception of parameters that describe the geometry of the gas diffusion. In this case, a numerical process is not necessary for the evaluation. Using the transport parameters of mechanically stable anode substrates, which can be measured both in the old and the new setups, the old and

  3. Impact of anode catalyst layer porosity on the performance of a direct formic acid fuel cell

    International Nuclear Information System (INIS)

    Highlights: ► Lithium carbonate is used as a pore-former to increase porosity of anode catalyst layer. ► Maximum power density increased by 25%. ► Onset potential for formic acid electro-oxidation reduced by 30 mV for anode catalyst layer with 17.5 wt% pore-former. ► Electrochemical impedance spectra confirm increased formic acid concentration inside the anode catalyst layer pores. - Abstract: Direct formic acid fuel cells (DFAFCs) have attracted much attention in the last few years for portable electronic devices, due to their potential of being high efficiency power sources. They have the potential to replace the state-of-the-art batteries in cell phones, PDAs, and laptop computers if their power density and durability can be improved. In the present investigation, the influence of increased anode catalyst layer porosity on DFAFC power density performance is studied. Lithium carbonate (Li2CO3) was used as a pore-former in this study because of its facile and complete removal after catalyst layer fabrication. The anode catalyst layers presented herein contained unsupported Pt/Ru catalyst and Li2CO3 (in the range of 0–50 wt%) bound with proton conducting ionomer. Higher DFAFC performance is obtained because of the increased porosity within the anode catalyst layer through enhanced reactant and product mass transport. The maximum power density of DFAFC increased by 25% when pore-former was added to the anode catalyst ink. The formic acid onset potential for the anode catalyst layer with 17.5 wt% pore-former was reduced by 30 mV. A constant phase element based equivalent-circuit model was used to investigate anode impedance spectra. Fitted values for the anode impedance spectra confirm the improvement in performance due to an increase in formic acid concentration inside the anode catalyst layer pores along with efficient transport of reactants and products.

  4. Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei;

    2014-01-01

    Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of...... uniform iron carbide (Fe3C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As...... a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide‐based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts....

  5. Highly-dispersed Ta-oxide catalysts prepared by electrodeposition in a non-aqueous plating bath for polymer electrolyte fuel cell cathodes

    KAUST Repository

    Seo, Jeongsuk

    2012-01-01

    The Ta-oxide cathode catalysts were prepared by electrodeposition in a non-aqueous solution. These catalysts showed excellent catalytic activity and have an onset potential of 0.92 V RHE for the oxygen reduction reaction (ORR). The highly-dispersed Ta species at the nanometer scale on the carbon black was an important contributor to the high activity. © 2012 The Royal Society of Chemistry.

  6. Long-term performance of activated carbon air cathodes with different diffusion layer porosities in microbial fuel cells

    KAUST Repository

    Zhang, Fang

    2011-08-01

    Activated carbon (AC) air-cathodes are inexpensive and useful alternatives to Pt-catalyzed electrodes in microbial fuel cells (MFCs), but information is needed on their long-term stability for oxygen reduction. AC cathodes were constructed with diffusion layers (DLs) with two different porosities (30% and 70%) to evaluate the effects of increased oxygen transfer on power. The 70% DL cathode initially produced a maximum power density of 1214±123mW/m 2 (cathode projected surface area; 35±4W/m 3 based on liquid volume), but it decreased by 40% after 1 year to 734±18mW/m 2. The 30% DL cathode initially produced less power than the 70% DL cathode, but it only decreased by 22% after 1 year (from 1014±2mW/m 2 to 789±68mW/m 2). Electrochemical tests were used to examine the reasons for the degraded performance. Diffusion resistance in the cathode was found to be the primary component of the internal resistance, and it increased over time. Replacing the cathode after 1 year completely restored the original power densities. These results suggest that the degradation in cathode performance was due to clogging of the AC micropores. These findings show that AC is a cost-effective material for oxygen reduction that can still produce ~750mW/m 2 after 1 year. © 2011 Elsevier B.V.

  7. EFFECT OF PRETREATMENT ON PT-CO/C CATHODE CATALYSTS FOR THE OXYGEN-REDUCTION REACTION

    Energy Technology Data Exchange (ETDEWEB)

    Fox, E.; Colon-Mercado, H.

    2010-01-19

    Carbon supported Pt and Pt-Co electrocatalysts for the oxygen reduction reaction in low temperature fuel cells were prepared by the reduction of the metal salts with sodium borohydride and sodium formate. The effect of surface treatment with nitric acid on the carbon surface and Co on the surface of carbon prior to the deposition of Pt was studied. The catalysts where Pt was deposited on treated carbon the ORR reaction preceded more through the two electron pathway and favored peroxide production, while the fresh carbon catalysts proceeded more through the four electron pathway to complete the oxygen reduction reaction. NaCOOH reduced Pt/C catalysts showed higher activity that NaBH{sub 4} reduced Pt/C catalysts. It was determined that the Co addition has a higher impact on catalyst activity and active surface area when used with NaBH{sub 4} as reducing agent as compared to NaCOOH.

  8. The dependence of the cathode architecture on the photoactive layer morphology in bulk-heterojunction polymeric solar cells

    International Nuclear Information System (INIS)

    Poly (3-hexylthiophene) (P3HT), [6,6]-phenyl C61-butyric acid methyl ester (PCBM), and polymethylmethacrylate (PMMA) have been chosen to prepare binary and ternary blend thin films. In the case of the binary blend thin films of P3HT:PCBM used as the photoactive layers, the LiF/Al cathode offered nearly the same power conversion efficiency (PCE) as bathocuproine (BCP) 2 nm Al−1 and BCP 10 nm Al−1 cathodes. While ternary blend thin films of P3HT:PCBM:PMMA were applied as the photoactive layers, the BCP 2 nm Al−1 cathode showed an increase of roughly 42% in the PCE relative to ternary blend thin film with LiF/Al and BCP 10 nm Al−1 cathodes. The vertical phase separation of P3HT and PCBM was found to be more suppressed in the ternary blend films than in the binary ones, due to the confinement of PMMA. The P3HT:PCBM:PMMA with the BCP 2 nm Al−1 cathode showed an increase of 20% in the PCE as compared to the binary thin film of P3HT:PCBM with the LiF/Al cathode. We provide some insights into the correlation between the morphology control of active layer and cathode structure, useful for the development of polymeric solar cells towards the commercialization. (paper)

  9. Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC)

    International Nuclear Information System (INIS)

    Cobalt-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cell (PEMFC) have been successfully incorporated cobalt oxide (Co3O4) onto Vulcan XC-72 carbon powder by thermal decomposition of Co-ethylenediamine complex (ethylenediamine, NH2CH2CH2NH2, denoted en) at 850 oC. The catalysts were prepared by adsorbing the cobalt complexes [Co(en)(H2O)4]3+, [Co(en)2(H2O)2]3+ and [Co(en)3]3+ on commercial XC-72 carbon black supports, loading amount of Co with respect to carbon black was about 2%, the resulting materials have been pyrolyzed under nitrogen atmosphere to create CoOx/C catalysts, donated as E1, E2, and E3, respectively. The composite materials were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Chemical compositions of prepared catalysts were determined using inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The catalytic activities for ORR have been analyzed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrocatalytic activity for oxygen reduction of E2 is superior to that of E1 and E3. Membrane electrode assemblies (MEAs) containing the synthesized CoOx/C cathode catalysts were fabricated and evaluated by single cell tests. The E2 cathode performed better than that of E1 and E3 cathode. This can be attributed to the enhanced activity for ORR, in agreement with the composition of the catalyst that CoO co-existed with Co3O4. The maximum power density 73 mW cm-2 was obtained at 0.3 V with a current density of 240 mA cm-2 for E2 and the normalized power density of E2 is larger than that that of commercial 20 wt.% Pt/C-ETEK. -- Highlights: → Non-noble catalysts have been attracting increasing attention due to become a low-cost alternative catalyst for oxygen reduction in PEMFC. → This method for the production of nanoparticle cobalt oxides which can be incorporated into Vulcan XC-72

  10. Simulation of the catalyst layer in PEMFC based on a novel two-phase lattice model

    International Nuclear Information System (INIS)

    Highlights: → We propose a novel two phase lattice model of catalyst layer in PEMFC. → The model features a catalyst phase and a mixed ionomer and pores phase. → Transport and electrochemical reaction in the lattice are simulated. → The model enables more accurate results than pore-solid two phase model. → Profiles of oxygen level and reaction rate across catalyst layer vary with cell current. - Abstract: A lattice model of catalyst layer in proton exchange membrane fuel cells (PEMFCs), consisting of randomly distributed catalyst phase (C phase) and mixed ionomer-pore phase (IP phase), was established by means of Monte Carlo method. Transport and electrochemical reactions in the model catalyst layer were calculated. The newly proposed C-IP model was compared with previously established pore-solid two phase model. The variation of oxygen level and reaction rate along the thickness of catalyst layer with cell current was discussed. The effect of ionomer distribution across catalyst layer was studied by comparing profiles of oxygen level, reaction rate and overpotential, as well as corresponding polarization curves.

  11. Microbial fuel cells using natural pyrrhotite as the cathodic heterogeneous Fenton catalyst towards the degradation of biorefractory organics in landfill leachate

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Lu, Anhuai; Ding, Hongrui; Wang, Xin; Wang, Changqiu; Zeng, Cuiping; Yan, Yunhua [The Key Laboratory of Orogenic Belts and Crustal Evolution, School of Earth and Space Sciences, Peking University, Beijing 100871 (China)

    2010-07-15

    An investigation aimed at checking the integration of cathodic pyrrhotite Fenton's reaction with anodic microbial respiration for the enhancement of MFC performance and treatment of a real landfill leachate was carried out. The MFC equipped with a pyrrhotite-coated graphite-cathode generated the maximum power density of 4.2 W/m{sup 3} that was 133% higher than graphite-cathode. Concomitantly, electrochemical impedance spectroscopy (EIS) showed that the polarization resistance of pyrrhotite-cathode (92 {omega}) was much lower than the graphite-cathode (1057 {omega}), indicating that the cathodic overpotential was significantly lowered, probably due to the occurrence of pyrrhotite Fenton's reaction. The in situ generation of Fenton's reagents (Fe{sup 2+} and H{sub 2}O{sub 2}) at the pyrrhotite-cathode was demonstrated by the cyclic voltammetry measurement. Besides, reactive oxygen species produced from the pyrrhotite Fenton's reaction were detected and demonstrated to be vital to the enhancement of MFC power output. Further, the effectiveness of this system was examined by treating an old-aged landfill leachate. 77% of color and 78% of COD were removed from the original leachate, indicating that the pyrrhotite not only acted as a cost-effective cathodic catalyst for MFCs in power generation, but also extended the practical merits of traditional MFCs towards advanced oxidation of biorefractory pollutants. (author)

  12. Solution-processed cathode interfacial layer materials for high-efficiency polymer solar cells

    Directory of Open Access Journals (Sweden)

    Biao Xiao

    2015-09-01

    Full Text Available Polymer solar cells (PSCs are a new type of renewable energy source currently being extensively investigated due to perceived advantages; such as being lightweight, low-cost and because of the unlimited materials resource. The power conversion efficiency of state-of-the-art PSCs has increased dramatically in the past few years, obtained mainly through the development of new electron donor polymers, acceptors, and novel device structures through the use of various electrode interfacial materials. In this short review, recent progress in solution-processed cathode interfacial layers that could significantly improve device performances is summarized and highlighted.

  13. Inkjet printing of carbon supported platinum 3-D catalyst layers for use in fuel cells

    Science.gov (United States)

    Taylor, André D.; Kim, Edward Y.; Humes, Virgil P.; Kizuka, Jeremy; Thompson, Levi T.

    We present a method of using inkjet printing (IJP) to deposit catalyst materials onto gas diffusion layers (GDLs) that are made into membrane electrode assemblies (MEAs) for polymer electrolyte fuel cell (PEMFC). Existing ink deposition methods such as spray painting or screen printing are not well suited for ultra low (Monarch 700, Black Pearls 2000, etc.). Our ink jet printed MEAs with catalyst loadings of 0.020 mg Pt cm -2 have shown Pt utilizations in excess of 16,000 mW mg -1 Pt which is higher than our traditional screen printed MEAs (800 mW mg -1 Pt). As a further demonstration of IJP versatility, we present results of a graded distribution of Pt/C catalyst structure using standard Johnson Matthey (JM) catalyst. Compared to a continuous catalyst layer of JM Pt/C (20% Pt), the graded catalyst structure showed enhanced performance.

  14. Effect of Nafion and platinum content in a catalyst layer processed in a radio frequency helicon plasma system

    International Nuclear Information System (INIS)

    A helicon plasma sputtering system is used to deposit small amounts of platinum on microporous carbon support composed of Vulcan XC 72 carbon particles (known as gas diffusion layer) to form Pt catalyzed electrodes for proton exchange membrane fuel cells. Electrodes with low Pt loading are prepared, assembled in custom-made membrane electrode assemblies (MEAs) and tested for the hydrogen oxydation and the oxygen reduction. Initially, the Nafion (registered) loading spread on these plasma prepared electrodes is optimized by measuring the MEA performance. It is found that the optimum Nafion (registered) loading is 1 mg cm-2 for an electrode previously covered with 0.1 mgPt cm-2 using the helicon plasma system. For a commercial electrode prepared by ink processes with 0.5 mgPt cm-2, the optimized Nafion (registered) loading is 2 mg cm-2. Using the respective optimized Nafion (registered) loading, the electrical performance of the custom-made MEA with one plasma prepared electrode (either anode or cathode) is compared with that of a reference MEA from Electrochem Inc. (Pt loading per electrode of 0.5 mg cm-2 and maximum power density of 425 mW cm-2) without gas humidification. The custom-made MEA fitted with an anode covered with 0.005 mgPt cm-2 leads to the same performance as that of the reference MEA at low current density (-2) and high gas backpressure (3 bar). This result indicates that the catalyst utilization efficiency in the plasma prepared anode is 100 times higher than that in the commercial anode ( 85 kW gPt-1 versus 0.85 kW gPt-1). For plasma prepared cathodes with 0.1 mgPt cm-2, the cathodic Pt utilization efficiency is 2.7 kW gPt-1, which is 3 times higher than that obtained in the commercial cathode.

  15. Electrochemical properties of Atomic layer deposition processed CeO2 as a protective layer for the molten carbonate fuel cell cathode

    International Nuclear Information System (INIS)

    Highlights: • Nano-structured CeO2-coated Ni by Atomic Layer Deposition, crystalline as-deposited. • Progressive transformation into a complex surface stable in molten carbonates. • Lower Ni solubility with CeO2 protective coating. • Feasibility of CeO2 coating in Molten Carbonate Fuel Cell cathode conditions. - Abstract: In order to increase the lifetime and performance of the molten carbonate fuel cell, it is compulsory to control the corrosion and dissolution of the state of the art porous nickel oxide cathode. A protective coating constituted by more stable oxides appears to be the best approach. Previous research on CeO2 coatings obtained by DC reactive magnetron sputtering to protect the Molten carbonate fuel cell cathode gave promising results but it was necessary to improve the coating adhesion. In this paper Atomic Layer Deposition, producing high quality, homogeneous and conformal layers, was used to obtain thin layers of CeO2 (20 nm and 120 nm) deposited over porous nickel. CeO2-Ni coated samples were tested as cathodes in Li2CO3-K2CO3 (62-38 mol %) eutectic mixture under standard cathode atmosphere (CO2/air 30:70 vol. %). Structural and morphological characterizations of the nickel coated cathode before and after electrochemical tests in the molten carbonate melt are reported together with the Open Circuit Potential evolution all over 230 h for both the bare porous nickel and the CeO2-coated samples

  16. Investigation of surface layer composition of the rhodium-ruthenium catalysts by means of auger spectroscopy

    International Nuclear Information System (INIS)

    The surface layer composition of skeleton catalysts of the rhodium-ruthenium system by means of Auger-electron spectroscopy and electron spectroscopy for the chemical analysis is investigated. It is shown that apart from rhodium, ruthenium aluminium and silicon there is a certain quantity of chemosorbed oxygen accumulated in case of catalysts conservation over a long period of time. The dependence of filling catalysts by chemosorbed oxygen on the alloy composition has been found

  17. Preparation of Supported Metal Catalysts by Atomic and Molecular Layer Deposition for Improved Catalytic Performance

    Science.gov (United States)

    Gould, Troy D.

    Creating catalysts with enhanced selectivity and activity requires precise control over particle shape, composition, and size. Here we report the use of atomic layer deposition (ALD) to synthesize supported Ni, Pt, and Ni-Pt catalysts in the size regime (number of ALD cycles, Ni weight loadings were varied from 4.7 wt% to 16.7 wt% and the average particle sizes ranged from 2.5 to 3.3 nm, which increased the selectivity for C 3H6 hydrogenolysis by an order of magnitude over a much larger Ni/Al2O3 catalyst. Pt particles were deposited by varying the number of ALD cycles and the reaction chemistry (H2 or O 2) to control the particle size from approximately 1 to 2 nm, which allowed lower-coordinated surface atoms to populate the particle surface. These Pt ALD catalysts demonstrated some of the highest oxidative dehydrogenation of propane selectivities (37%) of a Pt catalyst synthesized by a scalable technique. Dry reforming of methane (DRM) is a reaction of interest due to the recent increased recovery of natural gas, but this reaction is hindered from industrial implementation because the Ni catalysts are plagued by deactivation from sintering and coking. This work utilized Ni ALD and NiPt ALD catalysts for the DRM reaction. These catalysts did not form destructive carbon whiskers and had enhanced reaction rates due to increased bimetallic interaction. To further limit sintering, the Ni and NiPt ALD catalysts were coated with a porous alumina matrix by molecular layer deposition (MLD). The catalysts were evaluated for DRM at 973 K, and the MLD-coated Ni catalysts outperformed the uncoated Ni catalysts in either activity (with 5 MLD cycles) or stability (with 10 MLD cycles). In summary, this thesis developed a new Ni nanoparticle ALD chemistry, explored possibilities for changing Pt ALD particle size, brought the two techniques together to create enhanced bimetallic catalysts, and stabilized the catalysts using MLD.

  18. A multi-layered Fe2O3/graphene composite with mesopores as a catalyst for rechargeable aprotic lithium–oxygen batteries

    Science.gov (United States)

    Feng, Ningning; Mu, Xiaowei; Zheng, Mingbo; Wang, Chaoqiang; Lin, Zixia; Zhang, Xueping; Shi, Yi; He, Ping; Zhou, Haoshen

    2016-09-01

    Aprotic Li–O2 batteries have attracted a huge amount of interest in the past decade owing to their extremely high energy density. However, identifying a desirable cathodic catalyst for this promising battery system is one of the biggest challenges at present. In this work, a multi-layered Fe2O3/graphene nanosheets (Fe2O3/GNS) composite with sandwich structure was synthesized using an easy thermal casting method, and served as a cathodic catalyst for aprotic Li–O2 batteries. The aprotic Li–O2 cell with the Fe2O3/GNS catalyst demonstrated a better reversibility, lower overpotential for oxygen evolution, and a higher Coulombic efficiency (close to 100%) than those of pure GNS. An excellent rate performance and good cycle stability were also confirmed. The results, characterized by ex and in situ methods, revealed that the dominant discharge product Li2O2 was decomposed below 4.35 V. This superior electrochemical performance is mainly attributed to the unique sandwich structure of the Fe2O3/GNS catalyst with mesopores, which can provide substantially more catalytic sites and prevent direct contact between carbon and Li2O2.

  19. Studies on Co-based catalysts supported on modified carbon substrates for PEMFC cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, Nalini P.; Kumaraguru, Swaminatha P.; Colon-Mercado, Hector; Popov, Branko N. [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Kim, Hansung [Department of Chemical Engineering Yonsei University, Seoul (Korea, Republic of); Black, Timothy; Chen, Donna A. [Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208 (United States)

    2006-06-19

    Cobalt based non-precious metal catalysts were prepared by supporting cobalt-ethylene diamine complex on carbon followed by a heat treatment at elevated temperatures (800{sup o}C). Surface oxygen groups on carbon were introduced with HNO{sub 3} oxidation. Co catalysts supported on oxidized carbon showed improved activity and selectivity towards four-electron reduction of molecular oxygen. Quinone groups introduced by nitric acid treatment, in addition to increasing the dispersion of the chelate complexes, play a role in forming the active site for oxygen reduction. (author)

  20. Factors influencing electrochemical properties and performance of hydrocarbon based ionomer PEMFC catalyst layers

    OpenAIRE

    Astill, Toby Duncan

    2008-01-01

    This work investigated the properties of catalyst layers for proton exchange membrane fuel cells (PEMFC) that contained sulfonated poly(ether ether ketone) (SPEEK). A series of SPEEK polymers were prepared with varying ion exchange capacity (IEC) to test their oxygen mass transport properties, electrochemical kinetic parameters, proton conductivity, and water sorption characteristics. A simple method to fabricate catalyst layers containing SPEEK and polytetrafluoroethylene (PTFE) was develope...

  1. Final Report: Cathode Catalysis in Hydrogen/Oxygen Fuel Cells: New Catalysts, Mechanism, and Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Gewirth, Andrew A. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry; Kenis, Paul J. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemical and Biomolecular Engineering; Nuzzo, Ralph G. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry; Rauchfuss, Thomas B. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry

    2016-01-18

    In this research, we prosecuted a comprehensive plan of research directed at developing new catalysts and new understandings relevant to the operation of low temperature hydrogen-oxygen fuel cells. The focal point of this work was one centered on the Oxygen Reduction Reaction (ORR), the electrochemical process that most fundamentally limits the technological utility of these environmentally benign energy conversion devices. Over the period of grant support, we developed new ORR catalysts, based on Cu dimers and multimers. In this area, we developed substantial new insight into design rules required to establish better ORR materials, inspired by the three-Cu active site in laccase which has the highest ORR onset potential of any material known. We also developed new methods of characterization for the ORR on conventional (metal-based) catalysts. Finally, we developed a new platform to study the rate of proton transfer relevant to proton coupled electron transfer (PCET) reactions, of which the ORR is an exemplar. Other aspects of work involved theory and prototype catalyst testing.

  2. Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Description of recent in operando and in situ analysis methodology. • Surface science approach using photoemission for analysis of cathode surfaces and interfaces. • Ageing and fatigue of layered oxide Li-ion battery cathode materials from the atomistic point of view. • Defect formation and electronic structure evolution as causes for cathode degradation. • Significance of interfacial energy alignment and contact potential for side reactions. - Abstract: This overview addresses the atomistic aspects of degradation of layered LiMO2 (M = Ni, Co, Mn) oxide Li-ion battery cathode materials, aiming to shed light on the fundamental degradation mechanisms especially inside active cathode materials and at their interfaces. It includes recent results obtained by novel in situ/in operando diffraction methods, modelling, and quasi in situ surface science analysis. Degradation of the active cathode material occurs upon overcharge, resulting from a positive potential shift of the anode. Oxygen loss and eventual phase transformation resulting in dead regions are ascribed to changes in electronic structure and defect formation. The anode potential shift results from loss of free lithium due to side reactions occurring at electrode/electrolyte interfaces. Such side reactions are caused by electron transfer, and depend on the electron energy level alignment at the interface. Side reactions at electrode/electrolyte interfaces and capacity fade may be overcome by the use of suitable solid-state electrolytes and Li-containing anodes

  3. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-05-01

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the other catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.

  4. Wire or no wire-Depends on the catalyst layer thickness

    Science.gov (United States)

    Li, Feng Ji; Zhang, Sam; Lee, Jyh-Wei; Zhao, Dongliang

    2013-10-01

    Crystalline silicon (Si) nanowire could be directly grown from Si wafer upon thermal annealing in the presence of catalyst such as gold (Au). However, the role of the catalyst layer thickness is yet elucidated. In this work, 10 nm, 20 nm, and 40 nm Au layers were respectively sputtered on Si wafer substrates, followed by 2 min thermal annealing at 1000 °C under Ar atmosphere, to find the relationship between the catalyst layer thickness and formation of the nanowire. Results show that in the case of thin layer of catalyst, crystalline-Si/amorphous-SiOx coaxial nanowires grew. But with thicker layers of catalyst, no wires were found but crystalline Au particles capsulated with amorphous SiOx. The catalyst and nanowire morphologies and structures were carefully examined through a scanning electron microscope, X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy and selected area diffraction. A model is developed to explain the formation mechanism of the Si/SiOx and Au/SiOx core-shell nanostructures.

  5. A Comparison of Fick and Maxwell-Stefan Diffusion Formulations in PEMFC Cathode Gas Diffusion Layers

    CERN Document Server

    Lindstrom, Michael

    2013-01-01

    This paper explores the mathematical formulations of Fick and Maxwell-Stefan diffusion in the context of polymer electrolyte membrane fuel cell cathode gas diffusion layers. Formulations of diffusion combined with mass-averaged Darcy flow are considered for three component gases. Fick formulations can be considered as approximations of Maxwell-Stefan in a certain sense. For this application, the formulations can be compared computationally in a simple, one dimensional setting. We observe that the predictions of the formulations are very similar, despite their seemingly different structure. Analytic insight is given to the result. In addition, it is seen that for both formulations, diffusion laws are small perturbations from bulk flow. The work is also intended as a reference to multi-component gas diffusion formulations in the fuel cell setting.

  6. Estimating the optimal number of membrane electrode assembly catalyst layers for proton exchange membrane fuel cell by considering open circuit voltage and polarization

    International Nuclear Information System (INIS)

    This paper reports on a thin polymer membrane with a self-humidifying membrane electrode assembly (MEA) using water generated from the cathode. However, the open circuit voltage was low because the activation and diffusion polarizations were high. Therefore, a multilayered MEA was prepared for a proton exchange membrane fuel cell by the screen-printing method to reduce the two polarizations and improve the open circuit voltage and power density. The MEA consists of a Nafion 115 membrane and a Vulcan XC-72 commercial catalyst (20 wt.% Pt/C) on the anode and cathode. The performances of the multilayered MEA were evaluated for the current-voltage (I-V) characteristics of single cells. In addition, the activation and diffusion polarizations and the open circuit voltage were analyzed for a prepared sample. Excellent characteristics were obtained for the MEA multilayered structure (anode: two layers; cathode: three layers). The activity of both electrodes was increased and a high power density was obtained compared to single-layered MEA.

  7. Nanoscale alloying effect of gold–platinum nanoparticles as cathode catalysts on the performance of a rechargeable lithium–oxygen battery

    International Nuclear Information System (INIS)

    The understanding of nanoscale alloying or the phase segregation effect of alloy nanoparticles on the catalytic properties is important for a rational design of the desired catalysts for a specific reaction. This paper describes findings of an investigation into this type of structural effect for carbon-supported bimetallic gold–platinum nanoparticles as cathode catalysts in a rechargeable lithium–oxygen battery. The nanoscale structural characteristics in terms of size, alloying and phase segregation were shown to affect the catalytic properties of the catalysts in the Li–O2 battery. In addition to the composition effect, the catalysts with a fully alloyed phase structure were found to exhibit a smaller discharge–charge voltage difference and a higher discharge capacity than those with a partial phase segregation structure. This finding is significant for the design of alloy nanoparticles as air cathode catalysts in rechargeable lithium–air batteries, demonstrating the importance of the control of the nanoscale composition and phase properties. (paper)

  8. Controllable syntheses of α- and δ-MnO2 as cathode catalysts for zinc-air battery

    International Nuclear Information System (INIS)

    Highlights: • A simple method to prepare α-MnO2 and δ-MnO2 for cathode materials of zinc-air battery is developed. • The as-prepared samples have larger specific surface area than commercial γ-MnO2. • The samples exhibit improved catalytic activity for oxygen reduction reaction compared to γ-MnO2. -- Abstract: Four MnO2 samples were synthesized through a simple reaction of KMnO4 with high-purity graphite in different concentrations of sulfuric acid at low temperature. Their morphology, crystal structure and performance as cathode catalysts of zinc-air battery were investigated with X-ray diffraction (XRD), Fourier transformation infrared spectrometer (FTIR), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) and electrochemical tests. It is found that the crystal structure and the morphology of the synthesized samples depend on the sulfuric acid concentration. The synthesized samples have large specific surface area and exhibit excellent performance compared to the commercial electrolytic manganese dioxide (γ-MnO2). Two varieties of manganese dioxides, δ-MnO2 (the as-prepared samples a and b) and α-MnO2 (the as-prepared sample c and d), were obtained when using low and high sulfuric acid concentration, respectively. Higher sulfuric acid concentration favors the agglomeration of the particles. The specific surface area of samples a, b, c, d, and γ-MnO2 is 83.2, 81.1, 88.5, 86.8, and 43.5 m2 g−1, corresponding to discharge capacity of zinc-air batteries is 169.5, 160.3, 175.2, 171.5, and 112.2 mAh, respectively

  9. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries.

    Science.gov (United States)

    Lin, Feng; Markus, Isaac M; Nordlund, Dennis; Weng, Tsu-Chien; Asta, Mark D; Xin, Huolin L; Doeff, Marca M

    2014-01-01

    The present study sheds light on the long-standing challenges associated with high-voltage operation of LiNi(x)Mn(x)Co(1-2x)O2 cathode materials for lithium-ion batteries. Using correlated ensemble-averaged high-throughput X-ray absorption spectroscopy and spatially resolved electron microscopy and spectroscopy, here we report structural reconstruction (formation of a surface reduced layer, to transition) and chemical evolution (formation of a surface reaction layer) at the surface of LiNi(x)Mn(x)Co(1-2x)O2 particles. These are primarily responsible for the prevailing capacity fading and impedance buildup under high-voltage cycling conditions, as well as the first-cycle coulombic inefficiency. It was found that the surface reconstruction exhibits a strong anisotropic characteristic, which predominantly occurs along lithium diffusion channels. Furthermore, the surface reaction layer is composed of lithium fluoride embedded in a complex organic matrix. This work sets a refined example for the study of surface reconstruction and chemical evolution in battery materials using combined diagnostic tools at complementary length scales. PMID:24670975

  10. Porous Perovskite LaNiO3 Nanocubes as Cathode Catalysts for Li-O2 Batteries with Low Charge Potential

    Science.gov (United States)

    Zhang, Jian; Zhao, Yubao; Zhao, Xiao; Liu, Zhaolin; Chen, Wei

    2014-08-01

    Developing efficient catalyst for oxygen evolution reaction (OER) is essential for rechargeable Li-O2 battery. In our present work, porous LaNiO3 nanocubes were employed as electrocatalyst in Li-O2 battery cell. The as-prepared battery showed excellent charging performance with significantly reduced overpotential (3.40 V). The synergistic effect of porous structure, large specific surface area and high electrocatalytic activity of porous LaNiO3 nanocubes ensured the Li-O2 battery with enchanced capacity and good cycle stability. Furthermore, it was found that the lithium anode corrosion and cathode passivation were responsible for the capacity fading of Li-O2 battery. Our results indicated that porous LaNiO3 nanocubes represent a promising cathode catalyst for Li-O2 battery.

  11. Optimization of catalyst layer composition for PEMFC using graphene-based oxygen reduction reaction catalysts

    Science.gov (United States)

    Park, Jong Cheol; Park, Sung Hyeon; Chung, Min Wook; Choi, Chang Hyuck; Kho, Back Kyun; Woo, Seong Ihl

    2015-07-01

    The focus in recent years is on developing high performance non-precious metal catalysts (NPMCs) to reduce the catalyst cost in fuel cells. However, little attention has been paid to improve the utilization of NPMCs. Thus, this study focuses on the optimization of electrode component, particularly the Nafion content. With the synthesized graphene based oxygen reduction reaction (ORR) catalyst, the catalyst inks were prepared at various Nafion contents with suitable amounts of catalysts sprayed on the gas diffusion media. Twenty different single cells were assembled and measured for polarization, resistance and electrochemical impedance. Electrodes of 66.7 and 50.0% Nafion contents showed the highest performance for hydrogen/oxygen and hydrogen/air operation, respectively. These results were explained using the electrochemical impedance spectra, where the highest performance electrode resulted with the lowest charge transfer resistance. Moreover, negligible change in performance was observed during the 80 h of stability test. The optimization compositions of NPMC-based MEAs were very different to Pt-based MEAs, indicating the importance of optimization studies for the practical use of NPMCs.

  12. Nb doped TiO2 as a Cathode Catalyst Support Material for Polymer Electrolyte Membrane Fuel Cells

    Science.gov (United States)

    O'Toole, Alexander W.

    In order to reduce the emissions of greenhouse gases and reduce dependence on the use of fossil fuels, it is necessary to pursue alternative sources of energy. Transportation is a major contributor to the emission of greenhouse gases due to the use of fossil fuels in the internal combustion engine. To reduce emission of these pollutants into the atmosphere, research is needed to produce alternative solutions for vehicle transportation. Low temperature polymer electrolyte membrane fuel cells are energy conversion devices that provide an alternative to the internal combustion engine, however, they still have obstacles to overcome to achieve large scale implementation. T he following work presents original research with regards to the development of Nb doped TiO2 as a cathode catalyst support material for low temperature polymer electrolyte membrane fuel cells. The development of a new process to synthesize nanoparticles of Nb doped TiO2 with controlled compositions is presented as well as methods to scale up the process and optimize the synthesis for the aforementioned application. In addition to this, comparison of both electrochemical activity and durability with current state of the art Pt on high surface area carbon black (Vulcan XC-72) is investigated. Effects of the strong metal-support interaction on the electrochemical behavior of these materials is also observed and discussed.

  13. Improved performance of polymer solar cells by using inorganic, organic, and doped cathode buffer layers

    Science.gov (United States)

    Taohong, Wang; Changbo, Chen; Kunping, Guo; Guo, Chen; Tao, Xu; Bin, Wei

    2016-03-01

    The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester (P3HT:PCBM) polymer solar cell, we studied the effect of the cathode buffer layer (CBL) between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode (OLED) were employed as the CBL in the P3HT:PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs2CO3, bathophenanthroline (Bphen), and 8-hydroxyquinolatolithium (Liq) can be used as CBL to efficiently improve the device performance of the P3HT:PCBM polymer solar cells. The P3HT:PCBM devices employed various CBLs possess power conversion efficiencies (PCEs) of 3.0%-3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen:Cs2CO3 and Bphen:Liq as the CBL, the PCE of the P3HT:PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL. Project supported by the National Natural Science Foundation of China (Grant No. 61204014), the “Chenguang” Project (13CG42) supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation, China, and the Shanghai University Young Teacher Training Program of Shanghai Municipality, China.

  14. Dynamic wet-ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere

    International Nuclear Information System (INIS)

    The gas injection line of the latest spherical aberration-corrected environmental transmission electron microscope has been modified for achieving real-time/atomic-scale observations in moisturised gas atmospheres for the first time. The newly developed Wet-TEM system is applied to platinum carbon electrode catalysts to investigate the effect of water molecules on the platinum/carbon interface during deactivation processes such as sintering and corrosion. Dynamic in situ movies obtained in dry and 24% moisturised nitrogen environments visualize the rapid rotation, migration and agglomeration of platinum nanoparticles due to the physical adsorption of water and the hydroxylation of the carbon surface. The origin of the long-interconnected aggregation of platinum nanoparticles was discovered to be a major deactivation process in addition to conventional carbon corrosion. (paper)

  15. Porous layered lithium-rich oxide nanorods: Synthesis and performances as cathode of lithium ion battery

    International Nuclear Information System (INIS)

    Highlights: • One-step co-crystallization of oxalates was developed to synthesize layered lithium-rich oxide. • The oxalates provide the product with nanorod morphology and hierarchically porous structure. • The product exhibits improved rate capability and cyclic stability. - Abstract: A layered lithium-rich oxide, Li[Li0.19Mn0.32Co0.49]O2, is synthesized by introducing manganese and cobalt via oxalates co-crystallization in reverse micellar microemulsion. The physical and electrochemical performances of the as-synthesized oxide are evaluated as cathode of lithium ion battery. The physical characterizations, from X-ray diffraction, scanning electron microscope and transmission electron microscope, indicate that the as-synthesized oxide takes a nanorod morphology of up to 1 μm in length and 200 nm in diameter, which is composed of about 20 nm subunit nanoparticles, and possesses a hierarchical pore structure. Electrochemical measurements demonstrate that the as-synthesized oxide exhibits improved charge/discharge performances: less polarization, larger discharge capacity, higher rate capability, and better cyclic stability, compared to the sample synthesized by introducing the transition metals in solid-state reaction

  16. Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES.

    Science.gov (United States)

    Doubaji, Siham; Philippe, Bertrand; Saadoune, Ismael; Gorgoi, Mihaela; Gustafsson, Torbjorn; Solhy, Abderrahim; Valvo, Mario; Rensmo, Håkan; Edström, Kristina

    2016-01-01

    The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V). PMID:26692568

  17. Layer-by-layer polypyrrole coated graphite oxide and graphene nanosheets as catalyst support materials for fuel cells

    OpenAIRE

    Saner Okan, Burcu; Alkan Gürsel, Selmiye; Alkan Gursel, Selmiye; YÜRÜM, YUDA; Yurum, Yuda

    2013-01-01

    For the production of advanced type of catalyst support materials, the distinguished properties of graphene nanosheets were combined with the structural properties of conducting polypyrrole by the incorporation of graphene nanosheets into a polymer matrix by the proposed simple and low-cost fabrication technique. A precise tuning of electrical conductivity and thermal stability was also achieved by controlling the thickness of randomly dispersed graphene nanosheets by a layer-by-layer polymer...

  18. Ni And Co Segregations On Selective Surface Facets And Rational Design Of Layered Lithium Transition-metal Oxide Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Pengfei; Zheng, Jianming; Zheng, Jiaxin; Wang, Zhiguo; Teng, Gaofeng; Kuppan, Saravanan; Xiao, Jie; Chen, Guoying; Pan, Feng; Zhang, Jiguang; Wang, Chong M.

    2016-05-05

    The chemical processes occurring on the surface of cathode materials during battery cycling play a crucial role in determining battery’s performance. However, our understanding on such surface chemistry is far from clear due to the complexity of redox chemistry during battery charge/discharge. In this work, through intensive aberration corrected STEM investigation on eight layered oxide cathode materials, we report two important findings on the pristine oxides. First, Ni and Co show strong plane selectivity when building up their respective surface segregation layers (SSL). Specifically, Ni-SSL is exclusively developed on (200)m facet in Li-Mn-rich oxides (monoclinic C2/m symmetry) and (012)h facet in Mn-Ni equally rich oxides (hexagonal R-3m symmetry), while Co-SSL has a strong preference to (20-2)m plane with minimal Co-SSL also developed on some other planes in LMR cathodes. Structurally, Ni-SSLs tend to form spinel-like lattice while Co-SSLs are in a rock-salt-like structure. Secondly, by increasing Ni concentration in these layered oxides, Ni and Co SSLs can be suppressed and even eliminated. Our findings indicate that Ni and Co SSLs are tunable through controlling particle morphology and oxide composition, which opens up a new way for future rational design and synthesis of cathode materials.

  19. Performance and durability of carbon black-supported Pd catalyst covered with silica layers in membrane-electrode assemblies of proton exchange membrane fuel cells

    Science.gov (United States)

    Fujii, Keitaro; Ito, Mizuki; Sato, Yasushi; Takenaka, Sakae; Kishida, Masahiro

    2015-04-01

    Pd metal particles supported on a high surface area carbon black (Pd/CB) were covered with silica layers to improve the durability under severe cathode condition of proton exchange membrane fuel cells (PEMFCs). The performance and the durability of the silica-coated Pd/CB (SiO2/Pd/CB) were investigated by rotating disk electrode (RDE) in aqueous HClO4 and single cell test of the membrane-electrode assemblies (MEAs). SiO2/Pd/CB showed excellent durability exceeding Pt/CB during potential cycle in single cell test as well as in RDE measurement while Pd/CB significantly degraded. Furthermore, the MEA using SiO2/Pd/CB as the cathode catalyst showed higher performance than that using Pd/CB even in the initial state. The catalytic activity of SiO2/Pd/CB was higher than that of Pd/CB, and the drop of the cell performances due to the inhibition of electron conduction, proton conduction, and oxygen diffusion by the silica layer was not significant. It has been shown that the silica-coating is a very practical technique that can stabilize metal species originally unstable in the cathode condition of PEMFCs without a decrease in the cell performance.

  20. Research progress on the cathode catalysts for Li-air batteries%锂-空气电池正极催化剂研究进展

    Institute of Scientific and Technical Information of China (English)

    李月艳; 王莉; 何向明; 金云学; 李建军

    2014-01-01

    具有超高比能量的锂-空气电池是近年来的研究热点,电解质和空气电极催化剂是锂-空气电池的重要研究内容。介绍了有机体系锂-空气电池空气电极催化剂的研究进展,分析了碳、贵金属、氧化物三类催化剂材料的特征及性能,进而提出了新型、高效、兼具催化氧还原/氧析出功能的纳米催化剂的发展方向。%Lithium-air battery becomes a research hotspot in recent years due to its ultra-high ener-gy density.To develop lithium-air batteries of practical value,plenty of investigation on corre-sponding electrolytes and cathode catalysts have been explored.Air electrode catalysts in lithium-air batteries of aprotic electrolyte architecture are reviewed in this paper.In addition,the charac-teristics and electrochemical performances of carbon material,transition metal oxide catalysts,as well as noble metal based catalysts were introduced,along with a perspective of future research for efficient oxygen reduction/evolution bifunctional cathode nanocatalysts.

  1. Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

    International Nuclear Information System (INIS)

    Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated

  2. Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

    Energy Technology Data Exchange (ETDEWEB)

    Szamocki, R.; Flexer, V. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Levin, L.; Forchiasin, F. [Micologia Experimental, Departamento de Biodiversidad y Biologia Experimental. Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Calvo, E.J. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina)], E-mail: calvo@qi.fcen.uba.ar

    2009-02-28

    Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated.

  3. Theoretical modeling of the PEMFC catalyst layer: A review of atomistic methods

    International Nuclear Information System (INIS)

    This article reviews recent progress in the catalyst layer modeling of polymer electrolyte membrane fuel cells. Theoretical modeling is important to understand the basic chemical, and physical phenomena at the atomistic level in materials and relating these fundamentals to the properties and performance of the catalyst layer. Two fundamentally important theoretical methods have been chosen to represent atomistic models, namely density functional theory (DFT) and classical molecular dynamics. In addition, some reactive force field models are highlighted, and the mathematical framework is sufficiently described. The literature review includes important contributions that help to understand the oxygen reduction reaction including gas-phase reaction trends, and the solvation effects are also presented. Moreover, the electric field effect is discussed along with the recently established double reference method in the DFT framework. Using two atomistic simulations based on different axiomatic theories, the production of current density in the molecular junctions is considered with respect to voltage, elucidating applications to simple systems. The models of water transportation via polymer electrolyte membrane, as well as the catalyst and support oxidation are described. Epoxidized carbon support, oxidizable metal-oxide support and electron localization function analysis have provided insights for improving catalyst support material and enable characterization of the bonding between the catalyst and support. Conclusions and future outlook are outlined at the end. Thus the present work enlightens the future of the catalyst modeling towards more realistic models

  4. Self-Supporting Metal-Organic Layers as Single-Site Solid Catalysts.

    Science.gov (United States)

    Cao, Lingyun; Lin, Zekai; Peng, Fei; Wang, Weiwei; Huang, Ruiyun; Wang, Cheng; Yan, Jiawei; Liang, Jie; Zhang, Zhiming; Zhang, Teng; Long, Lasheng; Sun, Junliang; Lin, Wenbin

    2016-04-11

    Metal-organic layers (MOLs) represent an emerging class of tunable and functionalizable two-dimensional materials. In this work, the scalable solvothermal synthesis of self-supporting MOLs composed of [Hf6 O4 (OH)4 (HCO2 )6 ] secondary building units (SBUs) and benzene-1,3,5-tribenzoate (BTB) bridging ligands is reported. The MOL structures were directly imaged by TEM and AFM, and doped with 4'-(4-benzoate)-(2,2',2''-terpyridine)-5,5''-dicarboxylate (TPY) before being coordinated with iron centers to afford highly active and reusable single-site solid catalysts for the hydrosilylation of terminal olefins. MOL-based heterogeneous catalysts are free from the diffusional constraints placed on all known porous solid catalysts, including metal-organic frameworks. This work uncovers an entirely new strategy for designing single-site solid catalysts and opens the door to a new class of two-dimensional coordination materials with molecular functionalities. PMID:26954885

  5. Electrochemical investigation of Li-excess layered oxide cathode materials/mesocarbon microbead in 18650 batteries

    International Nuclear Information System (INIS)

    The electrochemical performance of the 18650 lithium-ion batteries for layered Li-excess oxide Li1.144Ni0.136Co0.136Mn0.544O2(LNCMO) cathode material and mesocarbon microbead (MCMB) anode material is investigated. The battery shows an excellent rate capability with the capacity of 227 mAh g−1 at 8 C-rate (the cut-off voltage is 4.5 V). Furthermore, it exhibits excellent cycle performance that the capacity retention over 300 cycles in the voltage ranges of 2.5-4.5 V (vs. MCMB) and at 0.2 C-rate is about 85%. Although the medium voltage of the battery greatly reduces during the first 30 cycles, it keeps stable in the following cycles. The mechanisms of the capacity fade and voltage decay are also studied based on energy dispersive spectrometry, X-ray photoelectron spectroscopy, charge-discharge curves, and dQ/dV plots

  6. Inverted Organic Solar Cells with Improved Performance using Varied Cathode Buffer Layers

    Institute of Scientific and Technical Information of China (English)

    Zhi-qiang Guan; Jun-sheng Yu; Yue Zang; Xing-xin Zeng

    2012-01-01

    Organic solar cells with inverted planar heterojunction structure based on subphthalocyanine and C60 were fabricated using several kinds of materials as cathode buffer layer (CBL),including tris-8-hydroxy-quinolinato aluminum (Alq3),bathophenanthroline (Bphen),bathocuproine,2,3,8,9,14,15-hexakis-dodecyl-sulfanyl-5,6,11,12,17,18-hexaazatrinaphthylene (HATNA),and an inorganic compound of Cs2CO3.The influence of the lowest unoccupied molecular orbital level and the electron mobility of organic CBL on the solar cells performance was compared.The results showed that Alq3,Bphen,and HATNA could significantly improve the device performance.The highest efficiency was obtained from device with annealed HATNA as CBL and increased for more than 7 times compared with device without CBL.Furthermore,the simulation results with space charge-limited current theory indicated that the Schottky barrier at the organic/electrode interface in inverted OSC structure was reduced for 27% by inserting HATNA CBL.

  7. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    Directory of Open Access Journals (Sweden)

    Johanna K. Dombrovskis

    2014-12-01

    Full Text Available Transition metal ion-chelating ordered mesoporous carbon (TM-OMC materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  8. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts a

    Science.gov (United States)

    Dombrovskis, Johanna K.; Prestel, Cathrin; Palmqvist, Anders E. C.

    2014-12-01

    Transition metal ion-chelating ordered mesoporous carbon (TM-OMC) materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC) catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA) preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  9. Simple template fabrication of porous MnCo2O4 hollow nanocages as high-performance cathode catalysts for rechargeable Li-O2 batteries

    Science.gov (United States)

    Cao, Y. L.; Lv, F. C.; Yu, S. C.; Xu, J.; Yang, X.; Lu, Z. G.

    2016-04-01

    Porous MnCo2O4 hollow nanocages have been fabricated via a simple template method using carbon spheres as a template. The hydrophilic surface of carbon spheres can adsorb Mn2+ and Co2+ ions simultaneously to form Mn,Co-adsorbed carbon spheres. The calcination of Mn,Co-adsorbed carbon spheres can result in porous hollow nanocages of MnCo2O4. The MnCo2O4 hollow nanocages are built by nanoscale MnCo2O4 crystals. Because of the unique porous hollow nanostructures, the resulting MnCo2O4/KB cathode shows an efficient electrocatalytic performance in LiTFSI/TEGDME electrolyte-based Li-O2 batteries. The MnCo2O4 hollow nanocages as the cathode catalysts can deliver better performance during the discharge/charge processes and good cycle stability compared with that of the pure KB carbon. The preliminary results manifest that porous MnCo2O4 hollow nanocages are promising high-performance cathode catalysts for Li-O2 batteries. This template technique is a simple, general, low-cost and controllable method and can be extended to prepare other transition metal oxide hollow nanostructures.

  10. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    OpenAIRE

    Johanna K. Dombrovskis; Cathrin Prestel; Anders E. C. Palmqvist

    2014-01-01

    Transition metal ion-chelating ordered mesoporous carbon (TM-OMC) materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC) catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA) preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate...

  11. Solid Catalyst with Ionic Liquid Layer (SCILL). A concept to improve the selectivity of selective hydrogenations

    Energy Technology Data Exchange (ETDEWEB)

    Jess, A.; Korth, W. [Bayreuth Univ. (Germany). Chair of Chemical Engineering

    2011-07-01

    Catalytic hydrogenations are important for refinery processes, petrochemical applications as well as for numerous processes of the fine chemicals industry. In some cases, hydrogenations consist of a sequence of consecutive reactions, and the desired product is the intermediate. An important goal is then a high yield and selectivity to the intermediate, if possible at a high conversion degree. The selectivity to an intermediate primarily depends on the chemical nature of the catalyst, but may also be influenced by diffusion processes. Ionic liquids (ILs) are low melting salts (< 100 C) and represent a promising solvent class. This paper focuses on the concept of a Solid Catalyst with Ionic Liquid Layer (SCILL), where the solid catalyst is coated with a thin IL layer to improve the selectivity. (orig.)

  12. A proposed agglomerate model for oxygen reduction in the catalyst layer of proton exchange membrane fuel cells

    International Nuclear Information System (INIS)

    Highlights: • We developed a new agglomerate model to describe oxygen reduction reaction. • We showed how to calculate the model parameters from catalyst layer structure. • We verified the agglomerate model. - Abstract: Oxygen diffusion and reduction in the catalyst layer of PEM fuel cell is an important process in fuel cell modelling, but models able to link the reduction rate to catalyst-layer structure are lack; this paper makes such an effort. We first link the average reduction rate over the agglomerate within a catalyst layer to a probability that an oxygen molecule, which is initially on the agglomerate surface, will enter and remain in the agglomerate at any time in the absence of any electrochemical reaction. We then propose a method to directly calculate distribution function of this probability and apply it to two catalyst layers with contrasting structures. A formula is proposed to describe these calculated distribution functions, from which the agglomerate model is derived. The model has two parameters and both can be independently calculated from catalyst layer structures. We verify the model by first showing that it is an improvement and able to reproduce what the spherical model describes, and then testing it against the average oxygen reductions directly calculated from pore-scale simulations of oxygen diffusion and reaction in the two catalyst layers. The proposed model is simple, but significant as it links the average oxygen reduction to catalyst layer structures, and its two parameters can be directly calculated rather than by calibration

  13. Optical characteristics of silicon nanowires grown from tin catalyst layers on silicon coated glass

    KAUST Repository

    Ball, Jeremy

    2012-08-20

    The optical characteristics of silicon nanowires grown on Si layers on glass have been modeled using the FDTD (Finite Difference Time Domain) technique and compared with experimental results. The wires were grown by the VLS (vapour-liquid-solid) method using Sn catalyst layers and exhibit a conical shape. The resulting measured and modeled absorption, reflectance and transmittance spectra have been investigated as a function of the thickness of the underlying Si layer and the initial catalyst layer, the latter having a strong influence on wire density. High levels of absorption (>90% in the visible wavelength range) and good agreement between the modeling and experiment have been observed when the nanowires have a relatively high density of ∼4 wires/μ m2. The experimental and modeled results diverge for samples with a lower density of wire growth. The results are discussed along with some implications for solar cell fabrication. © 2012 Optical Society of America.

  14. Optimization of cathode and intermediate layers for polymer solar cells; Optimierung von Kathoden und Zwischenschichten fuer Polymersolarzellen

    Energy Technology Data Exchange (ETDEWEB)

    Hanisch, Jonas

    2010-07-01

    This work deals with the influence of the cathode on the characteristics of polymer solar cells. In addition to studying various Abscheidearten the focus is primarily on the exploration of the effect of intermediate layers. Analysis using Sekundaerteilchenmassenspektrometrie (SIMS and SNMS) allow insight into the underlying mechanisms and interactions. The knowledge gained will be used in the realization of semi-transparent solar cells. (orig.)

  15. Near- infrared spectroscopy of palladium-containing layered double hydroxides used as catalysts

    OpenAIRE

    Mora, Manuel; Lopez, María I.; Jiménez-Sanchidrián, César; Ruiz, José R.

    2011-01-01

    ABSTRACT Three catalysts consisting of layered double hydroxides (LDHs) of magnesium and aluminium, and containing palladium in various forms, were synthesized and subsequently characterized by mid- and near-infrared spectroscopies. The results thus obtained are compared with those for a pure Mg/Al layered double hydroxide. The spectra for the Pd-containing LDHs (particularly the strength of the bands) were found to depend on the particular palladium form present. As a rule, the mi...

  16. Inkjet printing of catalyst layers into microchannels for direct DME synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung Cheol; Ding, Wenjin; Mogalicherla, Aswani Kumar; Pfeifer, Peter; Dittmeyer, Roland [Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen (Germany). Inst. for Micro Process Engineering

    2013-09-01

    In this paper, a preliminary study of inkjet printing for catalyst coating is described. Ethanol glycol as a test ink was used to investigate droplet generation in the printing nozzle. Ethanol based Cerium-sol was further printed into microchannels and the surface coating was investigated after drying the layer. (orig.)

  17. Application of Calcined Layered Double Hydroxides as Catalysts for Abatement of N2O Emissions

    Czech Academy of Sciences Publication Activity Database

    Obalová, L.; Kovanda, F.; Jirátová, Květa; Pacultová, K.; Lacný, Z.

    Prague : JHI, 2008, S.54-55. [Symposium on Catalysis /40./. Prague (CZ), 03.11.2008-05.11.2008] Institutional research plan: CEZ:AV0Z40720504 Keywords : layered double hydroxides * mixed oxide catalysts * N2O abatement Subject RIV: CF - Physical ; Theoretical Chemistry

  18. Electrocatalytic activity of atomic layer deposited Pt–Ru catalysts onto N-doped carbon nanotubes

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta; Larsen, Jackie Vincent; Verheijen, Marcel A.;

    2014-01-01

    Pt–Ru catalysts of various compositions, between 0 and 100at.% of Ru, were deposited onto N-doped multi-walled carbon nanotubes (N-CNTs) by atomic layer deposition (ALD) at 250°C. The Pt and Ru precursors were trimethyl(methylcyclopentadienyl)platinum (MeCpPtMe3) and bis...

  19. Enhanced Oxygen and Hydroxide Transport in a Cathode Interface by Efficient Antibacterial Property of a Silver Nanoparticle-Modified, Activated Carbon Cathode in Microbial Fuel Cells.

    Science.gov (United States)

    Li, Da; Qu, Youpeng; Liu, Jia; Liu, Guohong; Zhang, Jie; Feng, Yujie

    2016-08-17

    A biofilm growing on an air cathode is responsible for the decreased performance of microbial fuel cells (MFCs). For the undesired biofilm to be minimized, silver nanoparticles were synthesized on activated carbon as the cathodic catalyst (Ag/AC) in MFCs. Ag/AC enhanced maximum power density by 14.6% compared to that of a bare activated carbon cathode (AC) due to the additional silver catalysis. After operating MFCs over five months, protein content on the Ag/AC cathode was only 38.3% of that on the AC cathode, which resulted in a higher oxygen concentration diffusing through the Ag/AC cathode. In addition, a lower pH increment (0.2 units) was obtained near the Ag/AC catalyst surface after biofouling compared to 0.8 units of the AC cathode, indicating that less biofilm on the Ag/AC cathode had a minor resistance on hydroxide transported from the catalyst layer interfaces to the bulk solution. Therefore, less decrements of the Ag/AC activity and MFC performance were obtained. This result indicated that accelerated transport of oxygen and hydroxide, benefitting from the antibacterial property of the cathode, could efficiently maintain higher cathode stability during long-term operation. PMID:27441786

  20. Optimization of the Energy Level Alignment between the Photoactive Layer and the Cathode Contact Utilizing Solution-Processed Hafnium Acetylacetonate as Buffer Layer for Efficient Polymer Solar Cells.

    Science.gov (United States)

    Yu, Lu; Li, Qiuxiang; Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Wang, Fuzhi; Zhang, Bing; Dai, Songyuan; Lin, Jun; Tan, Zhan'ao

    2016-01-13

    The insertion of an appropriate interfacial buffer layer between the photoactive layer and the contact electrodes makes a great impact on the performance of polymer solar cells (PSCs). Ideal interfacial buffer layers could minimize the interfacial traps and the interfacial barriers caused by the incompatibility between the photoactive layer and the electrodes. In this work, we utilized solution-processed hafnium(IV) acetylacetonate (Hf(acac)4) as an effective cathode buffer layer (CBL) in PSCs to optimize the energy level alignment between the photoactive layer and the cathode contact, with the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) all simultaneously improved with Hf(acac)4 CBL, leading to enhanced power conversion efficiencies (PCEs). Ultraviolet photoemission spectroscopy (UPS) and scanning Kelvin probe microscopy (SKPM) were performed to confirm that the interfacial dipoles were formed with the same orientation direction as the built-in potential between the photoactive layer and Hf(acac)4 CBL, benefiting the exciton separation and electron transport/extraction. In addition, the optical characteristics and surface morphology of the Hf(acac)4 CBL were also investigated. PMID:26684416

  1. Nanoporous silver cathode surface treated by atomic layer deposition of CeO(x) for low-temperature solid oxide fuel cells.

    Science.gov (United States)

    Neoh, Ke Chean; Han, Gwon Deok; Kim, Manjin; Kim, Jun Woo; Choi, Hyung Jong; Park, Suk Won; Shim, Joon Hyung

    2016-05-01

    We evaluated the performance of solid oxide fuel cells (SOFCs) with a 50 nm thin silver (Ag) cathode surface treated with cerium oxide (CeO(x)) by atomic layer deposition (ALD). The performances of bare and ALD-treated Ag cathodes were evaluated on gadolinia-doped ceria (GDC) electrolyte supporting cells with a platinum (Pt) anode over 300 °C-450 °C. Our work confirms that ALD CeO(x) treatment enhances cathodic performance and thermal stability of the Ag cathode. The performance difference between cells using a Ag cathode optimally treated with an ALD CeO(x) surface and a reference Pt cathode is about 50% at 450 °C in terms of fuel cell power output in our experiment. The bare Ag cathode completely agglomerated into islands during fuel cell operation at 450 °C, while the ALD CeO(x) treatment effectively protects the porosity of the cathode. We also discuss the long-term stability of ALD CeO(x)-treated Ag cathodes related to the microstructure of the layers. PMID:27008979

  2. Nanoporous silver cathode surface treated by atomic layer deposition of CeO x for low-temperature solid oxide fuel cells

    Science.gov (United States)

    Chean Neoh, Ke; Han, Gwon Deok; Kim, Manjin; Kim, Jun Woo; Jong Choi, Hyung; Park, Suk Won; Shim, Joon Hyung

    2016-05-01

    We evaluated the performance of solid oxide fuel cells (SOFCs) with a 50 nm thin silver (Ag) cathode surface treated with cerium oxide (CeO x ) by atomic layer deposition (ALD). The performances of bare and ALD-treated Ag cathodes were evaluated on gadolinia-doped ceria (GDC) electrolyte supporting cells with a platinum (Pt) anode over 300 °C-450 °C. Our work confirms that ALD CeO x treatment enhances cathodic performance and thermal stability of the Ag cathode. The performance difference between cells using a Ag cathode optimally treated with an ALD CeO x surface and a reference Pt cathode is about 50% at 450 °C in terms of fuel cell power output in our experiment. The bare Ag cathode completely agglomerated into islands during fuel cell operation at 450 °C, while the ALD CeO x treatment effectively protects the porosity of the cathode. We also discuss the long-term stability of ALD CeO x -treated Ag cathodes related to the microstructure of the layers.

  3. Performance improvement of polymer solar cells by using a solution processible titanium chelate as cathode buffer layer

    Science.gov (United States)

    Tan, Zhan'ao; Yang, Chunhe; Zhou, Erjun; Wang, Xiang; Li, Yongfang

    2007-07-01

    A solution processible titanium chelate, titanium (diisopropoxide) bis (2,4-pentanedionate) (TIPD), was used as the cathode buffer layer in the polymer solar cells (PSCs) based on the blend of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and [6,6]-phenyl-C61-butyric acid methyl ester. Introducing TIPD buffer layer reduced the interface resistance between the active layer and Al electrode, leading to a lower device resistance. The power conversion efficiency of the PSC with TIPD buffer layer reached 2.52% under the illumination of AM1.5, 100mW/cm2, which is increased by 51.8% in comparison with that (1.66%) of the device without TIPD buffer layer under the same experimental conditions.

  4. Novel strategy to mitigate cathode catalyst degradation during air/air startup cycling via the atmospheric resistive switching mechanism of a hydrogen anode with a platinum catalyst supported on tantalum-doped titanium dioxide

    Science.gov (United States)

    Shintani, Haruhiko; Kojima, Yuya; Kakinuma, Katsuyoshi; Watanabe, Masahiro; Uchida, Makoto

    2015-10-01

    We propose a new strategy for alleviating the reverse current phenomenon using a unique "atmospheric resistive switching mechanism" (ARSM) of a metal oxide semiconductor support, such that the electrical resistivity changes depending on the gas atmosphere. The membrane-electrode assembly (MEA) using Ta-doped TiO2-supported platinum (Pt/Ta-TiO2) as the anode catalyst showed approximately one order of magnitude greater resistance in air than in hydrogen. The overpotential of the hydrogen oxidation reaction was negligible up to at least 1.5 A cm-2. The losses of electrochemically active surface area and carbon corrosion of the cathode catalyst during air/air startup cycling were significantly suppressed by the use of the Pt/Ta-TiO2 anode. The decrease in the degradation is attributed to a reduction of the reverse current due to a low oxygen reduction reaction rate at the anode, which showed high resistivity in air. These results demonstrate the effectiveness of the ARSM in mitigating cathode catalyst degradation during air/air startup cycling.

  5. Layered metal laurates as active catalysts in the methyl/ethyl esterification reactions of lauric acid

    Energy Technology Data Exchange (ETDEWEB)

    Lisboa, Fabio da Silva; Cordeiro, Claudiney S.; Wypych, Fernando, E-mail: wypych@ufpr.br [Centro de Pesquisas em Quimica Aplicada (CEPESQ), Departamento de Quimica, Universidade Federal do Parana, Curitiba, PR (Brazil); Gardolinski, Jose Eduardo F. da Costa [Laboratorio de Analise de Minerais e Rochas (LAMIR), Departamento de Geologia, Universidade Federal do Parana, Curitiba, PR (Brazil)

    2012-07-01

    In this work we report the synthesis, characterization and investigation of the catalytic activity of layered copper(II), manganese(II), lanthanum(III) and nickel(II) laurates in the methyl and ethyl esterification reactions of lauric acid. In the methyl esterification, conversions between 80 and 90% were observed for all catalysts, while for the ethyl esterification only manganese laurate showed reasonable catalytic activity, with conversions close to 75%. Reuse of copper and lanthanum laurates in three cycles of reaction was also investigated and both catalysts preserved the structure and retained catalytic activity close to that observed for the first reaction cycle. (author)

  6. Effect of the porous carbon layer in the cathode gas diffusion media on direct methanol fuel cell performances

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jun-Young [Department of Advanced Materials Engineering, Sejong University, 98 Gunja-dong, Gwangjin-gu, Seoul 143-747 (Korea); Kim, Hee-Tak; Son, In-Hyuk; Han, Sangil [Energy Lab, Corporate R and D Center, Samsung SDI Co., LTD, 575, Shin-dong, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-391 (Korea); Lee, Eun Sook [Energy Research Center, Jinwoo Engineering, Co., LTD., 143-2, Gwelang-Ri, Jungnam-Myun, Hwasung-City, Kyunggi-Do 445-963 (Korea)

    2009-10-15

    The effect of cathode gas diffusion media with microporous layers (MPLs) on direct methanol fuel cell (DMFC) performances is studied by combining electrochemical analysis and physicochemical investigation. The membrane electrode assemblies (MEAs) using MPL-modified cathode gas diffusion layers (GDLs, GDL-1) showed slightly better performances (117 mW cm{sup -2}) at 0.4 V and 70 C than commercial GDL (SIGRACET {sup registered} product version: GDL-35BC, SGL Co.) DMFC MEAs (110 mW cm{sup -2}). This might be due to high gas permeability, uniform pore distributions, and low water transport coefficient including methanol crossover. For GDL-1, the air permeability was 31.0 cm{sup 3} cm{sup -2} s{sup -1}, while the one for SGL 35BC GDLs was 21.7 cm{sup 3} cm{sup -2} s{sup -1}. Also, the GDL-1 in the pore-size distribution diagrams had distinct peaks due to more uniform distributions of macropores and micropores with smaller holes between aggregates of carbon particles compared to GDL-35 BC as confirmed by SEM images. Furthermore, the MEA using GDL-1 for the cathode had a lower water transfer coefficient compared to an MEA with a commercial 35 BC GDL. (author)

  7. Transient behavior of CO poisoning of the anode catalyst layer of a PEM fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Chu, H.S.; Wang, C.P.; Liao, W.C. [Department of Mechanical Engineering, National Chiao Tung University, Hsinchu, Taiwan 300 (ROC); Yan, W.M. [Department of Mechatronic Engineering, Huafan University, Shih Ting, Taipei, Taiwan 223 (ROC)

    2006-09-22

    A one-dimensional transient mathematical model is applied to simulate the carbon monoxide poisoning effect on the performance of a PEM fuel cell. Based on the CO kinetic model developed by Springer et al. [T.E. Springer, T. Rockward, T.A. Zawodzinski, S. Gottesfeld, J. Electrochem. Soc. 148 (2001) A11-A23], the transient behaviors of the CO poisoning process across the anode catalyst layer is investigated. The results show that the hydrogen coverage, {theta}{sub H}, decreases with the time due to CO adsorption on the catalyst sites. A higher CO concentration results in fewer available catalyst sites for hydrogen electro-oxidation and a significant decrease in the response time to reach steady state, t{sub ss}. Increasing the anode overpotential and the gas porosity would result in an increase in the current density, especially at low levels of CO concentration. (author)

  8. Effect of the nanosized TiO2 particles in Pd/C catalysts as cathode materials in direct methanol fuel cells.

    Science.gov (United States)

    Choi, Mahnsoo; Han, Choonsoo; Kim, In-Tae; Lee, Ji-Jung; Lee, Hong-Ki; Shim, Joongpyo

    2011-07-01

    Pd-TiO2/C catalysts were prepared by impregnating titanium dioxide (TiO2) on carbon-supported Pd (Pd/C) for use as the catalyst for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFCs). Transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses were carried to confirm the distribution, morphology and structure of Pd and TiO2 on the carbon support. In fuel cell test, we confirmed that the addition of TiO2 nanoparticles make the improved catalytic activity of oxygen reduction. The electrochemical characterization of the Pd-TiO2/C catalyst for the ORR was carried out by cyclic voltammetry (CV) in the voltage window of 0.04 V to 1.2 V with scan rate of 25 mV/s. With the increase in the crystallite size of TiO2, the peak potential for OH(ads) desorption on the surface of Pd particle shifted to higher potential. This implies that TiO2 might affect the adsorption and desorption of oxygen molecules on Pd catalyst. The performance of Pd-TiO2/C as a cathode material was found to be similar to or better performance than that of Pt/C. PMID:22121727

  9. Analytical electron microscopy of interface layers between Ti(6% Al, 4% V) and a CrN cathodic arc coating

    International Nuclear Information System (INIS)

    This paper reports on the applications of analytical electron microscopy to the study of cathodic arc deposited CrN coating on a Ti(6% Al, 4% V) substrate. Particular attention is given to analysis of the coating/substrate interface. Electron energy loss spectroscopy is used to show that the Cr sputter cleaning of the Ti(6% Al, 4% V) results in penetration of Cr into the substrate giving a bcc alloy layer whose composition varies from Ti(6% Al, 4% V) at the substrate interface to almost pure Cr at the coating interface. Subsequent deposition of CrN results in an initial deposition of sub-stoichiometric Cr2N followed by sub-stoichiometric CrN with a } 022{ texture and a columnar structure. The degree of sub-stoichiometry of the nitrides depends on the substrate bias and the substrate orientation relative to the cathode. (author)

  10. Atomic to Nanoscale Investigation of Functionalities of an Al2O3 Coating Layer on a Cathode for Enhanced Battery Performance

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Pengfei; Zheng, Jianming; Zhang, Xiaofeng; Xu, Rui; Amine, Khalil; Xiao, J; Zhang, Ji-Guang; Wang, Chong-Min

    2016-02-09

    Surface coating has been identified as an effective approach for enhancing the capacity retention of layered structure cathode. However, the underlying operating mechanism of such a thin coating layer, in terms of surface chemical functionality and capacity retention, remains unclear. In this work, we use aberration-corrected scanning transmission electron microscopy and high-efficiency spectroscopy to probe the delicate functioning mechanism of an Al2O3 coating layer on a Li1.2Ni0.2Mn0.6O2 cathode. We discovered that in terms of surface chemical function, the Al2O3 coating suppresses the side reaction between the cathode and the electrolyte during battery cycling. At the same time, the Al2O3 coating layer also eliminates the chemical reduction of Mn from the cathode particle surface, therefore preventing the dissolution of the reduced Mn into the electrolyte. In terms of structural stability, we found that the Al2O3 coating layer can mitigate the layer to spinel phase transformation, which otherwise will be initiated from the particle surface and propagate toward the interior of the particle with the progression of battery cycling. The atomic to nanoscale effects of the coating layer observed here provide insight into the optimized design of a coating layer on a cathode to enhance the battery properties.

  11. Multi-Directional Growth of Aligned Carbon Nanotubes Over Catalyst Film Prepared by Atomic Layer Deposition

    Directory of Open Access Journals (Sweden)

    Zhou Kai

    2010-01-01

    Full Text Available Abstract The structure of vertically aligned carbon nanotubes (CNTs severely depends on the properties of pre-prepared catalyst films. Aiming for the preparation of precisely controlled catalyst film, atomic layer deposition (ALD was employed to deposit uniform Fe2O3 film for the growth of CNT arrays on planar substrate surfaces as well as the curved ones. Iron acetylacetonate and ozone were introduced into the reactor alternately as precursors to realize the formation of catalyst films. By varying the deposition cycles, uniform and smooth Fe2O3 catalyst films with different thicknesses were obtained on Si/SiO2 substrate, which supported the growth of highly oriented few-walled CNT arrays. Utilizing the advantage of ALD process in coating non-planar surfaces, uniform catalyst films can also be successfully deposited onto quartz fibers. Aligned few-walled CNTs can be grafted on the quartz fibers, and they self-organized into a leaf-shaped structure due to the curved surface morphology. The growth of aligned CNTs on non-planar surfaces holds promise in constructing hierarchical CNT architectures in future.

  12. Nano-nitride cathode catalysts of Ti, Ta, and Nb for polymer electrolyte fuel cells: Temperature-programmed desorption investigation of molecularly adsorbed oxygen at low temperature

    KAUST Repository

    Ohnishi, Ryohji

    2013-01-10

    TiN, NbN, TaN, and Ta3N5 nanoparticles synthesized using mesoporous graphitic (mpg)-C3N4 templates were investigated for the oxygen reduction reaction (ORR) as cathode catalysts for polymer electrolyte fuel cells. The temperature-programmed desorption (TPD) of molecularly adsorbed O2 at 120-170 K from these nanoparticles was examined, and the resulting amount and temperature of desorption were key factors determining the ORR activity. The size-dependent TiN nanoparticles (5-8 and 100 nm) were then examined. With decreasing particle size, the density of molecularly adsorbed O2 per unit of surface area increased, indicating that a decrease in particle size increases the number of active sites. It is hard to determine the electrochemical active surface area for nonmetal electrocatalysts (such as oxides or nitrides), because of the absence of proton adsorption/desorption peaks in the voltammograms. In this study, O2-TPD for molecularly adsorbed O2 at low temperature demonstrated that the amount and strength of adsorbed O2 were key factors determining the ORR activity. The properties of molecularly adsorbed O2 on cathode catalysts are discussed against the ORR activity. © 2012 American Chemical Society.

  13. Fibrous polyaniline@manganese oxide nanocomposites as supercapacitor electrode materials and cathode catalysts for improved power production in microbial fuel cells.

    Science.gov (United States)

    Ansari, Sajid Ali; Parveen, Nazish; Han, Thi Hiep; Ansari, Mohammad Omaish; Cho, Moo Hwan

    2016-03-23

    Fibrous Pani-MnO2 nanocomposite were prepared using a one-step and scalable in situ chemical oxidative polymerization method. The formation, structural and morphological properties were investigated using a range of characterization techniques. The electrochemical capacitive behavior of the fibrous Pani-MnO2 nanocomposite was examined by cyclic voltammetry and galvanostatic charge-discharge measurements using a three-electrode experimental setup in an aqueous electrolyte. The fibrous Pani-MnO2 nanocomposite achieved high capacitance (525 F g(-1) at a current density of 2 A g(-1)) and excellent cycling stability of 76.9% after 1000 cycles at 10 A g(-1). Furthermore, the microbial fuel cell constructed with the fibrous Pani-MnO2 cathode catalyst showed an improved power density of 0.0588 W m(-2), which was higher than that of pure Pani and carbon paper, respectively. The improved electrochemical supercapacitive performance and cathode catalyst performance in microbial fuel cells were attributed mainly to the synergistic effect of Pani and MnO2 in fibrous Pani-MnO2, which provides high surface area for the electrode/electrolyte contact as well as electronic conductive channels and exhibits pseudocapacitance behavior. PMID:26967202

  14. A catalyst layer optimisation approach using electrochemical impedance spectroscopy for PEM fuel cells operated with pyrolysed transition metal-N-C catalysts

    Science.gov (United States)

    Malko, Daniel; Lopes, Thiago; Ticianelli, Edson A.; Kucernak, Anthony

    2016-08-01

    The effect of the ionomer to carbon (I/C) ratio on the performance of single cell polymer electrolyte fuel cells is investigated for three different types of non-precious metal cathodic catalysts. Polarisation curves as well as impedance spectra are recorded at different potentials in the presence of argon or oxygen at the cathode and hydrogen at the anode. It is found that a optimised ionomer content is a key factor for improving the performance of the catalyst. Non-optimal ionomer loading can be assessed by two different factors from the impedance spectra. Hence this observation could be used as a diagnostic element to determine the ideal ionomer content and distribution in newly developed catalyst-electrodes. An electrode morphology based on the presence of inhomogeneous resistance distribution within the porous structure is suggested to explain the observed phenomena. The back-pressure and relative humidity effect on this feature is also investigated and supports the above hypothesis. We give a simple flowchart to aid optimisation of electrodes with the minimum number of trials.

  15. Synthesis of Nitrogen-Doped Carbon Nanocoils with Adjustable Morphology using Ni–Fe Layered Double Hydroxides as Catalyst Precursors

    OpenAIRE

    Tomohiro Iwasaki; Masashi Tomisawa; Takuma Yoshimura; Hideya Nakamura; Masao Ohyama; Katsuya Asao; Satoru Watano

    2015-01-01

    Nitrogen-doped carbon nanocoils (CNCs) with adjusted morphologies were synthesized in a one-step catalytic chemical vapour deposition (CVD) process using acetoni‐ trile as the carbon and nitrogen source. The nickel iron oxide/nickel oxide nanocomposites, which were derived from nickel–iron layered double hydroxide (LDH) precur‐ sors, were employed as catalysts for the synthesis of CNCs. In this method, precursor-to-catalyst transformation, catalyst activation, formation of CNCs, and nitrogen ...

  16. Nanoporous silver cathodes surface-treated by atomic layer deposition of Y:ZrO2 for high-performance low-temperature solid oxide fuel cells

    Science.gov (United States)

    Li, You Kai; Choi, Hyung Jong; Kim, Ho Keun; Chean, Neoh Ke; Kim, Manjin; Koo, Junmo; Jeong, Heon Jae; Jang, Dong Young; Shim, Joon Hyung

    2015-11-01

    We report high-performance solid-oxide fuel cells (SOFCs) with silver cathodes surface-treated using yttria-stabilized zirconia (YSZ) nano-particulates fabricated by atomic layer deposition (ALD). Fuel cell tests are conducted on gadolinia-doped ceria electrolyte pellets with a platinum anode at 250-450 °C. In our tests, the fuel cell performance of the SOFCs with an optimized ALD YSZ surface treatment is close to that of SOFCs with porous Pt, which is known as the best performing catalyst in the low-temperature regime. Electrochemical impedance spectroscopy confirms that the performance enhancement is due to improved electrode kinetics by the increase in charge transfer reaction sites between the surface of supporting silver and the ALD-YSZ particulates. Fuel cell durability tests shows that the ALD YSZ surface treatment improves the long-term stability. X-ray photoelectron spectroscopy also confirms that the ALD YSZ capping prevents reduction of the surface silver oxide and destruction of the mesh morphology.

  17. Cobalt-Lead-Manganese oxides combined cathode catalyst for air electrode in Zinc –air battery

    International Nuclear Information System (INIS)

    Highlights: • Bi and trimetallic oxides based on Mn, Pb and Co were prepared and characterized. • Introduction of Pb and Co in MnOx catalyst promote four electron ORR. • Zinc air battery with Mn2Pb2CoOx catalyst displays much smaller charge transfer resistance in contrast to the pure MnOx. • Mn2Pb2CoOx catalyst has lower loss of performance after 500C-D cycles than the rest of the catalysts. • Zinc air battery containing Mn2Pb2CoOx has promising current and power density and also discharge capacity. - Abstract: Bi and tri metalic oxides based on Mn, Pb and Co composite catalysts were prepared by oxidation of metal acetates with KMnO4. The structure of the catalysts was characterized by X-ray diffraction (XRD). It is found that the Mn2Pb2CoOx catalyst has amorphous structure and contains various oxides of Mn, Pb and Co. Electrocatalytic activity of catalysts in 6 M KOH was studied using Cyclic Voltammetry (CV) and polarization. Cyclic Voltammetry plot of Mn2Pb2CoOx catalyst showed higher electrocatalytic activity towards the Oxygen Reduction Reaction (ORR) compared to other tri and bimetallic composite catalysts. The kinetics of ORR on the catalysts was investigated using the rotating disk electrode technique in 6 M KOH solution. From the slope of Koutecky–Levich plots, it is evident that the ORR on Mn2Pb2CoOx is a 4-electron transfer process. With these inherent features, the zinc–air battery was fabricated using various catalysts and their performance was examined for practical applications

  18. The Effect of Catalyst Layer Cracks on the Mechanical Fatigue of Membrane Electrode Assemblies

    OpenAIRE

    Pestrak, Michael Thomas

    2010-01-01

    Mechanical fatigue testing has shown that MEAs (membrane electrode assemblies) fail at lower stresses than PEMs (proton exchange membranes) at comparable times under load. The failure of MEAs at lower stresses is influenced by the presence of mud cracks in the catalyst layers acting as stress concentrators. Fatigue testing of MEAs has shown that smaller-scale cracking occurs in the membrane within these mud cracks, leading to leaking during mechanical fatigue testing and the failure of the ...

  19. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    Science.gov (United States)

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; Han, Lili; Grillon, Nathanael; Guy-Bouyssou, Delphine; Bouyssou, Emilien; Proust, Marina; Meng, Ying Shirley

    2016-08-01

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte - electrode interfaces will be critical to improve performance. In this study, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grew in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. The stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.

  20. A design strategy of large grain lithium-rich layered oxides for lithium-ion batteries cathode

    International Nuclear Information System (INIS)

    Highlights: • Ultrasound-assisted mixing lithium was used to synthesize Lithium-rich layered oxides. • Lithium-rich layered oxides composed of large grain had high capacity and high cycling stability. • This unique large grain overcomes stress-induced structural collapse caused by Li-ion insertion/extraction and reduces dissolution of Mn ions. • A new strategy of large grain could be employed to synthesize the other complex architectures for various applications. - Abstract: Li-rich materials are considered the most promising for Li-ion battery cathodes, as high capacity can be achieved. However, poor cycling stability is a critical drawback that leads to poor capacity retention. Here a strategy is used to synthesize a large-grain lithium-rich layered oxides to overcome this difficulty without sacrificing rate capability. This material is designed with micron scale grain with a width of about 300 nm and length of 1–3 μm. This unique structure has a better ability to overcome stress-induced structural collapse caused by Li-ion insertion/extraction and reduce the dissolution of Mn ions, which enable a reversible and stable capacity. As a result, this cathode material delivered a highest discharge capacity of around 308 mAh g−1 at a current density of 30 mA g−1 with retention of 88.3% (according to the highest discharge capacity) after 100 cycles, 190 mAh g−1 at a current density of 300 mA g−1 and almost no capacity fading after 100 cycles. Therefore, Lithium-rich material of large-grain structure is a promising cathode candidate in Lithium-ion batteries with high capacity and high cycle stability for application. This strategy of large grain may furthermore open the door to synthesize the other complex architectures for various applications

  1. Atomic layer deposition of amorphous iron phosphates on carbon nanotubes as cathode materials for lithium-ion batteries

    International Nuclear Information System (INIS)

    A non-aqueous approach was developed to synthesize iron phosphate cathode materials by the atomic layer deposition (ALD) technique. Deposition of iron phosphate thin films was achieved on nitrogen-doped carbon nanotubes (NCNTs) by combining ALD subcycles of Fe2O3 (ferrocene-ozone) and POx (trimethyl phosphate-water) at 200 – 350 °C. The thickness of iron phosphate thin films depends linearly on the ALD cycle, indicating their self-limiting growth behavior. The growth per cycle of iron phosphate thin films was determined to be ∼ 0.2, 0.4, 0.6, and 0.5 Å, at 200, 250, 300, and 350 °C, respectively. Characterization by SEM, TEM, and HRTEM techniques revealed uniform and conformal coating of amorphous iron phosphates on the surface of NCNTs. XANES analysis confirmed Fe−O−P bonding in the iron phosphates prepared by ALD. Furthermore, electrochemical measurement verified the high electrochemical activity of the amorphous iron phosphate as a cathode material in lithium-ion batteries. It is expected that the amorphous iron phosphate prepared by this facile and cost-effective ALD approach will find applications in the next generation of lithium-ion batteries and thin film batteries as either cathode materials or surface coating materials

  2. Layered double hydroxide catalyst for the conversion of crude vegetable oils to a sustainable biofuel

    Science.gov (United States)

    Mollaeian, Keyvan

    Over the last two decades, the U.S. has developed the production of biodiesel, a mixture of fatty acid methyl esters, using chiefly vegetable oils as feedstocks. However, there is much concern about the availability of high-quality vegetable oils for longterm biodiesel production. Problems have also risen due to the production of glycerol, an unwanted byproduct, as well as the need for process wash water. Therefore, this study was initiated to produce not only fatty acid methyl esters (FAMEs) but also fatty acid glycerol carbonates (FAGCs) by replacing methanol with dimethyl carbonate (DMC). The process would have no unnecessary byproducts and would be a simplified process compared to traditional biodiesel. In addition, this altering of the methylating agent could convert triglycerides, free fatty acids, and phospholipids to a sustainable biofuel. In this project, Mg-Al Layered Double Hydroxide (LDH) was optimized by calcination in different temperature varied from 250°C to 450°C. The gallery between layers was increased by intercalating sodium dodecylsulfate (SDS). During catalyst preparation, the pH was controlled ~10. In our experiment, triazabicyclodecene (TBD) was attached with trimethoxysilane (3GPS) as a coupling agent, and N-cetyl-N,N,N-trimethylammonium bromide (CTAB) was added to remove SDS from the catalyst. The catalyst was characterized by XRD, FTIR, and Raman spectroscopy. The effect of the heterogeneous catalyst on the conversion of canola oil, corn oil, and free fatty acids was investigated. To analyze the conversion of lipid oils to biofuel an in situ Raman spectroscopic method was developed. Catalyst synthesis methods and a proposed mechanism for converting triglycerides and free fatty acids to biofuel will be presented.

  3. The catalyst layer and its dimensionality - A look into its ingredients and how to characterize their effects

    Science.gov (United States)

    Zamel, Nada

    2016-03-01

    Development of polymer electrolyte membrane (PEM) fuel cells throughout the years is established through its component optimization. This is especially true of its catalyst layer, where structuring of the layer has led to many breakthroughs. The catalyst layer acts as the heart of the cell, where it controls the half-cell reactions and their products. The complex nature of various transport phenomena simultaneously taking place in the layer requires the layer to be heterogeneous in structure. Hence, a delicate balance of the layer's ingredients, coupled with the understanding of the ingredients' interaction, is required. State-of-the-art catalyst layers are composed of a catalyst, its support, a solvent and a binder. Changes in the morphology, structure or material of any of these components ultimately affects the layer's activity and durability. In this review paper, we provide an overview of the various works tailored to understand how each component in the catalyst's ink affects the stability and life-time of the layer.

  4. Novel layered Li3V2(PO4)3/rGO&C sheets as high-rate and long-life lithium ion battery cathodes.

    Science.gov (United States)

    Wei, Qiulong; Xu, Yanan; Li, Qidong; Tan, Shuangshuang; Ren, Wenhao; An, Qinyou; Mai, Liqiang

    2016-07-01

    Novel layered Li3V2(PO4)3/rGO&C sheets are synthesized by novel interfacial modified assembly, freeze-drying and confined annealing processes. The uniform LVP layers are alternated with rGO&C layers to form the composite layered structure, providing effective electron and ion transport. As a lithium-ion battery cathode, the composite displays excellent electrochemical performance. PMID:27334928

  5. Deconstruction of Lignin Model Compounds and Biomass-Derived Lignin using Layered Double Hydroxide Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chmely, S. C.; McKinney, K. A.; Lawrence, K. R.; Sturgeon, M.; Katahira, R.; Beckham, G. T.

    2013-01-01

    Lignin is an underutilized value stream in current biomass conversion technologies because there exist no economic and technically feasible routes for lignin depolymerization and upgrading. Base-catalyzed deconstruction (BCD) has been applied for lignin depolymerization (e.g., the Kraft process) in the pulp and paper industry for more than a century using aqueous-phase media. However, these efforts require treatment to neutralize the resulting streams, which adds significantly to the cost of lignin deconstruction. To circumvent the need for downstream treatment, here we report recent advances in the synthesis of layered double hydroxide and metal oxide catalysts to be applied to the BCD of lignin. These catalysts may prove more cost-effective than liquid-phase, non-recyclable base, and their use obviates downstream processing steps such as neutralization. Synthetic procedures for various transition-metal containing catalysts, detailed kinetics measurements using lignin model compounds, and results of the application of these catalysts to biomass-derived lignin will be presented.

  6. Synthesis of Highly Ordered Hydrothermally Stable Mesoporous Niobia Catalysts by Atomic Layer Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Pagan-Torres, Yomaira J; Gallo, Jean Marcel R; Wang, Dong; Pham, Hien N; Libera, J.A.; Marshall, Christopher L; Elam, Jeffrey W.; Datye, Abhaya K; Dumesic, James A

    2011-10-07

    A new class of mesoporous niobia catalysts has been synthesized by atomic layer deposition (ALD) of niobia within the pores of a mesoporous silica (SBA-15). Mesoporous materials after ALD cycles of niobia maintained the structural organization of SBA-15. Increasing loadings of niobia cause a decrease in the surface area, pore volume, and pore diameter due to the conformal coating of niobia within the pores. Materials containing 10, 19, and 30 cycles show remarkable hydrothermal stability, with minimal change in porosity and structural properties upon treatment in liquid water at 473 K. The mesoporous niobia material produced by 19 cycles has been studied as an acid catalyst for the gas-phase dehydration of 2-propanol, and for the dehydration of 2-butanol in both the gas and liquid phases, showing catalytic activity superior to commercial niobia (HY-340) per mass of material. Furthermore, deposition of Pd nanoparticles on this material consisting of SBA-15 coated with 19 cycles of niobia leads to a bifunctional catalyst for the transformation of γ-valerolactone to pentanoic acid, showing better stability versus time-on-stream compared to a conventional catalyst consisting of Pd supported on HY-340.

  7. Enhanced Dry Reforming of Methane on Ni and Ni-Pt Catalysts Synthesized by Atomic Layer Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Gould, Troy D.; Montemore, Matthew M.; Lubers, Alia M.; Ellis, Lucas D.; Weimer, Alan; Falconer, John L.; Medlin, James W.

    2015-02-25

    Atomic layer deposition (ALD) was used to deposit Ni and Pt on alumina supports to form monometallic and bimetallic catalysts with initial particle sizes of 1–2.4 nm. The ALD catalysts were more active (per mass of metal) than catalysts prepared by incipient wetness (IW) for dry reforming of methane (DRM), and they did not form carbon whiskers during reaction due to their sufficiently small size. Catalysts modified by Pt ALD had higher rates of reaction per mass of metal and inhibited coking, whereas NiPt catalysts synthesized by IW still formed carbon whiskers. Temperature-programmed reduction of Ni catalysts modified by Pt ALD indicated the presence of bimetallic interaction. Density functional theory calculations suggested that under reaction conditions, the NiPt surfaces form Ni-terminated surfaces that are associated with higher DRM rates (due to their C and O adsorption energies, as well as the CO formation and CH4 dissociation energies).

  8. Atomic layer deposited cobalt oxide: An efficient catalyst for NaBH{sub 4} hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Nandi, Dip K.; Manna, Joydev; Dhara, Arpan; Sharma, Pratibha; Sarkar, Shaibal K., E-mail: shaibal.sarkar@iitb.ac.in [Department of Energy Science and Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400076 (India)

    2016-01-15

    Thin films of cobalt oxide are deposited by atomic layer deposition using dicobalt octacarbonyl [Co{sub 2}(CO){sub 8}] and ozone (O{sub 3}) at 50 °C on microscope glass substrates and polished Si(111) wafers. Self-saturated growth mechanism is verified by x-ray reflectivity measurements. As-deposited films consist of both the crystalline phases; CoO and Co{sub 3}O{sub 4} that gets converted to pure cubic-Co{sub 3}O{sub 4} phase upon annealing at 500 °C under ambient condition. Elemental composition and uniformity of the films is examined by x-ray photoelectron spectroscopy and secondary ion-mass spectroscopy. Both as-deposited and the annealed films have been successfully tested as a catalyst for hydrogen evolution from sodium borohydride hydrolysis. The activation energy of the hydrolysis reaction in the presence of the as-grown catalyst is found to be ca. 38 kJ mol{sup −1}. Further implementation of multiwalled carbon nanotube, as a scaffold layer, improves the hydrogen generation rate by providing higher surface area of the deposited catalyst.

  9. Characteristics of the nitrided layer formed on AISI 304 austenitic stainless steel by high temperature nitriding assisted hollow cathode discharge

    International Nuclear Information System (INIS)

    Highlights: • AISI 304 austenite steel was nitrided at high temperatures in short time. • It could critically reduce time compared with low temperature nitriding. • The nitrided layer was mainly composed of nitrogen expanded austenite. • It could improve pitting corrosion resistance in NaCl solution. - Abstract: A series of experiments have been conducted on AISI 304 stainless steel using a hollow cathode discharge assisted plasma nitriding apparatus. Specimens were nitrided at high temperatures (520–560 °C) in order to produce nitrogen expanded austenite phase within a short time. The nitrided specimen was characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, potentiodynamic polarization and microhardness tester. The corrosion properties of nitrided samples were evaluated using anodic polarization tests in 3.5% NaCl solution. The nitrided layer was shown to consist of nitrogen expanded austenite and possibly a small amount of CrN precipitates and iron nitrides. The results indicated that rapid nitriding assisted hollow cathode discharge not only increased the surface hardness but also improved the corrosion resistance of the untreated substrate

  10. Effect of the semi-conductive properties of the passive layer on the current provided by stainless steel microbial cathodes

    International Nuclear Information System (INIS)

    Geobacter sulfurreducens biofilms were formed under constant polarisation at -0.6 V vs. Ag/AgCl on stainless steel cathodes to catalyse the reduction of fumarate. The time-evolution of the current strongly depended on the quality of the inoculum. Inoculating with young cells significantly shortened the initial lag-phase and using the same inoculum improved the reproducibility of the current-time curves. The whole set of experiments showed that 254SMO stainless steel provided higher current densities (on average 14.1 A/m2) than biofilms formed on 316L stainless steel (on average 4.5 A/m2). Biofilm coverage assessed by epifluorescent microscopy showed that coverage ratios were generally higher for 316L than for 254SMO. It must be concluded that 254SMO is more efficient in transferring electrons to bacterial cells than 316L. Mott-Schottky diagrams recorded on both materials under conditions of electrolysis in the absence of microorganisms showed that the surface oxide layers had similar n-type semi-conductive behaviour for potential values higher than the flat band potential. In contrast, 316L exhibited slight p-type behaviour at potential lower than the flat band potential, while 254SMO did not. The higher electrochemical performances of biocathodes formed on 254SMO are explained by semi-conductive properties of its passive layer, which prevented the p-type behaviour occurring in cathodic electrolysis conditions.

  11. Effect of the semi-conductive properties of the passive layer on the current provided by stainless steel microbial cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Pons, Liz; Delia, Marie-Line; Basseguy, Regine [Laboratoire de Genie Chimique, CNRS - Universite de Toulouse, 4 allee Emile Monso BP 84234, 31030 Toulouse (France); Bergel, Alain, E-mail: alain.bergel@ensiacet.f [Laboratoire de Genie Chimique, CNRS - Universite de Toulouse, 4 allee Emile Monso BP 84234, 31030 Toulouse (France)

    2011-02-15

    Geobacter sulfurreducens biofilms were formed under constant polarisation at -0.6 V vs. Ag/AgCl on stainless steel cathodes to catalyse the reduction of fumarate. The time-evolution of the current strongly depended on the quality of the inoculum. Inoculating with young cells significantly shortened the initial lag-phase and using the same inoculum improved the reproducibility of the current-time curves. The whole set of experiments showed that 254SMO stainless steel provided higher current densities (on average 14.1 A/m{sup 2}) than biofilms formed on 316L stainless steel (on average 4.5 A/m{sup 2}). Biofilm coverage assessed by epifluorescent microscopy showed that coverage ratios were generally higher for 316L than for 254SMO. It must be concluded that 254SMO is more efficient in transferring electrons to bacterial cells than 316L. Mott-Schottky diagrams recorded on both materials under conditions of electrolysis in the absence of microorganisms showed that the surface oxide layers had similar n-type semi-conductive behaviour for potential values higher than the flat band potential. In contrast, 316L exhibited slight p-type behaviour at potential lower than the flat band potential, while 254SMO did not. The higher electrochemical performances of biocathodes formed on 254SMO are explained by semi-conductive properties of its passive layer, which prevented the p-type behaviour occurring in cathodic electrolysis conditions.

  12. Low temperature thin film transistors with hollow cathode plasma-assisted atomic layer deposition based GaN channels

    International Nuclear Information System (INIS)

    We report GaN thin film transistors (TFT) with a thermal budget below 250 °C. GaN thin films are grown at 200 °C by hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD). HCPA-ALD-based GaN thin films are found to have a polycrystalline wurtzite structure with an average crystallite size of 9.3 nm. TFTs with bottom gate configuration are fabricated with HCPA-ALD grown GaN channel layers. Fabricated TFTs exhibit n-type field effect characteristics. N-channel GaN TFTs demonstrated on-to-off ratios (ION/IOFF) of 103 and sub-threshold swing of 3.3 V/decade. The entire TFT device fabrication process temperature is below 250 °C, which is the lowest process temperature reported for GaN based transistors, so far.

  13. Novel growth method of carbon nanotubes using catalyst-support layer developed by alumina grit blasting

    Science.gov (United States)

    Watanabe, Hiromichi; Ishii, Juntaro; Ota, Keishin

    2016-08-01

    We propose an efficient method of growing carbon nanotube (CNT) arrays on a variety of metals, alloys, and carbon materials using chemical vapor deposition (CVD) assisted by a simple surface treatment of the materials. The main feature of this method is the application of grit blasting with fine alumina particles to the development of a catalyst-support layer required for the growth of CNTs on various conductive materials, including ultra-hard metals such as tungsten. Auger electron spectroscopy shows that grit blasting can form a non-continuous layer where alumina nanoparticles are embedded as residues in the blasting media left on the treated surfaces. This work reveals that such a non-continuous alumina layer can behave as the catalyst-support layer, which is generally prepared by sputter or a vacuum evaporation coating process that considerably restricts the practical applications of CNTs. We have attempted to grow CNTs on grit-blasted substrates of eighteen conventionally used conductive materials using CVD together with a floating iron catalyst. The proposed method was successful in growing multi-walled CNT arrays on the grit-blasted surfaces of all the examined materials, demonstrating its versatility. Furthermore, we found that the group IV metal oxide films thermally grown on the as-received substrates can support the catalytic activity of iron nanoparticles in the CVD process just as well as the alumina film developed by grit blasting. Spectral emissivity of the CNT arrays in the visible and infrared wavelength ranges has been determined to assess the applicability of the CNT arrays as a black coating media.

  14. Novel growth method of carbon nanotubes using catalyst-support layer developed by alumina grit blasting.

    Science.gov (United States)

    Watanabe, Hiromichi; Ishii, Juntaro; Ota, Keishin

    2016-08-19

    We propose an efficient method of growing carbon nanotube (CNT) arrays on a variety of metals, alloys, and carbon materials using chemical vapor deposition (CVD) assisted by a simple surface treatment of the materials. The main feature of this method is the application of grit blasting with fine alumina particles to the development of a catalyst-support layer required for the growth of CNTs on various conductive materials, including ultra-hard metals such as tungsten. Auger electron spectroscopy shows that grit blasting can form a non-continuous layer where alumina nanoparticles are embedded as residues in the blasting media left on the treated surfaces. This work reveals that such a non-continuous alumina layer can behave as the catalyst-support layer, which is generally prepared by sputter or a vacuum evaporation coating process that considerably restricts the practical applications of CNTs. We have attempted to grow CNTs on grit-blasted substrates of eighteen conventionally used conductive materials using CVD together with a floating iron catalyst. The proposed method was successful in growing multi-walled CNT arrays on the grit-blasted surfaces of all the examined materials, demonstrating its versatility. Furthermore, we found that the group IV metal oxide films thermally grown on the as-received substrates can support the catalytic activity of iron nanoparticles in the CVD process just as well as the alumina film developed by grit blasting. Spectral emissivity of the CNT arrays in the visible and infrared wavelength ranges has been determined to assess the applicability of the CNT arrays as a black coating media. PMID:27389659

  15. Investigating the performance of catalyst layer micro-structures with different platinum loadings

    Energy Technology Data Exchange (ETDEWEB)

    Khakaz-Baboli, Moben; Harvey, David; Pharoah, Jon

    2012-07-01

    In this study a four-phase micro-structure of a PEFC catalyst layer was reconstructed by randomly placing overlapping spheres for each solid catalyst phase. The micro-structure was mirrored to make a micro-structure. A body-fit computational mesh was produced for the reconstructed micro-structure in OpenFOAM. Associated conservation equations were solved within all the phases with electrochemical reaction as the boundary condition at the interface between ionomer and platinum phases. The study is focused on the platinum loading of CL. The polarization curves of the micro-structure performance have been compared for different platinum loadings. This paper gives increased insight into the relatively greater losses at decreased platinum loadings.

  16. Study on the oxygen adsorption property of nitrogen-containing metal-free carbon-based cathode catalysts for oxygen reduction reaction

    International Nuclear Information System (INIS)

    We study the characteristics of oxygen adsorption on metal-free carbon-based cathode catalysts derived from nitrogen-containing polyamide (PA) and nitrogen-free phenolic resin (PhRs). Electrochemical analysis and Raman spectroscopy showed higher 2-electron oxygen reduction reaction (ORR) activity and more defect sites in PA than PhRs. The increase in the amount of adsorbed oxygen in PA was also identified by oxygen adsorption isotherms. In situ X-ray photoelectron spectroscopy revealed that graphite-like nitrogen contributes to oxygen adsorption and C=O components are dominant in PA. These experimental results indicate that the adsorbed C=O components near the graphite-like nitrogen can be assigned as active sites for 2-electron ORR.

  17. Measurement of capillary pressure in fuel cell diffusion media, micro-porous layers, catalyst layers, and interfaces

    Science.gov (United States)

    LaManna, Jacob M.; Bothe, James V.; Zhang, Feng Yuan; Mench, Matthew M.

    2014-12-01

    In this work, semi-empirical Leverett J-Function relationships relating capillary pressure and water saturation are experimentally derived for commercial and experimental polymer electrolyte fuel cell materials developed for automotive applications. Relationships were derived for Mitsubishi Rayon Corp. (MRC) U105 and General Motors (GM) experimental high tortuosity diffusion media (DM), the micro-porous layer (MPL), and the catalyst layer (CL). The standard Leverett J-Function under-predicted drainage curves for the DM at high saturation levels and significantly under-predicted the capillary pressure requirements for the MPL and CL across the entire saturation range. Composite structures were tested to understand interfacial effects for DM|MPL and MPL|CL. Each additional layer was found to superimpose its effects on capillary pressure onto the previous layers. The MPL formulation tested increased in porosity from a 136 nm peak average to a 153 nm peak average with increased surface porosity of the substrate. Additionally, small voids and pockets that accumulate liquid water were found to exist in the MPL|CL interface. The results of this work are useful for computational modelers seeking to enhance the resolution of their macroscopic multi-phase flow models which underestimate capillary pressure using the standard Leverett J-Function.

  18. Highly Active and Redox-Stable Ce-Doped LaSrCrFeO-Based Cathode Catalyst for CO2 SOECs.

    Science.gov (United States)

    Zhang, Ya-Qian; Li, Jian-Hui; Sun, Yi-Fei; Hua, Bin; Luo, Jing-Li

    2016-03-16

    Lanthanum chromate-based perovskite oxides have attracted great attention as the cathode materials in the high-temperature CO2 electrolysis because of its good redox stability. However, the unsatisfied electrochemical catalytic activity and insufficient adsorption of CO2 at operating temperature still hindered the further improvement of electrochemical performance and the Faraday efficiency of the electrolysis cell. In this work, the catalytic and redox active Ce was doped into A site of La0.7Sr0.3Cr0.5Fe0.5O3-δ (LSCrF) to promote the catalytic performance, and to introduce oxygen vacancies in the lattice in situ after reduction under the operational condition. The increased amount of oxygen vacancies not only facilitates the mobility of oxygen ions, but also provides favorable accommodation for chemical adsorption of CO2. The CO2 electrolysis tests demonstrated the superior electrochemical performances, higher Faraday efficiencies of the Ce-doped LSCrF cathode catalyst in comparison with that without Ce doping, indicating the perspective application of this functional material. PMID:26901862

  19. Investigation of modified thin SnO2 layers treated by rapid thermal annealing by means of hollow cathode spectroscopy and AFM technique

    International Nuclear Information System (INIS)

    By means of hollow cathode spectroscopy and atomic force microscopy the surface morphology and composition of SnO2 thin film, modified with hexamethyldisilazane after rapid thermal annealing treatment (800-1200 deg. C), are investigated. Formation of crystalline structure is suggested at lower temperatures. Depolimerization, destruction and dehydration are developed at temperatures of 1200 deg. C. It is shown that the rapid thermal annealing treatment could modify both the surface morphology and the composition of the layer, thus changing the adsorption ability of the sensing layer. The results confirm the ability of hollow cathode emission spectroscopy for depth profiling of new materials especially combined with standard techniques

  20. Study of pyrolyzed hemin/C as non-platinum cathodic catalyst for direct methanol fuel cells

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Biological reduction of O2 to H2O justifies a serious look at heme as a potential O2 reduction reaction(ORR) catalyst for low temperature fuel cells.In this study,a novel non-platinum electrocatalyst for ORR was prepared through hemin,which is hydrochloride of heme,supported on Black Pearls 2000 carbon black(Hm-BP) pyrolyzed at 700-900℃ in Ar atmosphere.The physical and electrocatalytic properties of as-prepared catalysts were characterized by TGA,XRD,XPS,TEM,rotating disk electrode(RDE) and rotating ring disk electrode(RRDE).It has found that the catalyst treated at 750℃(Hm-BP-750) exhibits the best property among the Hm-BP catalysts prepared.The onset potential of ORR on the Hm-BP-750 at 30℃ was measured ca.0.90 V(vs.RHE) in 0.1 M H2SO4,and mass current density was reached 15.3 mA mg-1 at 0.75 V.It has revealed that O2 could be reduced directly to water in a 4e process between 0.9 and 0.83V,and the yield of H2O2 was 0-18% in the potential range of 0.83-0.63 V.This methanol-tolerant catalyst also presents excellent stability in medium-term test of direct methanol fuel cell at 80℃.

  1. Carbon nanotube growth on nanozirconia under strong cathodic polarization in steam and carbon dioxide

    DEFF Research Database (Denmark)

    Tao, Youkun; Ebbesen, Sune Dalgaard; Zhang, Wei; Mogensen, Mogens Bjerg

    2014-01-01

    observed. Apart from the CNTs, graphitic layers covering zirconia nanoparticles are also widely observed. This work describes nano-zirconia acting as a catalyst for the growth of CNT during electrochemical conversion of CO2 and H2O in a Ni-YSZ cermet under strong cathodic polarization. An electrocatalytic......Growth of carbon nanotubes (CNTs) catalyzed by zirconia nanoparticles was observed in the Ni-yttria doped zirconia (YSZ) composite cathode of a solid oxide electrolysis cell (SOEC) at approximately 875 °C during co-electrolysis of CO2 and H2O to produce CO and H 2. CNT was observed to grow under...... large cathodic polarizations specifically at the first 1 to 2 μm Ni-YSZ active cathode layer next to the YSZ electrolyte. High resolution transmission electron microscopy (HRTEM) shows that the CNTs are multi-walled with diameters of approximately 20 nm and the catalyst particles have diameters in the...

  2. Catalytic characterization of bi-functional catalysts derived from Pd–Mg–Al layered double hydroxides

    Indian Academy of Sciences (India)

    N N Das; S C Srivastava

    2002-08-01

    Hydrotalcite like precursors containing PdII–MgII–AlIII with varying molar ratios, (Pd + Mg)/Al ≈ 3 and Mg/Pd ≈ 750 to 35, were prepared by coprecipitation of metal nitrates at constant pH. Characterization of samples as synthesized and their calcined products by elemental analyses, powder XRD, TG–DTA, FT–IR spectroscopy, TPR and N2 physisorption indicated a well crystalline hydrotalcite like structure with incorporation of Pd2+ in the brucite layers. Thermal decomposition of hydrotalcite precursors at intermediate temperatures led to amorphous mixed oxides, Pd/MgAl(O), which on reduction yielded bi-functional catalyst, Pd°/MgAl(O). The resultant catalysts with acid, base and hydrogenating sites, were highly active and selective for one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen. The results showed an optimal balance between acid-base and metallic sites were required to increase the selectivity of MIBK and stability of the catalysts.

  3. Synthesis and electrochemical performances of LiNiCuZn oxides as anode and cathode catalyst for low temperature solid oxide fuel cell.

    Science.gov (United States)

    Jing, Y; Qin, H; Liu, Q; Singh, M; Zhu, B

    2012-06-01

    Low temperature solid oxide fuel cell (LTSOFC, 300-600 degrees C) is developed with advantages compared to conventional SOFC (800-1000 degrees C). The electrodes with good catalytic activity, high electronic and ionic conductivity are required to achieve high power output. In this work, a LiNiCuZn oxides as anode and cathode catalyst is prepared by slurry method. The structure and morphology of the prepared LiNiCuZn oxides are characterized by X-ray diffraction and field emission scanning electron microscopy. The LiNiCuZn oxides prepared by slurry method are nano Li0.28Ni0.72O, ZnO and CuO compound. The nano-crystallites are congregated to form ball-shape particles with diameter of 800-1000 nm. The LiNiCuZn oxides electrodes exhibits high ion conductivity and low polarization resistance to hydrogen oxidation reaction and oxygen reduction reaction at low temperature. The LTSOFC using the LiNiCuZn oxides electrodes demonstrates good cell performance of 1000 mW cm(-2) when it operates at 470 degrees C. It is considered that nano-composite would be an effective way to develop catalyst for LTSOFC. PMID:22905585

  4. Low Pt content on the Pd{sub 45}Pt{sub 5}Sn{sub 50} cathode catalyst for PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Salvador-Pascual, J.J.; Solorza-Feria, O. [Depto. Quimica, Centro de Investigacion y de Estudios Avanzados del IPN, A. Postal 14-740, 07360 Mexico D.F. (Mexico); Collins-Martinez, V.; Lopez-Ortiz, A. [Centro de Investigacion en Materiales Avanzados, Miguel de Cervantes 120, 31109 Chihuahua (Mexico)

    2010-06-01

    Pd{sub 45}Pt{sub 5}Sn{sub 50} electrocatalyst was prepared by a NaBH{sub 4} reduction of PdCl{sub 2}, H{sub 2}PtCl{sub 6} and SnCl{sub 2} in THF at 0 C. This catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) microanalysis and hydrodynamic electrochemical technique. XRD, SEM and TEM results demonstrate that the borohydrate reduction methodology enable the synthesis of conglomerated particles nanometric in size ranging from 1 to 6 nm. Oxygen reduction reaction (ORR) activity was investigated on carbon dispersed catalyst by rotating disk electrode (RDE) technique in H{sub 2}SO{sub 4} 0.5 M. The effect of temperature on the kinetics was analyzing resulting in an apparent activation energy of 42.54 {+-} 1 kJ mol{sup -1}, value which is less than the obtained for the nanostructured bimetallic PdSn electrocatalyst under the same experimental condition. The Pd{sub 45}Pt{sub 5}Sn{sub 50} electrocatalyst dispersed on a carbon powder was tested as cathode electrocatalyst in a membrane-electrode assembly (MEA) arriving to a power density of 210 mW cm{sup -2} at 0.35 V and 80 C. (author)

  5. Hydrothermal synthesis of highly crystalline RuS2 nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

    International Nuclear Information System (INIS)

    Highlights: • Highly crystalline RuS2 nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS2 with average particle size of 14.8 nm. • RuS2 nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl−. - Abstract: Highly crystalline ruthenium sulfide (RuS2) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS2 and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S22−. Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS2 nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS2 is active towards oxygen reduction reaction. Although the activity of RuS2 is lower than that of Pt/C, the RuS2 catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl−

  6. Surface-Regulated Nano-SnO2/Pt3Co/C Cathode Catalysts for Polymer Electrolyte Fuel Cells Fabricated by a Selective Electrochemical Sn Deposition Method.

    Science.gov (United States)

    Nagasawa, Kensaku; Takao, Shinobu; Nagamatsu, Shin-ichi; Samjeské, Gabor; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Yamamoto, Takashi; Uruga, Tomoya; Iwasawa, Yasuhiro

    2015-10-14

    We have achieved significant improvements for the oxygen reduction reaction activity and durability with new SnO2-nanoislands/Pt3Co/C catalysts in 0.1 M HClO4, which were regulated by a strategic fabrication using a new selective electrochemical Sn deposition method. The nano-SnO2/Pt3Co/C catalysts with Pt/Sn = 4/1, 9/1, 11/1, and 15/1 were characterized by STEM-EDS, XRD, XRF, XPS, in situ XAFS, and electrochemical measurements to have a Pt3Co core/Pt skeleton-skin structure decorated with SnO2 nanoislands at the compressive Pt surface with the defects and dislocations. The high performances of nano-SnO2/Pt3Co/C originate from efficient electronic modification of the Pt skin surface (site 1) by both the Co of the Pt3Co core and surface nano-SnO2 and more from the unique property of the periphery sites of the SnO2 nanoislands at the compressive Pt skeleton-skin surface (more active site 2), which were much more active than expected from the d-band center values. The white line peak intensity of the nano-SnO2/Pt3Co/C revealed no hysteresis in the potential up-down operations between 0.4 and 1.0 V versus RHE, unlike the cases of Pt/C and Pt3Co/C, resulting in the high ORR performance. Here we report development of a new class of cathode catalysts with two different active sites for next-generation polymer electrolyte fuel cells. PMID:26412503

  7. Understanding Voltage Decay in Lithium-Rich Manganese-Based Layered Cathode Materials by Limiting Cutoff Voltage.

    Science.gov (United States)

    Yang, Jingsong; Xiao, Lifen; He, Wei; Fan, Jiangwei; Chen, Zhongxue; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    2016-07-27

    The effect of the cutoff voltages on the working voltage decay and cyclability of the lithium-rich manganese-based layered cathode (LRMO) was investigated by electrochemical measurements, electrochemical impedance spectroscopy, ex situ X-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy line scan technologies. It was found that both lower (2.0 V) and upper (4.8 V) cutoff voltages cause severe voltage decay with cycling due to formation of the spinel phase and migration of the transition metals inside the particles. Appropriate cutoff voltage between 2.8 and 4.4 V can effectively inhibit structural variation as the electrode demonstrates 92% capacity retention and indiscernible working voltage decay over 430 cycles. The results also show that phase transformation not only on high charge voltage but also on low discharge voltage should be addressed to obtain highly stable LRMO materials. PMID:27383918

  8. Electronic and optical device applications of hollow cathode plasma assisted atomic layer deposition based GaN thin films

    International Nuclear Information System (INIS)

    Electronic and optoelectronic devices, namely, thin film transistors (TFTs) and metal–semiconductor–metal (MSM) photodetectors, based on GaN films grown by hollow cathode plasma-assisted atomic layer deposition (PA-ALD) are demonstrated. Resistivity of GaN thin films and metal-GaN contact resistance are investigated as a function of annealing temperature. Effect of the plasma gas and postmetallization annealing on the performances of the TFTs as well as the effect of the annealing on the performance of MSM photodetectors are studied. Dark current to voltage and responsivity behavior of MSM devices are investigated as well. TFTs with the N2/H2 PA-ALD based GaN channels are observed to have improved stability and transfer characteristics with respect to NH3 PA-ALD based transistors. Dark current of the MSM photodetectors is suppressed strongly after high-temperature annealing in N2:H2 ambient

  9. Electricity generation of microbial fuel cell with waterproof breathable membrane cathode

    Science.gov (United States)

    Xing, Defeng; Tang, Yu; Mei, Xiaoxue; Liu, Bingfeng

    2015-12-01

    Simplification of fabrication and reduction of capital cost are important for scale-up and application of microbial electrochemical systems (MES). A fast and inexpensive method of making cathode was developed via assembling stainless steel mesh (SSM) with waterproof breathable membrane (WBM). Three assemble types of cathodes were fabricated; Pt@SSM/WBM (SSM as cathode skeleton, WBM as diffusion layer, platinum (Pt) catalyst applied on SSM), SSM/Pt@WBM and Pt@WBM. SSM/Pt@WBM cathode showed relatively preferable with long-term stability and favorable power output (24.7 W/m3). Compared to conventional cathode fabrication, air-cathode was made for 0.5 h. The results indicated that the novel fabrication method could remarkably reduce capital cost and simplify fabrication procedures with a comparable power output, making MFC more prospective for future application.

  10. Flexible inverted polymer solar cells with an indium-free tri-layer cathode

    International Nuclear Information System (INIS)

    Indium tin oxide (ITO)-free inverted polymer solar cells (PSCs) have been fabricated without the need of an additional electron transport layer. The indium-free transparent electrode consists of a tri-layer stack ZnO (30 nm)/Ag (14 nm)/ZnO (30 nm) deposited on glass and plastic substrates via ion-beam sputtering. The tri-layer electrodes exhibit similar physical properties to its ITO counterpart, specifically yielding high transmittance and low resistivity (76.5% T at 550 nm, Rsq of 8 Ω/◻) on plastic substrates. The novel tri-layer electrode allows for the fabrication of inverted PSCs without the additional ZnO interfacial layer commonly deposited between ITO and the photoactive layer. This allows for the preparation of thinner plastic solar cells using less material than conventional architectures. Initial studies involving the newly realized architecture (tri-layer electrode/P3HT:PCBM/PEDOT:PSS/Ag) have shown great promise for the transition from ITO to other viable electrodes in organic electronics

  11. Multi-variable mathematical models for the air-cathode microbial fuel cell system

    Science.gov (United States)

    Ou, Shiqi; Kashima, Hiroyuki; Aaron, Douglas S.; Regan, John M.; Mench, Matthew M.

    2016-05-01

    This research adopted the version control system into the model construction for the single chamber air-cathode microbial fuel cell (MFC) system, to understand the interrelation of biological, chemical, and electrochemical reactions. The anodic steady state model was used to consider the chemical species diffusion and electric migration influence to the MFC performance. In the cathodic steady state model, the mass transport and reactions in a multi-layer, abiotic cathode and multi-bacteria cathode biofilm were simulated. Transport of hydroxide was assumed for cathodic pH change. This assumption is an alternative to the typical notion of proton consumption during oxygen reduction to explain elevated cathode pH. The cathodic steady state model provided the power density and polarization curve performance results that can be compared to an experimental MFC system. Another aspect considered was the relative contributions of platinum catalyst and microbes on the cathode to the oxygen reduction reaction (ORR). Simulation results showed that the biocatalyst in a cathode that includes a Pt/C catalyst likely plays a minor role in ORR, contributing up to 8% of the total power calculated by the models.

  12. Synthesis of higher alcohols over highly dispersed Cu-Fe based catalysts derived from layered double hydroxides.

    Science.gov (United States)

    Han, Xinyou; Fang, Kegong; Zhou, Juan; Zhao, Lu; Sun, Yuhan

    2016-05-15

    Highly dispersed Cu-Fe based catalysts with Fe/Cu molar ratios ranging from 0.2 to 1 were prepared via thermal decomposition of layered double hydroxides (LDHs) precursors and tested for higher alcohol synthesis (HAS) via CO hydrogenation. The catalysts were characterized using different techniques such as XRD, TEM, XPS, and H2-TPR. It was demonstrated that the Cu and Fe ions were highly dispersed in the brucite-like layers of the LDHs. With increased Fe/Cu atomic ratio, the tetrahedrally coordinated Cu ion content, Cu reduction temperatures, and the spacing of layers initially increase until the Fe/Cu ratio reaches 0.5 and then decrease. In addition to the catalytic evaluation for CO hydrogenation and catalyst characterization, the relationships between the physical-chemical properties of the catalysts and their catalytic performances were also investigated. It was also found that the alcohols/hydrocarbons ratios correlate linearly with the tetrahedrally coordinated Cu ion content. Moreover, higher reduction temperatures of Cu species as well as larger spacing between the layers in the catalyst are favorable for the synthesis of alcohols. The incorporation of a suitable amount of Fe is beneficial for the production of higher alcohols, with the best catalytic performance (alcohol selectivity of 20.77% and C2+ alcohol selectivity of 48.06%) obtained from a Fe/Cu atomic ratio of 0.5. PMID:26943001

  13. Influence of Ni Catalyst Layer and TiN Diffusion Barrier on Carbon Nanotube Growth Rate

    Directory of Open Access Journals (Sweden)

    Mérel Philippe

    2010-01-01

    Full Text Available Abstract Dense, vertically aligned multiwall carbon nanotubes were synthesized on TiN electrode layers for infrared sensing applications. Microwave plasma-enhanced chemical vapor deposition and Ni catalyst were used for the nanotubes synthesis. The resultant nanotubes were characterized by SEM, AFM, and TEM. Since the length of the nanotubes influences sensor characteristics, we study in details the effects of changing Ni and TiN thickness on the physical properties of the nanotubes. In this paper, we report the observation of a threshold Ni thickness of about 4 nm, when the average CNT growth rate switches from an increasing to a decreasing function of increasing Ni thickness, for a process temperature of 700°C. This behavior is likely related to a transition in the growth mode from a predominantly “base growth” to that of a “tip growth.” For Ni layer greater than 9 nm the growth rate, as well as the CNT diameter, variations become insignificant. We have also observed that a TiN barrier layer appears to favor the growth of thinner CNTs compared to a SiO2 layer.

  14. H2O2 detection analysis of oxygen reduction reaction on cathode and anode catalysts for polymer electrolyte fuel cells

    Science.gov (United States)

    Kishi, Akira; Shironita, Sayoko; Umeda, Minoru

    2012-01-01

    The generation percentage of H2O2 during oxygen reduction reaction (ORR) at practical powder electrocatalysts was evaluated using a scanning electrochemical microscope (SECM). We employed a porous microelectrode that contains electrocatalysts, namely, Pt/C, Pt-Co/C, and Pt-Ru/C as the oxygen reduction electrode of the SECM, and the Pt microelectrode was used as the H2O2 detector. First, the H2O2 generation amount at Pt/Cs was measured by changing the Pt loading amount. A Pt/C with a higher Pt loading has a higher ORR activity and generates a larger amount of H2O2. However, the percentage of H2O2 generated with respect to the ORR is the same regardless of the Pt loading amount. Next, H2O2 generation is markedly suppressed at the Pt-Co/C and Pt-Ru/C in the potential ranges of practical fuel cell cathode and anode, respectively. This explains that the Pt-Co/C is effective when used as a cathode, and the anode Pt-Ru/C enables the reduction of the H2O2 generation even if O2 crossleak occurs in the practical polymer electrolyte fuel cell.

  15. Improved electrochemical reversibility of over-lithiated layered Li2RuO3 cathodes: Understanding aliovalent Co3+ substitution with excess lithium

    Science.gov (United States)

    Arunkumar, Paulraj; Jeong, Woo Jin; Won, Seob; Im, Won Bin

    2016-08-01

    Over-lithiated layered Li2+xRu1-xCoxO3 (x = 0, 0.1, 0.2, and 0.5) cathodes were synthesized through a solid-state reaction, which exhibits a superlattice structure. We investigated the effects of aliovalent Co3+ doping with excess lithium on the structural and electrochemical properties of layered Li2RuO3 cathodes. X-ray diffraction suggests the formation of a solid-solution where Co3+ occupies the Ru4+ sites in the transition metal layer while maintaining the layered Li2RuO3 structure. The electrochemical results indicate an enhanced electrochemical lithium reversibility of the cathodes at high C-rates (1C) than the pristine Li2RuO3. In particular, the high-performance Li2.1Ru0.9Co0.1O3 cathode delivered an initial capacity of 250 mAh g-1 with an enhanced Li+ extraction of 0.66 mol (52% capacity retention) after 100 cycles at 1C compared to the 0.28 mol of Li+ extraction (21% capacity retention) associated with the pristine Li2RuO3. Low content of Co3+ could realize an enhanced reversible Li+ extraction that originated from the improved reversible anionic redox chemistry, cation ordering with superlattice structure, and facile charge transfer process. The role of Co3+ content on the lithium reversibility of over-lithiated layered cathodes, containing excess lithium were investigated.

  16. Fundamental Investigations and Rational Design of Durable High-Performance SOFC Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu [Georgia Inst. of Technology, Atlanta, GA (United States); Ding, Dong [Georgia Inst. of Technology, Atlanta, GA (United States); Wei, Tao [Georgia Inst. of Technology, Atlanta, GA (United States); Liu, Meilin [Georgia Inst. of Technology, Atlanta, GA (United States)

    2016-03-31

    The main objective of this project is to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants, aiming towards the rational design of cathodes with high-performance and enhanced durability by combining a porous backbone (such as LSCF) with a thin catalyst coating. The mechanistic understanding will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance and durability. More specifically, the technical objectives include: (1) to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants using in situ and ex situ measurements performed on specially-designed cathodes; (2) to examine the microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions; (3) to correlate the fuel cell performance instability and degradation with the microstructural and morphological evolution and surface chemistry change of the cathode under realistic operating conditions; (4) to explore new catalyst materials and electrode structures to enhance the stability of the LSCF cathode under realistic operating conditions; and (5) to validate the long term stability of the modified LSCF cathode in commercially available cells under realistic operating conditions. We have systematically evaluated LSCF cathodes in symmetrical cells and anode supported cells under realistic conditions with different types of contaminants such as humidity, CO2, and Cr. Electrochemical models for the design of test cells and understanding of mechanisms have been developed for the exploration of fundamental properties of electrode materials. It is demonstrated that the activity and stability of LSCF cathodes can be degraded by the introduction of contaminants. The microstructural and compositional evolution of LSCF

  17. A novel (ex situ) method to quantify oxygen diffusion coefficient of polymer fuel cells backing and catalyst layers

    Science.gov (United States)

    Baricci, Andrea; Casalegno, Andrea

    2016-09-01

    Limiting current density of oxygen reduction reaction in polymer electrolyte fuel cells is determined by several mass transport resistances that lower the concentration of oxygen on the catalyst active site. Among them, diffusion across porous media plays a significant role. Despite the extensive experimental activity documented in PEMFC literature, only few efforts have been dedicated to the measurement of the effective transport properties in porous layers. In the present work, a methodology for ex situ measurement of the effective diffusion coefficient and Knudsen radius of porous layers for polymer electrolyte fuel cells (gas diffusion layer, micro porous layer and catalyst layer) is described and applied to high temperature polymer fuel cells State of Art materials. Regression of the measured quantities by means of a quasi 2D physical model is performed to quantify the Knudsen effect, which is reported to account, respectively, for 30% and 50% of the mass transport resistance in micro porous layer and catalyst layer. On the other side, the model reveals that pressure gradient consequent to permeation in porous layers of high temperature polymer fuel cells has a negligible effect on oxygen concentration in relevant operating conditions.

  18. Power generation by packed-bed air-cathode microbial fuel cells

    KAUST Repository

    Zhang, Xiaoyuan

    2013-08-01

    Catalysts and catalyst binders are significant portions of the cost of microbial fuel cell (MFC) cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. Packed-bed air-cathodes were constructed without expensive binders or diffusion layers using four inexpensive carbon-based materials. Cathodes made from activated carbon produced the largest maximum power density of 676±93mW/m2, followed by semi-coke (376±47mW/m2), graphite (122±14mW/m2) and carbon felt (60±43mW/m2). Increasing the mass of activated carbon and semi-coke from 5 to ≥15g significantly reduced power generation because of a reduction in oxygen transfer due to a thicker water layer in the cathode (~3 or ~6cm). These results indicate that a thin packed layer of activated carbon or semi-coke can be used to make inexpensive air-cathodes for MFCs. © 2013 Elsevier Ltd.

  19. Interface control of atomic layer deposited oxide coatings by filtered cathodic arc deposited sublayers for improved corrosion protection

    Energy Technology Data Exchange (ETDEWEB)

    Härkönen, Emma, E-mail: emma.harkonen@helsinki.fi [Laboratory of Inorganic Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki (Finland); Tervakangas, Sanna; Kolehmainen, Jukka [DIARC-Technology Inc., Espoo (Finland); Díaz, Belén; Światowska, Jolanta; Maurice, Vincent; Seyeux, Antoine; Marcus, Philippe [Laboratoire de Physico-Chimie des Surfaces, CNRS (UMR 7075) – Chimie ParisTech (ENSCP), F-75005 Paris (France); Fenker, Martin [FEM Research Institute, Precious Metals and Metals Chemistry, D-73525 Schwäbisch Gmünd (Germany); Tóth, Lajos; Radnóczi, György [Research Centre for Natural Sciences HAS, (MTA TKK), Budapest (Hungary); Ritala, Mikko [Laboratory of Inorganic Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki (Finland)

    2014-10-15

    Sublayers grown with filtered cathodic arc deposition (FCAD) were added under atomic layer deposited (ALD) oxide coatings for interface control and improved corrosion protection of low alloy steel. The FCAD sublayer was either Ta:O or Cr:O–Ta:O nanolaminate, and the ALD layer was Al{sub 2}O{sub 3}–Ta{sub 2}O{sub 5} nanolaminate, Al{sub x}Ta{sub y}O{sub z} mixture or graded mixture. The total thicknesses of the FCAD/ALD duplex coatings were between 65 and 120 nm. Thorough analysis of the coatings was conducted to gain insight into the influence of the FCAD sublayer on the overall coating performance. Similar characteristics as with single FCAD and ALD coatings on steel were found in the morphology and composition of the duplex coatings. However, the FCAD process allowed better control of the interface with the steel by reducing the native oxide and preventing its regrowth during the initial stages of the ALD process. Residual hydrocarbon impurities were buried in the interface between the FCAD layer and steel. This enabled growth of ALD layers with improved electrochemical sealing properties, inhibiting the development of localized corrosion by pitting during immersion in acidic NaCl and enhancing durability in neutral salt spray testing. - Highlights: • Corrosion protection properties of ALD coatings were improved by FCAD sublayers. • The FCAD sublayer enabled control of the coating-substrate interface. • The duplex coatings offered improved sealing properties and durability in NSS. • The protective properties were maintained during immersion in a corrosive solution. • The improvements were due to a more ideal ALD growth on the homogeneous FCAD oxide.

  20. Significant influence of insufficient lithium on electrochemical performance of lithium-rich layered oxide cathodes for lithium ion batteries

    International Nuclear Information System (INIS)

    With an aim to broaden the understanding of the factors that govern electrochemical performance of lithium-rich layered oxide, the influences of insufficient lithium on reversible capacity, cyclic stability and rate capability of the oxide as cathode of lithium ion battery are investigated in this study. Various concentrations of lithium precursor are introduced to synthesize a target composition Li[Li0.13Ni0.30Ni0.57]O2, and the resulting products are characterized with inductively coupled plasma spectrum, scanning electron microscope, X-ray diffraction, Raman spectroscopy, and electrochemical measurements. The results indicate that the lithium content in the resulting oxide decreases with reducing the concentration of lithium precursor from 10wt%-excess lithium to stoichiometric lithium, due to insufficient compensation for lithium volatilization during synthesis process at high temperature. However, all these oxides still exhibit typically structural and electrochemical characteristics of lithium-rich layered oxides. Interestingly, with decreasing the Li content in the oxide, its reversible capacity increases due to relatively higher content of active transition-metal ions, while the cyclic stability degrades severely because of structural instability induced by higher content of Mn3+ ions and deeper lithium extraction

  1. Catalyst synthesis and evaluation using an integrated atomic layer deposition synthesis-catalysis testing tool

    Science.gov (United States)

    Camacho-Bunquin, Jeffrey; Shou, Heng; Aich, Payoli; Beaulieu, David R.; Klotzsch, Helmut; Bachman, Stephen; Marshall, Christopher L.; Hock, Adam; Stair, Peter

    2015-08-01

    An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10-3 to 1 bar and 300-1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al2O3 overcoats, and evaluation of catalyst propylene hydrogenation activity.

  2. Catalyst synthesis and evaluation using an integrated atomic layer deposition synthesis–catalysis testing tool

    Energy Technology Data Exchange (ETDEWEB)

    Camacho-Bunquin, Jeffrey; Shou, Heng; Marshall, Christopher L. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Aich, Payoli [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Department of Chemical Engineering, University of Illinois at Chicago, Chicago, Illinois 60607 (United States); Beaulieu, David R.; Klotzsch, Helmut; Bachman, Stephen [Arradiance Inc., Sudbury, Massachusetts 01776 (United States); Hock, Adam [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616 (United States); Stair, Peter [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Department of Chemistry, Northwestern University, Evanston, Illinois 60208 (United States)

    2015-08-15

    An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10{sup −3} to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al{sub 2}O{sub 3} overcoats, and evaluation of catalyst propylene hydrogenation activity.

  3. An extended stochastic reconstruction method for catalyst layers in proton exchange membrane fuel cells

    Science.gov (United States)

    Kang, Jinfen; Moriyama, Koji; Kim, Seung Hyun

    2016-09-01

    This paper presents an extended, stochastic reconstruction method for catalyst layers (CLs) of Proton Exchange Membrane Fuel Cells (PEMFCs). The focus is placed on the reconstruction of customized, low platinum (Pt) loading CLs where the microstructure of CLs can substantially influence the performance. The sphere-based simulated annealing (SSA) method is extended to generate the CL microstructures with specified and controllable structural properties for agglomerates, ionomer, and Pt catalysts. In the present method, the agglomerate structures are controlled by employing a trial two-point correlation function used in the simulated annealing process. An off-set method is proposed to generate more realistic ionomer structures. The variations of ionomer structures at different humidity conditions are considered to mimic the swelling effects. A method to control Pt loading, distribution, and utilization is presented. The extension of the method to consider heterogeneity in structural properties, which can be found in manufactured CL samples, is presented. Various reconstructed CLs are generated to demonstrate the capability of the proposed method. Proton transport properties of the reconstructed CLs are calculated and validated with experimental data.

  4. Theoretical and Experimental Co K-edge XAS of Layered Cobalt Oxides Catalysts

    Science.gov (United States)

    Bajdich, Michal; Friebel, Daniel; Yeo, Boon S.; Louie, Mary; Miller, Daniel J.; Casalongue, Hernan S.; Mbuga, Felix; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenes; Bell, Alexis T.; Nilsson, Anders

    2013-03-01

    The efficient water oxidation for fuel production from sunlight, with the use of earth-abundant catalysts, is of high importance to photo-fuel cell research. Recent experimental investigations of Co-oxide based catalysts under active conditions of water oxidation show evidence for layered cobalt-oxide structures with possible cation intercalation from electrolyte. To gain insight into our experimentally measured Co K-edge x-ray absorption spectra of Co-oxide anodes compared to spectra of powder standards such as CoOOH, Co(OH)2 and Co33O4, we perform theoretical investigations of these spectra. We employ density functional theory plus U (DFT+U) calculations of K-edge x-ray absorption spectra using core-hole approach which has been shown to accurately capture the pre-edge features of similar α-LiCoO2 [1]. We consider β-CoOOH, α-KCoO2, γ-K0.5CoO2 structures as possible candidates. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported under Award Number DE-SC0004993

  5. Catalyst synthesis and evaluation using an integrated atomic layer deposition synthesis–catalysis testing tool

    International Nuclear Information System (INIS)

    An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10−3 to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al2O3 overcoats, and evaluation of catalyst propylene hydrogenation activity

  6. Synthesis of Nitrogen-Doped Carbon Nanocoils with Adjustable Morphology using Ni–Fe Layered Double Hydroxides as Catalyst Precursors

    Directory of Open Access Journals (Sweden)

    Tomohiro Iwasaki

    2015-01-01

    Full Text Available Nitrogen-doped carbon nanocoils (CNCs with adjusted morphologies were synthesized in a one-step catalytic chemical vapour deposition (CVD process using acetoni‐ trile as the carbon and nitrogen source. The nickel iron oxide/nickel oxide nanocomposites, which were derived from nickel–iron layered double hydroxide (LDH precur‐ sors, were employed as catalysts for the synthesis of CNCs. In this method, precursor-to-catalyst transformation, catalyst activation, formation of CNCs, and nitrogen doping were all performed in situ in a single process. The morphology (coil diameter, coil pitch, and fibre diameter and nitrogen content of the synthesized CNCs was indi‐ vidually adjusted by modulation of the catalyst composi‐ tion and CVD reaction temperature, respectively. The adjustable ranges of the coil diameter, coil pitch, fibre diameter, and nitrogen content were confirmed to be approximately 500±100 nm, 600±100 nm, 100±20 nm, and 1.1±0.3 atom%, respectively.

  7. Investigation of the electrospun carbon web as the catalyst layer for vanadium redox flow battery

    Science.gov (United States)

    Wei, Guanjie; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

    2014-12-01

    Polyacrylonitrile (PAN) carbon nonwoven web consisting of 100-200 nm ultrafine fibers has been developed by electrospinning and subsequent carbonization process at 1000 °C for different times. The surface morphology, composition, structure, and electrical conductivity of the electrospun carbon webs (ECWs) as well as their electrochemical properties toward vanadium redox couples have been characterized. With the increasing of carbonization time, the electrochemical reversibility of the vanadium redox couples on the ECW is enhanced greatly. As the carbonization time increases up to 120 min, the hydrogen evolution is facilitated while the reversibility is promoted a little bit further. The excellent performance of ECW may be attributed to the conversion of fibers carbon structure and improvement of electrical conductivity. Due to the good electrochemical activity and freestanding 3-dimensional structure, the ECW carbonized for 90 min is used as catalyst layer in vanadium redox flow battery (VRFB) and enhances the cell performance.

  8. Fluorination Induced the Surface Segregation of High Voltage Spinel on Lithium-Rich Layered Cathodes for Enhanced Rate Capability in Lithium Ion Batteries.

    Science.gov (United States)

    Jin, Yi-Chun; Duh, Jenq-Gong

    2016-02-17

    This study is aimed to explore the effect of fluoride doping and the associated structural transformation on lithium-rich layered cathode materials. The polymeric fluoride source is first adopted for synthesizing lithium intercalated oxide through a newly developed organic precipitation process. A heterostructured spinel/layered composite cathode material is obtained after appreciable fluorination and a superior rate capability is successfully achieved. The fluoride dopant amount and the surface spinel phase are evidenced and systematically examined by various structural spectroscopy and electrochemical analysis. It appears the reversible Ni(2+/4+) redox couple at high voltage regime around 4.8 V because of the formation of spinel LiNi1/2Mn3/2O4 phase. The mechanism of "layer to spinel" phase transformation is discussed in detail. PMID:26807506

  9. Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

    KAUST Repository

    Arashi, Takuya

    2014-09-01

    Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

  10. Layer-by-layer self-assembled osmium polymer-mediated laccase oxygen cathodes for biofuel cells: the role of hydrogen peroxide.

    Science.gov (United States)

    Scodeller, Pablo; Carballo, Romina; Szamocki, Rafael; Levin, Laura; Forchiassin, Flavia; Calvo, Ernesto J

    2010-08-18

    High potential purified Trametes trogii laccase has been studied as a biocatalyst for oxygen cathodes composed of layer-by-layer self-assembled thin films by sequential immersion of mercaptopropane sulfonate-modified Au electrode surfaces in solutions containing laccase and osmium-complex bound to poly(allylamine), (PAH-Os). The polycation backbone carries the Os redox relay, and the polyanion is the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. Enzyme thin films were characterized by quartz crystal microbalance, ellipsometry, cyclic voltammetry, and oxygen reduction electrocatalysis under variable oxygen partial pressures with a rotating disk electrode. New kinetic evidence relevant to biofuel cells is presented on the detection of traces of H(2)O(2), intermediate in the O(2) reduction, with scanning electrochemical microscopy (SECM). Furthermore the inhibitory effect of peroxide on the biocatalytic current resulted in abnormal current dependence on the O(2) partial pressure and peak shape with hysteresis in the polarization curves under stagnant conditions, which is offset upon stirring with the RDE. The new kinetic evidence reported in the present work is very relevant for the operation of biofuel cells under stagnant conditions of O(2) mass transport. PMID:20698679

  11. Electrochemical properties of yolk-shell structured layered-layered composite cathode powders prepared by spray pyrolysis

    International Nuclear Information System (INIS)

    Graphical abstract: - Abstract: Layered-layered yolk-shell powders with composition 0.6Li(Li1/3Mn2/3)O2· 0.4Li(Ni1/3Co1/3Mn1/3)O2 are prepared by spray pyrolysis. Metal oxides-carbon composite powders are first formed as an intermediate product near the reactor entrance by drying and decomposition of droplets. Combustion, contraction, and recombustion processes of intermediate product produce yolk-shell-structured powders. The yolk-shell structure of the powders prepared directly by spray pyrolysis is maintained even after post-treatment at 800 °C; this treatment temperature yields the best electrochemical performance. The composition of the powders post-treated at 800 °C is Li1.12Ni0.14Co0.14Mn0.59O2. Mean grain sizes of the yolk-shell 0.6Li(Li1/3Mn2/3)O2·0.4Li(Ni1/3Co1/3Mn1/3)O2 powders, post-treated at 700, 750, and 800 °C, measured from high resolution TEM images, are 47, 54, and 79 nm, respectively, and their BET surface areas are 14, 9, and 7 m2 g−1. The initial discharge capacities of the powders, post-treated at the above temperatures, are 188, 280, and 239 mA h g−1, respectively, and their initial Coulombic efficiencies are 87, 80, and 78%. Discharge capacities after 50 cycles of the post-treated powders are 81, 194, and 183 mA h g−1, respectively, and the corresponding capacity retentions are 43, 70, and 77%

  12. Hydrothermal synthesis of highly crystalline RuS{sub 2} nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yanjuan [Key Laboratory of Marine Chemistry Theory and Technology, Minisry of Education Ocean University of China, Qingdao, 266100 (China); College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Li, Nan, E-mail: lin@jlu.edu.cn [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yanagisawa, Kazumichi [Research Laboratory of Hydrothermal Chemistry, Kochi University, Kochi 780-8520 (Japan); Li, Xiaotian [College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Yan, Xiao [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun 130012 (China)

    2015-05-15

    Highlights: • Highly crystalline RuS{sub 2} nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} with average particle size of 14.8 nm. • RuS{sub 2} nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}. - Abstract: Highly crystalline ruthenium sulfide (RuS{sub 2}) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S{sub 2}{sup 2−}. Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS{sub 2} nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS{sub 2} is active towards oxygen reduction reaction. Although the activity of RuS{sub 2} is lower than that of Pt/C, the RuS{sub 2} catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}.

  13. Electronic and optical device applications of hollow cathode plasma assisted atomic layer deposition based GaN thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bolat, Sami, E-mail: bolat@ee.bilkent.edu.tr; Tekcan, Burak [Department of Electrical and Electronics Engineering, Bilkent University, 06800, Ankara, Turkey and UNAM, National Nanotechnology Research Center, Bilkent University, 06800, Ankara (Turkey); Ozgit-Akgun, Cagla; Biyikli, Necmi [UNAM, National Nanotechnology Research Center, Bilkent University, 06800, Ankara, Turkey and Institute of Materials Science and Nanotechnology, Bilkent University, 06800, Ankara (Turkey); Okyay, Ali Kemal, E-mail: aokyay@ee.bilkent.edu.tr [Department of Electrical and Electronics Engineering, Bilkent University, 06800, Ankara (Turkey); UNAM, National Nanotechnology Research Center, Bilkent University, 06800, Ankara (Turkey); Institute of Materials Science and Nanotechnology, Bilkent University, 06800, Ankara (Turkey)

    2015-01-15

    Electronic and optoelectronic devices, namely, thin film transistors (TFTs) and metal–semiconductor–metal (MSM) photodetectors, based on GaN films grown by hollow cathode plasma-assisted atomic layer deposition (PA-ALD) are demonstrated. Resistivity of GaN thin films and metal-GaN contact resistance are investigated as a function of annealing temperature. Effect of the plasma gas and postmetallization annealing on the performances of the TFTs as well as the effect of the annealing on the performance of MSM photodetectors are studied. Dark current to voltage and responsivity behavior of MSM devices are investigated as well. TFTs with the N{sub 2}/H{sub 2} PA-ALD based GaN channels are observed to have improved stability and transfer characteristics with respect to NH{sub 3} PA-ALD based transistors. Dark current of the MSM photodetectors is suppressed strongly after high-temperature annealing in N{sub 2}:H{sub 2} ambient.

  14. Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Cleemann, Lars Nilausen; Xing, Wei; Bjerrum, Niels J.; Li, Qingfeng

    2014-01-01

    Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of unif...

  15. Platinum–boron doped graphene intercalated by carbon black for cathode catalyst in proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    In order to enhance the electrochemical properties, especially durability and cell performance in proton exchange membrane fuel cell, electron deficient boron is doped into graphene, followed by deposition of Pt nanoparticles. Successful synthesis of Pt-boron doped graphene (Pt–B–Gr) by pyrolytic process is confirmed by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and Transmission electron microscopy analyses. Pt–B–Gr is intercalated by different amount of CB (carbon black) based on Pt–B–Gr/CBx (x = 0.0, 0.2, 0.3, 0.4) and applied to cathode in proton exchange membrane fuel cell. The ECSA (electrochemical active surface area) is increased with CB content up to 30 wt.% of Pt–B–Gr from 21.4 to 33.6 m2 g−1 beyond which it is rather slightly decreased to 29.6 m2 g−1. The ADT (accelerated durability test) is conducted where the ECSA is compared at every 400 cycles up to 1200 cycles for durability. The result exhibits that boron doping into graphene significantly enhances the durability. It might be attributed to more tight binding between Pt and B due to the electron transfer from graphene to boron. The cell performance is enhanced and it is attributed to the combined effect of B-doping and intercalation. - Highlights: • Graphene was successfully doped with boron using pyrolytic process. • Pt nanoparticles were deposited onto boron-doped graphene. • Pt-boron doped graphene was intercalated by carbon black to prevent restacking. • Boron doping significantly enhanced the durability. • The combined effect of boron doping and intercalation enhanced the cell performance

  16. Nanoscale study of reactive transport in catalyst layer of proton exchange membrane fuel cells with precious and non-precious catalysts using lattice Boltzmann method

    CERN Document Server

    Chen, Li; Kang, Qinjun; Holby, Edward F; Tao, Wen-Quan

    2014-01-01

    High-resolution porous structures of catalyst layer (CL) with multicomponent in proton exchange membrane fuel cells are reconstructed using a reconstruction method called quartet structure generation set. Characterization analyses of nanoscale structures are implemented including pore size distribution, specific area and phase connectivity. Pore-scale simulation methods based on the lattice Boltzmann method are developed and used to predict the macroscopic transport properties including effective diffusivity and proton conductivity. Nonuniform distributions of ionomer in CL generates more tortuous pathway for reactant transport and greatly reduces the effective diffusivity. Tortuosity of CL is much higher than conventional Bruggeman equation adopted. Knudsen diffusion plays a significant role in oxygen diffusion and significantly reduces the effective diffusivity. Reactive transport inside the CL is also investigated. Although the reactive surface area of non-precious metal catalyst (NPMC) CL is much higher t...

  17. Catalytic Combustion of Low Concentration Methane over Catalysts Prepared from Co/Mg-Mn Layered Double Hydroxides

    OpenAIRE

    Hongfeng Liu; Xingrui Fu; Xiaole Weng; Yue Liu; Haiqiang Wang; Zhongbiao Wu

    2014-01-01

    A series of Co/Mg-Mn mixed oxides were synthesized through thermal decomposition of layered double hydroxides (LDHs) precursors. The resulted catalysts were then subjected for catalytic combustion of methane. Experimental results revealed that the Co4.5Mg1.5Mn2LDO catalyst possessed the best performance with the T90=485°C. After being analyzed via XRD, BET-BJH, SEM, H2-TPR, and XPS techniques, it was observed that the addition of cobalt had significantly improved the redox ability of the cata...

  18. A sodium layered manganese oxides as 3 V cathode materials for secondary lithium batteries

    International Nuclear Information System (INIS)

    The synthesis of a new anhydrous sodium manganese oxide α-Na0.66MnO2.13 obtained via a sol-gel process in organic medium is reported. The partial and limited removal of sodium ions from the layered host lattice (hexagonal symmetry; a = 2.84 A, c = 11.09 A) allows to get a high and stable specific capacity of 180 mAh g-1 at C/20 in the cycling limits 4.3/2 V with a mean working voltage of 3 V without the emergence of a spinel phase. By introducing acetylene black in solution during the sol-gel reaction, a composite material containing 8 wt.% AB has been obtained. The rate capability is shown to be significantly improved leading to an increase of the available specific capacity with for instance 200 and 90 mAh g-1 at C/20 and C rate. This effect is ascribed to a better electronic contact between particles and/or the modification of the oxide surface which makes the intercalation process more homogeneous and more efficient

  19. Theory, Investigation and Stability of Cathode Electrocatalytic Activity

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Dong; Liu, Mingfei; Lai, Samson; Blinn, Kevin; Liu, Meilin

    2012-09-30

    The main objective of this project is to systematically characterize the surface composition, morphology, and electro-catalytic properties of catalysts coated on LSCF, aiming to establish the scientific basis for rational design of high-performance cathodes by combining a porous backbone (such as LSCF) with a thin catalyst coating. The understanding gained will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance. More specifically, the technical objectives include: (1) to characterize the surface composition, morphology, and electro-catalytic properties of catalysts coated on LSCF; (2) to characterize the microscopic details and stability of the LSCF-catalyst (e.g., LSM) interfaces; (3) to establish the scientific basis for rational design of high-performance cathodes by combining a porous backbone (such as LSCF) with a thin catalyst coating; and (4) to demonstrate that the performance and stability of porous LSCF cathodes can be enhanced by the application of a thin-film coating of LSM through a solution infiltration process in small homemade button cells and in commercially available cells of larger dimension. We have successfully developed dense, conformal LSM films with desired structure, composition, morphology, and thickness on the LSCF surfaces by two different infiltration processes: a non-aqueous and a water-based sol-gel process. It is demonstrated that the activity and stability of LSCF cathodes can be improved by the introduction of a thin-film LSM coating through an infiltration process. Surface and interface of the LSM-coated LSCF cathode were systematically characterized using advanced microscopy and spectroscopy techniques. TEM observation suggests that a layer of La and Sr oxide was formed on LSCF surfaces after annealing. With LSM infiltration, in contrast, we no longer observe such La/Sr oxide layer on the LSM-coated LSCF samples after annealing under similar

  20. Atomic layer deposition-Sequential self-limiting surface reactions for advanced catalyst "bottom-up" synthesis

    Science.gov (United States)

    Lu, Junling; Elam, Jeffrey W.; Stair, Peter C.

    2016-06-01

    Catalyst synthesis with precise control over the structure of catalytic active sites at the atomic level is of essential importance for the scientific understanding of reaction mechanisms and for rational design of advanced catalysts with high performance. Such precise control is achievable using atomic layer deposition (ALD). ALD is similar to chemical vapor deposition (CVD), except that the deposition is split into a sequence of two self-limiting surface reactions between gaseous precursor molecules and a substrate. The unique self-limiting feature of ALD allows conformal deposition of catalytic materials on a high surface area catalyst support at the atomic level. The deposited catalytic materials can be precisely constructed on the support by varying the number and type of ALD cycles. As an alternative to the wet-chemistry based conventional methods, ALD provides a cycle-by-cycle "bottom-up" approach for nanostructuring supported catalysts with near atomic precision. In this review, we summarize recent attempts to synthesize supported catalysts with ALD. Nucleation and growth of metals by ALD on oxides and carbon materials for precise synthesis of supported monometallic catalyst are reviewed. The capability of achieving precise control over the particle size of monometallic nanoparticles by ALD is emphasized. The resulting metal catalysts with high dispersions and uniformity often show comparable or remarkably higher activity than those prepared by conventional methods. For supported bimetallic catalyst synthesis, we summarize the strategies for controlling the deposition of the secondary metal selectively on the primary metal nanoparticle but not on the support to exclude monometallic formation. As a review of the surface chemistry and growth behavior of metal ALD on metal surfaces, we demonstrate the ways to precisely tune size, composition and structure of bimetallic metal nanoparticles. The cycle-by-cycle "bottom up" construction of bimetallic (or multiple

  1. Catalytic Combustion of Low Concentration Methane over Catalysts Prepared from Co/Mg-Mn Layered Double Hydroxides

    Directory of Open Access Journals (Sweden)

    Hongfeng Liu

    2014-01-01

    Full Text Available A series of Co/Mg-Mn mixed oxides were synthesized through thermal decomposition of layered double hydroxides (LDHs precursors. The resulted catalysts were then subjected for catalytic combustion of methane. Experimental results revealed that the Co4.5Mg1.5Mn2LDO catalyst possessed the best performance with the T90=485°C. After being analyzed via XRD, BET-BJH, SEM, H2-TPR, and XPS techniques, it was observed that the addition of cobalt had significantly improved the redox ability of the catalysts whilst certain amount of magnesium was essential to guarantee the catalytic activity. The presence of Mg was helpful to enhance the oxygen mobility and, meanwhile, improved the dispersion of Co and Mn oxides, preventing the surface area loss after calcination.

  2. Power Conversion Efficiency and Device Stability Improvement of Inverted Perovskite Solar Cells by Using a ZnO:PFN Composite Cathode Buffer Layer.

    Science.gov (United States)

    Jia, Xiaorui; Zhang, Lianping; Luo, Qun; Lu, Hui; Li, Xueyuan; Xie, Zhongzhi; Yang, Yongzhen; Li, Yan-Qing; Liu, Xuguang; Ma, Chang-Qi

    2016-07-20

    We have demonstrated in this article that both power conversion efficiency (PCE) and performance stability of inverted planar heterojunction perovskite solar cells can be improved by using a ZnO:PFN nanocomposite (PFN: poly[(9,9-bis(3'-(N,N-dimethylamion)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl)-fluorene]) as the cathode buffer layer (CBL). This nanocomposite could form a compact and defect-less CBL film on the perovskite/PC61BM surface (PC61BM: phenyl-C61-butyric acid methyl ester). In addition, the high conductivity of the nanocomposite layer makes it works well at a layer thickness of 150 nm. Both advantages of the composite layer are helpful in reducing interface charge recombination and improving device performance. The power conversion efficiency (PCE) of the best ZnO:PFN CBL based device was measured to be 12.76%, which is higher than that of device without CBL (9.00%), or device with ZnO (7.93%) or PFN (11.30%) as the cathode buffer layer. In addition, the long-term stability is improved by using ZnO:PFN composite cathode buffer layer when compare to that of the reference cells. Almost no degradation of open circuit voltage (VOC) and fill factor (FF) was found for the device having ZnO:PFN, suggesting that ZnO:PFN is able to stabilize the interface property and consequently improve the solar cell performance stability. PMID:27349330

  3. Supported catalysts based on layered double hydroxides for catalytic oxidation and hydrogenation: general functionality and promising application prospects.

    Science.gov (United States)

    Feng, Junting; He, Yufei; Liu, Yanan; Du, Yiyun; Li, Dianqing

    2015-08-01

    Oxidation and hydrogenation catalysis plays a crucial role in the current chemical industry for the production of key chemicals and intermediates. Because of their easy separation and recyclability, supported catalysts are widely used in these two processes. Layered double hydroxides (LDHs) with the advantages of unique structure, composition diversity, high stability, ease of preparation and low cost have shown great potential in the design and synthesis of novel supported catalysts. This review summarizes the recent progress in supported catalysts by using LDHs as supports/precursors for catalytic oxidation and hydrogenation. Particularly, partial hydrogenation of acetylene, hydrogenation of dimethyl terephthalate, methanation, epoxidation of olefins, elimination of NOx and SOx emissions, and selective oxidation of biomass have been chosen as representative reactions in the petrochemical, fine chemicals, environmental protection and clean energy fields to highlight the potential application and the general functionality of LDH-based catalysts in catalytic oxidation and hydrogenation. Finally, we concisely discuss some of the scientific challenges and opportunities of supported catalysts based on LDH materials. PMID:25962432

  4. CO-induced inversion of the layer sequence of a model CoCu catalyst

    Science.gov (United States)

    Collinge, Greg; Xiang, Yizhi; Barbosa, Roland; McEwen, Jean-Sabin; Kruse, Norbert

    2016-06-01

    Experimental X-ray photoelectron spectroscopy (XPS) and theoretical density functional theory (DFT) calculations reveal the electronic and structural properties of CoCu catalysts before and after CO adsorption. DFT calculations show that, prior to CO adsorption, CoCu has a high tendency to self-assemble into a Co@Cu core-shell structure, which is in accordance with previous atom probe tomography (APT) results for CoCu-based systems and the known mutually low miscibility of Co and Cu. We demonstrate that Co and Cu are electronically immiscible using a density of states (DOS) analysis wherein neither metal's electronic structure is greatly perturbed by the other in "mixed" CoCu. However, CO adsorption on Co is in fact weakened in CoCu compared to CO adsorption on pure Co despite being electronically unchanged in the alloy. Differential charge density analysis suggests that this is likely due to a lower electron density made available to Co by Cu. CO adsorption at coverages up to 1.00 ML are then investigated on a Cu/Co(0001) model slab to demonstrate CO-induced segregation effects in CoCu. Accordingly, a large driving force for a Co surface enrichment is found. At high coverages, CO can completely invert the layer sequence of Co and Cu. This result is echoed by XPS evidence, which shows that the surface Co/Cu ratio of CoCu is much larger in the presence of CO than in H2.

  5. Sb implantation for bipolar buried layers using SbF5 in a cold-cathode implantation system

    International Nuclear Information System (INIS)

    Antimony pentafluoride (SbF5) has been successfully used as a source for antimony implantation into silicon substrates. Modifications of a cold-cathode implantation system to accommodate the use of SbF5 are discussed. The dominant antimony current peaks of the ion beam current spectrum were implanted, and identified by Auger analysis. Using a graphical analysis method, other ionic species of the beam spectrum were identified. It was determined that both singly and doubly ionized Sb in isotype forms of mass 121 and 123 amu are formed in concentrations which correlate to the naturally found concentrations of approximately 57% and 43%. Other ionic species were identified as 19F+, 121SbF2+, 123SbF2+, 121SbF2+, 123SbF+, 121SbF+2, and 123SbF2+. Beam current levels of singly ionized 121Sb were found to be approximately 30 μA with no attempt made to maximize the beam current available. SUPREM II simulations were performed to determine approximate dose and energy levels consistent with buried layer profile parameters. Based on these simulations, the 30 μA beam current was found to result in acceptable implantation times of approximately 15 min for dose levels of 3 x 1015 cm-2. Both and silicon wafers were implanted and the annealing and defect nature studied. It was found that the defect nature of and silicon differ significantly in that a residual subsurface dislocation network was observed on silicon wafers. (orig.)

  6. Enhanced brightness of organic light-emitting diodes based on Mg:Ag cathode using alkali metal chlorides as an electron injection layer

    International Nuclear Information System (INIS)

    Different thicknesses of cesium chloride (CsCl) and various alkali metal chlorides were inserted into organic light-emitting diodes (OLEDs) as electron injection layers (EILs). The basic structure of OLED is indium tin oxide (ITO)/N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1.1′-biphenyl-4.4′-diamine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq3)/Mg:Ag/Ag. The electroluminescent (EL) performance curves show that both the brightness and efficiency of the OLEDs can be obviously enhanced by using a thin alkali metal chloride layer as an EIL. The electron injection barrier height between the Alq3 layer and Mg:Ag cathode is reduced by inserting a thin alkali metal chloride as an EIL, which results in enhanced electron injection and electron current. Therefore, a better balance of hole and electron currents at the emissive interface is achieved and consequently the brightness and efficiency of OLEDs are improved. - Highlights: ► Alkaline metal chlorides were used as electron injection layers in organic light-emitting diodes based on Mg:Ag cathode. ► Brightness and efficiency of OLEDs with alkaline metal chlorides as electron injection layers were all greatly enhanced. ► The Improved OLED performance was attributed to the possible interfacial chemical reaction. ► Electron-only devices are fabricated to demonstrate the electron injection enhancement.

  7. Enhanced brightness of organic light-emitting diodes based on Mg:Ag cathode using alkali metal chlorides as an electron injection layer

    Energy Technology Data Exchange (ETDEWEB)

    Zou Ye [Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044 (China); Deng Zhenbo, E-mail: zbdeng@bjtu.edu.cn [Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044 (China); Xu Denghui [Department of Mathematics and Physics, Beijing Technology and Business University, Beijing 100037 (China); Lue Zhaoyue; Yin Yuehong; Du Hailiang; Chen Zheng; Wang Yongsheng [Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044 (China)

    2012-02-15

    Different thicknesses of cesium chloride (CsCl) and various alkali metal chlorides were inserted into organic light-emitting diodes (OLEDs) as electron injection layers (EILs). The basic structure of OLED is indium tin oxide (ITO)/N,N Prime -diphenyl-N,N Prime -bis(1-napthyl-phenyl)-1.1 Prime -biphenyl-4.4 Prime -diamine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq{sub 3})/Mg:Ag/Ag. The electroluminescent (EL) performance curves show that both the brightness and efficiency of the OLEDs can be obviously enhanced by using a thin alkali metal chloride layer as an EIL. The electron injection barrier height between the Alq{sub 3} layer and Mg:Ag cathode is reduced by inserting a thin alkali metal chloride as an EIL, which results in enhanced electron injection and electron current. Therefore, a better balance of hole and electron currents at the emissive interface is achieved and consequently the brightness and efficiency of OLEDs are improved. - Highlights: Black-Right-Pointing-Pointer Alkaline metal chlorides were used as electron injection layers in organic light-emitting diodes based on Mg:Ag cathode. Black-Right-Pointing-Pointer Brightness and efficiency of OLEDs with alkaline metal chlorides as electron injection layers were all greatly enhanced. Black-Right-Pointing-Pointer The Improved OLED performance was attributed to the possible interfacial chemical reaction. Black-Right-Pointing-Pointer Electron-only devices are fabricated to demonstrate the electron injection enhancement.

  8. On the actual cathode mixed potential in direct methanol fuel cells

    Science.gov (United States)

    Zago, M.; Bisello, A.; Baricci, A.; Rabissi, C.; Brightman, E.; Hinds, G.; Casalegno, A.

    2016-09-01

    Methanol crossover is one of the most critical issues hindering commercialization of direct methanol fuel cells since it leads to waste of fuel and significantly affects cathode potential, forming a so-called mixed potential. Unfortunately, due to the sluggish anode kinetics, it is not possible to obtain a reliable estimation of cathode potential by simply measuring the cell voltage. In this work we address this limitation, quantifying the mixed potential by means of innovative open circuit voltage (OCV) tests with a methanol-hydrogen mixture fed to the anode. Over a wide range of operating conditions, the resulting cathode overpotential is between 250 and 430 mV and is strongly influenced by methanol crossover. We show using combined experimental and modelling analysis of cathode impedance that the methanol oxidation at the cathode mainly follows an electrochemical pathway. Finally, reference electrode measurements at both cathode inlet and outlet provide a local measurement of cathode potential, confirming the reliability of the innovative OCV tests and permitting the evaluation of cathode potential up to typical operating current. At 0.25 A cm-2 the operating cathode potential is around 0.85 V and the Ohmic drop through the catalyst layer is almost 50 mV, which is comparable to that in the membrane.

  9. Ruthenium catalyst on carbon nanofiber support layers for use in silicon-based structured microreactors, Part II: Catalytic reduction of bromate contaminants in aqueous phase

    NARCIS (Netherlands)

    Thakur, D.B.; Tiggelaar, R.M.; Weber, Y.; Gardeniers, J.G.E.; Lefferts, L.; Seshan, K.

    2011-01-01

    Catalyst layers were synthesized inside a structured channel of silicon based microreactor and used to remove bromate contaminants in water. It is demonstrated that Ru/CNF based catalyst is active for bromate reduction, resulting in turn over frequencies (TOFs) higher than conventional powdered cata

  10. Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Shuifen; Choi, Sang; Lu, Ning; Roling, Luke T.; Herron, Jeffrey A.; Zhang, Lei; Park, Jinho; Wang, Jinguo; Kim, Moon J.; Xie, Zhaoxiong; Mavrikakis, Manos; Xia, Younan

    2014-06-11

    An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PnL (n = 1-6) core-shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt2-3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.

  11. Development and evaluation of carbon and binder loading in low-cost activated carbon cathodes for air-cathode microbial fuel cells

    KAUST Repository

    Wei, Bin

    2012-01-01

    Activated carbon (AC) air cathodes were constructed using variable amounts of carbon (43-171 mg cm-2) and an inexpensive binder (10 wt% polytetrafluoroethylene, PTFE), and with or without a porous cloth wipe-based diffusion layer (DL) that was sealed with PDMS. The cathodes with the highest AC loading of 171 mg cm-2, and no diffusion layer, produced 1255 ± 75 mW m-2 and did not appreciably vary in performance after 1.5 months of operation. Slightly higher power densities were initially obtained using 100 mg cm-2 of AC (1310 ± 70 mW m-2) and a PDMS/wipe diffusion layer, although the performance of this cathode decreased to 1050 ± 70 mW m-2 after 1.5 months, and 1010 ± 190 mW m-2 after 5 months. AC loadings of 43 mg cm-2 and 100 mg cm-2 did not appreciably affect performance (with diffusion layers). MFCs with the Pt catalyst and Nafion binder initially produced 1295 ± 13 mW m-2, but the performance decreased to 930 ± 50 mW m -2 after 1.5 months, and then to 890 ± 20 mW m-2 after 5 months. Cathode performance was optimized for all cathodes by using the least amount of PTFE binder (10%, in tests using up to 40%). These results provide a method to construct cathodes for MFCs that use only inexpensive AC and a PTFE, while producing power densities similar to those of Pt/C cathodes. The methods used here to make these cathodes will enable further tests on carbon materials in order to optimize and extend the lifetime of AC cathodes in MFCs. © 2012 The Royal Society of Chemistry.

  12. Surface analysis for catalyst layer (PT/PTFE/C) and diffusion layer (PTFE/C) for proton exchange membrane fuel cells systems (PEMFCs)

    International Nuclear Information System (INIS)

    X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) studies have been used to analyze the surface of diffusion layer (PTFE/C) and catalyst layer (Pt/C/PTFE) of electrode. Detail analysis of carbon C1s peak showed that the carbon was of the form of C, C-O, C=O, CF, CF2 and CF3 with CF2 is more dominated on the surface compared to CF and CF3. The oxygen O1s photoelectron peak showed that the oxygen was of the form of C=O and C-O. The platinum was of the form of Pt0 with some Pt oxidized to PtO. The scanning electron microscopy was used to observe the dispersion of Teflon in the diffusion layer, the distribution of platinum in the catalyst layer loaded with 0.38 mg Pt/cm2 and also the cross section of the membrane electrode assembly. The prepared electrode delivers a superior performance compared with the commercial electrode (E-TEK). The difference in performance between the two electrodes is due to the good localization of the platinum particles.

  13. Nano-scale investigations of electric-dipole-layer enhanced field and thermionic emission from high current density cathodes

    Science.gov (United States)

    Vlahos, Vasilios

    Cesium iodide coated graphitic fibers and scandate cathodes are two important electron emission technologies. The coated fibers are utilized as field emitters for high power microwave sources. The scandate cathodes are promising thermionic cathode materials for pulsed power vacuum electron devices. This work attempts to understand the fundamental physical and chemical relationships between the atomic structure of the emitting cathode surfaces and the superior emission characteristics of these cathodes. Ab initio computational modeling in conjunction with experimental investigations was performed on coated fiber cathodes to understand the origin of their very low turn on electric field, which can be reduced by as much as ten-fold compared to uncoated fibers. Copious amounts of cesium and oxygen were found co-localized on the fiber, but no iodine was detected on the surface. Additional ab initio studies confirmed that cesium oxide dimers could lower the work function significantly. Surface cesium oxide dipoles are therefore proposed as the source of the observed reduction in the turn on electric field. It is also proposed that emission may be further enhanced by secondary electrons from cesium oxide during operation. Thermal conditioning of the coated cathode may be a mechanism by which surface cesium iodide is converted into cesium oxide, promoting the depletion of iodine by formation of volatile gas. Ab initio modeling was also utilized to investigate the stability and work functions of scandate structures. The work demonstrated that monolayer barium-scandium-oxygen surface structures on tungsten can dramatically lower the work function of the underlying tungsten substrate from 4.6 eV down to 1.16 eV, by the formation of multiple surface dipoles. On the basis of this work, we conclude that high temperature kinetics force conventional dispenser cathodes (barium-oxygen monolayers on tungsten) to operate in a non-equilibrium compositional steady state with higher than

  14. Improving cycling performance of Li-rich layered cathode materials through combination of Al2O3-based surface modification and stepwise precycling

    Science.gov (United States)

    Kobayashi, Genki; Irii, Yuta; Matsumoto, Futoshi; Ito, Atsushi; Ohsawa, Yasuhiko; Yamamoto, Shinji; Cui, Yitao; Son, Jin-Young; Sato, Yuichi

    2016-01-01

    Controlling a cathode/electrolyte interface by modifying the surface of a cathode material with metal oxides or phosphates is a concept being explored as a possible strategy for improving the electrochemical performance of such materials. This study therefore looks at the crystal structure and chemical bonding state from bulk to surface of Al2O3-coated Li[Li0.2Ni0.18Co0.03Mn0.58]O2 and explores the influence that surface modification has on the electrochemical performance. Investigation by X-ray diffraction, hard X-ray photoelectron spectroscopy (HAXPES) and galvanostatic charge/discharge reaction reveals that the surface-modification layer is composed of Li-Al oxides and Al oxides, with a LiM1-xAlxO2 (M = transition metal) interlayer formed between the modification layer and Li[Li0.2Ni0.18Co0.03Mn0.58]O2 particles. The cycling performance of the Li-rich layered oxide is enhanced by its surface modification with Al2O3, achieving a discharge capacity of more than 310 mA h-1 and excellent cycling stability at 50 °C when combined with a more gradual Li-insertion/de-insertion process (i.e., stepwise precycling treatment).

  15. High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

    International Nuclear Information System (INIS)

    Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH3NH3PbI3−XClX. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than that of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (Jsc). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface

  16. High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaodong; Zhou, Yi, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn; Song, Bo, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn [Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123 (China); Lei, Ming [Department of Chemistry, Zhejiang University, Hangzhou 310027 (China); Li, Yongfang, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn [Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123 (China); Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)

    2015-08-10

    Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH{sub 3}NH{sub 3}PbI{sub 3−X}Cl{sub X}. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than that of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (J{sub sc}). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.

  17. Efficiency improvement of electrospun TiO/sub 2/ nanofibers based double heterojunction organic photovoltaic devices by zno cathode buffer layer

    International Nuclear Information System (INIS)

    Polymer/fullerene solar cells with cathode buffer layer and double heterojunction electrospun metal oxide nanofibers are presented in this study. Electrospun TiO/sub 2/ nanofibers on solution processed ZnO cathode buffer layer (CBL) are synthesized and introduced to inverted organic photovoltaic devices for improving their power conversion efficiency. It is found that a combination of ZnO (CBL) with electrospun TiO/sub 2/ nanofibers covers a large wavelength range for light absorption and reduced device series resistance, which improved current density and fill factor of the devices. The structural and optical properties of the various structure/ layers are investigated by FESEM and UV-Vis spectrophotometer, while the devices were characterized under 1.5G illuminations by solar simulator. The resultant efficient inverted solar cells exhibit an open circuit voltage of 0.62V, short circuit current density of 12.98mA/cm2, fill factor of 0.53 and power conversion efficiency of 4.27+-0.01%. (author)

  18. Design of Efficient Catalysts with Double Transition Metal Atoms on C2N Layer.

    Science.gov (United States)

    Li, Xiyu; Zhong, Wenhui; Cui, Peng; Li, Jun; Jiang, Jun

    2016-05-01

    Heterogeneous catalysis often involves molecular adsorptions to charged catalyst site and reactions triggered by catalyst charges. Here we use first-principles simulations to design oxygen reduction reaction (ORR) catalyst based on double transition metal (TM) atoms stably supported by 2D crystal C2N. It not only holds characters of low cost and high durability but also effectively accumulates surface polarization charges on TMs and later deliveries to adsorbed O2 molecule. The Co-Co, Ni-Ni, and Cu-Cu catalysts exhibit high adsorption energies and extremely low dissociation barriers for O2, as compared with their single-atom counterparts. Co-Co on C2N presents less than half the value of the reaction barrier of bulk Pt catalysts in the ORR rate-determining steps. These catalytic improvements are well explained by the dependences of charge polarization on various systems, which opens up a new strategy for optimizing TM catalytic performance with the least metal atoms on porous low-dimensional materials. PMID:27093364

  19. Platinum Nanoparticles Supported on Exfoliated Layered Double Hydroxides Nanosheet as a Reusable Catalyst for the Reduction of 4-Nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Na, Jungwoon; Moon, Jiwon; Cho, Hye Ran; Hwang, Jiye; Lee, Jong Hyeon [The Catholic Univ. of Korea, Bucheon (Korea, Republic of)

    2013-08-15

    The well-defined spherical Pt NPs have been synthesized on the exfoliated LDH nanosheets by in situ reduction of H{sub 2}PtCl{sub 6} in the formamide. The positively charged LDH nanosheet could effectively provide the formation of Pt NPs on the nanosheet and induce the strong interaction between the LDH layer and the Pt NPs. The Pt NP-LDH nanocomposite exhibited an excellent reusability in the reduction of 4-nitrophenol due to the tightly assembled Pt NPs on the LDH nanosheets during the recycling reactions. The utilization of the double hydroxide nanosheet as a new type of supports for transition metal NPs will dramatically improve the durability in heterogeneous catalysts. Supported transition metal nanoparticles (NPs) have attracted much interest in the field of heterogeneous catalysts, because the nature of supporting materials offers a strong possibility of controlling metal particle size and preventing the aggregation of metal NPs, which can consequently affect the catalytic performance of the supported NPs. Meso-porous silica, graphitic carbons, polymer nanobeads and layered double hydroxides (LDHs) have been potentially used as the supports to immobilize the metal NPs. Recently, two-dimensional nanosheets of exfoliated LDHs have emerged as a new type of supports to immobilize the metal NPs due to the unique two dimensional structure and large reactive surface of the LDH host layers.

  20. Platinum Nanoparticles Supported on Exfoliated Layered Double Hydroxides Nanosheet as a Reusable Catalyst for the Reduction of 4-Nitrophenol

    International Nuclear Information System (INIS)

    The well-defined spherical Pt NPs have been synthesized on the exfoliated LDH nanosheets by in situ reduction of H2PtCl6 in the formamide. The positively charged LDH nanosheet could effectively provide the formation of Pt NPs on the nanosheet and induce the strong interaction between the LDH layer and the Pt NPs. The Pt NP-LDH nanocomposite exhibited an excellent reusability in the reduction of 4-nitrophenol due to the tightly assembled Pt NPs on the LDH nanosheets during the recycling reactions. The utilization of the double hydroxide nanosheet as a new type of supports for transition metal NPs will dramatically improve the durability in heterogeneous catalysts. Supported transition metal nanoparticles (NPs) have attracted much interest in the field of heterogeneous catalysts, because the nature of supporting materials offers a strong possibility of controlling metal particle size and preventing the aggregation of metal NPs, which can consequently affect the catalytic performance of the supported NPs. Meso-porous silica, graphitic carbons, polymer nanobeads and layered double hydroxides (LDHs) have been potentially used as the supports to immobilize the metal NPs. Recently, two-dimensional nanosheets of exfoliated LDHs have emerged as a new type of supports to immobilize the metal NPs due to the unique two dimensional structure and large reactive surface of the LDH host layers

  1. Single-Step Fabrication Using a Phase Inversion Method of Poly(vinylidene fluoride) (PVDF) Activated Carbon Air Cathodes for Microbial Fuel Cells

    KAUST Repository

    Yang, Wulin

    2014-10-14

    Air cathodes used in microbial fuel cells (MFCs) need to have high catalytic activity for oxygen reduction, but they must also be easy to manufacture, inexpensive, and watertight. A simple one-step, phase inversion process was used here to construct an inexpensive MFC cathode using a poly(vinylidene fluoride) (PVDF) binder and an activated carbon catalyst. The phase inversion process enabled cathode preparation at room temperatures, without the need for additional heat treatment, and it produced for the first time a cathode that did not require a separate diffusion layer to prevent water leakage. MFCs using this new type of cathode produced a maximum power density of 1470 ± 50 mW m–2 with acetate as a substrate, and 230 ± 10 mW m–2 with domestic wastewater. These power densities were similar to those obtained using cathodes made using more expensive materials or more complex procedures, such as cathodes with a polytetrafluoroethylene (PTFE) binder and a poly(dimethylsiloxane) (PDMS) diffusion layer, or a Pt catalyst. Even though the PVDF cathodes did not have a diffusion layer, they withstood up to 1.22 ± 0.04 m of water head (∼12 kPa) without leakage, compared to 0.18 ± 0.02 m for cathodes made using PTFE binder and PDMS diffusion layer. The cost of PVDF and activated carbon ($3 m–2) was less than that of the stainless steel mesh current collector ($12 m–2). PVDF-based AC cathodes therefore are inexpensive, have excellent performance in terms of power and water leakage, and they can be easily manufactured using a single phase inversion process at room temperature.

  2. Photooxidation of dibenzothiophene on TiO(2)/hectorite thin films layered catalyst.

    Science.gov (United States)

    Robertson, Jamie; Bandosz, Teresa J

    2006-07-01

    A new titanium(IV) oxide-hectorite nanofilm photocatalyst was prepared on quartz slides. It was evaluated in the photooxidation of dibenzothiophene (DBT) in nonpolar organic solution (tetradecane), as a model for diesel fuel. A removal regimen was developed consisting of catalytic photooxidation followed by adsorption of products on silica gel. Photooxidation of DBT was performed with and without catalyst, at 254 and 300 nm. Comparison was made with a commercially available TiO(2) catalyst, Degussa P25. The catalyst was analyzed by nitrogen adsorption, XRD, SEM, and TGA-DTA. DBT concentrations were measured by HPLC and UV spectrophotometry. Preliminary qualititative analysis of products was performed by UV and HPLC. Results indicated that the outlined process was effective in reducing sulfur levels to below 10 ppm sulfur. PMID:16600276

  3. Reversible lithium intercalation in a lithium-rich layered rocksalt Li2RuO3 cathode through a Li3PO4 solid electrolyte

    Science.gov (United States)

    Zheng, Yueming; Hirayama, Masaaki; Taminato, Sou; Lee, Soyeon; Oshima, Yoshifumi; Takayanagi, Kunio; Suzuki, Kota; Kanno, Ryoji

    2015-12-01

    Li2RuO3 (001) films with a lithium-rich layered rocksalt structure are epitaxially grown on a Al2O3(0001) substrate through pulsed laser deposition, followed by stacking of an amorphous Li3PO4 solid electrolyte. A half solid-state battery with a Li3PO4/Li2RuO3 cathode, liquid electrolyte, and lithium anode exhibits two redox peak pairs at 3.4 and 3.6 V, demonstrating lithium intercalation in the Li2RuO3 through the Li3PO4 solid electrolyte. All-solid-state batteries are fabricated by Li or In metal anode deposition on the Li3PO4/Li2RuO3. The Li/Li3PO4/Li2RuO3 cell delivers an initial discharge capacity of 101 mAh g-1, which does not fade significantly over 30 cycles. Furthermore, the Li2RuO3 rate capability is comparable to that of a liquid-type battery. Lithium-rich layered materials are available for use as cathodes in all-solid-state batteries.

  4. The evolution of catalyst layer morphology and sub-surface growth of CNTs over the hot filament grown Fe-Cr thin films

    International Nuclear Information System (INIS)

    In this study a hot filament chemical vapour deposition (HFCVD) technique was used to prepare Fe-Cr films on Si substrate as catalysts for thermal CVD (TCVD) growing of carbon nanotubes (CNTs) from liquid petroleum gas (LPG) at 800 deg. C. To characterize the catalysts or CNTs, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy were used. The XPS spectra obtained at different stages of Ar+ sputtering revealed that in the depth of catalyst layers, the relative Fe-Cr concentrations are higher than the top-surface. SEM images of samples after TCVD indicate a significant CNT growing at the backside of catalyst layer compared with its top which is accompanied with morphological changes on catalyst layer such as formation of cone-shape structures, rippling, cracking and rolling of the layer. These observations were attributed to the more catalytic activity of the sub-surface beside the poor activity of the top-surface as well as the presence of individual active islands over the surface of the catalyst thin film.

  5. The evolution of catalyst layer morphology and sub-surface growth of CNTs over the hot filament grown Fe-Cr thin films

    Science.gov (United States)

    Pasha, M. Akbarzadeh; Ranjbar, M.; Vesaghi, M. A.; Shafiekhani, A.

    2010-12-01

    In this study a hot filament chemical vapour deposition (HFCVD) technique was used to prepare Fe-Cr films on Si substrate as catalysts for thermal CVD (TCVD) growing of carbon nanotubes (CNTs) from liquid petroleum gas (LPG) at 800 °C. To characterize the catalysts or CNTs, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy were used. The XPS spectra obtained at different stages of Ar + sputtering revealed that in the depth of catalyst layers, the relative Fe-Cr concentrations are higher than the top-surface. SEM images of samples after TCVD indicate a significant CNT growing at the backside of catalyst layer compared with its top which is accompanied with morphological changes on catalyst layer such as formation of cone-shape structures, rippling, cracking and rolling of the layer. These observations were attributed to the more catalytic activity of the sub-surface beside the poor activity of the top-surface as well as the presence of individual active islands over the surface of the catalyst thin film.

  6. Alloy catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...

  7. The platinum catalyst layer in polymer-electrolyte fuel cells[Dissertation 17127]; Die Platinkatalysatorschicht in Polymerelektrolyt-Brennstoffzellen. Beitraege zum Verstaendnis und zur Optimierung

    Energy Technology Data Exchange (ETDEWEB)

    Reiner, A.

    2007-07-01

    This illustrated, comprehensive dissertation by Dr. Andreas Reiner presents an in-depth analysis of polymer electrolyte fuel cells (PEFC) and in particular, their platinum catalyst layer. First of all, the thermodynamics and kinetics involved are reviewed, along with components, their efficiencies and the catalyst layer. The methods used, including scanning electron microscope, x-ray and Rutherford spectroscopy are discussed. The structure and composition of co-sputtered catalyst layers and their production are described. Electro-chemical activation and the electro-chemical properties of the layers are discussed. The second part of the dissertation deals with the principle of hydrogen under-potential deposition. This method provides information about the electrochemically active platinum surface fraction. The results of investigations made are presented and discussed.

  8. Mg-Cu-Al layered double hydroxides based catalysts for the reduction of nitrates in aqueous solutions

    Directory of Open Access Journals (Sweden)

    Vulić Tatjana J.

    2010-01-01

    Full Text Available The secondary waste and bacterial contamination in physico-chemical and biological separation processes used today for nitrate removal from ground water make novel catalytic technologies that convert nitrates to unharmful gaseous nitrogen, very attractive for scientific research. The Mg-Cu-Al layered double hydroxide (LDH based catalysts with different Mg/Al ratio were investigated in water denitrification reaction in the presence of hydrogen and with solely copper as an active phase. Since LDHs have ion exchange properties and their derived mixed oxides possess memory effect (restoration of layered structure after thermal decomposition, their adsorption capacity for nitrates was also measured in the same model system. All studied samples showed nitrate removal from 23% to 62% following the decrease in Al content, as well as the substantial adsorption capacity ranging from 18% to 38%. These results underlie the necessity to take into account the effects of the adsorption in all future investigations.

  9. Co3O4-Pt/graphene as air cathode catalyst for lithium-air battery%四氧化三钴-铂/石墨烯锂空气电池阴极材料

    Institute of Scientific and Technical Information of China (English)

    顾大明; 杨丹丹; 李加展; 王余; 于晨涛

    2015-01-01

    It is reported that the preparation of Co3 O4-Pt/graphene hybrid and its use as air cathode catalyst for enhanced specific capacity in Lithium-air battery. Co3O4-Pt/graphene was synthesized by a two-step method. More specifically, Pt/graphene was prepared by microwave-assisted polyol process, and then it was mixed with Co3 O4 uniformly to get highly efficient Co3O4-Pt/graphene as air-cathode catalyst. Micromorphology, composition and compositional dispersion of the obtained hybrid catalyst were then characterized by X-ray diffraction ( XRD ) , scanning electron microscopy ( SEM ) , X-ray energy dispersive spectroscopy ( XEDS ) , transmission electron microscopy (TEM),Raman Spectroscopy(Ram). Co3O4-Pt/graphene air cathode catalyst was assembled with metal lithium anode, LiPF6/EC-DMC-EMC electrolyte, and PP/PE/PP to construct a lithium-air battery. The constant current charge-discharge tests of the lithium-air battery exhibit enhanced specific capacity: the discharge specific capacity reaches up to 8 000 mAh/g and the voltage is above 2. 6 V, which is superior to alternative cathode catalysts. The enhanced performance of lithium-air battery is attributed to the joint effect of preparation process, composition, and compositional dispersion.%为提高锂空气电池的比容量,采用微波辅助乙二醇还原法将H2 PtCl6 ·6H2 O及氧化石墨还原为Pt/石墨烯,再将其与Co3 O4混合均匀,得到高效Co3 O4-Pt/石墨烯锂空气电池复合阴极材料,作为对比,同时制备了Co3 O4-石墨、Co3 O4-石墨烯等阴极材料,用其与金属锂阳极、LiPF6/EC-DMC-EMC电解液、PP/PE/PP隔膜组装锂空气电池.用X射线衍射( XRD)、扫描电子显微镜( SEM)、透射电子显微镜( TEM)、X射线能量散射能谱( XEDS)、拉曼光谱( Ram)等方法对材料的微观形貌、组成及各组分在材料中的分散程度进行了表征,对电池进行恒流充放电测试,结果显示,Co3 O4-Pt/石墨烯阴极材料的比容量可超过8 000 m

  10. Understanding the interfacial phenomena of a 4.7 V and 55 °C Li-ion battery with Li-rich layered oxide cathode and grap2hite anode and its correlation to high-energy cycling performance

    Science.gov (United States)

    Pham, Hieu Quang; Hwang, Eui-Hyung; Kwon, Young-Gil; Song, Seung-Wan

    2016-08-01

    Research progress of high-energy performance and interfacial phenomena of Li1.13Mn0.463Ni0.203Co0.203O2 cathode and graphite anode in a 55 °C full-cell under an aggressive charge cut-off voltage to 4.7 V (4.75 V vs. Li/Li+) is reported. Although anodic instability of conventional electrolyte is the critical issue on high-voltage and high-temperature cell operation, interfacial phenomena and the solution to performance improvement have not been reported. Surface spectroscopic evidence revealed that structural degradation of both cathode and anode materials, instability of surface film at cathode, and metal-dissolution from cathode and -deposition at anode, and a rise of interfacial resistance with high-voltage cycling in 55 °C conventional electrolyte are resolved by the formation of a stable surface film with organic/inorganic mixtures at cathode and solid electrolyte interphase (SEI) at anode using blended additives of fluorinated linear carbonate and vinylene carbonate. As a result, significantly improved cycling stability of 77% capacity retention delivering 227-174 mAhg-1 after 50 cycles is obtained, corresponding to 819-609 Wh per kg of cathode active material. Interfacial stabilization approach would pave the way of controlling the performance and safety, and widening the practical application of Li-rich layered oxide cathode materials and high-voltage electrolyte materials in various high-energy density Li-ion batteries.

  11. XPS and STEM study of the interface formation between ultra-thin Ru and Ir OER catalyst layers and perylene red support whiskers

    OpenAIRE

    Atanasoska Ljiljana L.; Cullen David A.; Atanasoski Radoslav T.

    2013-01-01

    The interface formation between nano-structured perylene red (PR) whiskers and oxygen evolution reaction (OER) catalysts ruthenium and iridium has been studied systematically by XPS and STEM. The OER catalyst over-layers with thicknesses ranging from ~0.1 to ~50 nm were vapor deposited onto PR ex-situ. STEM images demonstrate that, with increasing thickness, Ru and Ir transform from amorphous clusters to crystalline nanoparticles, which agglomerate with inc...

  12. Improvement of the Cycling Performance and Thermal Stability of Lithium-Ion Cells by Double-Layer Coating of Cathode Materials with Al₂O₃ Nanoparticles and Conductive Polymer.

    Science.gov (United States)

    Lee, Yoon-Sung; Shin, Won-Kyung; Kannan, Aravindaraj G; Koo, Sang Man; Kim, Dong-Won

    2015-07-01

    We demonstrate the effectiveness of dual-layer coating of cathode active materials for improving the cycling performance and thermal stability of lithium-ion cells. Layered nickel-rich LiNi0.6Co0.2Mn0.2O2 cathode material was synthesized and double-layer coated with alumina nanoparticles and poly(3,4-ethylenedioxythiophene)-co-poly(ethylene glycol). The lithium-ion cells assembled with a graphite negative electrode and a double-layer-coated LiNi0.6Co0.2Mn0.2O2 positive electrode exhibited high discharge capacity, good cycling stability, and improved rate capability. The protective double layer formed on the surface of LiNi0.6Co0.2Mn0.2O2 materials effectively inhibited the dissolution of Ni, Co, and Mn metals from cathode active materials and improved thermal stability by suppressing direct contact between electrolyte solution and delithiated Li(1-x)Ni0.6Co0.2Mn0.2O2 materials. This effective design strategy can be adopted to enhance the cycling performance and thermal stability of other layered nickel-rich cathode materials used in lithium-ion batteries. PMID:26083766

  13. Vacuum ultra-violet emission of plasma discharges with high Xe partial pressure using a cathode protective layer with high secondary electron emission

    International Nuclear Information System (INIS)

    In this work, the mechanism of the vacuum ultra-violet (VUV) emission of plasma discharges, with high Xe partial pressure and high ion-induced secondary electrons emission protective layer, is studied by measuring the VUV light emission directly and comparing it with two-dimensional simulations. From the panel measurement, we find that the high intensity of excimer VUV mainly contributes to the high luminous efficacy of SrCaO-plasma display panels (PDP) at a low sustain voltage. The unchanged Xe excitation efficiency indicates that the electron temperature is not decreased by the high secondary electrons emission protective layer, even though the sustain voltage is much lower. From the two-dimensional simulations, we can find that the ratio of excimer VUV to resonant VUV, which is determined by the collision rate in the discharge, is only significantly affected by the Xe partial pressure, while it is independent of the sustain voltage and the secondary-electrons-emission capability of protective layer. The unchanged average electron energy at the moment when the electric field becomes maximum confirms that the improvement of the VUV production efficiency mainly is attributed to the increase in electron heating efficiency of a PDP with high ion-induced secondary electrons emission protective layer. Combining the experimental and the simulation results, we conclude about the mechanism by which the VUV production is improved for the plasma display panel with a high Xe partial pressure and a cold cathode with high ion-induced secondary electrons emission

  14. Cobalt based layered perovskites as cathode material for intermediate temperature Solid Oxide Fuel Cells: A brief review

    Science.gov (United States)

    Pelosato, Renato; Cordaro, Giulio; Stucchi, Davide; Cristiani, Cinzia; Dotelli, Giovanni

    2015-12-01

    Nowadays, the cathode is the most studied component in Intermediate Temperature-Solid Oxide Fuel Cells (IT-SOFCs). Decreasing SOFCs operating temperature implies slow oxygen reduction kinetics and large polarization losses. Double perovskites with general formula REBaCo2O5+δ are promising mixed ionic-electronic conductors, offering a remarkable enhancement of the oxygen diffusivity and surface exchange respect to disordered perovskites. In this review, more than 250 compositions investigated in the literature were analyzed. The evaluation was performed in terms of electrical conductivity, Area Specific Resistance (ASR), chemical compatibility with electrolytes and Thermal Expansion Coefficient (TEC). The most promising materials have been identified as those bearing the mid-sized rare earths (Pr, Nd, Sm, Gd). Doping strategies have been analyzed: Sr doping on A site promotes higher electrical conductivity, but worsen ASR and TECs; B-site doping (Fe, Ni, Mn) helps lowering TECs, but is detrimental for the electrochemical properties. A promising boost of the electrochemical activity is obtained by simply introducing a slight Ba under-stoichiometry. Still, the high sensitivity of the electrochemical properties against slight changes in the stoichiometry hamper a conclusive comparison of all the investigated compounds. Opportunities for an improvement of double perovskite cathodes performance is tentatively foreseen in combining together the diverse effective doping strategies.

  15. Mitigated phase transition during first cycle of a Li-rich layered cathode studied by in operando synchrotron X-ray powder diffraction.

    Science.gov (United States)

    Song, Bohang; Day, Sarah J; Sui, Tan; Lu, Li; Tang, Chiu C; Korsunsky, Alexander M

    2016-02-14

    In operando synchrotron X-ray powder diffraction (SXPD) studies were conducted to investigate the phase transition of Li-rich Li(Li0.2Ni0.13Mn0.54Co0.13)O2 and Cr-doped Li(Li0.2Ni0.13Mn0.54Co0.03Cr0.10)O2 cathodes during the first charge/discharge cycle. Crystallographic (lattice parameters) and mechanical (domain size and microstrain) information was collected from SXPD full pattern refinement. It was found that Cr substitution at Co-site benefits in suppressing the activation of Li2MnO3 domains upon 1st charge, and thus mitigates the phase transition. As a consequence, Cr-doped layered cathode holds a better reversibility in terms of a full recovery of both lattice parameters and nano-domain size after a whole charge/discharge cycle. The effects of different cycling rates on the structural change were also discussed. PMID:26799191

  16. The positive roles of integrated layered-spinel structures combined with nanocoating in low-cost Li-rich cathode Li[Li₀.₂Fe₀.₁Ni₀.₁₅Mn₀.₅₅]O₂ for lithium-ion batteries.

    Science.gov (United States)

    Zhao, Taolin; Chen, Shi; Chen, Renjie; Li, Li; Zhang, Xiaoxiao; Xie, Man; Wu, Feng

    2014-12-10

    As the most promising cathodes of lithium-ion batteries, lithium-rich manganese-based layered oxides with high capacity suffer from poor cycle stability, poor rate capability, and fast voltage fading. Here we introduced AlF3 into the surface of layered lithium-rich cathode (Li[Li0.2Fe0.1Ni0.15Mn0.55]O2) as an artificial protective layer as well as an inducer of integrated layered-spinel structures to achieve both low cost and high capacity. The reduced irreversible capacity loss, improved cycling stability, and superior high-rate capability were ascribed to the combination of AlF3 nanocoating and the unique structures as well as the low charge transfer resistance. Besides, the intractable issue, fast voltage fading of the layered lithium-rich cathode was also alleviated. Such materials with both low cost and high capacity are considered to be promising candidate cathodes to achieve lithium-ion batteries with high energy and high power. PMID:25402183

  17. Single-Step Electrophoretic Deposition of Non-noble Metal Catalyst Layer with Low Onset Voltage for Ethanol Electro-oxidation.

    Science.gov (United States)

    Ahmadi Daryakenari, Ahmad; Hosseini, Davood; Ho, Ya-Lun; Saito, Takumi; Apostoluk, Aleksandra; Müller, Christoph R; Delaunay, Jean-Jacques

    2016-06-29

    A single-step electrophoretic deposition (EPD) process is used to fabricate catalyst layers which consist of nickel oxide nanoparticles attached on the surface of nanographitic flakes. Magnesium ions present in the colloid charge positively the flake's surface as they attach on it and are also used to bind nanographitic flakes together. The fabricated catalyst layers showed a very low onset voltage (-0.2 V vs Ag/AgCl) in the electro-oxidation of ethanol. To clarify the occurring catalytic mechanism, we performed annealing treatment to produce samples having a different electrochemical behavior with a large onset voltage. Temperature dependence measurements of the layer conductivity pointed toward a charge transport mechanism based on hopping for the nonannealed layers, while the drift transport is observed in the annealed layers. The hopping charge transport is responsible for the appearance of the low onset voltage in ethanol electro-oxidation. PMID:27295080

  18. Substrate temperature influence on the properties of GaN thin films grown by hollow-cathode plasma-assisted atomic layer deposition

    International Nuclear Information System (INIS)

    Gallium nitride films were grown by hollow cathode plasma-assisted atomic layer deposition using triethylgallium and N2/H2 plasma. An optimized recipe for GaN film was developed, and the effect of substrate temperature was studied in both self-limiting growth window and thermal decomposition-limited growth region. With increased substrate temperature, film crystallinity improved, and the optical band edge decreased from 3.60 to 3.52 eV. The refractive index and reflectivity in Reststrahlen band increased with the substrate temperature. Compressive strain is observed for both samples, and the surface roughness is observed to increase with the substrate temperature. Despite these temperature dependent material properties, the chemical composition, E1(TO), phonon position, and crystalline phases present in the GaN film were relatively independent from growth temperature

  19. Substrate temperature influence on the properties of GaN thin films grown by hollow-cathode plasma-assisted atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Alevli, Mustafa, E-mail: mustafaalevli@marmara.edu.tr; Gungor, Neşe [Department of Physics, Faculty of Arts and Sciences, Marmara University, Goztepe, 34722 Istanbul (Turkey); Haider, Ali; Kizir, Seda; Leghari, Shahid A.; Biyikli, Necmi, E-mail: biyikli@unam.bilkent.edu.tr [Institute of Materials Science and Nanotechnology, Bilkent University, Bilkent, 06800 Ankara, Turkey and National Nanotechnology Research Center (UNAM), Bilkent University, Bilkent, 06800 Ankara (Turkey)

    2016-01-15

    Gallium nitride films were grown by hollow cathode plasma-assisted atomic layer deposition using triethylgallium and N{sub 2}/H{sub 2} plasma. An optimized recipe for GaN film was developed, and the effect of substrate temperature was studied in both self-limiting growth window and thermal decomposition-limited growth region. With increased substrate temperature, film crystallinity improved, and the optical band edge decreased from 3.60 to 3.52 eV. The refractive index and reflectivity in Reststrahlen band increased with the substrate temperature. Compressive strain is observed for both samples, and the surface roughness is observed to increase with the substrate temperature. Despite these temperature dependent material properties, the chemical composition, E{sub 1}(TO), phonon position, and crystalline phases present in the GaN film were relatively independent from growth temperature.

  20. Nickel-Doped La0.8Sr0.2Mn1-xNixO3 Nanoparticles Containing Abundant Oxygen Vacancies as an Optimized Bifunctional Catalyst for Oxygen Cathode in Rechargeable Lithium-Air Batteries.

    Science.gov (United States)

    Wang, Zhaodong; You, Ya; Yuan, Jing; Yin, Ya-Xia; Li, Yu-Tao; Xin, Sen; Zhang, Dawei

    2016-03-16

    In this work, Ni-doped manganite perovskite oxides (La0.8Sr0.2Mn1-xNixO3, x = 0.2 and 0.4) and undoped La0.8Sr0.2MnO3 were synthesized via a general and facile sol-gel route and used as bifunctional catalysts for oxygen cathode in rechargeable lithium-air batteries. The structural and compositional characterization results showed that the obtained La0.8Sr0.2Mn1-xNixO3 (x = 0.2 and 0.4) contained more oxygen vacancies than did the undoped La0.8Sr0.2MnO3 as well as a certain amount of Ni(3+) (eg = 1) on their surface. The Ni-doped La0.8Sr0.2Mn1-xNixO3 (x = 0.2 and 0.4) was provided with higher bifunctional catalytic activities than that of the undoped La0.8Sr0.2MnO3. In particular, the La0.8Sr0.2Mn0.6Ni0.4O3 had a lower total over potential between the oxygen evolution reaction and the oxygen reduction reaction than that of the La0.8Sr0.2MnO3, and the value is even comparable to that of the commercial Pt/C yet is provided with a much reduced cost. In the lithium-air battery, oxygen cathodes containing the La0.8Sr0.2Mn0.6Ni0.4O3 catalyst delivered the optimized electrochemical performance in terms of specific capacity and cycle life, and a reasonable reaction mechanism was given to explain the improved performance. PMID:26900959

  1. Catalyst-free growth of ZnO nanowires on ITO seed layer/glass by thermal evaporation method: Effects of ITO seed layer laser annealing temperature

    Science.gov (United States)

    Alsultany, Forat H.; Hassan, Z.; Ahmed, Naser M.

    2016-04-01

    Novel catalyst-free growth of ZnO nanowires (ZnO-NWs) on ITO seeds/glass substrate by thermal evaporation method, and effects of continuous wave CO2 laser thermal annealed seed layer on the morphology and properties of ZnO-NWs growth were investigated. The effects of sputtered ITO seed layer laser annealing temperature on the morphological, structural, and optical properties of ZnO-NWs was systematically investigated at temperatures 250, 350, and 450 °C, respectively. The surface morphology and structure of the seeds and the products of ZnO-NWs were characterized in detail by using field emission scanning electron microscopy, atomic force microscopy, and X-ray diffraction. Optical properties were further examined through photoluminescence, and UV-Vis spectrophotometer. A growth mechanism was proposed on the basis of obtained results. The results showed that the nanowires were strongly dependent on the seed layer annealing temperatures, which played an important role in nucleation and dissimilar growth of the nanowires with varying sizes and geometric shapes.

  2. A non-noble material cathode catalyst dual-doped with sulfur and nitrogen as efficient electrocatalysts for oxygen reduction reaction

    International Nuclear Information System (INIS)

    The behavior of Fe-based dual-doped non-noble metal electrocatalyst (Fe-N/C-TsOH) pyrolyzed at different condition and the repercussion for the oxygen reduction reaction (ORR) has been studied. Cyclic voltammetry (CV) and rotating disk electrode (RDE) with Tafel theory as well as Koutecky-Levich were used to quantitatively obtain the oxygen reduction reaction (ORR) kinetic constants and the reaction mechanisms. The pyrolyzed catalysts showed significantly improved ORR activity as well as different ORR mechanism, indicating that heat-treatment is a necessary step for improving catalyst activity. In addition, the optimal heat-treatment temperature was found to be 600 °C, and the overall ORR electron transfer numbers were found to be about 3.899, suggesting that the ORR catalyzed by Fe-N/C-TsOH-600 is a 4-electron transfer process from O2 to H2O. Furthermore, the catalysts also have been subjected to chemical treatments in 0.5 mol·L−1 H2SO4 to remove impurities and reheating was emplyed to optimize the electrocatalytic activity of the catalyst towards the ORR in alkaline medium. And the activity of the catalyst for the ORR increases obviously after H2SO4 leaching and reheating. This effect account to the removal of impurities and purify the active sites as well as the factor that increase the amount of smaller pores which can provide a large surface area and expose more ORR-relevant active sites. In order to understand the heat-treatmen effect on catalyst, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) are employed to detect surface structure changes. The results revealed a fact that the temperature of thermal treatment has a direct influence on crystal structure and compositions of the catalysts

  3. Ternary NiFeMn layered double hydroxides as highly-efficient oxygen evolution catalysts.

    Science.gov (United States)

    Lu, Zhiyi; Qian, Li; Tian, Yang; Li, Yaping; Sun, Xiaoming; Duan, Xue

    2016-01-18

    Layered double hydroxides (LDHs) are a family of layer materials that receive heightened attention. Herein a ternary NiFeMn-LDH is investigated with superior oxygen evolution activity, which is attributed to the Mn(4+) doping in the intralayer, which modifies the electronic structure and improves the conductivity of the electrocatalyst. PMID:26579843

  4. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries.

    Science.gov (United States)

    Mohanty, Debasish; Dahlberg, Kevin; King, David M; David, Lamuel A; Sefat, Athena S; Wood, David L; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; Albano, Fabio

    2016-01-01

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/-1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs. PMID:27226071

  5. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries

    Science.gov (United States)

    Mohanty, Debasish; Dahlberg, Kevin; King, David M.; David, Lamuel A.; Sefat, Athena S.; Wood, David L.; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; Albano, Fabio

    2016-05-01

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/‑1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs.

  6. Titanium oxide:fullerene composite films as electron collector layer in organic solar cells and the use of an easy-deposition cathode

    Science.gov (United States)

    Pérez-Gutiérrez, Enrique; Maldonado, José-Luis; Nolasco, Jairo; Ramos-Ortíz, Gabriel; Rodríguez, Mario; Torre, Ulises Mendoza-De la; Meneses-Nava, Marco-Antonio; Barbosa-García, Oracio; García-Ortega, Héctor; Farfán, Norberto; Granados, Giovana; Santillan, Rosa; Juaristi, Eusebio

    2014-06-01

    Here is reported the use of a titanium oxide:fullerene (TiOx:PC71BM) composite film as electron collector layer in organic photovoltaic devices (OPV cells). OPV cells were fabricated under the bulk heterojunction architecture: the active layer was a blend of either the photoconductor polymer MEH-PPV or P3HT with the fullerene derivative PC71BM. As cathode the eutectic alloy of Bi, In and Sn, known as Field’s metal, was used. The melting point of this alloy is above 62 °C, which makes it suitable for a vacuum-free deposition process and easy and fast device test. Cell fabrication and testing were carried out at normal room conditions. For OPV cells based on MEH-PPV, the composite thin electron collector layer improved the power conversion efficiency (η) from 1.12% to 2.07%, thus the η increase was about 85%. Meanwhile, for devices based on P3HT the use of the composite film improved the photocurrent in almost 1 mA/cm2 and the efficiency slightly increase from 2.48% to 2.68%.

  7. Improvement in the Lifetime of Planar Organic Photovoltaic Cells through the Introduction of MoO3 into Their Cathode Buffer Layers

    Directory of Open Access Journals (Sweden)

    Linda Cattin

    2014-03-01

    Full Text Available Recently, MoO3, which is typically used as an anode buffer layer in organic photovoltaic cells (OPVCs, has also been used as a cathode buffer layer (CBL. Here, we check its efficiency as a CBL using a planar heterojunction based on the CuPc/C60 couple. The CBL is a bi-layer tris-(8-hydroxyquinoline aluminum (Alq3/MoO3. We show that the OPVC with MoO3 in its CBL almost immediately exhibits lower efficiency than those using Alq3 alone. Nevertheless, the OPVCs increase their efficiency during the first five to six days of air exposure. We explain this evolution of the efficiency of the OPVCs over time through the variation in the MoO3 work function due to air contamination. By comparison to a classical OPVC using a CBL containing only Alq3, if it is found that the initial efficiency of the latter is higher, this result is no longer the same after one week of exposure to ambient air. Indeed, this result is due to the fact that the lifetime of the cells is significantly increased by the presence of MoO3 in the CBL.

  8. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries

    Science.gov (United States)

    Mohanty, Debasish; Dahlberg, Kevin; King, David M.; David, Lamuel A.; Sefat, Athena S.; Wood, David L.; Daniel, Claus; Dhar, Subhash; Mahajan, Vishal; Lee, Myongjai; Albano, Fabio

    2016-01-01

    The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/−1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs. PMID:27226071

  9. Catalytic synthesis of nitrogen-doped multi-walled carbon nanotubes using layered double hydroxides as catalyst precursors

    Indian Academy of Sciences (India)

    Yong Cao; Yun Zhao; Qingxia Li; Qingze Jiao

    2009-03-01

    The nitrogen (N)-doped carbon (CN) nanotubes were synthesized by pyrolysis of ethylenediamine with Ni1.07Mg1.01AlO3.58, Ni1.99Mg0.29AlO3.78, and Ni2.31Mg0.08AlO3.89 mixed oxides as catalysts at 650°C. Those mixed oxides were obtained by calcination of corresponding layered double hydroxide precursors (LDHs). Structure and composition of LDHs and mixed oxides were characterized by X-ray diffraction (XRD) and Inductively coupled plasma spectrum. X-ray photoelectron spectroscopy and transmission electron microscope were used to characterize the N content, proportion of pyridine-like N structure and morphology of CN nanotubes. The results showed that the tubes grown with Ni2.31Mg0.08AlO3.89 as catalysts had more obvious bamboo-like structure, larger diameter than those grown with Ni1.07Mg1.01AlO3.58 and Ni1.99Mg0.29AlO3.78. The N content and proportion of graphitic-like N structures increased with the content of Ni2+ increasing in LDH precursors. The morphology, N content and pyridine-like N structures for CN nanotubes can be controlled to a certain extent by varying the content of Ni2+ in LDH precursors.

  10. CVD synthesis of carbon nanotubes using a finely dispersed cobalt catalyst and their use in double layer electrochemical capacitors

    International Nuclear Information System (INIS)

    Carbon nanotubes (CNT) were obtained by chemical vapour deposition (CVD), decomposing turpentine oil over finely dispersed Co metal as a catalyst at 675 deg. C. Scanning electron microscope (SEM) and transmission electron microscope (TEM) images reveal that the nanotubes are densely packed and of 10-50 nm in diameter. The XRD pattern of purified CNT shows that they are graphitic in nature. Resistivity measurements of these CNT indicate that they are highly conducting. Hall measurements of CNT reveal that electrons are the majority carriers with a carrier concentration of 1.35x1020 cm-3. Cyclic voltammetry (CV) and constant current charging/discharging was used to characterise the behaviour of electrochemical double layer capacitors of purified CNT with H2SO4. For CNT/2 M H2SO4/CNT, a capacitance of 12 F g-1 (based on the weight of the active material) was obtained

  11. Properties of the hydrogen oxidation reaction on Pt/C catalysts at optimised high mass transport conditions and its relevance to the anode reaction in PEFCs and cathode reactions in electrolysers

    International Nuclear Information System (INIS)

    Using a high mass transport floating electrode technique with an ultra-low catalyst loading (0.84–3.5 μgPt cm−2) of commonly used Pt/C catalyst (HiSPEC 9100, Johnson Matthey), features in the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) were resolved and defined, which have rarely been previously observed. These features include fine structure in the hydrogen adsorption region between 0.18 < V vs. RHE < 0.36 V vs. RHE consisting of two peaks, an asymptotic decrease at potentials greater than 0.36 V vs. RHE, and a hysteresis above 0.1 V vs. RHE which corresponded to a decrease in the cathodic scan current by up to 50% of the anodic scan. These features are examined as a function of hydrogen and proton concentration, anion type and concentration, potential scan limit, and temperature. We provide an analytical solution to the Heyrovsky–Volmer equation and use it to analyse our results. Using this model we are able to extract catalytic properties (without mass transport corrections; a possible source of error) by simultaneously fitting the model to HOR curves in a variety of conditions including temperature, hydrogen partial pressure and anion/H+ concentration. Using our model we are able to rationalise the pH and hydrogen concentration dependence of the hydrogen reaction. This model may be useful in application to fuel cell and electrolyser simulation studies

  12. Modular polyoxometalate-layered double hydroxide composites as efficient oxidative catalysts

    OpenAIRE

    Chen, Yang; Yao, Zhixiao; Miras, Haralampos N.; Song, Yu-Fei

    2015-01-01

    The exploitation of intercalation techniques in the field of two-dimensional layered materials offers unique opportunities for controlling chemical reactions in confined spaces and developing nanocomposites with desired functionality. In this paper, we demonstrate the exploitation of the novel and facile ‘one-pot’ anion-exchange method for the functionalization of layered double hydroxides (LDHs). As a proof of concept, we demonstrate the intercalation of a series of polyoxometalate (POM) clu...

  13. Enhanced high voltage performances of layered lithium nickel cobalt manganese oxide cathode by using trimethylboroxine as electrolyte additive

    International Nuclear Information System (INIS)

    Highlights: • Addition of 3% TMB improves the cyclic and rate performances of LNCM under high voltage. • TMB oxidizes previously to the carbonate base electrolyte and generates a protective film. • Electrolyte oxidation and LNCM dissolution under high voltage are effective suppressed. - Abstract: In this work, trimethylboroxine is used as electrolyte additive to improve the electrode/electrolyte interface stability of LiNi1/3Co1/3Mn1/3O2 (LNCM) cathode for high voltage lithium ion battery. Charge/discharge tests show that addition of 3% TMB is the optimal amount for LNCM. After 300 cycled at 1C rate under the cut-off charge voltage of 4.5 V, the LNCM with 3% TMB achieves a capacity retention of 99%, compared to the 40% of that using STD electrolyte (1 M LiPF6 in ethylene carbonate/diethyl carbonate /dimethyl carbonate). The results from LSV, EIS and physical characterizations, including SEM, TEM, XPS and ICP–MS, demonstrate that TMB oxidizes preferentially to the STD electrolyte, and catalyzes the decomposition of base electrolyte subsequently, generating a thin and low impedance film on the LNCM surface, which effectively stabilizes the electrode/electrolyte interface by suppressing the continuous oxidation of STD electrolyte and the dissolution of LNCM, and hence, improves the cyclic and rate performances of LNCM under high voltage

  14. Identification of liquid water constraints in micro polymer electrolyte fuel cells without gas diffusion layers

    International Nuclear Information System (INIS)

    A simplified, miniaturized polymer electrolyte fuel cell without gas diffusion layers was investigated under operation by neutron radiography. By visualizing liquid water, it was possible to identify limiting effects, which are directly related to the simplified construction principle. Depending on the operation conditions, undesired water accumulation either in particular micro-channels or on the cathode catalyst layer as well as drying of the anode catalyst layer was observed. As a consequence, the design of a fuel cell without gas diffusion layers must take into account these limitations visualized by neutron radiography.

  15. Improved Cathode Structure for a Direct Methanol Fuel Cell

    Science.gov (United States)

    Valdez, Thomas; Narayanan, Sekharipuram

    2005-01-01

    An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been

  16. A study of thermally activated Mg–Fe layered double hydroxides as potential environmental catalysts

    OpenAIRE

    MILICA S. HADNAĐEV-KOSTIĆ; TATJANA J. VULIĆ; RADMILA P. MARINKOVIĆ-NEDUČIN

    2010-01-01

    Layered double hydroxides (LDHs) and mixed oxides derived after thermal decomposition of LDHs with different Mg–Fe contents were investigated. These materials were chosen because of the possibility to tailor their various properties, such as ion-exchange capability, redox and acid–base and surface area. Layered double hydroxides, [Mg1-xFex(OH)2](CO3)x/2×mH2O (where x presents the content of trivalent ions, x = M(III)/(M(II) + M(III)) were synthesized using the low supersaturation precipitatio...

  17. Cathode encapsulation of organic light emitting diodes by atomic layer deposited Al2O3 films and Al2O3/a-SiNx:H stacks

    International Nuclear Information System (INIS)

    Al2O3 thin films synthesized by plasma-enhanced atomic layer deposition (ALD) at room temperature (25 deg. C) have been tested as water vapor permeation barriers for organic light emitting diode devices. Silicon nitride films (a-SiNx:H) deposited by plasma-enhanced chemical vapor deposition served as reference and were used to develop Al2O3/a-SiNx:H stacks. On the basis of Ca test measurements, a very low intrinsic water vapor transmission rate of ≤ 2 x 10-6 g m-2 day-1 and 4 x 10-6 g m-2 day-1 (20 deg. C/50% relative humidity) were found for 20-40 nm Al2O3 and 300 nm a-SiNx:H films, respectively. The cathode particle coverage was a factor of 4 better for the Al2O3 films compared to the a-SiNx:H films and an average of 0.12 defects per cm2 was obtained for a stack consisting of three barrier layers (Al2O3/a-SiNx:H/Al2O3).

  18. Interfacial chemical reaction and multiple gap state formation on three layer cathode in organic light-emitting diode: Ca/BaF{sub 2}/Alq{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Tae Gun; Kim, Jeong Won, E-mail: jeongwonk@kriss.re.kr [Korea Research Institute of Standards and Science (KRISS), 267 Gajeong-ro, Daejeon 305-340 (Korea, Republic of); Korea University of Science and Technology (UST), 206 Gajeong-ro, Daejeon 305-350 (Korea, Republic of); Lee, Hyunbok [Department of Physics, Kangwon National University, 1 Gangwondaehak-gil, Chuncheon-si, Gangwon-do 200-701 (Korea, Republic of); Yi, Yeonjin [Institute of Physics and Applied Physics, Yonsei University, 50 Yonsei-ro, Seodaemoon-Gu, Seoul 120-749 (Korea, Republic of); Lee, Seung Mi [Korea Research Institute of Standards and Science (KRISS), 267 Gajeong-ro, Daejeon 305-340 (Korea, Republic of)

    2015-07-14

    A three layer cathode is a promising stack structure for long lifetime and high efficiency in organic light-emitting diodes. The interfacial chemical reactions and their effects on electronic structures for alkaline-earth metal (Ca, Ba)/Alq{sub 3} [tris(8-hydroxyquinolinato)aluminum] and Ca/BaF{sub 2}/Alq{sub 3} are investigated using in-situ X-ray and ultraviolet photoelectron spectroscopy, as well as molecular model calculation. The BaF{sub 2} interlayer initially prevents direct contact between Alq{sub 3} and the reactive Ca metal, but it is dissociated into Ba and CaF{sub 2} by the addition of Ca. As the Ca thickness increases, the Ca penetrates the interlayer to directly participate in the reaction with the underlying Alq{sub 3}. This series of chemical reactions takes place irrespective of the BaF{sub 2} buffer layer thickness as long as the Ca overlayer thickness is sufficient. The interface reaction between the alkaline-earth metal and Alq{sub 3} generates two energetically separated gap states in a sequential manner. This phenomenon is explained by step-by-step charge transfer from the alkaline-earth metal to the lowest unoccupied molecular orbital states of Alq{sub 3}, forming new occupied states below the Fermi level.

  19. Interfacial chemical reaction and multiple gap state formation on three layer cathode in organic light-emitting diode: Ca/BaF2/Alq3

    International Nuclear Information System (INIS)

    A three layer cathode is a promising stack structure for long lifetime and high efficiency in organic light-emitting diodes. The interfacial chemical reactions and their effects on electronic structures for alkaline-earth metal (Ca, Ba)/Alq3 [tris(8-hydroxyquinolinato)aluminum] and Ca/BaF2/Alq3 are investigated using in-situ X-ray and ultraviolet photoelectron spectroscopy, as well as molecular model calculation. The BaF2 interlayer initially prevents direct contact between Alq3 and the reactive Ca metal, but it is dissociated into Ba and CaF2 by the addition of Ca. As the Ca thickness increases, the Ca penetrates the interlayer to directly participate in the reaction with the underlying Alq3. This series of chemical reactions takes place irrespective of the BaF2 buffer layer thickness as long as the Ca overlayer thickness is sufficient. The interface reaction between the alkaline-earth metal and Alq3 generates two energetically separated gap states in a sequential manner. This phenomenon is explained by step-by-step charge transfer from the alkaline-earth metal to the lowest unoccupied molecular orbital states of Alq3, forming new occupied states below the Fermi level

  20. Growth of cerium oxide thin layers for the manufacture of dosemeters and/or irradiation detectors by magnetron RF cathodic sputtering

    International Nuclear Information System (INIS)

    Oxide thin films deposited on silicon substrate are interesting for the manufacture of dosemeters and detectors of gas, humidity, temperature and irradiation. The irradiation dose measurement is required for assessing the risks and advantages of the use of ionizing radiations in fields such as biology, medicine and more generally in all the civil and military nuclear applications. According to literature, cerium oxide seems to be potentially interesting for the manufacture of dosemeters and/or irradiation detectors. The influence of the deposition parameters, such as the inter-electrodes distance, the temperature, the RF power, the work pressure, on the crystalline quality of the CeO2 layers deposited on a silicon (111) substrate by magnetron RF cathodic sputtering has been studied. All these thin films have been characterized by X-ray diffraction and by Raman spectroscopy. At the present time, studies are carried out on 'flash' annealing in order to improve the crystalline state of the thin layers. The aim is to study the influence of gamma and neutrons irradiations on the electric properties of capacities made of CeO2 thin films. (O.M.)

  1. Electrical conduction and dielectric relaxation properties of AlN thin films grown by hollow-cathode plasma-assisted atomic layer deposition

    Science.gov (United States)

    Altuntas, Halit; Bayrak, Turkan; Kizir, Seda; Haider, Ali; Biyikli, Necmi

    2016-07-01

    In this study, aluminum nitride (AlN) thin films were deposited at 200 °C, on p-type silicon substrates utilizing a capacitively coupled hollow-cathode plasma source integrated atomic layer deposition (ALD) reactor. The structural properties of AlN were characterized by grazing incidence x-ray diffraction, by which we confirmed the hexagonal wurtzite single-phase crystalline structure. The films exhibited an optical band edge around ∼5.7 eV. The refractive index and extinction coefficient of the AlN films were measured via a spectroscopic ellipsometer. In addition, to investigate the electrical conduction mechanisms and dielectric properties, Al/AlN/p-Si metal-insulator-semiconductor capacitor structures were fabricated, and current density–voltage and frequency dependent (7 kHz–5 MHz) dielectric constant measurements (within the strong accumulation region) were performed. A peak of dielectric loss was observed at a frequency of 3 MHz and the Cole–Davidson empirical formula was used to determine the relaxation time. It was concluded that the native point defects such as nitrogen vacancies and DX centers formed with the involvement of Si atoms into the AlN layers might have influenced the electrical conduction and dielectric relaxation properties of the plasma-assisted ALD grown AlN films.

  2. Natural and gamma radiation-induced conduction of silica and metaphosphate glass layers deposed by radiofrequency cathode sputtering

    International Nuclear Information System (INIS)

    We present a study of natural and 60Co induced conductions in radiofrequency sputtering deposed layers. Capacimetry and electronic microscopy observations permit a knowledge of the physical characteristics, mainly: homogeneity and thickness of these layers. A study of the natural current permit to characterise electrically the deposited films, the electrode and bulk insulator effects. In induced conduction, the behaviour of currents as a function of dose rate is interpreted in terms of ROSE'S and FOWLER'S photoconductivity theories. Induced currents versus applied fields are observed and compared with these obtained in the case of dielectric liquids and glasses. (author)

  3. 层状钴基正极材料的改性研究%Modification of layered Co-based cathode material

    Institute of Scientific and Technical Information of China (English)

    杨占旭; 乔庆东; 任铁强; 李琪

    2012-01-01

    Layered LiCoO2 has been the dominant cathode material for commercial Li-ion batteries because of its ease of production, good rate capability and stable discharge voltage platform. However, layered LiCoO2 shows poor overcharge tolerance and thermal stability, which restrict its commercialization. In this article, the progress in ion substitution and surface treatment of layered LiCoO2 to improve the structural and thermal stability at home and abroad has been described in detail. The mechanism has been discussed as well.%层状LiCoO2是目前商品化的主要正极材料,具有易于制备、较好的倍率性能以及放电电压平稳等优点,但其抗过充电性能和热稳定性差限制了其应用.详细阐述了国内外关于层状LiCoO2正极材料的改性研究进展,包括体相掺杂和表面包覆改性两种方法提高材料的抗过充电性能和热稳定性,并对体相掺杂和表面包覆层状LiCoO2正极材料电化学性能提高的机理进行了讨论.

  4. Layered perovskite PrBa0.5Sr0.5CoCuO5+δ as a cathode for intermediate-temperature solid oxide fuel cells

    International Nuclear Information System (INIS)

    Highlights: • A single-phase layered-perovskite PrBa0.5Sr0.5CoCuO5+δ (PBSCCu) is prepared by the EDTA–citrate complexing method. • PBSCCu cathode has a good chemical compatible with GDC electrolyte. • Partial substitution of Cu for Co can efficiently lower the thermal expansion coefficient. • Performances of PrBa0.5Sr0.5CoCuO5+δ cathode based on Gd0.1Ce0.9O1.95 electrolyte is reported firstly. - Abstract: Layered perovskite PrBa0.5Sr0.5CoCuO5+δ (PBSCCo) oxide is synthesized by EDTA–citrate complexing method and investigated as a novel cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). X-ray diffraction results show that PBSCCo is chemical compatible with Gd0.1Ce0.9O1.95 (GDC) electrolyte below 950 °C. The thermal expansion coefficient of PBSCCo is 17.58 × 10−6 K−1 between 30 °C and 900 °C. The maximum electrical conductivity of PBSCCo is 483 S cm−1 at 325 °C. The polarization resistance of PBSCCo cathode on GDC electrolyte is as low as 0.06 Ω cm2 at 800 °C. The maximum power density of the electrolyte-supported single cell with PBSCCo cathode achieves 521 mW cm−2 at 800 °C. Preliminary results indicate that PBSCCo is a potential cathode material for application in IT-SOFCs

  5. Crystalline TiO2: A Generic and Effective Electron-Conducting Protection Layer for Photoanodes and -cathodes

    DEFF Research Database (Denmark)

    Mei, Bastian Timo; Pedersen, Thomas; Malacrida, Paolo;

    2015-01-01

    shows that under certain conditions n-type semiconductors, such as TiO2, can be used as protection layers for Si-based photoanodes. It also provides evidence that even in a photoanode assembly TiO2 is conducting only electrons (not holes as in p-type protection layers), and therefore TiO2 can be...... described as a simple ohmic contact. This renders n-type semiconductors, such as TiO2, to be versatile and simple protection layers, which can be used for photoanodes and as previously shown for photocathodes. The ohmic behavior of n-type TiO2 in a Si/TiO2-photoanode assembly is demonstrated under dark and...... illuminated conditions by performing the oxygen evolution reaction (OER) and using the Fe(II)/Fe(III) redox couple. These measurements reveal that the performance of the Si/TiO2-photoanode assembly is strongly dependent on the TiO2/electrolyte interaction. Finally, the conditions and requirements that make Ti...

  6. Butanol Dehydration over V2O5-TiO2/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition

    OpenAIRE

    Jong-Ki Jeon; Young-Kwon Park; Do Heui Kim; Jung-Hyun Bae; Hyeonhee Choi

    2013-01-01

    MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO2-V2O5/MCM-41 catalysts were analyzed using XRF, BET, NH3-TPD, XRD, Py-IR, and XPS. The deh...

  7. Mesh optimization for microbial fuel cell cathodes constructed around stainless steel mesh current collectors

    KAUST Repository

    Zhang, Fang

    2011-02-01

    Mesh current collectors made of stainless steel (SS) can be integrated into microbial fuel cell (MFC) cathodes constructed of a reactive carbon black and Pt catalyst mixture and a poly(dimethylsiloxane) (PDMS) diffusion layer. It is shown here that the mesh properties of these cathodes can significantly affect performance. Cathodes made from the coarsest mesh (30-mesh) achieved the highest maximum power of 1616 ± 25 mW m-2 (normalized to cathode projected surface area; 47.1 ± 0.7 W m-3 based on liquid volume), while the finest mesh (120-mesh) had the lowest power density (599 ± 57 mW m-2). Electrochemical impedance spectroscopy showed that charge transfer and diffusion resistances decreased with increasing mesh opening size. In MFC tests, the cathode performance was primarily limited by reaction kinetics, and not mass transfer. Oxygen permeability increased with mesh opening size, accounting for the decreased diffusion resistance. At higher current densities, diffusion became a limiting factor, especially for fine mesh with low oxygen transfer coefficients. These results demonstrate the critical nature of the mesh size used for constructing MFC cathodes. © 2010 Elsevier B.V. All rights reserved.

  8. Bifunctional quaternary ammonium compounds to inhibit biofilm growth and enhance performance for activated carbon air-cathode in microbial fuel cells

    Science.gov (United States)

    Li, Nan; Liu, Yinan; An, Jingkun; Feng, Cuijuan; Wang, Xin

    2014-12-01

    The slow diffusion of hydroxyl out of the catalyst layer as well as the biofouling on the surface of cathode are two problems affecting power for membrane-less air-cathode microbial fuel cells (MFCs). In order to solve both of them simultaneously, here we simply modify activated carbon air-cathode using a bifunctional quaternary ammonium compound (QAC) by forced evaporation. The maximum power density reaches 1041 ± 12 mW m-2 in an unbuffered medium (0.5 g L-1 NaCl), which is 17% higher than the control, probably due to the accelerated anion transport in the catalyst layer. After 2 months, the protein content reduced by a factor of 26 and the power density increases by 33%, indicating that the QAC modification can effectively inhibit the growth of cathodic biofilm and improve the stability of performance. The addition of NaOH and QAC epoxy have a negative effect on power production due to the clogging of pores in catalyst layer.

  9. A study of thermally activated Mg–Fe layered double hydroxides as potential environmental catalysts

    Directory of Open Access Journals (Sweden)

    MILICA S. HADNAĐEV-KOSTIĆ

    2010-09-01

    Full Text Available Layered double hydroxides (LDHs and mixed oxides derived after thermal decomposition of LDHs with different Mg–Fe contents were investigated. These materials were chosen because of the possibility to tailor their various properties, such as ion-exchange capability, redox and acid–base and surface area. Layered double hydroxides, [Mg1-xFex(OH2](CO3x/2×mH2O (where x presents the content of trivalent ions, x = M(III/(M(II + M(III were synthesized using the low supersaturation precipitation method. The influence of different Mg/Fe ratios on the structure and surface properties of the LDH and derived mixed oxides was investigated in correlation to their catalytic properties in the chosen test reaction (Fischer–Tropsch synthesis. It was determined that the presence of active sites in the mixed oxides is influenced by the structural properties of the initial LDH and by the presence of additional Fe phases. Furthermore, a synthesis outside the optimal range for the synthesis of single phase LDHs leads to the formation of metastable, multiphase systems with specific characteristics and active sites.

  10. Properties of Cu(thd)2 as a precursor to prepare Cu/SiO2 catalyst using the atomic layer epitaxy technique.

    Science.gov (United States)

    Chen, Ching S; Lin, Jarrn H; You, Jainn H; Chen, Chi R

    2006-12-20

    The new Cu/SiO2 catalyst is developed by the atomic layer epitaxy (ALE) method. The ALE-Cu/SiO2 catalyst with high dispersion and nanoscale Cu particles appears to have very different catalytic properties from those of the typical Cu-based catalysts, which have satisfactory thermal stability to resist the sintering of Cu particles at 773 K. Due to the formation of small Cu particles, the ALE-Cu/SiO2 can strongly bind CO and give high catalytic activity for CO2 converted to CO in the reverse water-gas-shift reaction. The catalytic activity decreases in the order of 2.4% ALE-Cu/SiO2 =... 2% Pt/SiO2 > 2% Pd/SiO2 > 10.3% IM-Cu/SiO2. PMID:17165704

  11. Platinium Nanoparticles Deposited on Oxygen-Containing Functional Groups at Carbon Vulcane XC-72 as a Cathode Catalyst for Direct Methanol Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    Sajjad; Sadaghat; Sharehjini; Ahmad; Nozad; Golikand; Mohammad; Yari

    2007-01-01

    1 Results Surface oxidized carbon vulcane XC-72 as catalyst support, prepared by chemically anchoring Pt onto the surface modified carbon vulcane XC-72. The nanoparticles of Pt are synthesized by reduction of H2PtCl6 with sodium borohydride in a 5.5 buffer solution of sodium citrate, the complexation of citrate with metal ions is beneficial to the formation of nanoparticles. For comparison, an electrode is prepared by E-Tek Pt/C 20 Wt% with a typical Pt loading of 50 μg·cm-2, that shows higher specifi...

  12. Porous Perovskite LaNiO3 Nanocubes as Cathode Catalysts for Li-O2 Batteries with Low Charge Potential

    OpenAIRE

    Jian Zhang; Yubao Zhao; Xiao Zhao; Zhaolin Liu; Wei Chen

    2014-01-01

    Developing efficient catalyst for oxygen evolution reaction (OER) is essential for rechargeable Li-O2 battery. In our present work, porous LaNiO3 nanocubes were employed as electrocatalyst in Li-O2 battery cell. The as-prepared battery showed excellent charging performance with significantly reduced overpotential (3.40 V). The synergistic effect of porous structure, large specific surface area and high electrocatalytic activity of porous LaNiO3 nanocubes ensured the Li-O2 battery with enchanc...

  13. Recent Advances in Solid Catalysts Obtained by Metalloporphyrins Immobilization on Layered Anionic Exchangers: A Short Review and Some New Catalytic Results

    Directory of Open Access Journals (Sweden)

    Shirley Nakagaki

    2016-02-01

    Full Text Available Layered materials are a very interesting class of compounds obtained by stacking of two-dimensional layers along the basal axis. A remarkable property of these materials is their capacity to interact with a variety of chemical species, irrespective of their charge (neutral, cationic or anionic. These species can be grafted onto the surface of the layered materials or intercalated between the layers, to expand or contract the interlayer distance. Metalloporphyrins, which are typically soluble oxidation catalysts, are examples of molecules that can interact with layered materials. This work presents a short review of the studies involving metalloporphyrin immobilization on two different anionic exchangers, Layered Double Hydroxides (LDHs and Layered Hydroxide Salts (LHSs, published over the past year. After immobilization of anionic porphyrins, the resulting solids behave as reusable catalysts for heterogeneous oxidation processes. Although a large number of publications involving metalloporphyrin immobilization on LDHs exist, only a few papers have dealt with LHSs as supports, so metalloporphyrins immobilized on LHSs represent a new and promising research field. This work also describes new results on an anionic manganese porphyrin (MnP immobilized on Mg/Al-LDH solids with different nominal Mg/Al molar ratios (2:1, 3:1 and 4:1 and intercalated with different anions (CO32− or NO3−. The influence of the support composition on the MnP immobilization rates and the catalytic performance of the resulting solid in cyclooctene oxidation reactions will be reported.

  14. Recent Advances in Solid Catalysts Obtained by Metalloporphyrins Immobilization on Layered Anionic Exchangers: A Short Review and Some New Catalytic Results.

    Science.gov (United States)

    Nakagaki, Shirley; Mantovani, Karen Mary; Machado, Guilherme Sippel; Castro, Kelly Aparecida Dias de Freitas; Wypych, Fernando

    2016-01-01

    Layered materials are a very interesting class of compounds obtained by stacking of two-dimensional layers along the basal axis. A remarkable property of these materials is their capacity to interact with a variety of chemical species, irrespective of their charge (neutral, cationic or anionic). These species can be grafted onto the surface of the layered materials or intercalated between the layers, to expand or contract the interlayer distance. Metalloporphyrins, which are typically soluble oxidation catalysts, are examples of molecules that can interact with layered materials. This work presents a short review of the studies involving metalloporphyrin immobilization on two different anionic exchangers, Layered Double Hydroxides (LDHs) and Layered Hydroxide Salts (LHSs), published over the past year. After immobilization of anionic porphyrins, the resulting solids behave as reusable catalysts for heterogeneous oxidation processes. Although a large number of publications involving metalloporphyrin immobilization on LDHs exist, only a few papers have dealt with LHSs as supports, so metalloporphyrins immobilized on LHSs represent a new and promising research field. This work also describes new results on an anionic manganese porphyrin (MnP) immobilized on Mg/Al-LDH solids with different nominal Mg/Al molar ratios (2:1, 3:1 and 4:1) and intercalated with different anions (CO₃(2-) or NO₃(-)). The influence of the support composition on the MnP immobilization rates and the catalytic performance of the resulting solid in cyclooctene oxidation reactions will be reported. PMID:26938518

  15. Layered-MnO₂ Nanosheet Grown on Nitrogen-Doped Graphene Template as a Composite Cathode for Flexible Solid-State Asymmetric Supercapacitor.

    Science.gov (United States)

    Liu, Yongchuan; Miao, Xiaofei; Fang, Jianhui; Zhang, Xiangxin; Chen, Sujing; Li, Wei; Feng, Wendou; Chen, Yuanqiang; Wang, Wei; Zhang, Yining

    2016-03-01

    Flexible solid-state supercapacitors provide a promising energy-storage alternative for the rapidly growing flexible and wearable electronic industry. Further improving device energy density and developing a cheap flexible current collector are two major challenges in pushing the technology forward. In this work, we synthesize a nitrogen-doped graphene/MnO2 nanosheet (NGMn) composite by a simple hydrothermal method. Nitrogen-doped graphene acts as a template to induce the growth of layered δ-MnO2 and improves the electronic conductivity of the composite. The NGMn composite exhibits a large specific capacitance of about 305 F g(-1) at a scan rate of 5 mV s(-1). We also create a cheap and highly conductive flexible current collector using Scotch tape. Flexible solid-state asymmetric supercapacitors are fabricated with NGMn cathode, activated carbon anode, and PVA-LiCl gel electrolyte. The device can achieve a high operation voltage of 1.8 V and exhibits a maximum energy density of 3.5 mWh cm(-3) at a power density of 0.019 W cm(-3). Moreover, it retains >90% of its initial capacitance after 1500 cycles. Because of its flexibility, high energy density, and good cycle life, NGMn-based flexible solid state asymmetric supercapacitors have great potential for application in next-generation portable and wearable electronics. PMID:26842681

  16. The action mechanism of TiO2:NaYF4:Yb3+,Tm3+ cathode buffer layer in highly efficient inverted organic solar cells

    International Nuclear Information System (INIS)

    We report the fabrication and characteristics of organic solar cells with 6.86% power conversion efficiency (PCE) by doping NaYF4:Yb3+,Tm3+ into TiO2 cathode buffer layer. The dependence of devices performance on doping concentration of NaYF4:Yb3+,Tm3+ is investigated. Results indicate that short-circuit current density (Jsc) has an apparent improvement, leading to an enhancement of 22.7% in PCE for the optimized doping concentration of 0.05 mmol ml−1 compared to the control devices. NaYF4:Yb3+,Tm3+ nanoparticles (NPs) can play threefold roles, one is that the incident light in visible region can be scattered by NaYF4 NPs, the second is that solar irradiation in infrared region can be better utilized by Up-conversion effect of Yb3+ and Tm3+ ions, the third is that electron transport property in TiO2 thin film can be greatly improved

  17. Molybdenum Disulfide as a Protection Layer and Catalyst for Gallium Indium Phosphide Solar Water Splitting Photocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Britto, Reuben J.; Benck, Jesse D.; Young, James L.; Hahn, Christopher; Deutsch, Todd G.; Jaramillo, Thomas F.

    2016-06-02

    Gallium indium phosphide (GaInP2) is a semiconductor with promising optical and electronic properties for solar water splitting, but its surface stability is problematic as it undergoes significant chemical and electrochemical corrosion in aqueous electrolytes. Molybdenum disulfide (MoS2) nanomaterials are promising to both protect GaInP2 and to improve catalysis since MoS2 is resistant to corrosion and also possesses high activity for the hydrogen evolution reaction (HER). In this work, we demonstrate that GaInP2 photocathodes coated with thin MoS2 surface protecting layers exhibit excellent activity and stability for solar hydrogen production, with no loss in performance (photocurrent onset potential, fill factor, and light limited current density) after 60 hours of operation. This represents a five-hundred fold increase in stability compared to bare p-GaInP2 samples tested in identical conditions.

  18. Tantalum oxide nanocoatings prepared by atomic layer and filtered cathodic arc deposition for corrosion protection of steel: Comparative surface and electrochemical analysis

    International Nuclear Information System (INIS)

    Highlights: ► 50 nm Ta2O5 coatings grown by ALD at 160 °C and FCAD for protection of steel. ► Combined analysis by ToF-SIMS, XPS, polarization curves and EIS. ► Relation between chemical architecture and corrosion protection properties studied. ► Localized corrosion by pitting with absence of coating dissolution demonstrated. ► Origin and role of spurious interfacial oxide promoting coating breakdown emphasized. -- Abstract: A comparative study by Time-of-Flight Secondary Ions Mass Spectrometry and X-ray Photoelectron Spectroscopy, i–E polarization curves and Electrochemical Impedance Spectroscopy of the corrosion protection of low alloy steel by 50 nm thick tantalum oxide coatings prepared by low temperature Atomic Layer Deposition (ALD) and Filtered Cathodic Arc Deposition (FCAD) is reported. The data evidence the presence of a spurious oxide layer mostly consisting of iron grown by transient thermal oxidation at the ALD film/substrate interface in the initial stages of deposition and its suppression by pre-treatment in the FCAD process. Carbonaceous contamination (organic and carbidic) resulting from incomplete removal of the organic precursor is the major cause of the poorer sealing properties of the ALD film. No coating dissolution is demonstrated in neutral or acid 0.2 M NaCl solutions. In acid solution localized corrosion by pitting proceeds faster with the ALD than with the FCAD coating. The roles of the pre-existing channel defects exposing the substrate surface and of the spurious interfacial oxide promoting coating breakdown and/or delamination are emphasized

  19. Low-temperature atomic layer deposited Al2O3 thin film on layer structure cathode for enhanced cycleability in lithium-ion batteries

    International Nuclear Information System (INIS)

    The deposition of Al2O3 on LiCoO2 electrodes using a low-temperature atomic layer deposition has been investigated. Scanning electron microscopy confirms that Al2O3 films can be homogeneously deposited on LiCoO2 particles of porous electrodes at 120 deg. C. The results of X-ray photoelectron spectroscopy show that the Al2O3 preferentially deposits on the LiCoO2. Furthermore, the results of cycling stability tests show that the cells with Al2O3-coated LiCoO2 electrodes have enhanced performance.

  20. Effect of nitriding/nanostructuration of few layer graphene supported iron-based particles; catalyst in graphene etching and carbon nanofilament growth.

    Science.gov (United States)

    Baaziz, Walid; Melinte, Georgian; Ersen, Ovidiu; Pham-Huu, Cuong; Janowska, Izabela

    2014-08-14

    Stable, highly faceted and dispersed iron nitride particles supported on few layer graphene are obtained by ammonia decomposition on iron-based particles at the temperature commonly used for the synthesis of N-doped CNTs and graphene etching. The TEM/EELS analysis reveals nitrogen diffusion in a bulk of the particles. The resulting facet FeNx catalyst exhibits high activity in the etching of graphene, which is assisted by catalyst reorganization. Ammonia decomposition is used for the first time for graphene etching, while the highly faceted catalyst has an impact on the etched channels structures. According to the shape of the active planes of the catalyst, the etching results in sharp "V" channel ends and often "step-like" edges. The FeNx morphology proves previously reported triangularisation of arches in highly N-doped carbon nanotubes. The conditioning of the catalyst by its shaping and nitrogen incorporation is investigated additionally in the carbon nanostructure formation, for decomposition of ethane. The herringbone CNFs, "hollow" bamboo-like CNFs/CNTs or CNTs are effectively observed. PMID:24964374

  1. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid

    Directory of Open Access Journals (Sweden)

    Loïc Assaud

    2014-02-01

    Full Text Available Three-dimensionally (3D nanoarchitectured palladium/nickel (Pd/Ni catalysts, which were prepared by atomic layer deposition (ALD on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4. Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects.

  2. Chemiluminescence flow biosensor for glucose using Mg-Al carbonate layered double hydroxides as catalysts and buffer solutions.

    Science.gov (United States)

    Wang, Zhihua; Liu, Fang; Lu, Chao

    2012-01-01

    In this work, serving as supports in immobilizing luminol reagent, catalysts of luminol chemiluminescence (CL), and buffer solutions for the CL reaction, Mg-Al-CO(3) layered double hydroxides (LDHs) were found to trigger luminol CL in weak acid solutions (pH 5.8). The silica sol-gel with glucose oxidase and horseradish peroxidase was immobilized in the first half of the inside surface of a clear quartz tube, and luminol-hybrid Mg-Al-CO(3) LDHs were packed in the second half. Therefore, a novel CL flow-through biosensor for glucose was constructed in weak acid solutions. The CL intensity was linear with glucose concentration in the range of 0.005-1.0mM, and the detection limit for glucose (S/N=3) was 0.1 μM. The proposed biosensor exhibited excellent stability, high reproducibility and high selectivity for the determination of glucose and has been successfully applied to determine glucose in human plasma samples with satisfactory results. The success of this work has broken the bottleneck of the pH incompatibility between luminol CL and enzyme activity. PMID:22770831

  3. Atomic Layer Deposition of Pt Nanoparticles within the Cages of MIL-101: A Mild and Recyclable Hydrogenation Catalyst

    Directory of Open Access Journals (Sweden)

    Karen Leus

    2016-03-01

    Full Text Available We present the in situ synthesis of Pt nanoparticles within MIL-101-Cr (MIL = Materials Institute Lavoisier by means of atomic layer deposition (ALD. The obtained Pt@MIL-101 materials were characterized by means of N2 adsorption and X-ray powder diffraction (XRPD measurements, showing that the structure of the metal organic framework was well preserved during the ALD deposition. X-ray fluorescence (XRF and transmission electron microscopy (TEM analysis confirmed the deposition of highly dispersed Pt nanoparticles with sizes determined by the MIL-101-Cr pore sizes and with an increased Pt loading for an increasing number of ALD cycles. The Pt@MIL-101 material was examined as catalyst in the hydrogenation of different linear and cyclic olefins at room temperature, showing full conversion for each substrate. Moreover, even under solvent free conditions, full conversion of the substrate was observed. A high concentration test has been performed showing that the Pt@MIL-101 is stable for a long reaction time without loss of activity, crystallinity and with very low Pt leaching.

  4. Re-Examination of the Pt Particle Size Effect on the Oxygen Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion

    Energy Technology Data Exchange (ETDEWEB)

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-02

    The platinum 'particle size effect' on the oxygen reduction reaction (ORR) has been re-evaluated using commercial Pt/C catalysts (2-10 nm Pt particle) and polycrystalline Pt (poly-Pt) in 0.1 M HClO4 with a rotating disk electrode method. Nafion-free catalyst layers were employed to obtain specific activities (SA) that were not perturbed (suppressed) by sulfonate anion adsorption/blocking. By using ultrathin uniform catalyst layers, O2 diffusion limitation was minimized as confirmed from the high SAs of our supported catalysts that were comparable to unsupported sputtered Pt having controlled sizes. The specific activity (SA) steeply increased for the particle sizes in the range -2-10 nm (0.8-1.8 mA/cm2Pt at 0.9 V vs. RHE) and plateaued over -10 nm to 2.7 mA/cm2Pt for bulk poly-Pt. On the basis of the activity trend for the range of particle sizes studied, it appears that the effect of carbon support on activity is negligible. The experimental results and the concomitant profile of SA vs. particle size was found to be in an agreement to a truncated octahedral particle model that assumes active terrace sites.

  5. 1,3,5-Tris(phenyl-2-benzimidazole)-benzene cathode buffer layer thickness dependence in solution-processable organic solar cell based on 1,4,8,11,15,18,22,25-octahexylphthalocyanine

    Science.gov (United States)

    De Roméo Banoukepa, Gilles; Fujii, Akihiko; Shimizu, Yo; Ozaki, Masanori

    2015-04-01

    Studies on the insertion effects of a cathode buffer layer on bulk heterojunction organic solar cell based on 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2) and 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM) by using 1,3,5-tris(phenyl-2-benzimidazole)-benzene (TPBi) as a cathode buffer layer material have been carried out. The external quantum efficiency and the short-circuit current markedly increased, resulting in the enhancement of the power conversion efficiency. The solar cell performance has been discussed from the atomic force microscopy, photoelectron yield spectroscopy and X-ray photoelectron spectroscopy measurements.

  6. Graphene growth at the interface between Ni catalyst layer and SiO2/Si substrate.

    Science.gov (United States)

    Lee, Jeong-Hoon; Song, Kwan-Woo; Park, Min-Ho; Kim, Hyung-Kyu; Yang, Cheol-Woong

    2011-07-01

    Graphene was synthesized deliberately at the interface between Ni film and SiO2/Si substrate as well as on top surface of Ni film using chemical vapor deposition (CVD) which is suitable for large-scale and low-cost synthesis of graphene. The carbon atom injected at the top surface of Ni film can penetrate and reach to the Ni/SiO2 interface for the formation of graphene. Once we have the graphene in between Ni film and SiO2/Si substrate, the substrate spontaneously provides insulating SiO2 layer and we may easily get graphene/SiO2/Si structure simply by discarding Ni film. This growth of graphene at the interface can exclude graphene transfer step for electronic application. Raman spectroscopy and optical microscopy show that graphene was successfully synthesized at the back of Ni film and the coverage of graphene varies with temperature and time of synthesis. The coverage of graphene at the interface depends on the amount of carbon atoms diffused into the back of Ni film. PMID:22121737

  7. Atomic layer deposition of NiS and its application as cathode material in dye sensitized solar cell

    International Nuclear Information System (INIS)

    Nickel sulfide (NiS) is grown by atomic layer deposition (ALD) using sequential exposures of bis(2,2,6,6-tetramethylheptane-3,5-dionate)nickel(II) [Ni(thd)2] and hydrogen sulfide (H2S) at 175 °C. Complementary combinations of in situ and ex situ characterization techniques are used to understand the deposition chemistry and the nature of film growth. The saturated growth rate of ca. 0.21 Å per ALD cycle is obtained, which is constant within the ALD temperature window (175–250 °C). As deposited films on glass substrates are found polycrystalline without any preferred orientation. Electrical transport measurement reveals degenerative/semimetallic characteristics with a carrier concentration of ca. 9 × 1022 cm−3 at room temperature. The ALD grown NiS thin film demonstrates high catalytic activity for the reduction of I−/I3− electrolyte that opens its usage as cost-effective counter electrode in dye sensitized solar cells, replacing Pt

  8. Electrochemical Effects of Silicon/Diamond-Like Carbon Layered Composite on Oxygen Cathodes in Lithium–Oxygen Batteries

    International Nuclear Information System (INIS)

    Lithium–oxygen batteries are one of the most promising energy storage systems because of their high energy density. However, lithium carbonate (Li2CO3) and lithium carboxylates (HCO2Li, CH3CO2Li) are formed on cycling, which results in high charging over-potential and limited cycle life. In this study, a silicon/diamond-like carbon (Si–DLC) coating film was deposited onto an O2 electrode uniformly by plasma-enhanced chemical vapor deposition to improve the electrochemical properties of lithium–oxygen batteries. The coated layer prevented the direct contact of carbon with both the Li2O2 and the electrolyte, resulting in suppression of side-reaction product formation. For this reason, the coated cell showed better cycle life and round-trip efficiency than the pristine cell. When the charge was terminated, the potentials of the coated cell were 4.15 V for both the 1st and 5th cycles, whereas those of a pristine cell were 4.34 V for the 1st cycle and 4.51 V for the 5th cycle at a current density of 100 mA g−1 with a limited duration of 10 h for a single charge and discharge cycle. The coated cell was able to stably reach 50 cycles, whereas the pristine cell only lasted 7 cycles

  9. Atomic layer deposition of NiS and its application as cathode material in dye sensitized solar cell

    Energy Technology Data Exchange (ETDEWEB)

    Mahuli, Neha [Center for Research in Nanotechnology and Sciences, Indian Institute of Technology Bombay, Powai, Mumbai 400076 (India); Sarkar, Shaibal K., E-mail: shaibal.sarkar@iitb.ac.in [Department of Energy Science and Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400076 (India)

    2016-01-15

    Nickel sulfide (NiS) is grown by atomic layer deposition (ALD) using sequential exposures of bis(2,2,6,6-tetramethylheptane-3,5-dionate)nickel(II) [Ni(thd){sub 2}] and hydrogen sulfide (H{sub 2}S) at 175 °C. Complementary combinations of in situ and ex situ characterization techniques are used to understand the deposition chemistry and the nature of film growth. The saturated growth rate of ca. 0.21 Å per ALD cycle is obtained, which is constant within the ALD temperature window (175–250 °C). As deposited films on glass substrates are found polycrystalline without any preferred orientation. Electrical transport measurement reveals degenerative/semimetallic characteristics with a carrier concentration of ca. 9 × 10{sup 22} cm{sup −3} at room temperature. The ALD grown NiS thin film demonstrates high catalytic activity for the reduction of I{sup −}/I{sub 3}{sup −} electrolyte that opens its usage as cost-effective counter electrode in dye sensitized solar cells, replacing Pt.

  10. Detrimental influence of catalyst seeding on the device properties of CVD-grown 2D layered materials: A case study on MoSe{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Utama, M. Iqbal Bakti; Lu, Xin; Yuan, Yanwen [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore); Xiong, Qihua, E-mail: Qihua@ntu.edu.sg [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore); NOVITAS, Nanoelectronics Centre of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore)

    2014-12-22

    Seed catalyst such as perylene-3,4,9,10-tetracarboxylic acid tetrapotassium (PTAS) salt has been used for promoting the growth of atomically thin layered materials in chemical vapor deposition (CVD) synthesis. However, the ramifications from the usage of such catalyst are not known comprehensively. Here, we report the influence of PTAS seeding on the transistor device performance from few-layered CVD-grown molybdenum diselenide (MoSe{sub 2}) flakes. While better repeatability and higher yield can be obtained with the use of PTAS seeds in synthesis, we observed that PTAS-seeded flakes contain particle impurities. Moreover, devices from PTAS-seeded MoSe{sub 2} flakes consistently displayed poorer field-effect mobility, current on-off ratio, and subthreshold swing as compared to unseeded flakes.

  11. Co-Mn-Al Layered Double Hydroxides on Al2O3/Al Foils and Their Use as Precursors of VOC Catalysts

    Czech Academy of Sciences Publication Activity Database

    Kovanda, F.; Jirátová, Květa; Ludvíková, Jana; Raabová, H.

    - : -, 2012, SP1-T2-P41. ISBN N. [International Conference on Environmental Catalysis /7./. Lyon (FR), 02.09.2012-06.09.2012] R&D Projects: GA ČR GAP106/10/1762 Institutional support: RVO:67985858 Keywords : Co-Mn-Al layered double hydroxide * hydrothermal reaction * supported mixed oxide catalysts Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.icec2012.fr/en/home.html

  12. Cu,Zn,Al layered double hydroxides as precursors for copper catalysts in methanol steam reforming – pH-controlled synthesis by microemulsion technique

    OpenAIRE

    Kühl, S.; Friedrich, M.; Armbrüster, M.; Behrens, M

    2012-01-01

    By co-precipitation inside microemulsion droplets a Cu-based catalyst precursor was prepared with a Cu:Zn:Al ratio of 50:17:33. A pH-controlled synthesis was applied by simultaneous dosing of metal solution and precipitation agent. This technique allows for continuous operation of the synthesis and enables easy and feasible up-scaling. For comparison conventional co-precipitation was applied with the same composition. Both techniques resulted in phase pure layered double hydroxide precursors ...

  13. Concurrent photocatalytic hydrogen production and organic degradation by a composite catalyst film in a two-chamber photo-reactor

    OpenAIRE

    X. Wang; LI, XY

    2013-01-01

    A novel visible light-driven photocatalyst film, MoS2/Ag/TiO2, was synthesized on a glass-fiber membrane. The composite catalyst film had a multi-layer structure with Ag as nanoconjunctions between the MoS2 and TiO2 layers. The catalyst film performed well for both photocatalytic hydrogen production and organic degradation in a two-chamber photo-reactor under either solar or visible light. Hydrogen was produced in the cathode side chamber while the model organic was decomposed in the anode si...

  14. Développement de cathodes performantes pour batteries lithium/air

    OpenAIRE

    Berenger, Sophie

    2014-01-01

    In this thesis, high-performance cathodes for lithium/air batteries have been investigated. The main limitations for lithium/air batteries are oxygen diffusion into the cathode and in the electrolyte and the progressive clogging of cathode pores by lithium oxide. The development of the air cathode is strongly dependant on the organic electrolyte used, thus the nature of the electrolyte has been here considered. Electrode porosity and the kind of catalyst employed influence the cathode perform...

  15. Development of cathode material for lithium-ion batteries

    OpenAIRE

    Rustam Mukhtaruly Turganaly; Ivan Trussov; Andrey Petrovich Kurbatov

    2014-01-01

    The electrochemical characteristics of the cathode material coated with carbon layer has been developed. Various carbon coating methods. There  has been carried out a comparative electrochemical analysis of the coated and uncoated with carbon cathode material. 

  16. Comparison of trimethylgallium and triethylgallium as “Ga” source materials for the growth of ultrathin GaN films on Si (100) substrates via hollow-cathode plasma-assisted atomic layer deposition

    International Nuclear Information System (INIS)

    GaN films grown by hollow cathode plasma-assisted atomic layer deposition using trimethylgallium (TMG) and triethylgallium (TEG) as gallium precursors are compared. Optimized and saturated TMG/TEG pulse widths were used in order to study the effect of group-III precursors. The films were characterized by grazing incidence x-ray diffraction, atomic force microscopy, x-ray photoelectron spectroscopy, and spectroscopic ellipsometry. Refractive index follows the same trend of crystalline quality, mean grain, and crystallite sizes. GaN layers grown using TMG precursor exhibited improved structural and optical properties when compared to GaN films grown with TEG precursor

  17. Comparison of trimethylgallium and triethylgallium as “Ga” source materials for the growth of ultrathin GaN films on Si (100) substrates via hollow-cathode plasma-assisted atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Alevli, Mustafa, E-mail: mustafaalevli@marmara.edu.tr [Department of Physics, Marmara University, Göztepe Kadıköy, 34722 İstanbul (Turkey); Haider, Ali; Kizir, Seda; Leghari, Shahid A.; Biyikli, Necmi, E-mail: biyikli@unam.bilkent.edu.tr [Institute of Materials Science and Nanotechnology, Bilkent University, Bilkent, 06800 Ankara, Turkey and National Nanotechnology Research Center (UNAM), Bilkent University, Bilkent, 06800 Ankara (Turkey)

    2016-01-15

    GaN films grown by hollow cathode plasma-assisted atomic layer deposition using trimethylgallium (TMG) and triethylgallium (TEG) as gallium precursors are compared. Optimized and saturated TMG/TEG pulse widths were used in order to study the effect of group-III precursors. The films were characterized by grazing incidence x-ray diffraction, atomic force microscopy, x-ray photoelectron spectroscopy, and spectroscopic ellipsometry. Refractive index follows the same trend of crystalline quality, mean grain, and crystallite sizes. GaN layers grown using TMG precursor exhibited improved structural and optical properties when compared to GaN films grown with TEG precursor.

  18. Feature of "Cold" Fusion Reaction in a Deuterated Complex Cathode

    OpenAIRE

    ARATA, Yoshiaki; ZHANG, Yue-Chang

    1992-01-01

    [Abstract] In order to corroborate the evidence of "cold" fusion reaction, a new-type, complex cathode was developed, consisting of a Ni rod with a Pd layer applied by plasma spraying. High reproducibility of a "cold" fusion reaction was confirmed, using a deuterated complex cathode. The Pd layer showed to have activated the surface functions of the deuterated cathode, and a reliable evidence was obtained that a new type of heat generation occurred in the complex cathode.

  19. Following ORR intermediates adsorbed on a Pt cathode catalyst during break-in of a PEM fuel cell by in operando X-ray absorption spectroscopy.

    Science.gov (United States)

    Ramaker, D E; Korovina, A; Croze, V; Melke, J; Roth, C

    2014-07-21

    In operando X-ray absorption spectroscopy data using the Δμ X-ray Absorption Near Edge Spectroscopy (XANES) analysis procedure is used to follow the ORR intermediate adsorbate coverage on a working catalyst in a PEMFC during initial activation and break-in. The adsorbate coverage and log i (Tafel) curves reveal a strong correlation, i.e., an increase in adsorbate intermediate coverage poisons Pt sites thereby decreasing the current. A decrease in Pt-O bond strength commensurate with decrease in potential causes a sequence of different dominant adsorbate volcano curves to exist, namely first O, then OH, and then OOH exactly as predicted by the different ORR kinetics mechanisms. During break-in, the incipient O coverage coming from exposure to air during storage and MEA preparation is rather quickly removed, compared to the slower and more subtle nanoparticle morphological changes, such as the rounding of the Pt nanoparticle edges/corners and smoothing of the planar surfaces, driven by the nanoparticle's tendency to lower its surface energy. These morphological changes increase the Pt-Pt average coordination number, decrease the average Pt-O bond strength, and thereby decrease the coverage of ORR intermediates, allowing increase in the current. PMID:24664398

  20. Evolution Of Lattice Structure And Chemical Composition Of The Surface Reconstruction Layer In Li1.2Ni0.2Mn0.6O2 Cathode Material For Lithium Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Pengfei; Nie, Anmin; Zheng, Jianming; Zhou, Yungang; Lu, Dongping; Zhang, Xiaofeng; Xu, Rui; Belharouak, Ilias; Zu, Xiaotao; Xiao, Jie; Amine, Khalil; Liu, Jun; Gao, Fei; Shahbazian-Yassar, Reza; Zhang, Jiguang; Wang, Chong M.

    2015-01-14

    Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. Based on atomic level structural imaging, elemental mapping of the pristine and cycled samples and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions towards the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41→Spinel. For the first time, it is found that the surface facet terminated with pure cation is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for designing of cathode materials with both high capacity and voltage stability during cycling.

  1. Selective hydrogenation of 1,3-butadiene from crude C{sub 4} cracker stream with a solid catalyst with ionic liquid layer (SCILL). DSC and solubility study

    Energy Technology Data Exchange (ETDEWEB)

    Mangartz, T.; Korth, W.; Kern, C.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2013-11-01

    In petroleum as well as in fine chemical industry, selective catalytic hydrogenation is an important reaction. The selective hydrogenation of 1,3-butadiene (BD) to butene (trans-,1- and cis-butene) from the crude C4 steam cracker fraction represents one example, but under today's technical conditions undesired butane forms inevitably in relevant amounts. To increase the butene yield, the concept of Solid Catalyst with Ionic Liquid Layer (SCILL) was employed. The SCILL catalyst, in contrast to the uncoated catalyst, yielded a remarkably high selectivity to butenes (S{sub butenes} > 99 %) even at high residence times or at high hydrogen partial pressure. Nearly no butane (S{sub butane} {approx} 0 %) was analytically detected. We expected that due to different solubility, the poorer soluble compounds discharged from the ionic liquid and, thus, caused the shift in selectivity to a great extent. Temperature dependent solubility measurements in the used ionic liquid ([DMIM][DMP]) revealed that the order of increasing solubility is 1,3-butadiene > butenes > butane which matches the assumption. However, since differences in solubility cannot explain this SCILL effect satisfyingly, ionic liquids are expected to affect the surface of the catalyst (side-specific ligand-type effect). Investigations using spectroscopic methods (e.g. FTIR) confirmed this suggestion. (orig.)

  2. The Science and Engineering of Durable Ultralow PGM Catalysts- 2012 DOE-EERE-FCT annual progress report

    Energy Technology Data Exchange (ETDEWEB)

    Garzon, Fernando H. [Los Alamos National Laboratory

    2012-07-16

    Minimizing the quantity of Pt group metals used in polymer membrane fuel cells (PEMFCs) is one of the remaining grand challenges for fuel cell commercialization. Tremendous progress has been achieved over the last two decades in decreasing the Pt loading required for efficient fuel cell performance. Unfortunately, the fluctuations in the price of Pt represent a substantial barrier to the economics of widespread fuel cell use. Durability and impurity tolerance are also challenges that are tightly coupled to fuel cell Pt electrode loading. Traditional approaches to decreasing the amount of Pt required for good performance include: (1) Increasing mass activity by decreasing Pt particle size by supporting on carbon; (2) Alloy formulation Pt-Co, Pt-Cr alloys to improve mass activity; (3) Increasing Pt utilization by optimization of electronic and ionic contact of the Pt particles; (4) Improving conductivity of the electronic and ionic conducting constituents of the membrane electrode assembly; and (5) Improving reactant to and product mass transport away from the electroactive sites. Recent novel approaches include the nanoengineering of core shell catalysts and Pt particles of unusual geometries such as nanowires/whiskers. The success of the aforementioned approaches has been great; however further advances using such approaches have been hampered by a lack of underlining scientific understanding of the catalyst activity, particle growth mechanisms, and optimization strategies for designing composite electrodes The objectives of this report are: (1) Development of durable, high mass activity Platinum Group Metal (PGM) cathode catalysts-enabling lower cost fuel cells; (2) Elucidation of the fundamental relationships between PGM catalyst shape, particle size and activity to help design better catalysts; (3) Optimization of the cathode electrode layer to maximize the performance of PGM catalysts-improving fuel cell performance and lowering cost; (4) Understanding the

  3. Synthesis and electrochemical characterization of palladium-based cathode catalysts, resistant to the presence of methanol; Sintesis y caracterizacion electroquimica de catalizadores catodicos base paladio, resistentes a la presencia de metanol

    Energy Technology Data Exchange (ETDEWEB)

    Salvador, Jose J. [Centro de Investigacion y de Estudios Avanzados del IPN, Mexico D.F. (Mexico)] e-mail: jsalvador@cinvestav.mx; Collins, Virginia H. [Centro de Investigacion en Materiales Avanzados, Chihuahua, Chihuahua (Mexico); Solorza Feria, Omar [Centro de Investigacion y de Estudios Avanzados del IPN, Mexico D.F. (Mexico)

    2009-09-15

    This work presents the synthesis and characterization of palladium-based electrocatalysts (PdSn and PdPtSn) prepared with the salt-reduction method for oxygen reduction reaction (ORR). The compounds obtained are characterized by sweep electron microscopy, electron transmission microscopy and x-ray diffraction of powder. The electrocatalysts obtained had particle sizes less than 10 nm. The evaluation of the catalytic activity of the catalysts was performed using cyclic voltametry and rotating disc electrode. These experiments were conducted in an H{sub 2}SO{sub 4} 0.5 M solution with different methanol concentrations. The presence of methanol improved the catalytic activity of PdSn, but did not show any effect on the PdPtSn alloy. The performance of the DMFC mono cell using PdPtSn as a cathode showed a potential of 10 mW cm{sup -2} at 50 degrees Celsius. [Spanish] En este trabajo se presenta la sintesis y caracterizacion de electrocatalizadores de base Paladio (PdSn y PdPtSn) preparados mediante el metodo de reduccion de sales, para la reaccion de reduccion de oxigeno (RRO). Los compuestos obtenidos se caracterizaron por microscopia electronica de barrido, microscopia electronica de transmision y difraccion de rayos X de polvos. Los electrocatalizadores obtenidos presentaron un tamano de particula menores a 10 nm. La evaluacion de la actividad catalitica de los catalizadores se llevo a cabo mediante voltametria Ciclica y electrodo de disco rotatorio, estos experimentos fueron realizados en una solucion de H{sub 2}SO{sub 4} 0.5 M con diferentes concentraciones de metanol. La presencia de metanol mejoro la actividad catalitica de PdSn, pero no mostro ningun efecto sobre la aleacion PdPtSn. El desempeno de la monocelda de DMFC usando como catodo PdPtSn, mostro una potencia de 10 mW cm{sup -2} a 50 grados centigrados.

  4. XPS and STEM Study of the Interface Formation between Ultra-Thin Ru and Ir OER Catalyst Layers and Perylene Red Support Whiskers

    Energy Technology Data Exchange (ETDEWEB)

    Atanasoska, Liliana [3M Industrial Mineral Products; Cullen, David A [ORNL; Hester, Amy E [3M Industrial Mineral Products; Atanasoski, Radoslav [3M Industrial Mineral Products

    2013-01-01

    The interface formation between perylene red (PR) and ruthenium or iridium OER catalysts has been studied systematically by XPS and STEM. The OER catalyst over-layers with thicknesses ranging from ~0.1 to ~50 nm were vapor deposited onto PR ex-situ. As seen by STEM, Ru and Ir form into nanoparticles, which agglomerate with increased loading. XPS data show a strong interaction between Ru and PR. Ir also interacts with PR although not to the extent seen for Ru. At low coverages, the entire Ru deposit is in the reacted state while a small portion of the deposited Ir remains metallic. Ru and Ir bonding occur at the PR carbonyl sites as evidenced by the attenuation of carbonyl photoemission and the emergence of new peak assigned to C-O single bond. The curve fitting analysis and the derived stoichiometry indicates the formation of metallo-organic bonds. The co-existence of oxide bonds is also apparent.

  5. Single-Atom Pd₁/Graphene Catalyst Achieved by Atomic Layer Deposition: Remarkable Performance in Selective Hydrogenation of 1,3-Butadiene.

    Science.gov (United States)

    Yan, Huan; Cheng, Hao; Yi, Hong; Lin, Yue; Yao, Tao; Wang, Chunlei; Li, Junjie; Wei, Shiqiang; Lu, Junling

    2015-08-26

    We reported that atomically dispersed Pd on graphene can be fabricated using the atomic layer deposition technique. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy both confirmed that isolated Pd single atoms dominantly existed on the graphene support. In selective hydrogenation of 1,3-butadiene, the single-atom Pd1/graphene catalyst showed about 100% butenes selectivity at 95% conversion at a mild reaction condition of about 50 °C, which is likely due to the changes of 1,3-butadiene adsorption mode and enhanced steric effect on the isolated Pd atoms. More importantly, excellent durability against deactivation via either aggregation of metal atoms or carbonaceous deposits during a total 100 h of reaction time on stream was achieved. Therefore, the single-atom catalysts may open up more opportunities to optimize the activity, selectivity, and durability in selective hydrogenation reactions. PMID:26268551

  6. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials.

    Science.gov (United States)

    Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander; Malik, Rahul; Kang, ShinYoung; Ceder, Gerbrand

    2016-07-01

    Lithium-ion batteries are now reaching the energy density limits set by their electrode materials, requiring new paradigms for Li(+) and electron hosting in solid-state electrodes. Reversible oxygen redox in the solid state in particular has the potential to enable high energy density as it can deliver excess capacity beyond the theoretical transition-metal redox-capacity at a high voltage. Nevertheless, the structural and chemical origin of the process is not understood, preventing the rational design of better cathode materials. Here, we demonstrate how very specific local Li-excess environments around oxygen atoms necessarily lead to labile oxygen electrons that can be more easily extracted and participate in the practical capacity of cathodes. The identification of the local structural components that create oxygen redox sets a new direction for the design of high-energy-density cathode materials. PMID:27325096

  7. Highly Dispersed Alloy Catalyst for Durability

    Energy Technology Data Exchange (ETDEWEB)

    Murthi, Vivek S.; Izzo, Elise; Bi, Wu; Guerrero, Sandra; Protsailo, Lesia

    2013-01-08

    Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them with existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.

  8. High performance, high durability non-precious metal fuel cell catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Thomas E.; Atanasoski, Radoslav; Schmoeckel, Alison K.

    2016-03-15

    This invention relates to non-precious metal fuel cell cathode catalysts, fuel cells that contain these catalysts, and methods of making the same. The fuel cell cathode catalysts are highly nitrogenated carbon materials that can contain a transition metal. The highly nitrogenated carbon materials can be supported on a nanoparticle substrate.

  9. Microscale X-ray tomographic investigation of the interfacial morphology between the catalyst and micro porous layers in proton exchange membrane fuel cells

    Science.gov (United States)

    Prass, Sebastian; Hasanpour, Sadegh; Sow, Pradeep Kumar; Phillion, André B.; Mérida, Walter

    2016-07-01

    The interfacial morphology between the catalyst layer (CL) and micro porous layer (MPL) influences the performance of proton exchange membrane fuel cells (PEMFCs). Here we report a direct method to investigate the CL-MPL interfacial morphology of stacked and compressed gas diffusion layer (GDL with MPL)-catalyst coated membrane (CCM) assemblies. The area, origin and dimensions of interfacial gaps are studied with high-resolution X-ray micro computed tomography (X-μCT). The projected gap area (fraction of the CL-MPL interface separated by gaps) is higher for GDL-CCM assemblies with large differences in the surface roughness between CL and MPL but reduces with increasing compression and similarity in roughness. Relatively large continuous gaps are found in proximity to cracks in the MPL. These are hypothesized to form due to the presence of large pores on the surface of the GDL. Smaller gaps are induced by the surface roughness features throughout the CL-MPL interface. By modification of the pore sizes on the GDL surface serving as substrate for the MPL, the number and dimension of MPL crack induced gaps can be manipulated. Moreover, adjusting the CL and MPL surface roughness parameters to achieve similar orders of roughness can improve the surface mating characteristics of these two components.

  10. XPS analysis by exclusion of a-carbon layer on silicon carbide nanowires by a gold catalyst-supported metal-organic chemical vapor deposition method.

    Science.gov (United States)

    Nam, Sang-Hun; Kim, Myoung-Hwa; Hyun, Jae-Sung; Kim, Young Dok; Boo, Jin-Hyo

    2010-04-01

    Silicon carbide (SiC) nano-structures would be favorable for application in high temperature, high power, and high frequency nanoelectronic devices. In this study, we have deposited cubic-SiC nanowires on Au-deposited Si(001) substrates using 1,3-disilabutane as a single molecular precursor through a metal-organic chemical vapor deposition (MOCVD) method. The general deposition pressure and temperature were 3.0 x 10(-6) Torr and 1000 degrees C respectively, with the deposition carried out for 1 h. Au played an important role as a catalyst in growing the SiC nanowires. SiC nanowires were grown using a gold catalyst, with amorphous carbon surrounding the final SiC nanowire. Thus, the first step involved removal of the remaining SiO2, followed by slicing of the amorphous carbon into thin layers using a heating method. Finally, the thinly sliced amorphous carbon is perfectly removed using an Ar sputtering method. As a result, this method may provide more field emission properties for the SiC nanowires that are normally inhibited by the amorphous carbon layer. Therefore, exclusion of the amorphous carbon layer is expected to improve the overall emission properties of SiC nanowires. PMID:20355494

  11. Degradation reduction of polymer electrolyte membranes using CeO2 as a free-radical scavenger in catalyst layer

    International Nuclear Information System (INIS)

    Highlights: • CeO2 was added to the electrode to improve the chemical stability of the membrane. • The durability of the MEAs with CeO2 in cathode and anode was compared. • Accelerated durability tests, gas crossover and SEM were conducted. -- Abstract: Ceria nanoparticles were added to the electrodes of proton exchange membrane fuel cells as free-radical scavengers to minimize the degradation of membrane electrode assembly (MEA) components. Accelerated durability tests were performed at low humidity under open circuit voltage (OCV) conditions, and the results were compared with traditional MEAs without CeO2. Gas crossover was monitored during the durability test, and the MEAs were examined by SEM before and after the durability test. The results showed that adding CeO2 as free-radical scavengers to the electrode greatly improves the chemical stability of the membrane. The degradation rate of the MEA with CeO2 in the anode was similar to that of the MEA with CeO2 in the cathode. The fuel cell with CeO2 in the cathode showed better MEA performance that the fuel cell with CeO2 in the anode

  12. Butanol Dehydration over V2O5-TiO2/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition

    Directory of Open Access Journals (Sweden)

    Jong-Ki Jeon

    2013-04-01

    Full Text Available MCM-41 was used as a support and, by using atomic layer deposition (ALD in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO2-V2O5/MCM-41 catalysts were analyzed using XRF, BET, NH3-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO2/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH3-TPD and Py-IR results indicated that weak acid sites were produced over the TiO2/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V2O5(12.1-TiO2/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

  13. Preparation of manganese oxide immobilized on SBA-15 by atomic layer deposition as an efficient and reusable catalyst for selective oxidation of benzyl alcohol in the liquid phase

    International Nuclear Information System (INIS)

    Manganese oxide supported on mesoporous silica SBA-15 catalyst (Mn-SBA-15) was tested with Mn contents in the range of 0.8–23 wt%. Samples were prepared by the controlled grafting process of atomic layer deposition (ALD). Other sample was prepared for comparisons by the wet impregnation method. These samples were characterized by the techniques of ICP, XRD, SEM, Raman, FT-IR spectroscopy, diffuse reflectance UV–Vis, TGA-DSC, and N2 absorption–desorption surface area measurement. Results indicated that anchored manganese oxide particles have been successfully synthesized over the surface of SBA-15. These samples contained Red-Ox ion pairs of Mn2+ and Mn3+ highly dispersed on the mesoporous silica surface. The impregnated sample exhibited lower surface area and contained Red-Ox ion pairs of Mn3+ and Mn4+ more aggregated particles on the SBA-15 surface. Results determined Mn-SBA-15 as an efficient and selective catalyst for oxidation of benzyl alcohol with tert-butylhydroperoxide in liquid phase. In accordance with expectations, there was a negligible amount of leaching of immobilized manganese oxide from the support during the reaction, because of strong surface interaction between manganese oxide and hydroxyls groups. The influences of reaction temperature, reaction time, solvent, TBHP/benzyl alcohol molar ratio, amount of catalyst and reusability were investigated. Under optimized conditions (0.2 g catalyst, TBHP/benzyl alcohol molar ratio 1, solvent acetonitrile; T = 90 °C; reaction time 8 h), results achieved 70% conversion of benzyl alcohol and 100% selectivity to benzaldehyde. - Highlights: • Manganese oxide immobilized on SBA-15 were prepared by atomic layer deposition (ALD). • Oxidation of benzyl alcohol to benzaldehyde over this catalyst were investigated. • Effects of loading of manganese oxide, T, oxidant/alcohol ratio were investigated. • The leaching of manganese oxide from support during the reaction was negligible. • Under optimized

  14. Preparation of manganese oxide immobilized on SBA-15 by atomic layer deposition as an efficient and reusable catalyst for selective oxidation of benzyl alcohol in the liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Mahdavi, Vahid, E-mail: v-mahdavi@araku.ac.ir; Mardani, Mahdieh

    2015-04-01

    Manganese oxide supported on mesoporous silica SBA-15 catalyst (Mn-SBA-15) was tested with Mn contents in the range of 0.8–23 wt%. Samples were prepared by the controlled grafting process of atomic layer deposition (ALD). Other sample was prepared for comparisons by the wet impregnation method. These samples were characterized by the techniques of ICP, XRD, SEM, Raman, FT-IR spectroscopy, diffuse reflectance UV–Vis, TGA-DSC, and N{sub 2} absorption–desorption surface area measurement. Results indicated that anchored manganese oxide particles have been successfully synthesized over the surface of SBA-15. These samples contained Red-Ox ion pairs of Mn{sup 2+} and Mn{sup 3+} highly dispersed on the mesoporous silica surface. The impregnated sample exhibited lower surface area and contained Red-Ox ion pairs of Mn{sup 3+} and Mn{sup 4+} more aggregated particles on the SBA-15 surface. Results determined Mn-SBA-15 as an efficient and selective catalyst for oxidation of benzyl alcohol with tert-butylhydroperoxide in liquid phase. In accordance with expectations, there was a negligible amount of leaching of immobilized manganese oxide from the support during the reaction, because of strong surface interaction between manganese oxide and hydroxyls groups. The influences of reaction temperature, reaction time, solvent, TBHP/benzyl alcohol molar ratio, amount of catalyst and reusability were investigated. Under optimized conditions (0.2 g catalyst, TBHP/benzyl alcohol molar ratio 1, solvent acetonitrile; T = 90 °C; reaction time 8 h), results achieved 70% conversion of benzyl alcohol and 100% selectivity to benzaldehyde. - Highlights: • Manganese oxide immobilized on SBA-15 were prepared by atomic layer deposition (ALD). • Oxidation of benzyl alcohol to benzaldehyde over this catalyst were investigated. • Effects of loading of manganese oxide, T, oxidant/alcohol ratio were investigated. • The leaching of manganese oxide from support during the reaction was

  15. Plasma versus thermal annealing for the Au-catalyst growth of ZnO nanocones and nanowires on Al-doped ZnO buffer layers

    Science.gov (United States)

    Güell, Frank; Martínez-Alanis, Paulina R.; Roso, Sergio; Salas-Pérez, Carlos I.; García-Sánchez, Mario F.; Santana, Guillermo; Marel Monroy, B.

    2016-06-01

    We successfully synthesized ZnO nanocones and nanowires over polycrystalline Al-doped ZnO (AZO) buffer layers on fused silica substrates by a vapor-transport process using Au-catalyst thin films. Different Au film thicknesses were thermal or plasma annealed in order to analyze their influence on the ZnO nanostructure growth morphology. Striking differences have been observed. Thermal annealing generates a distribution of Au nanoclusters and plasma annealing induces a fragmentation of the Au thin films. While ZnO nanowires are found in the thermal-annealed samples, ZnO nanocones and nanowires have been obtained on the plasma-annealed samples. Enhancement of the preferred c-axis (0001) growth orientation was demonstrated by x-ray diffraction when the ZnO nanocones and nanowires have been grown over the AZO buffer layer. The transmittance spectra of the ZnO nanocones and nanowires show a gradual increase from 375 to 900 nm, and photoluminescence characterization pointed out high concentration of defects leading to observation of a broad emission band in the visible range from 420 to 800 nm. The maximum emission intensity peak position of the broad visible band is related to the thickness of the Au-catalyst for the thermal-annealed samples and to the plasma power for the plasma-annealed samples. Finally, we proposed a model for the plasma versus thermal annealing of the Au-catalyst for the growth of the ZnO nanocones and nanowires. These results are promising for renewable energy applications, in particular for its potential application in solar cells.

  16. Ruthenium catalyst on carbon nanofiber support layers for use in silicon-based structured microreactors, Part I: Preparation and characterization

    NARCIS (Netherlands)

    Thakur, D.B.; Tiggelaar, R.M.; Hoang, T.M.C.; Gardeniers, J.G.E.; Lefferts, L.; Seshan, K.

    2011-01-01

    The preparation and characterization of ruthenium catalytic nanoparticles on carbon nanofiber (CNF) support layers via homogeneous deposition precipitation (HDP) and pulsed laser deposition (PLD) is presented. Prior to ruthenium deposition the CNF layers were functionalized via liquid phase oxidatio

  17. Selective oxidation catalysts obtained by immobilization of iron(III) porphyrins on thiosalicylic acid-modified Mg-Al layered double hydroxides.

    Science.gov (United States)

    de Freitas Castro, Kelly Aparecida Dias; Wypych, Fernando; Antonangelo, Ariana; Mantovani, Karen Mary; Bail, Alesandro; Ucoski, Geani Maria; Ciuffi, Kátia Jorge; Cintra, Thais Elita; Nakagaki, Shirley

    2016-09-15

    Nitrate-intercalated Mg-Al layered double hydroxides (LDHs) were synthesized and exfoliated in formamide. Reaction of the single layer suspension with thiosalicylic acid under different conditions afforded two types of solids: LDHA1, in which the outer surface was modified with the anion thiosalicylate, and LDHA2, which contained the anion thiosalicylate intercalated between the LDH layers. LDHA1 and LDHA2 were used as supports to immobilize neutral (FeP1 and FeP2) and anionic (FeP3) iron(III) porphyrins. For comparison purposes, the iron(III) porphyrins (FePs) were also immobilized on LDH intercalated with nitrate anions obtained by the co-precipitation method. Chemical modification of LDH facilitated immobilization of the FePs through interaction of the functionalizing groups in LDH with the peripheral substituents on the porphyrin ring. The resulting FePx-LDHAy solids were characterized by X-ray diffraction (powder) and UV-Vis and EPR spectroscopies and were investigated as catalysts in the oxidation of cyclooctene and cyclohexane. The immobilized neutral FePs and their homogeneous counterparts gave similar product yields in the oxidation of cyclooctene, suggesting that immobilization of the FePs on the thiosalicylate-modified LDHs only supported the catalyst species without interfering in the catalytic outcome. On the other hand, in the oxidation of cyclohexane, the thiosalicylate anions on the outer surface of LDHA1 or intercalated between the LDHA2 layers influenced the catalytic activity of FePx-LDHAy, leading to different efficiency and selectivity results. FeP1-LDHA2 performed the best (29.6% alcohol yield) due to changes in the polarity of the surface of the support and the presence of FeP1. Interestingly, FeP1 also performed better in solution as compared to the other FePs. Finally, it was possible to recycle FeP1-LDHA2 at least three times. PMID:27322950

  18. XPS and STEM study of the interface formation between ultra-thin Ru and Ir OER catalyst layers and perylene red support whiskers

    Directory of Open Access Journals (Sweden)

    Atanasoska Ljiljana L.

    2013-01-01

    Full Text Available The interface formation between nano-structured perylene red (PR whiskers and oxygen evolution reaction (OER catalysts ruthenium and iridium has been studied systematically by XPS and STEM. The OER catalyst over-layers with thicknesses ranging from ~0.1 to ~50 nm were vapor deposited onto PR ex-situ. STEM images demonstrate that, with increasing thickness, Ru and Ir transform from amorphous clusters to crystalline nanoparticles, which agglomerate with increased over-layer thickness. XPS data show a strong interaction between Ru and PR. Ir also interacts with PR although not to the extent seen for Ru. At low coverages, the entire Ru deposit is in the reacted state while a small portion of the deposited Ir remains metallic. Ru and Ir bonding occur at the PR carbonyl sites as evidenced by the attenuation of carbonyl photoemission and the emergence of new peak assigned to C-O single bond. The curve fitting analysis and the derived stoichiometry indicates the formation of metallo-organic bonds. The co-existence of oxide bonds is also apparent.

  19. Performance of a solid oxide fuel cell with cathode containing a functional layer of LSM/YSZ film; Desempenho de uma celula a combustivel de oxido solido com catodo contendo uma camada funcional de filme LSM/YSZ

    Energy Technology Data Exchange (ETDEWEB)

    Pires, Filipe Oliveira; Domingues, Rosana Z.; Brant, Marcia C.; Silva, Charles L.; Matencio, Tulio [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica]. E-mail: filipequiufmg@ufmg.br

    2008-07-01

    Performance of a SOFC may be evaluated by using the AC-Impedance and measuring power (P V x I). The objective of this study was to compare the performance of a fuel cell with LSM as a cathode and another one containing an additional functional composite film LSM/YSZ between the LSM and YSZ. Also it was studied variation in second cell resistance and power according to the temperature, hydrogen flux and operation time. For both cells platinum was used as anode. At 800 deg C was observed, in open current circuit, when the composite layer was introduced a decrease in resistance and high power. These results show an improvement of SOFC cathode performance with the introduction of composite LSM/YSZ layer. The maximum performance of the cell was achieved with 100 mL/min hydrogen flow at 800 deg C. The experiments also showed a performance improvement at 850 deg C. The cell behavior was stable during 318 hours of test. (author)

  20. Observation Of Electron-beam-induced Phase Evolution Mimicking The Effect Of Charge-discharge Cycle In Li-rich Layered Cathode Materials Used For Li-ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Ping; Yan, Pengfei; Romero, Eric; Spoerke, Erik D.; Zhang, Jiguang; Wang, Chong M.

    2015-02-24

    Capacity loss, and voltage fade upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[LixMnyTM1-x-y]O2 , TM = Ni, Co or Fe) have recently been identified to be correlated to the gradual phase transformation, featuring the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5 nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li0.2Ni0.2Mn0.6]O2 (LMR) particles, which are identical to those reported due to the charge-discharge cycle but are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200 kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by energy dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LMR is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. This study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.

  1. PEMFCs的膜及阴极催化层数值模拟%MEMBRANE AND CATHODE CATALYST LAYER NUMERICAL SIMULATION OF PEMFCS

    Institute of Scientific and Technical Information of China (English)

    叶芳; 陈峰; 郭航; 马重芳; 王朝阳

    2004-01-01

    本文提出了一个质子交换膜燃料电池的膜和阴极催化层的一维非稳态数学模型,模型考虑了电化学反应及反应中的传质过程.本文结合算例分析了燃料电池膜及阴极催化层的性能,结果能验证燃料电池内阻理论.论文结果表明:(1)随着输出电流密度的增大,氧浓度分布不均匀性增大;(2)阴极催化层厚度减小,可提高电池输出电压;(3)电池进口处氧气摩尔浓度增大,可增加电池的输出电压.

  2. Electrostatic layer-by-layer a of platinum-loaded multiwall carbon nanotube multilayer: A tunable catalyst film for anodic methanol oxidation

    International Nuclear Information System (INIS)

    A simple layer-by-layer (LBL) electrostatic adsorption technique was developed for deposition of films composed of alternating layers of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged multiwall carbon nanotubes bearing platinum nanoparticles (Pt-CNTs). PDDA/Pt-CNT film structure and morphology up to six layers were characterized by scanning electron microscopy and ultraviolet-visible spectroscopy, showing the Pt-CNT layers to be porous and uniformly deposited within the multilayer films. Electrochemical properties of the PDDA/Pt-CNT films, as well as electrocatalytic activity toward methanol oxidation, were investigated with cyclic voltammetry. Significant activity toward anodic methanol oxidation was observed and is readily tunable through changing film thickness and/or platinum-nanoparticle loading. Overall, the observed properties of these PDDA/Pt-CNT multilayer films indicated unique potential for application in direct methanol fuel cell

  3. Structural and Electronic Transformations of Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C Cathode Catalysts in Polymer Electrolyte Fuel Cells during Potential-step Operating Processes Characterized by In-situ Time-resolved XAFS

    Science.gov (United States)

    Nagamatsu, Shin-ichi; Takao, Shinobu; Samjeské, Gabor; Nagasawa, Kensaku; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Uruga, Tomoya; Gayen, Sirshendu; Velaga, Srihari; Saniyal, Milan K.; Iwasawa, Yasuhiro

    2016-06-01

    The dynamic structural and electronic transformations of Pt/C, Pd@Pt(1 ML)/C, Pd@Pt(2 ML)/C cathode catalysts in polymer electrolyte fuel cells (PEFCs) during the potential-step operating processes between 0.4 and 1.4 VRHE (potential vs RHE) were characterized by in-situ (operando) time-resolved Pt LIII-edge quick-XAFS at 100 ms time-resolution. Potential-dependent surface structures and oxidation states of Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticles on carbon at 0.4 and 1.4 VRHE were also analyzed by in-situ Pt LIII-edge and Pd K-edge quick-XAFS. The Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticle surfaces were restructured and disordered at 1.4 VRHE, which were induced by strong Pt-O bonds as well as alloying effects. The rate constants for the changes of Pt valence, CN(Pt-Pt), CN(Pt-Pd) and CN(Pt-O) (CN: coordination number) in the potential-step operating processes were also determined and discussed in relation to the origin of oxygen reduction reaction (ORR) activities of the Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C cathode catalysts.

  4. Catalyst containing oxygen transport membrane

    Science.gov (United States)

    Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

    2012-12-04

    A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

  5. Pd nanoparticles on ZnO-passivated porous carbon by atomic layer deposition: an effective electrochemical catalyst for Li-O2 battery.

    Science.gov (United States)

    Luo, Xiangyi; Piernavieja-Hermida, Mar; Lu, Jun; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Miller, Dean; Zak Fang, Zhigang; Lei, Yu; Amine, Khalil

    2015-04-24

    Uniformly dispersed Pd nanoparticles on ZnO-passivated porous carbon were synthesized via an atomic layer deposition (ALD) technique, which was tested as a cathode material in a rechargeable Li-O2 battery, showing a highly active catalytic effect toward the electrochemical reactions-in particular, the oxygen evolution reaction. Transmission electron microscopy (TEM) showed discrete crystalline nanoparticles decorating the surface of the ZnO-passivated porous carbon support in which the size could be controlled in the range of 3-6 nm, depending on the number of Pd ALD cycles performed. X-ray absorption spectroscopy (XAS) at the Pd K-edge revealed that the carbon-supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The ZnO-passivated layer effectively blocks the defect sites on the carbon surface, minimizing the electrolyte decomposition. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports for Li-O2 batteries. PMID:25829367

  6. High Performance Cathodes for Li-Air Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Xing, Yangchuan

    2013-08-22

    The overall objective of this project was to develop and fabricate a multifunctional cathode with high activities in acidic electrolytes for the oxygen reduction and evolution reactions for Li-air batteries. It should enable the development of Li-air batteries that operate on hybrid electrolytes, with acidic catholytes in particular. The use of hybrid electrolytes eliminates the problems of lithium reaction with water and of lithium oxide deposition in the cathode with sole organic electrolytes. The use of acid electrolytes can eliminate carbonate formation inside the cathode, making air breathing Li-air batteries viable. The tasks of the project were focused on developing hierarchical cathode structures and bifunctional catalysts. Development and testing of a prototype hybrid Li-air battery were also conducted. We succeeded in developing a hierarchical cathode structure and an effective bifunctional catalyst. We accomplished integrating the cathode with existing anode technologies and made a pouch prototype Li-air battery using sulfuric acid as catholyte. The battery cathodes contain a nanoscale multilayer structure made with carbon nanotubes and nanofibers. The structure was demonstrated to improve battery performance substantially. The bifunctional catalyst developed contains a conductive oxide support with ultra-low loading of platinum and iridium oxides. The work performed in this project has been documented in seven peer reviewed journal publications, five conference presentations, and filing of two U.S. patents. Technical details have been documented in the quarterly reports to DOE during the course of the project.

  7. Atomic layer deposition of ruthenium surface-coating on porous platinum catalysts for high-performance direct ethanol solid oxide fuel cells

    Science.gov (United States)

    Jeong, Heon Jae; Kim, Jun Woo; Jang, Dong Young; Shim, Joon Hyung

    2015-09-01

    Pt-Ru bi-metallic catalysts are synthesized by atomic layer deposition (ALD) of Ru surface-coating on sputtered Pt mesh. The catalysts are evaluated in direct ethanol solid oxide fuel cells (DESOFCs) in the temperature range of 300-500 °C. Island-growth of the ALD Ru coating is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) analyses. The performance of the DESOFCs is evaluated based on the current-voltage output and electrochemical impedance spectroscopy. Genuine reduction of the polarization impedance, and enhanced power output with improved surface kinetics are achieved with the optimized ALD Ru surface-coating compared to bare Pt. The chemical composition of the Pt/ALD Ru electrode surface after fuel cell operation is analyzed via XPS. Enhanced cell performance is clearly achieved, attributed to the effective Pt/ALD Ru bi-metallic catalysis, including oxidation of Cdbnd O by Ru, and de-protonation of ethanol and cleavage of C-C bonds by Pt, as supported by surface morphology analysis which confirms formation of a large amount of carbon on bare Pt after the ethanol-fuel-cell test.

  8. SSZ-52, a zeolite with an 18-layer aluminosilicate framework structure related to that of the DeNOx catalyst Cu-SSZ-13.

    Science.gov (United States)

    Xie, Dan; McCusker, Lynne B; Baerlocher, Christian; Zones, Stacey I; Wan, Wei; Zou, Xiaodong

    2013-07-17

    A new zeolite (SSZ-52, |(C14H28N)6Na6(H2O)18|[Al12Si96O216]), related to the DeNOx catalyst Cu-SSZ-13 (CHA framework type), has been synthesized using an unusual polycyclic quaternary ammonium cation as the structure-directing agent. By combining X-ray powder diffraction (XPD), high-resolution transmission electron microscopy (HRTEM) and molecular modeling techniques, its porous aluminosilicate framework structure (R3m, a = 13.6373(1) Å, c = 44.7311(4) Å), which can be viewed as an 18-layer stacking sequence of hexagonally arranged (Si,Al)6O6 rings (6-rings), has been elucidated. The structure has a three-dimensional 8-ring channel system and is a member of the ABC-6 family of zeolites (those that can be described in terms of 6-ring stacking sequences) like SSZ-13, but it has cavities that are twice as large. The code SFW has been assigned to this new framework type. The large cavities contain pairs of the bulky organic cations. HRTEM and XPD simulations show that stacking faults do occur, but only at the 5-10% level. SSZ-52 has considerable potential as a catalyst in the areas of gas conversion and sequestration. PMID:23782259

  9. Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

    Science.gov (United States)

    Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

    2015-01-01

    Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity. PMID:26593096

  10. Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

    Science.gov (United States)

    Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E.; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

    2015-11-01

    Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity.

  11. Erosion behaviour of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

    CERN Document Server

    Franz, Robert; Hawranek, Gerhard; Polcik, Peter

    2015-01-01

    Al$_{x}$Cr$_{1-x}$ composite cathodes with Al contents of x = 0.75, 0.5 and 0.25 were exposed to cathodic arc plasmas in Ar, N$_2$ and O$_2$ atmospheres and their erosion behaviour was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by X-ray diffraction analysis. Cathode poisoning effects in the reactive N$_2$ and O$_2$ atmospheres were non-uniform as a result of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded centre region of the cathodes.

  12. Erosion behavior of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

    International Nuclear Information System (INIS)

    AlxCr1−x composite cathodes with Al contents of x = 0.75, 0.5, and 0.25 were exposed to cathodic arc plasmas in Ar, N2, and O2 atmospheres and their erosion behavior was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by x-ray diffraction analysis. Cathode poisoning effects in the reactive N2 and O2 atmospheres were nonuniform as a result of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded center region of the cathodes

  13. Catalyst-free growth of InP nanowires on patterned Si (001) substrate by using GaAs buffer layer

    Science.gov (United States)

    Li, Shiyan; Zhou, Xuliang; Kong, Xiangting; Li, Mengke; Mi, Junping; Pan, Jiaoqing

    2016-04-01

    The catalyst-free metal organic vapor phase epitaxial growth of InP nanowires on silicon (001) substrate is investigated using selectively grown GaAs buffer layers in V-shaped trenches. A yield up to 70% of nanowires is self-aligned in uncommon directions under the optimized growth conditions. The evolution mechanism of self-aligned directions for nanowires is discussed and demonstrated. Using this growth method, we can achieve branched and direction switched InP nanowires by varying the V/III ratio in situ. The structure of the nanowires is characterized by scanning electron microscope and transmission electron microscopy measurements. The crystal structure of the InP nanowires is stacking-faults-free wurtzite with its c axis perpendicular to the nanowire axis.

  14. Synthesis of Ni/Mg/Al Layered Double Hydroxides and Their Use as Catalyst Precursors in the Preparation of Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yun; JIAO Qing-ze; LIANG Ji; LI Chun-hua

    2005-01-01

    Ni/Mg/Al layered double hydroxides(LDHs) with different n(Ni):n(Mg):n(Al) ratio values were prepared via a coprecipitation reaction. Then Ni/Mg/Al mixed oxides were obtained by calcination of these LDHs precursors. Carbon nanotubes were produced in the catalytic decomposition of propane over the Ni/Mg/Al mixed oxide catalysts. The quality of as-made nanotubes was investigated by SEM and TEM. The nanotubes were multiwall with a high length-diameter ratio and appeared to be flexible. The catalytic activities of these mixed oxides increased with increasing the Ni content. The Ni/Mg/Al mixed oxide with the highest Ni content [n(Ni)/n(Mg)/n(Al)=1/1/1] showed the highest activity and the carbon nanotubes grown on its surface had the best quality.

  15. Layered perovskite oxide Y0.8Ca0.2BaCoFeO5+δas a novel cathode material for intermediate-temperature solid oxide fuel cells

    Institute of Scientific and Technical Information of China (English)

    余良浩; 陈永红; 顾庆文; 田冬; 卢肖永; 孟广耀; 林彬

    2015-01-01

    A layered perovskite oxide Y0.8Ca0.2BaCoFeO5+δ(YCBCF) was synthesized as a novel cathode material for intermedi-ate-temperature solid oxide fuel cells (IT-SOFCs) by citric acid-nitrates self-propagating combustion method. The phase and micro-structure of YCBCF were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The aver-age thermal expansion coefficient (TEC) of YCBCF was 14.6×10–6 K–1, which was close to other materials of SOFC at the range of RT–1000 ºC. An open-circuit potential of 0.75 V and a maximum output power density of 426 mW/cm2 were obtained at 650 ºC in a Sm0.2Ce0.8O1.9 (SDC)-based anode-supported SOFC by using humidified (~3%H2O) hydrogen as fuel and static air as oxidant. The results indicated that the YCBCF was a promising cathode candidate for IT-SOFCs.

  16. Microstructural study on degradation mechanism of layered LiNi0.6Co0.2Mn0.2O2 cathode materials by analytical transmission electron microscopy

    Science.gov (United States)

    Kim, Na Yeon; Yim, Taeeun; Song, Jun Ho; Yu, Ji-Sang; Lee, Zonghoon

    2016-03-01

    Electrochemical performance of lithium ion batteries is associated with structural and chemical stability of electrode materials. In the case of nickel-rich layered cathode materials LiNi0.6Co0.2Mn0.2O2, cation mixing, which results from the migration of transition metal ions into vacant lithium sites, is accelerated owing to similar ionic radii between nickel and lithium. However, the inevitable lattice distortions and chemical evolution have not been investigated intensely. In this paper, we report the structural evolution localized at surface regions through electron diffraction and high resolution imaging analyses with aberration-corrected transmission electron microscopy and scanning transmission electron microscopy. Repetition of volumetric change generates cracks and voids associated with deterioration of electrochemical performance. Structural change is related with (003) intensity in electron diffraction and it can be presented by dark field transmission electron microscopy imaging at a glance. Drastic structural degradation during early cycling shows relation with rapid capacity and voltage fade. Electron energy loss spectroscopy elucidates that the structural evolution caused by the migration of Ni ions accompanies chemical modification of Mn ions and creation of hole states at the O2p level. This study provides an insight into correlating structural and chemical evolution with degradation mechanism on battery performances of LiNi0.6Co0.2Mn0.2O2 cathode materials.

  17. Iron porphyrin-based cathode catalysts for polymer electrolyte membrane fuel cells: Effect of NH{sub 3} and Ar mixtures as pyrolysis gases on catalytic activity and stability

    Energy Technology Data Exchange (ETDEWEB)

    Meng Hui; Larouche, Nicholas; Lefevre, Michel; Jaouen, Frederic; Stansfield, Barry [INRS-Energie, Materiaux et Telecommunications, 1650 boulevard Lionel Boulet, Varennes, Quebec, J3X 1S2 (Canada); Dodelet, Jean-Pol, E-mail: dodelet@emt.inrs.c [INRS-Energie, Materiaux et Telecommunications, 1650 boulevard Lionel Boulet, Varennes, Quebec, J3X 1S2 (Canada)

    2010-09-01

    Ten different catalysts were prepared by loading 66 wt% ClFeTMPP on N330, a furnace grade carbon black, and pyrolyzing this catalyst precursor for 10 min at 950 {sup o}C in a NH{sub 3}/Ar gas mixture with various NH{sub 3} volume fractions (from 0% to 100%). The activity and stability of these catalysts were measured in a fuel cell and compared. The only stable catalyst, although the least active, among these was the one pyrolyzed in pure Ar. A notable leap in catalytic activity, but drop in stability, was observed for all catalysts pyrolyzed in gas mixtures containing NH{sub 3}, even with a mere volume fraction of 1.3% NH{sub 3} in the pyrolysis gas mixture. Catalytic activities increased, while stability decreased with increasing volume fraction of NH{sub 3}. The physicochemical properties of these catalysts were correlated with their electrochemical behaviour observed in fuel cell tests. It was found that a volume fraction of only 1.3% NH{sub 3} was enough to double the micropore surface area, the surface nitrogen and iron concentrations in the resulting catalyst. Since the active sites are believed to be of the Fe/N/C type, the sharp increase in catalytic activity with as little as 1.3% NH{sub 3} is attributed to the concurrent increase in microporous surface area, N and Fe surface contents in these catalysts. The only property that apparently correlates with stability is the degree of graphitization of the catalyst, which was estimated either from either X-ray diffraction and Raman spectroscopy measurements. Lastly, it was found that the catalysts' peroxide yield, resulting from the partial reduction of O{sub 2}, does not correlate with their degree of stability.

  18. Surface immobilization of a tetra-ruthenium substituted polyoxometalate water oxidation catalyst through the employment of conducting polypyrrole and the layer-by-layer (LBL) technique.

    Science.gov (United States)

    Anwar, Nargis; Sartorel, Andrea; Yaqub, Mustansara; Wearen, Kevin; Laffir, Fathima; Armstrong, Gordon; Dickinson, Calum; Bonchio, Marcella; McCormac, Timothy

    2014-06-11

    A tetra Ru-substituted polyoxometalate Na10[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2] (Ru4POM) has been successfully immobilised onto glassy carbon electrodes and indium tin oxide (ITO) coated glass slides through the employment of a conducting polypyrrole matrix and the layer-by-layer (LBL) technique. The resulting Ru4POM doped polypyrrole films showed stable redox behavior associated with the Ru centres within the Ru4POM, whereas, the POM's tungsten-oxo redox centres were not accessible. The films showed pH dependent redox behavior within the pH range 2-5 whilst exhibiting excellent stability towards redox cycling. The layer-by-layer assembly was constructed onto poly(diallyldimethylammonium chloride) (PDDA) modified carbon electrodes by alternate depositions of Ru4POM and a Ru(II) metallodendrimer. The resulting Ru4POM assemblies showed stable redox behavior for the redox processes associated with Ru4POM in the pH range 2-5. The charge transfer resistance of the LBL films was calculated through AC-Impedance. Surface characterization of both the polymer and LBL Ru4POM films was carried out using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Initial investigations into the ability of the Ru4POM LBL films to electrocatalytically oxidise water at pH 7 have also been conducted. PMID:24758586

  19. Air humidity and water pressure effects on the performance of air-cathode microbial fuel cell cathodes

    KAUST Repository

    Ahn, Yongtae

    2014-02-01

    To better understand how air cathode performance is affected by air humidification, microbial fuel cells were operated under different humidity conditions or water pressure conditions. Maximum power density decreased from 1130 ± 30 mW m-2 with dry air to 980 ± 80 mW m -2 with water-saturated air. When the cathode was exposed to higher water pressures by placing the cathode in a horizontal position, with the cathode oriented so it was on the reactor bottom, power was reduced for both with dry (1030 ± 130 mW m-2) and water-saturated (390 ± 190 mW m-2) air. Decreased performance was partly due to water flooding of the catalyst, which would hinder oxygen diffusion to the catalyst. However, drying used cathodes did not improve performance in electrochemical tests. Soaking the cathode in a weak acid solution, but not deionized water, mostly restored performance (960 ± 60 mW m-2), suggesting that there was salt precipitation in the cathode that was enhanced by higher relative humidity or water pressure. These results showed that cathode performance could be adversely affected by both flooding and the subsequent salt precipitation, and therefore control of air humidity and water pressure may need to be considered for long-term MFC operation. © 2013 Elsevier B.V. All rights reserved.

  20. Surface characterization of the carbon cathode and the lithium anode of Li-O₂ batteries using LiClO₄ or LiBOB salts.

    Science.gov (United States)

    Younesi, Reza; Hahlin, Maria; Edström, Kristina

    2013-02-01

    The surface compositions of a MnO₂ catalyst containing carbon cathode and a Li anode in a Li-O₂ battery were investigated using synchrotron-based photoelectron spectroscopy (PES). Electrolytes comprising LiClO₄ or LiBOB salts in PC or EC:DEC (1:1) solvents were used for this study. Decomposition products from LiClO₄ or LiBOB were observed on the cathode surface when using PC. However, no degradation of LiClO₄ was detected when using EC/DEC. We have demonstrated that both PC and EC/DEC solvents decompose during the cell cycling to form carbonate and ether containing compounds on the surface of the carbon cathode. However, EC/DEC decomposed to a lesser degree compared to PC. PES revealed that a surface layer with a thickness of at least 1-2 nm remained on the MnO₂ catalyst at the end of the charged state. It was shown that the detachment of Kynar binder influences the surface composition of both the carbon cathode and the Li anode of Li-O₂ cells. The PES results indicated that in the charged state the SEI on the Li anode is composed of PEO, carboxylates, carbonates, and LiClO₄ salt. PMID:23336349

  1. Research on the performance of AuPdPt-WC/C as a composite catalyst on cathode reaction of DMFC%AuPdPt-WC/C复合材料作为直接甲醇燃料电池阴极催化剂的性能研究

    Institute of Scientific and Technical Information of China (English)

    郑仓晟; 聂明; 李庆; 王宏煜; 袁宇; 刘晓卫; 杜胜娟; 刘其阳; 王孝益

    2015-01-01

    本实验以碳化钨(WC)增强的AuPdPt-WC/C复合催化剂作为直接甲醇燃料电池(DMFC)的阴极催化剂,选取了各组元比例,温度为变量,测试了其作为 DMFC催化剂的性能。首先,采用了间歇微波加热法(IHM)制备了纳米级的碳化钨(WC)颗粒,并采用还原法和真空干燥法制备了 AuPdPt-WC/C 复合催化剂,控制 Au、Pd、Pt的比例,制备了两组催化剂。通过循环伏安扫描,线性伏安扫描等手段进行电化学测试,表征其氧还原的性能。结果显示,复合催化剂具有高于传统 Pt/C催化剂的性能,并且与实验条件息息相关。%Our research mainly focuses on the preparation and characterization of tungsten carbide (WC) enhanced AuPdPt-WC/C composite catalyst of the cathode oxygen reduction reaction of direct methanol fuel cells (DMFC). By using intermittent mi-crowave heating method, we firstly synthesized nano tungsten carbide particle, then we prepared two AuPdPt-WC/C catalyst of different composition through reduction method and vacuum drying method. For characterization, we controlled composition and temperature as variable and used cyclic voltammetry and linear sweep voltammetry for electrochemistry test. The results indicated that the composite catalyst has a better performance than common single Pt catalyst and its performance is influenced by operating conditions.

  2. Power generation using an activated carbon and metal mesh cathode in a microbial fuel cell

    KAUST Repository

    Zhang, Fang

    2009-11-01

    An inexpensive activated carbon (AC) air cathode was developed as an alternative to a platinum-catalyzed electrode for oxygen reduction in a microbial fuel cell (MFC). AC was cold-pressed with a polytetrafluoroethylene (PTFE) binder to form the cathode around a Ni mesh current collector. This cathode construction avoided the need for carbon cloth or a metal catalyst, and produced a cathode with high activity for oxygen reduction at typical MFC current densities. Tests with the AC cathode produced a maximum power density of 1220 mW/m2 (normalized to cathode projected surface area; 36 W/m3 based on liquid volume) compared to 1060 mW/m2 obtained by Pt catalyzed carbon cloth cathode. The Coulombic efficiency ranged from 15% to 55%. These findings show that AC is a cost-effective material for achieving useful rates of oxygen reduction in air cathode MFCs. © 2009 Elsevier B.V. All rights reserved.

  3. LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

    Energy Technology Data Exchange (ETDEWEB)

    Harlan U. Anderson; Fatih Dogan; Vladimir Petrovsky

    2002-03-31

    This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and testing of Planar Single Cells. This period has continued to address the problem of making dense 1/2 to 5 {micro}m thick dense layers on porous substrates (the cathode LSM). Our current status is that we are making structures of 2-5 cm{sup 2} in area, which consist of either dense YSZ or CGO infiltrated into a 2-5 {micro}m thick 50% porous layer made of either nanoncrystalline CGO or YSZ powder. This composite structure coats a macroporous cathode or anode; which serves as the structural element of the bi-layer structure. These structures are being tested as SOFC elements. A number of structures have been evaluated both as symmetrical and as button cell configuration. Results of this testing indicates that the cathodes contribute the most to cell losses for temperatures below 750 C. In this investigation different cathode materials were studied using impedance spectroscopy of symmetric cells and IV characteristics of anode supported fuel cells. Cathode materials studied included La{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (LSCF), La{sub 0.7}Sr{sub 0.2}MnO{sub 3} (LSM), Pr{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}O{sub 3} (PSCF), Sm{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF), and Yb{sub .8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF). A new technique for filtering the Fourier transform of impedance data was used to increase the sensitivity of impedance analysis. By creating a filter specifically for impedance spectroscopy the resolution was increased. The filter was tailored to look for specific circuit elements like R//C, Warburg, or constant phase elements. As many as four peaks can be resolved using the filtering technique on symmetric cells. It may be possible to relate the different peaks to material parameters, like the oxygen exchange coefficient. The cathode grouped in order from lowest to highest ASR is

  4. Synthesis and characterization of layered Li(Ni1/3Mn1/3Co1/3)O2 cathode materials by spray-drying method

    Institute of Scientific and Technical Information of China (English)

    LIU Zhi-min; HU Guo-rong; PENG Zhong-dong; DENG Xin-rong; LIU Ye-xiang

    2007-01-01

    Spherical Li(Ni1/3Mn1/3Co1/3)O2 was prepared via the homogenous precursors produced by solution spray-drying method. The precursors were sintered at different temperatures between 600 and 1 000 ℃ for 10 h. The impacts of different sintering temperatures on the structure and electrochemical performances of Li(Ni1/3Mn1/3Co1/3)O2 were compared by means of X-ray diffractometry(XRD), scanning electron microscopy(SEM), and charge/discharge test as cathode materials for lithium ion batteries. The experimental results show that the spherical morphology of the spray-dried powers maintains during the subsequent heat treatment and the specific capacity increases with rising sintering temperature. When the sintering temperature rises up to 900 ℃, Li(Ni1/3Mn1/3Co1/3)O2 attains a reversible capacity of 153 mA·h/g between 3.00 and 4.35 V at 0.2C rate with excellent cyclability.

  5. Bifunctional, Carbon-Free Nickel/Cobalt-Oxide Cathodes for Lithium-Air Batteries with an Aqueous Alkaline Electrolyte

    International Nuclear Information System (INIS)

    Highlights: • High activity bi-functional catalyst combination for ORR and OER . • An optimum ratio of high active bi-functional catalysts was found. • Novel electrodes without carbon to avoid carbon corrosion during OER mode. • EIS model for OER describes influence of a growing oxide layers. • Long-term test exhibited an excellent long-term stability over 1200 cycles. - Abstract: Lithium-air batteries with an aqueous alkaline electrolyte promise a very high practical energy density and capacity. These batteries are mainly limited by high overpotentials on the bifunctional cathode during charge and discharge. To reduce overpotentials the bifunctional cathode of such batteries must be improved significantly. Nickel is relatively inexpensive and has a good catalytic activity in alkaline media. Co3O4 was found to be a promising metal oxide catalyst for oxygen evolution in alkaline media but it has a low electronic conductivity. On the other hand since nickel has a good electronic conductivity Co3O4 can be added to pure nickel electrodes to enhance performance due to a synergetic effect. Due to the poor stability of carbon materials at high anodic potentials, gas diffusion electrodes were prepared without carbon to improve especially long-term stability. Gas diffusion electrodes were electrochemically investigated in a half cell. In addition, cyclic voltammogrametry (CV) and electrochemical impedance spectroscopy (EIS) were carried out. SEM was used for the physical and morphological investigations. Investigations showed that electrodes containing 20 wt.% Co3O4 exhibited the highest performance

  6. Hydrophobic carbon nanostructured layer as bi-functional gas diffusion media and catalyst support for PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Pacheco Benito, S.; Beek, J.M. van; Hulsman, L.H.; Lefferts, L. [Twente Univ., Enschede (Netherlands). Catalytic Processes and Materials, IMPACT and MESA

    2010-07-01

    Carbon nanostructures have been grown in-situ on a carbon paper substrate constituting the gas diffusion media (GDM). Firstly, metal nanoparticles (such as Ni and/or Pt) from a precursor are deposited on the carbon substrate by chemical or physical methods. Secondly, carbon nanostructures are grown by catalytic chemical vapor decomposition of ethylene. By changing the growth conditions, the wettability of the layers can be tuned without further PTFE addition. Finally, platinum nanoparticles are deposited on the carbon nanostructures. Morphology, porosity, wettability and electrical conductivity are characterized by techniques such as SEM, contact angle, XRD, 4 point probe electrical conductivity, BET and MIP. (orig.)

  7. Calcined Ni-Al Layered Double Hydroxide as Catalyst for Total Oxidation of VOC: Effect of Precursor Crystallinity.

    Czech Academy of Sciences Publication Activity Database

    Mikulová, Zuzana; Čuba, Pavel; Balabánová, Jana; Rojka, T.; Kovanda, F.; Jirátová, Květa

    2007-01-01

    Roč. 61, 2 (2007) , s. 103-109. ISSN 0366-6352. [International Conference of Slovak Society of Chemical Engineering /33./. Matliare, 26.05.2006-30.05.2006] R&D Projects: GA ČR(CZ) GA104/04/2116; GA ČR(CZ) GD203/03/H140 Institutional research plan: CEZ:AV0Z40720504 Keywords : layered double hydroxide * mixed oxide * hydrothermal treatment Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.367, year: 2007

  8. A facile and novel organic coprecipitation strategy to prepare layered cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 with high capacity and excellent cycling stability

    Science.gov (United States)

    Yuan, Xiaolei; Xu, Qun-jie; Wang, Cong; Liu, Xinnuan; Liu, Haimei; Xia, Yongyao

    2015-04-01

    The lithium-rich layered cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 with high capacity and excellent cycling stability, is successfully synthesized through a facile organic co-precipitation route. The as-obtained material exhibits a well-crystallization and uniform size distribution, above which have been characterized and observed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, FT-IR spectra proves that the addition of metal ions Mn+ induces a red-shift of the bond of C-N groups of the 8-hydroxyquinoline, which is used as the precipitant in this work, and most probably due to the strong complexation effect of metal ions Mn+ with N and O atoms of 8-hydroxyquinoline, and simultaneously the co-precipitation process occurred. The electrochemical results reveal that the cathode material derived from this novel organic co-precipitation route exhibits improved electrochemical performance, of which could provide an initial discharge capacity of 287.2 mAhg-1at 0.2C within a potential range of 2.0-4.8 V at room temperature, even at high C-rate of 2C, this material could also deliver a capacity of 212.1 mAh g-1 with 97.7% capacity retention after 100 cycles. Therefore, it is proposed that this organic co-precipitation might be a high-efficiency strategy to synthesize alternative electrode materials with improved performance.

  9. Thin layers elaborated from new anodic and cathodic materials for lithium-ions micro-batteries; Nouveaux materiaux d'electrodes elabores sous forme de couches minces pour batteries lithium-ion

    Energy Technology Data Exchange (ETDEWEB)

    Benjelloun, N.

    2002-12-01

    Thin layers elaborated by R.F. sputtering from new anodic and cathodic materials were investigated as electrodes for lithium-ion micro-batteries. Anodic thin films based on the Tin Composite Oxides (TCOs) were found to exhibit interesting electrochemical characteristics. However, the irreversible capacity loss occurring during the first charge and due to the reduction of tin oxide remains a drawback. According to the gold collector contribution to the faradic yield, electrochemical behavior of metallic thin films (Au, Ag, Cu, Zn, etc...) was studied. AuCuAg and Ag based thin films were associated via an aprotic or solid electrolyte (LiPON) to Li{sub 1+x}Mn{sub 1,5}Ni{sub 0,5}O{sub 4} thin layers in order to build up mini or micro batteries with an average voltage close to 4,7 V. However, all solid state micro-batteries were found to present high ohmic drop. (author)

  10. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-02-20

    catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.

  11. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-03-03

    catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.

  12. Designing nanobowl arrays of mesoporous TiO2 as an alternative electron transporting layer for carbon cathode-based perovskite solar cells

    Science.gov (United States)

    Zheng, Xiaoli; Wei, Zhanhua; Chen, Haining; Zhang, Qianpeng; He, Hexiang; Xiao, Shuang; Fan, Zhiyong; Wong, Kam Sing; Yang, Shihe

    2016-03-01

    In this work, we have designed a mesoporous TiO2 nanobowl (NB) array with pore size, bowl size and film thickness being easily controllable by the sol-gel process and the polystyrene (PS) template diameter. Based on the TiO2 NB array, we fabricated carbon cathode based perovskite solar cells (C-PSCs) to investigate the impact of TiO2 NB nanostructures on the performance of the as-obtained C-PSCs devices. As expected, the TiO2 NB based devices show a higher power conversion efficiency (PCE) than that of the planar counterpart, mainly due to the enhanced light absorption arising from the NB-assisted light management, the improved pore-filling of high quality perovskite crystals and the increased interface contact for rapid electron extraction and fast charge transport. Leveraging these advantages of the novel TiO2 NB film, the 220 nm-PS templated TiO2 NB based devices performed the best on both light absorption capability and charge extraction, and achieved a PCE up to 12.02% with good stability, which is 37% higher than that of the planar counterpart. These results point to a viable and convenient route toward the fabrication of TiO2 ETL nanostructures for high performance PSCs.In this work, we have designed a mesoporous TiO2 nanobowl (NB) array with pore size, bowl size and film thickness being easily controllable by the sol-gel process and the polystyrene (PS) template diameter. Based on the TiO2 NB array, we fabricated carbon cathode based perovskite solar cells (C-PSCs) to investigate the impact of TiO2 NB nanostructures on the performance of the as-obtained C-PSCs devices. As expected, the TiO2 NB based devices show a higher power conversion efficiency (PCE) than that of the planar counterpart, mainly due to the enhanced light absorption arising from the NB-assisted light management, the improved pore-filling of high quality perovskite crystals and the increased interface contact for rapid electron extraction and fast charge transport. Leveraging these

  13. Photocatalytic hydrogen production on SOLECTRO {sup registered} titanium dioxide layers. Development and characterization of an efficient catalyst; Photokatalytische Wasserstoffgewinnung an SOLECTRO {sup registered} -Titandioxidschichten. Entwicklung und Charakterisierung eines geeigneten Katalysators

    Energy Technology Data Exchange (ETDEWEB)

    Saborowski, Sarah

    2010-03-03

    A catalyst for photocatalytic hydrogen production from methanol and water was developed on the basis of SOLECTRO {sup registered} titanium dioxide layers. A test facility was constructed in which several modified catalysts could be tested for this reaction. Detailed characterization of the electronic and optical characteristics of these catalysts made it possible to gain deeper insight into the processes involved in the reaction. (orig.) [German] Auf Basis der SOLECTRO {sup registered} -TiO{sub 2} -Schichten wurde ein Katalysator fuer die photokatalytische Wasserstoffdarstellung aus Methanol und Wasser entwickelt. Der Aufbau einer geeigneten Versuchsanlage ermoeglichte es, verschieden modifizierte Katalysatoren fuer diese Reaktion zu testen. Durch die ausfuehrliche Charakterisierung insbesondere der elektronischen und optischen Eigenschaften dieser Katalysatoren konnten vertiefende Erkenntnisse zu den waehrend der Reaktion ablaufenden Prozessen gewonnen werden. (orig.)

  14. Fuel cell development for transportation: Catalyst development

    Energy Technology Data Exchange (ETDEWEB)

    Doddapaneni, N. [Sandia National Lab., Albuquerque, NM (United States)

    1996-04-01

    Fuel cells are being considered as alternate power sources for transportation and stationary applications. With proton exchange membrane (PEM) fuel cells the fuel crossover to cathodes causes severe thermal management and cell voltage drop due to oxidation of fuel at the platinized cathodes. The main goal of this project was to design, synthesize, and evaluate stable and inexpensive transition metal macrocyclic catalysts for the reduction of oxygen and be electrochemically inert towards anode fuels such as hydrogen and methanol.

  15. High-throughput screening of binary catalysts for oxygen electroreduction

    Science.gov (United States)

    Liu, Jing Hua; Jeon, Min Ku; Woo, Seong Ihl

    2006-01-01

    A series of Pt based and non-Pt catalysts for proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC) have been evaluated towards oxygen reduction, by high-throughput optical screening. Fluorescein was first used as pH indicator for detecting pH change of the electrolyte in the vicinity of cathode caused by oxygen reduction. Arrays of catalyst spot comprised of binary catalysts and pure Pt were prepared by using robotic micro-dispenser. The analysis of fluorescence images has showed that some of Pt based catalysts including PtBi, PtCu, PtSe, PtTe and PtIr, as well as RuFe, as a non-Pt catalyst, exhibited higher activities and methanol tolerance than pure Pt. Moreover, acceptable stability of these catalysts at high potential in acid environment suits them to the requirements of cathode catalyst in PEMFC or DMFC.

  16. Process For Patterning Dispenser-Cathode Surfaces

    Science.gov (United States)

    Garner, Charles E.; Deininger, William D.

    1989-01-01

    Several microfabrication techniques combined into process cutting slots 100 micrometer long and 1 to 5 micrometer wide into tungsten dispenser cathodes for traveling-wave tubes. Patterned photoresist serves as mask for etching underlying aluminum. Chemically-assisted ion-beam etching with chlorine removes exposed parts of aluminum layer. Etching with fluorine or chlorine trifluoride removes tungsten not masked by aluminum layer. Slots enable more-uniform low-work function coating dispensed to electron-emitting surface. Emission of electrons therefore becomes more uniform over cathode surface.

  17. Microscopic Investigations into the Effect of Surface Treatment of Cathode and Electron Transport Layer on the Performance of Inverted Organic Solar Cells.

    Science.gov (United States)

    Gupta, Shailendra Kumar; Jindal, Rajeev; Garg, Ashish

    2015-08-01

    Surface treatments of various layers in organic solar cells play a vital role in determining device characteristics. In this manuscript, we report on the influence of surface treatment of indium tin oxide (ITO) electrode and electron transport layer (ETL), ZnO, on the photovoltaic performance of inverted organic solar cells (IOSC) and their correlation with the surface chemistry and surface potential as studied using X-ray photoelectron spectroscopy (XPS) and Kelvin probe force microscopy (KPFM), using the device structure glass/ITO/ZnO/P3HT: PCBM/MoO3/(Au or Ag) (P3HT, poly(3-hexylthiophene-2,5-diyl), and PCBM, phenyl-C61-butyric acid methyl ester). Our results show that although ozonization of ITO leads to an improvement in the device power conversion efficiency, the ozonization of a subsequent ZnO layer results in a decreased performance mainly because of a decrease in the fill factor (FF). However, subsequent methanol (CH3OH) treatment of ZnO layer on an ozonized ITO electrode shows substantial improvement with device efficiencies exceeding ∼4% along with superior reproducibility of the devices. Furthermore, a detailed analysis of the surface wettability, chemistry, and surface potential using contact angle measurements, XPS, and KPFM attribute the improvements to the elimination of surface defects and the changes in the surface potential. Finally, impedance analysis suggests that methanol treatment of the ZnO layers leads to the development of a favorable nanophase structure with higher conductivity, which is otherwise indiscernible using microscopic methods. PMID:26158508

  18. Cathode development for solid oxide electrolysis cells for high temperature hydrogen production

    OpenAIRE

    Yang, Xuedi

    2010-01-01

    This study has been mainly focused on high temperature solid oxide electrolysis cells (HT-SOECs) for steam electrolysis. The compositions, microstructures and metal catalysts for SOEC cathodes based on (La₀.₇₅Sr₀.₂₅)₀.₉₅Mn₀.₅Cr₀.₅O₃ (LSCM) have been investigated. Hydrogen production amounts from SOECs with LSCM cathodes have been detected and current-to-hydrogen efficiencies have been calculated. The effect of humidity on electrochemical performances from SOECs with cathodes ba...

  19. Preparation of ZnO/Al2O3 catalysts by using atomic layer deposition for plasma-assisted non-oxidative methane coupling

    Science.gov (United States)

    Jeong, Myung-Geun; Kim, Young Dok; Park, Sunyoung; Kasinathan, Palraj; Hwang, Young Kyu; Chang, Jong-San; Park, Yong-Ki

    2016-05-01

    We prepared a ZnO/mesoporous Al2O3-shell/core structure by using atomic layer deposition (ALD) of ZnO on commercially-available mesoporous Al2O3. We used various analysis techniques such as scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, inductively coupled plasma-atomic emission spectroscopy, and surface area and pore size analyses based on nitrogen isotherm data. A 200 nm-thick slab of mesoporous Al2O3 particles was decorated by ZnO upon ALD deposition, whereas the inner part of the Al2O3 particle was free of ZnO. We evaluated the catalytic activity of the bare and the ZnO-covered Al2O3 for plasma-assisted nonoxidative coupling of methane. The catalytic behavior was shown to be sensitive to the amount of ZnO deposited. Particularly, 40-cycled ZnO/Al2O3 showed an enhanced selectivity to the olefin product with almost the same CH4 conversion as that of bare Al2O3. Preparation of the shell/core structure by using ALD can be an interesting strategy for finding highly-efficient catalysts in a plasma-assisted catalytic reaction.

  20. Addition of sulfonated silicon dioxide on an anode catalyst layer to improve the performance of a self-humidifying proton exchange membrane fuel cell

    Science.gov (United States)

    Lin, Chien-Liang; Hsu, Shih-Chieh; Ho, Wei-Yu

    2016-03-01

    Sulfonated SiO2 was added on an anode catalyst layer to manufacture a hygroscopic electrode for self-humidifying proton exchange membrane fuel cells (PEMFCs). The inherent humidity of a proton exchange membrane (PEM) determines the electrical performance of PEMFCs. To maintain the high moisture content of the PEM, self-humidifying PEMFCs can use the water produced by the fuel cell reaction and, thus, do not require external humidification. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and water contact angle measurement tests were performed to characterize the structures and properties of sulfonated SiO2 and the related electrodes, and the electric current and voltage (I-V) performance curve tests for the fuel cells were conducted under differing gas humidification conditions. When 0.01mg/cm2 of sulfonated SiO2 was added, the electrical performance of the fuel cells (50∘C) increased 29% and 59% when the fuel cell reaction gases were humidified at 70∘C and 50∘C, respectively.

  1. Development of cathode material for lithium-ion batteries

    Directory of Open Access Journals (Sweden)

    Rustam Mukhtaruly Turganaly

    2014-08-01

    Full Text Available The electrochemical characteristics of the cathode material coated with carbon layer has been developed. Various carbon coating methods. There  has been carried out a comparative electrochemical analysis of the coated and uncoated with carbon cathode material. 

  2. Cathodic Protection Model Facility

    Data.gov (United States)

    Federal Laboratory Consortium — FUNCTION: Performs Navy design and engineering of ship and submarine impressed current cathodic protection (ICCP) systems for underwater hull corrosion control and...

  3. Fabrication of Ba0.5Sr0.5Co0.8Fe0.2O(3-δ) catalysts with enhanced electrochemical performance by removing an inherent heterogeneous surface film layer.

    Science.gov (United States)

    Jung, Jae-Il; Jeong, Hu Young; Kim, Min Gyu; Nam, Gyutae; Park, Joohyuk; Cho, Jaephil

    2015-01-14

    A heat-treatment approach for Ba0.5Sr0.5Co0.8Fe0.2O(3-δ) (BSCF5582) is introduced as a way of enhancing the electrocatalytic performance of perovskite catalysts. The perovskite made by heat-treatment in oxygen atmosphere loses around 30 nm of spinel layer on the surface relative to the untreated version, and demonstrates enhanced oxygen reduction reaction and oxygen evolution reaction catalytic activities. PMID:25413252

  4. Cathodic oxygen reduction catalyzed by bacteria in microbial fuel cells.

    Science.gov (United States)

    Rabaey, Korneel; Read, Suzanne T; Clauwaert, Peter; Freguia, Stefano; Bond, Philip L; Blackall, Linda L; Keller, Jurg

    2008-05-01

    Microbial fuel cells (MFCs) have the potential to combine wastewater treatment efficiency with energetic efficiency. One of the major impediments to MFC implementation is the operation of the cathode compartment, as it employs environmentally unfriendly catalysts such as platinum. As recently shown, bacteria can facilitate sustainable and cost-effective cathode catalysis for nitrate and also oxygen. Here we describe a carbon cathode open to the air, on which attached bacteria catalyzed oxygen reduction. The bacteria present were able to reduce oxygen as the ultimate electron acceptor using electrons provided by the solid-phase cathode. Current densities of up to 2.2 A m(-2) cathode projected surface were obtained (0.303+/-0.017 W m(-2), 15 W m(-3) total reactor volume). The cathodic microbial community was dominated by Sphingobacterium, Acinetobacter and Acidovorax sp., according to 16S rRNA gene clone library analysis. Isolates of Sphingobacterium sp. and Acinetobacter sp. were obtained using H(2)/O(2) mixtures. Some of the pure culture isolates obtained from the cathode showed an increase in the power output of up to three-fold compared to a non-inoculated control, that is, from 0.015+/-0.001 to 0.049+/-0.025 W m(-2) cathode projected surface. The strong decrease in activation losses indicates that bacteria function as true catalysts for oxygen reduction. Owing to the high overpotential for non-catalyzed reduction, oxygen is only to a limited extent competitive toward the electron donor, that is, the cathode. Further research to refine the operational parameters and increase the current density by modifying the electrode surface and elucidating the bacterial metabolism is warranted. PMID:18288216

  5. Durability and performance optimization of cathode materials for fuel cells

    Science.gov (United States)

    Colon-Mercado, Hector Rafael

    The primary objective of this dissertation is to develop an accelerated durability test (ADT) for the evaluation of cathode materials for fuel cells. The work has been divided in two main categories, namely high temperature fuel cells with emphasis on the Molten Carbonate Fuel Cell (MCFC) cathode current collector corrosion problems and low temperature fuel cells in particular Polymer Electrolyte Fuel Cell (PEMFC) cathode catalyst corrosion. The high operating temperature of MCFC has given it benefits over other fuel cells. These include higher efficiencies (>50%), faster electrode kinetics, etc. At 650°C, the theoretical open circuit voltage is established, providing low electrode overpotentials without requiring any noble metal catalysts and permitting high electrochemical efficiency. The waste heat is generated at sufficiently high temperatures to make it useful as a co-product. However, in order to commercialize the MCFC, a lifetime of 40,000 hours of operation must be achieved. The major limiting factor in the MCFC is the corrosion of cathode materials, which include cathode electrode and cathode current collector. In the first part of this dissertation the corrosion characteristics of bare, heat-treated and cobalt coated titanium alloys were studied using an ADT and compared with that of state of the art current collector material, SS 316. PEMFCs are the best choice for a wide range of portable, stationary and automotive applications because of their high power density and relatively low-temperature operation. However, a major impediment in the commercialization of the fuel cell technology is the cost involved due to the large amount of platinum electrocatalyst used in the cathode catalyst. In an effort to increase the power and decrease the cathode cost in polymer electrolyte fuel cell (PEMFC) systems, Pt-alloy catalysts were developed to increase its activity and stability. Extensive research has been conducted in the area of new alloy development and

  6. Li-ion storage performance and electrochemically induced phase evolution of layer-structured Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material

    Science.gov (United States)

    Wang, Ying; Zhang, Hong; Ma, Zhiyuan; Wang, Gaomin; Li, Zhicheng

    2016-04-01

    Li-rich Li[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNC) powders were synthesized by a gel-combustion method. The related microstructure, electrochemical performance and electrochemically induced phase evolution were characterized. The 900°C calcined powders have a hexagonal layered structure with high ordered degree and low cationic mixing level. The calcined materials as cathode electrode for Li-ion battery deliver the high electrochemical properties with an initial discharge capacity of 243.5 mA•h•g-1 at 25 mA•g-1 and 249.2 mA•h•g-1 even after 50 cycles. The electrochemically induced phase evolution investigated by a transmission electron microscopy indicates that Li+ ions deintercalated first from the LiMO2 (M = Mn, Co, Ni) component and then from Li2MnO3 component in the LMNC during the charge process, while Li+ ions intercalated into Li1-x MO2 component followed by into MnO2 component during the discharge process.

  7. Effect of cooling method on the electrochemical performance of layered-spinel composite cathode Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunjian [School of Material Science and Technology, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Wang, Qiliang; Gao, Yanyong [School of Material Science and Technology, Jiangsu University, Zhenjiang 212013 (China); Pan, Jun [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Su, Mingru, E-mail: lyjian122331@163.com [School of Material Science and Technology, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Hai, Bin; Zhu, Guangyan; Liu, Sanbing [Chery Science Research Institute, Chery Automobile Co., Ltd, Wuhu 241006 (China)

    2015-10-15

    Layered-spinel composite cathode material Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} has been synthesized and cooled by different methods (naturally cooled within the furnace and cooled in liquid nitrogen). The effect of cooling methods on physical and electrochemical properties are discussed using the characterizations of X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), charge/discharge, cyclic and rate tests. The layered-spinel composite structure has been detected in Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} electrodes from the XRD patterns and TEM images. XPS results show that the content of Mn{sup 3+} in the Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled in liquid nitrogen is more than that of Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled with furnace. The electrochemical performance results show that the Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled in liquid nitrogen has higher initial discharge capacity, coulomb efficiency, better cyclic and rate performance compared with Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled with furnace. EIS results show that the charge transfer resistance (R{sub ct}) of Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled in liquid nitrogen is lower than that of Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled with furnace. The improved cyclic and rate performances of Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} cooled in liquid nitrogen cathode are attributed to the lower R{sub ct} and more content of Mn{sup 3+}. - Graphical abstract: Layered-spinel composite cathode material Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.3} have been synthesized and cooled by different methods (naturally cooled within the furnace (‘a’) and cooled in liquid nitrogen (‘b’)). Compared with cooled with furnace (‘a’), the Li{sub 1.1}Ni{sub 0.25}Mn{sub 0.75}O{sub 2

  8. Efficient plasma-enhanced method for layered LiNi1/3Co1/3Mn1/3O2 cathodes with sulfur atom-scale modification for superior-performance Li-ion batteries

    Science.gov (United States)

    Jiang, Qianqian; Chen, Ning; Liu, Dongdong; Wang, Shuangyin; Zhang, Han

    2016-05-01

    In order to improve the electrochemical performance of LiNi1/3Co1/3Mn1/3O2 as a lithium insertion positive electrode material, atom-scale modification was realized to obtain the layered oxysulfide LiNi1/3Co1/3Mn1/3O2-xSx using a novel plasma-enhanced doping strategy. The structure and electrochemical performance of LiNi1/3Co1/3Mn1/3O2-xSx are investigated systematically, which confirms that the S doping can make the structure stable and benefit the electrochemical performance. The phys-chemical characterizations indicate that oxygen atoms in the initial LiNi1/3Co1/3Mn1/3O2 have been partially replaced by S atoms. It should be pointed out that the atom-scale modification does not significantly alter the intrinsic structure of the cathode. Compared to the pristine material, the LiNi1/3Co1/3Mn1/3O2-xSx shows a superior performance with a higher capacity (200.4 mA h g-1) and a significantly improved cycling stability (maintaining 94.46% of its initial discharge capacity after 100 cycles). Moreover, it has an excellent rate performance especially at elevated performance, which is probably due to the faster Li+ transportation after S doping into the layered structure. All the results show that the atom-scale modification with sulfur atoms on LiNi1/3Co1/3Mn1/3O2, which significantly improved the electrochemical performance, offers a novel anionic doping strategy to realize the atom-scale modification of electrode materials to improve their electrochemical performance.In order to improve the electrochemical performance of LiNi1/3Co1/3Mn1/3O2 as a lithium insertion positive electrode material, atom-scale modification was realized to obtain the layered oxysulfide LiNi1/3Co1/3Mn1/3O2-xSx using a novel plasma-enhanced doping strategy. The structure and electrochemical performance of LiNi1/3Co1/3Mn1/3O2-xSx are investigated systematically, which confirms that the S doping can make the structure stable and benefit the electrochemical performance. The phys

  9. Efficient plasma-enhanced method for layered LiNi1/3Co1/3Mn1/3O2 cathodes with sulfur atom-scale modification for superior-performance Li-ion batteries.

    Science.gov (United States)

    Jiang, Qianqian; Chen, Ning; Liu, Dongdong; Wang, Shuangyin; Zhang, Han

    2016-06-01

    In order to improve the electrochemical performance of LiNi1/3Co1/3Mn1/3O2 as a lithium insertion positive electrode material, atom-scale modification was realized to obtain the layered oxysulfide LiNi1/3Co1/3Mn1/3O2-xSx using a novel plasma-enhanced doping strategy. The structure and electrochemical performance of LiNi1/3Co1/3Mn1/3O2-xSx are investigated systematically, which confirms that the S doping can make the structure stable and benefit the electrochemical performance. The phys-chemical characterizations indicate that oxygen atoms in the initial LiNi1/3Co1/3Mn1/3O2 have been partially replaced by S atoms. It should be pointed out that the atom-scale modification does not significantly alter the intrinsic structure of the cathode. Compared to the pristine material, the LiNi1/3Co1/3Mn1/3O2-xSx shows a superior performance with a higher capacity (200.4 mA h g(-1)) and a significantly improved cycling stability (maintaining 94.46% of its initial discharge capacity after 100 cycles). Moreover, it has an excellent rate performance especially at elevated performance, which is probably due to the faster Li(+) transportation after S doping into the layered structure. All the results show that the atom-scale modification with sulfur atoms on LiNi1/3Co1/3Mn1/3O2, which significantly improved the electrochemical performance, offers a novel anionic doping strategy to realize the atom-scale modification of electrode materials to improve their electrochemical performance. PMID:27189799

  10. Cationic fluorinated polymer binders for microbial fuel cell cathodes

    KAUST Repository

    Chen, Guang

    2012-01-01

    Fluorinated quaternary ammonium-containing polymers were used as catalyst binders in microbial fuel cell (MFC) cathodes. The performance of the cathodes was examined and compared to NAFION ® and other sulfonated aromatic cathode catalyst binders using linear sweep voltammetry (LSV), impedance spectroscopy, and performance tests in single chamber air-cathode MFCs. The cathodes with quaternary ammonium functionalized fluorinated poly(arylene ether) (Q-FPAE) binders showed similar current density and charge transfer resistance (R ct) to cathodes with NAFION ® binders. Cathodes containing either of these fluorinated binders exhibited better electrochemical responses than cathodes with sulfonated or quaternary ammonium-functionalized RADEL ® poly(sulfone) (S-Radel or Q-Radel) binders. After 19 cycles (19 d), the power densities of all the MFCs declined compared to the initial cycles due to biofouling at the cathode. MFC cathodes with fluorinated polymer binders (1445 mW m -2, Q-FPAE-1.4-H; 1397 mW m -2, Q-FPAE-1.4-Cl; 1277 mW m -2, NAFION ®; and 1256 mW m -2, Q-FPAE-1.0-Cl) had better performance than those with non-fluorinated polymer binders (880 mW m -2, S-Radel; 670 mW m -2, Q-Radel). There was a 15% increase in the power density using the Q-FPAE binder with a 40% higher ion exchange capacity (Q-FPAE-1.4-H compared to Q-FPAE-1.0-Cl) after 19 cycles of operation, but there was no effect on the power production due to counter ions in the binder (Cl -vs. HCO 3 -). The highest-performance cathodes (NAFION ® and Q-FPAE binders) had the lowest charge transfer resistances (R ct) in fresh and in fouled cathodes despite the presence of thick biofilms on the surface of the electrodes. These results show that fluorinated binders may decrease the penetration of the biofilm and associated biopolymers into the cathode structure, which helps to combat MFC performance loss over time. © 2012 The Royal Society of Chemistry.

  11. Improved Dispenser Cathodes

    Science.gov (United States)

    Ives, R. Lawrence; Falce, Lou

    2006-01-01

    Variations in emission current from dispenser cathodes can be caused by variations in temperature and work function over the surface. This paper described research to reduce these variations using improved mechanical designs and controlled porosity cathodes made from sintered tungsten wires. The program goal is to reduce current emission variations to less than 5% over the surface of magnetron injection guns operating temperature limited.

  12. Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

    Science.gov (United States)

    Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

    2016-08-01

    Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as ‑0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at ‑0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under ‑0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination.

  13. High efficiency solution processed fluorescent yellow organic light-emitting diode through fluorinated alcohol treatment at the emissive layer/cathode interface

    International Nuclear Information System (INIS)

    We compare solvent treatments using fluorinated alcohol (2,2,3,3,4,4,5,5-octafluoro- 1-pentanol) and ethanol in improving the efficiency of a polymer organic light-emitting diode (OLED) by spin coating the solvent on top of the emissive layer. The presence of fluorinated alcohol is confirmed using x-ray photoelectron spectroscopy. The electron current is found to be significantly enhanced following solvent treatment while the hole current remains the same. The solvent treatment by fluorinated alcohol on top of a ‘super-yellow’ poly-(p-phenylenevinylene) (SY-PPV) based OLED results in efficiency as high as 19.2 lm W−1 (20.9 cd A−1) at a brightness of 1000 cd m−2. The improvement of device efficiency through the use of fluorinated alcohol treatment can be attributed to its large dipole, which lowers the electron injection barrier. This work also suggests that fluorinated alcohol might be a better trap passivator for electrons than ethanol. (paper)

  14. Effect of nickel and iron on structural and electrochemical properties of O3 type layer cathode materials for sodium-ion batteries

    Science.gov (United States)

    Hwang, Jang-Yeon; Myung, Seung-Taek; Aurbach, Doron; Sun, Yang-Kook

    2016-08-01

    We investigate that the effect of Ni and Fe contents on structural and electrochemical properties of O3-type layered Na[Ni0.75-xFexMn0.25]O2 (x = 0.4, 0.45, 0.5, and 0.55) in which Mn is fixed at 25%. As increasing the Ni contents, the capacities are gradually higher while the capacity retention and thermal properties are inferior. When Fe contents are increased, by contrast, the electrode exhibits stable capacity retention and satisfactory thermal stability although the resulting capacity slightly decreases. Structural investigation of post cycled electrodes indicate that lattice variation is greatly suppressed from x = 0.5 in Na[Ni0.75-xFexMn0.25]O2. This indicates that an appropriate amount of Fe into the Na[Ni0.75-xFexMn0.25]O2 stabilizes the crystal structure and this leads to the good cycling performances. Also, the better structural stability obtained by Fe addition is responsible for the less heat generation at elevated temperature for the desodiated Na1-δ[Ni0.75-xFexMn0.25]O2 (x = 0.4, 0.45, 0.5, and 0.55) caused by less evaporation of oxygen from the crystal structure.

  15. Synthesis and electrochemical properties of layered structure Li[Ni0.5Co0.25Mn0.25]O2 cathode material

    International Nuclear Information System (INIS)

    Lithium ion (Li-ion) batteries are currently the energy source of choice for cell phones, laptops, and other mobile electronic devices due to their balance of high energy density with high power density compared to other electrochemical energy carriers. In the present study, mixed hydroxide method is used to prepare Li[Ni0.5Co0.25Mn0.25]O2 from the precursors and analyze qualitatively and studied the electrochemical properties. The XRD spectrum exhibited predominant (003) orientation at 2θ =18.39o corresponding to hexagonal layered structure of R3m symmetry with evaluated lattice parameters are a= 2.84 Å, c= 14.43 Å. Raman measurements were performed to understand the microstructure and vibrational modes of the prepared sample. From the electrochemical (EC) studies an initial discharge capacity of about 140 mAhg−1 with good cyclic stability was observed for the prepared sample in the potential range 0.0 −1.0V in aqueous medium

  16. Synthesis and electrochemical properties of a new layered cathode material LiNi1/2Mn1/3V1/6O2

    International Nuclear Information System (INIS)

    A new layered type lithium nickel manganese vanadium oxide with the composition of LiNi1/2Mn1/3V1/6O2 was synthesized by rheological phase reaction method. The morphology, structural and electrochemical behavior were characterized by means of SEM, X-ray diffraction analysis and electrochemical charge–discharge tests. Phase-pure LiNi1/2Mn1/3V1/6O2 was obtained when the mixed precursors of Ni–Mn–V–O composite oxide and LiOH were calcined at 800 °C for 30 h. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation states of Ni, Mn and V. It is found that the submicro-sized LiNi1/2Mn1/3V1/6O2 delivers an initial discharge capacity of 142 mA h/g in the cut-off voltage of 2.5–4.8 V, and exhibits good cycle performance.

  17. A study of water transport as a function of the micro-porous layer arrangement in PEMFCs

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Taeyoung; Lee, Seungjae; Park, Heekyung [Department of Civil and Environmental Engineering, KAIST, Guseong-dong, Yuseong-gu, Daejeon, 305-701 (Korea)

    2010-08-15

    Electrochemical losses as a function of the micro-porous layer (MPL) arrangement in Proton Exchange Membrane Fuel Cells (PEMFCs) are investigated by electrochemical impedance spectroscopy (EIS). Net water flux across the polymer membrane in PEMFCs is investigated for various arrangements of the MPL, namely with MPL on the cathode side alone, with MPL on both the cathode and the anode sides and without MPL. EIS and water transport are recorded for various operating conditions, such as the relative humidity of the hydrogen inlet and current density, in a PEMFC fed by fully-saturated air. The cell with an MPL on the cathode side alone has better performance than two other types of cells. Furthermore, the cell with an MPL on only the cathode increases the water flux from cathode to anode as compared to the cells with MPLs on both electrodes and cells without MPL. Oxygen-mass-transport resistances of cells in the presence of an MPL on the cathode are lower than the values for the other two cells, which indicates that the molar concentration of oxygen at the reaction surface of the catalyst layer is higher. This suggests that the MPL forces the liquid water from the cathode side to the anode side and decreases the liquid saturation in GDL at high current densities. Consequently, the MPL helps in maintaining the water content in the polymer membrane and decreases the cathode charge transfer and oxygen-mass transport resistances in PEMFCs, even when the hydrogen inlet has a low relative humidity. (author)

  18. Enhancing phase stability and kinetics of lithium-rich layered oxide for an ultra-high performing cathode in Li-ion batteries

    Science.gov (United States)

    Lee, Sung Hoon; Moon, Jong-Seok; Lee, Mi-Sun; Yu, Tae-Hwan; Kim, Hyunbin; Park, Bong Mo

    2015-05-01

    To achieve a higher capacity and rate capability, the electrochemical performance of doped Li-rich layered oxide (LLO), in which Co and O ions are substituted with various dopants (Ti, Zr, Ce, Mo, W, and F), is investigated using first-principles calculations. W and Mo are candidate dopants to enhance the phase stability but are excluded due to the decreased average cell voltage of 2.5-5.4 %, lowering the energy density of a battery. Instead, F is selected as a promising dopant because F-doped LLO can achieve high structural stability without a reduction in the average cell voltage compared with un-doped LLO. The Li slab distance in F-doped LLO expands approximately 3-8% depending on the Li concentration, and the activation energy for Li hopping is reduced about 30%, suggesting faster Li ion diffusion. The enthalpy of formation of F-doped LLO is reduced to 5.3-12.4 kJ mol-1 during de-lithiation, implying an increase in phase stability. Based on the DFT prediction, we experimentally demonstrate F-doped LLO (Li1.17Ni0.17Co0.17Mn0.50O1.96F0.04) exhibits a high capacity of 252.2 mAh g-1 at 0.33C rate in the cut-off voltage range of 3.0-4.6 V. The rate capability is enhanced, and the capacity is retained up to 83% at 3C compared with the 0.33C rate.

  19. The double sheath on cathodes of discharges burning in cathode vapour

    Energy Technology Data Exchange (ETDEWEB)

    Benilov, M S; Benilova, L G [Departamento de Fisica, Universidade da Madeira, Largo do MunicIpio, 9000 Funchal (Portugal)

    2010-09-01

    The model of a collisionless near-cathode space-charge sheath with ionization of atoms emitted by the cathode surface is considered. Numerical calculations showed that the mathematical problem is solvable and its solution is unique. In the framework of this model, the sheath represents a double layer with a potential maximum, with the ions which are produced before the maximum returning to the cathode surface and those produced after the maximum escaping into the plasma. Numerical results are given in a form to be readily applicable in analysis of discharges burning in cathode vapour, such as vacuum arcs. In particular, the results indicate that the ion backflow coefficient in such discharges exceeds 0.5, in agreement with values extracted from the experiment.

  20. Highly active and stable platinum catalyst supported on porous carbon nanofibers for improved performance of PEMFC

    International Nuclear Information System (INIS)

    Porous carbon nanofibers (PCNFs) were used as the support to prepare platinum (Pt) catalyst (Pt/PCNFs) for proton exchange membrane fuel cell (PEMFC) applications. As a comparison, Pt supported on carbon black (Vulcan XC-72) (Pt/Vulcan) was also synthesized by the same ethylene glycol reduction method. Platinum was more uniformly deposited on PCNFs than that on the Vulcan XC-72. The electrocatalytic activity and stability of the resultant catalysts along with the commercial one (JM20) were investigated using cyclic voltammetry (CV) and linear sweep voltammetry (LSV) with a rotating disk electrode (RDE). The Pt/PCNFs exhibited much-enhanced electrocatalytic activity and stability compared with the Pt/Vulcan and JM20. The mass activity (at 0.80 V) of Pt/PCNFs is 2.6 times higher and 20% higher than that of Pt/Vulcan and JM20, respectively; the Pt/PCNFs retained about 50% of ECSA whereas JM20 and Pt/Vulcan kept only 25% and 5% of ECSA, respectively, even after 1000 cycles. Furthermore, the single cell performance of Pt/PCNFs was superior to that of Pt/Vulcan and even better than JM20 during high current densities. The cross-section of the membrane electrode assembly (MEA) showed that the Pt/PCNFs construct a loose three-dimensionally connected catalyst layer that is totally different from the tightly stacking catalyst layer composed of carbon black support. Thus, the mass transfer resistance is reduced and water drainage becomes easy when Pt/PCNFs were used as cathode catalyst. These results indicate PCNFs a promising candidate as catalyst supports for the enhancement of PEMFC performance

  1. Poly(vinyl alcohol) separators improve the coulombic efficiency of activated carbon cathodes in microbial fuel cells

    KAUST Repository

    Chen, Guang

    2013-09-01

    High-performance microbial fuel cell (MFC) air cathodes were constructed using a combination of inexpensive materials for the oxygen reduction cathode catalyst and the electrode separator. A poly(vinyl alcohol) (PVA)-based electrode separator enabled high coulombic efficiencies (CEs) in MFCs with activated carbon (AC) cathodes without significantly decreasing power output. MFCs with AC cathodes and PVA separators had CEs (43%-89%) about twice those of AC cathodes lacking a separator (17%-55%) or cathodes made with platinum supported on carbon catalyst (Pt/C) and carbon cloth (CE of 20%-50%). Similar maximum power densities were observed for AC-cathode MFCs with (840 ± 42 mW/m2) or without (860 ± 10 mW/m2) the PVA separator after 18 cycles (36 days). Compared to MFCs with Pt-based cathodes, the cost of the AC-based cathodes with PVA separators was substantially reduced. These results demonstrated that AC-based cathodes with PVA separators are an inexpensive alternative to expensive Pt-based cathodes for construction of larger-scale MFC reactors. © 2013 Elsevier B.V. All rights reserved.

  2. Nanostructured sulfur cathodes

    KAUST Repository

    Yang, Yuan

    2013-01-01

    Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes. © 2013 The Royal Society of Chemistry.

  3. Cathodes - Technological review

    International Nuclear Information System (INIS)

    Lithium cobalt oxide (LiCoO2) was already used in the first commercialized Li-ion battery by SONY in 1990. Still, it is the most frequently used cathode material nowadays. However, LiCoO2 is intrinsically unstable in the charged state, especially at elevated temperatures and in the overcharged state causing volume changes and transport limitation for high power batteries. In this paper, some technological aspects with large impact on cell performance from the cathode material point of view will be reviewed. At first it will be focused on the degradation processes and life-time mechanisms of the cathode material LiCoO2. Electrochemical and structural results on commercial Li-ion batteries recorded during the cycling will be discussed. Thereafter, advanced nanomaterials for new cathode materials will be presented

  4. A bipolar membrane combined with ferric iron reduction as an efficient cathode system in microbial fuel cells

    NARCIS (Netherlands)

    Heijne, ter A.; Hamelers, H.V.M.; Wilde, de V.; Rozendal, R.A.; Buisman, C.J.N.

    2006-01-01

    There is a need for alternative catalysts for oxygen reduction in the cathodic compartment of a microbial fuel cell (MFC). In this study, we show that a bipolar membrane combined with ferric iron reduction on a graphite electrode is an efficient cathode system in MFCs. A flat plate MFC with graphite

  5. Homogeneous catalysts

    CERN Document Server

    Chadwick, John C; Freixa, Zoraida; van Leeuwen, Piet W N M

    2011-01-01

    This first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste.The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.

  6. Performance of Stainless Steel Mesh Cathode and PVDF-graphite Cathode in Microbial Fuel Cells

    Science.gov (United States)

    Huang, Liping; Tian, Ying; Li, Mingliang; He, Gaohong; Li, Zhikao

    2010-11-01

    Inexpensive and conductive materials termed as stainless steel mesh and polyvinylidene fluoride (PVDF)-graphite were currently used as the air cathode electrodes in MFCs for the investigation of power production. By loading PTFE (poly(tetrafluoroethylene)) on the surface of stainless steel mesh, electricity production reached 3 times as high as that of the naked stainless steel. A much high catalytic activity for oxygen reduction was exhibited by Pt based and PTFE loading stainless steel mesh cathode, with an electricity generation of 1144±44 mW/m2 (31±1 W/m3) and a Coulombic efficiency (CE) of 77±2%. When Pt was replaced by an inexpensive transition metal based catalyst (cobalt tetramethylphenylporphyrin, CoTMPP), power production and CE were 845±21 mW/m2 (23±1 W/m3) and 68±1%, respectively. Accordingly, power production from PVDF-graphite (hydrophobic) MFC and PVDF-graphite (hydrophile) MFC were 286±20 mW/m2(8±1 W/m3) and 158±13 mW/m2(4±0.4 W/m3), respectively using CoTMPP as catalyst. These results give us new insight into materials like stainless steel mesh and PVDF-graphite as low cost cathode for reducing the costs of MFCs for wastewater treatment applications.

  7. Using elastin protein to develop highly efficient air cathodes for lithium-O2 batteries

    Science.gov (United States)

    Guo, Guilue; Yao, Xin; Ang, Huixiang; Tan, Huiteng; Zhang, Yu; Guo, Yuanyuan; Fong, Eileen; Yan, Qingyu

    2016-01-01

    Transition metal-nitrogen/carbon (M-N/C, M = Fe, Co) catalysts are synthesized using environmentally friendly histidine-tag-rich elastin protein beads, metal sulfate and water soluble carbon nanotubes followed by post-annealing and acid leaching processes. The obtained catalysts are used as cathode materials in lithium-O2 batteries. It has been discovered that during discharge, Li2O2 nanoparticles first nucleate and grow around the bead-decorated CNT regions (M-N/C centres) and coat on the catalysts at a high degree of discharge. The Fe-N/C catalyst-based cathodes deliver a capacity of 12 441 mAh g-1 at a current density of 100 mA g-1. When they were cycled at a limited capacity of 800 mAh g-1 at current densities of 200 or 400 mA g-1, these cathodes showed stable charge voltages of ˜3.65 or 3.90 V, corresponding to energy efficiencies of ˜71.2 or 65.1%, respectively. These results are considerably superior to those of the cathodes based on bare annealed CNTs, which prove that the Fe-N/C catalysts developed here are promising for use in non-aqueous lithium-O2 battery cathodes.

  8. New doped tungsten cathodes. Applications to power grid tubes

    International Nuclear Information System (INIS)

    Thermionic emission behavior of tungsten/tungsten carbide modified with rare earth (La, Ce, Y) oxides is examined on account of suitability to deliver important current densities in a thermo-emissive set up and for long lifetime. Work functions of potential cathodes have been determined from Richardson plots for La2O3 doped tungsten and for tungsten covered with variable compositions rare earth tungstates. The role of platinum layers covering the cathode was also examined. Given all cathodes containing mainly lanthanum oxides were good emitters, emphasis was put on service lifetime. Comparisons of lifetime in tungsten doped with rare earth oxides and with rare earth tungstates show that microstructure of the operating cathodes may play the major role in the research of very long lifetime cathodes. Based on these results, tests still running show lifetime compatible with power grid tubes applications. (author)

  9. The influence of cathode material on electrochemical degradation of trichloroethylene in aqueous solution.

    Science.gov (United States)

    Rajic, Ljiljana; Fallahpour, Noushin; Podlaha, Elizabeth; Alshawabkeh, Akram

    2016-03-01

    In this study, different cathode materials were evaluated for electrochemical degradation of aqueous phase trichloroethylene (TCE). A cathode followed by an anode electrode sequence was used to support reduction of TCE at the cathode via hydrodechlorination (HDC). The performance of iron (Fe), copper (Cu), nickel (Ni), aluminum (Al) and carbon (C) foam cathodes was evaluated. We tested commercially available foam materials, which provide large electrode surface area and important properties for field application of the technology. Ni foam cathode produced the highest TCE removal (68.4%) due to its high electrocatalytic activity for hydrogen generation and promotion of HDC. Different performances of the cathode materials originate from differences in the bond strength between atomic hydrogen and the material. With a higher electrocatalytic activity than Ni, Pd catalyst (used as cathode coating) increased TCE removal from 43.5% to 99.8% for Fe, from 56.2% to 79.6% for Cu, from 68.4% to 78.4% for Ni, from 42.0% to 63.6% for Al and from 64.9% to 86.2% for C cathode. The performance of the palladized Fe foam cathode was tested for degradation of TCE in the presence of nitrates, as another commonly found groundwater species. TCE removal decreased from 99% to 41.2% in presence of 100 mg L(-1) of nitrates due to the competition with TCE for HDC at the cathode. The results indicate that the cathode material affects TCE removal rate while the Pd catalyst significantly enhances cathode activity to degrade TCE via HDC. PMID:26761603

  10. Catalyst nanoscale assembly from the vapor phase on corrosion resistant supports

    International Nuclear Information System (INIS)

    The synthesis process, reactive spray deposition technology (RSDT), utilized a jet-flame to produce Pt nanoparticles. The RSDT process bypasses traditional wet chemical routes by simultaneously nucleating the catalyst on a support and sequential deposition of catalyst layer via the gas phase. Pt nanoparticles were attached, in the process gas during the time-of-flight, to the surface of several supports. The supports show promising corrosion resistance under the cathode conditions of a proton exchange membrane fuel cell (PEMFC). The supported Pt catalysts were then studied in regards to structure, stability and electrochemical behavior toward the oxygen reduction reaction (ORR) in perchloric acid. Transmission electron microscopy studies showed that the average Pt particle diameter is ∼2.5 nm. The average diameter and distribution of the Pt particles are independent of the support type and a high degree of catalyst dispersion has been achieved on all supports. The greatest surface area and electrochemical mass activity were obtained using Vulcan XC-72R, while a graphitized carbon support produced the highest specific activity. Based on X-ray photoelectric spectroscopy (XPS) measurements, approximately 30% of the surface of the Pt particles is comprised of Pt2+. This oxide coverage does not extend into the bulk and is below the detection limits of X-ray diffraction (XRD). The electrochemical reduction of oxygen exhibits a typical Tafel slope of −65 to 71 mV/dec

  11. Cathode materials review

    International Nuclear Information System (INIS)

    The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403-431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead-acid with a lead oxide cathode and a terminal voltage of 2.1 V and later the NiCd with a nickel(III) oxide-hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J. Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783-789) demonstrated a high-energy and high-power LiCoO2 cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research

  12. Bimetallic Catalysts.

    Science.gov (United States)

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  13. Cr(VI) reduction at rutile-catalyzed cathode in microbial fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Lu, Anhuai; Ding, Hongrui; Yan, Yunhua; Wang, Changqiu; Zen, Cuiping; Wang, Xin [The Key Laboratory of Orogenic Belts and Crustal Evolution, School of Earth and Space Sciences, Peking University, Beijing 100871 (China); Jin, Song [MWH Americas, 3665 JFK Parkway, Suite 206, Fort Collins, CO 80525 (United States); Department of Civil and Architectural Engineering, University of Wyoming, Laramie, WY 82071 (United States)

    2009-07-15

    Cathodic reduction of hexavalent chromium (Cr(VI)) and simultaneous power generation were successfully achieved in a microbial fuel cell (MFC) containing a novel rutile-coated cathode. The selected rutile was previously characterized to be sensitive to visible light and capable of both non-photo- and photocatalysis. In the MFCs containing rutile-coated cathode, Cr(VI) was rapidly reduced in the cathode chamber in presence and absence of light irradiation; and the rate of Cr(VI) reduction under light irradiation was substantially higher than that in the dark. Under light irradiation, 97% of Cr(VI) (initial concentration 26 mg/L) was reduced within 26 h, which was 1.6 x faster than that in the dark controls in which only background non-photocatalysis occurred. The maximal potential generated under light irradiation was 0.80 vs. 0.55 V in the dark controls. These results indicate that photocatalysis at the rutile-coated cathode in the MFCs might have lowered the cathodic overpotential, and enhanced electron transfer from the cathode to Cr(VI) for its reduction. In addition, photoexcited electrons generated during the cathode photocatalysis might also have contributed to the higher Cr(VI) reduction rates when under light irradiation. This work assessed natural rutile as a novel cathodic catalyst for MFCs in power generation; particularly it extended the practical merits of conventional MFCs to cathodic reduction of environmental contaminants such as Cr(VI). (author)

  14. Organometallic catalysts for primary phosphoric acid fuel cells

    Science.gov (United States)

    Walsh, Fraser

    1987-01-01

    A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

  15. Enhanced electrochemical performances of layered cathode material Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} by coating with LiAlO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunjian [School of Material Science and technology Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Wang, Qiliang; Lu, Yifan; Yang, Bailin [School of Material Science and technology Jiangsu University, Zhenjiang 212013 (China); Su, Mingru, E-mail: smrr1987@163.com [School of Material Science and technology Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Gao, Yanyong; Dou, Aichun [School of Material Science and technology Jiangsu University, Zhenjiang 212013 (China); Pan, Jun [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China)

    2015-07-25

    Highlights: • Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} powders are coated by LiAlO{sub 2} with different amounts. • The electrochemical properties of Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} are improved after coating. • The capacity retention of coated Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} is improved from 90.8% to 101.6% after 50 cycles. - Abstract: Layered solid solution cathode Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} has been synthesized and coated by composite oxides LiAlO{sub 2} with varying amounts (1, 3, 5 and 8 wt%) in this paper. The effect of coated LiAlO{sub 2} on the physical and electrochemical properties of the material has been discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), discharge, cyclic performance, rate capability and electrochemical impedance spectroscopy (EIS). The discharge capacity and coulombic efficiency of Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} in the first cycle have been improved after LiAlO{sub 2} coating. And the 5 wt% LiAlO{sub 2} coated Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} shows the best discharge capacity (257.6 mA h g{sup −1}), capacity retention (101.6% for 50 cycles) and rate capability (88.3 mA h g{sup −1} at 10 C). Electrochemical impedance spectroscopy (EIS) results show that the R{sub ct} of Li{sub 1.5}Ni{sub 0.25}Mn{sub 0.75}O{sub 2.5} electrode decreases after LiAlO{sub 2} coating, which is due to high lithium ion diffusion coefficient of LiAlO{sub 2}, is responsible for superior rate capability.

  16. Modification of porosity in the catalyst layer of membrane electrode assemblies using pore-forming agents; Modificacion de la porosidad en la capa catalitica de ensambles membrana-electrodo empleando agentes formadores de poros

    Energy Technology Data Exchange (ETDEWEB)

    Flores Hernandez, J. Roberto [Instituto de Investigaciones Electricas Cuernavaca, Morelos (Mexico)] e-mail: jrflores@iie.org.mx; Reyes, Brenda [UNAM. Facultad de Quimica, Mexico D.F. (Mexico); Barbosa P., Romeli [Centro de Investigacion en Energia, UNAM, Temixco, Morelos (Mexico); Cano Castillo, Ulises; Albarran, Lorena [Instituto de Investigaciones Electricas Cuernavaca, Morelos (Mexico)

    2009-09-15

    Membrane electrode assemblies (MEA) are the most important part of PEM fuel cells since their interface results in the electrochemical reactions that make the generation of electricity possible. The MEA is composed of a proton exchange membrane, both sides of which are impregnated with a catalyst layer, normally of carbon-supported platinum. Depending on the technique used for its fabrication (atomization, serigraphy, brush methods, chemical reduction, etc.), the properties of the MEA can be different in terms of porosity, distribution of the catalyst, thickness and structure of the catalyst layer, and the quality of the union between the catalyst layer and the membrane, etc. Currently, the porosity of the electrodes is generated by isopropanol evaporation (solvent used in the dye) during the fabrication process conducted in the Instituto de Investigaciones Electricas (IIE). This document presents the results obtained from adding a porous agent to the catalytic dye base composition used in the fabrication of MEA at the IIE. [Spanish] Los Ensambles Membrana-Electrodo (MEA's) son la parte mas importante en las celdas de combustibles tipo PEM, ya que en su interfaz se llevan a cabo las reacciones electroquimicas que hacen posible la generacion de electricidad. El MEA esta compuesto de una membrana de intercambio protonico a la cual se le impregna en ambos lados una capa catalitica normalmente de platino soportado en carbon. Dependiendo de la tecnica empleada en su fabricacion (atomizado, serigrafia, brocha, reduccion quimica, etc.), las propiedades del MEA pueden ser diferentes en cuanto a porosidad, distribucion del catalizador, grosor y estructura de la capa catalitica, asi como la calidad de la union entre la capa catalizadora y la membrana, etc. Actualmente, la porosidad de los electrodos es generada por la evaporacion del isopropanol (solvente utilizado en la tinta) durante el proceso de fabricacion que se realiza en el Instituto de Investigaciones

  17. Petroleum porphyrins as electrocatalysts for cathodic oxygen reduction

    International Nuclear Information System (INIS)

    This paper examines the possibilities for obtaining active catalysts for cathodic oxygen reduction by subjecting concentrates of vanadyl porphyrins (VONP) extracted from crude oils with dimethylformamide and then purified chromatographically on aluminum oxide and silica gel to pyrolysis on carbon. Data obtained with synthetic vanadyl tetra(nmethoxyphenyl)porphyrin (VOTMPP) are reported for comparison. It is shown that VONP-1 and VONP-3 containing more than 80 wt.% of VONP are sufficiently active catalysts for O2 reduction in alkaline solution. The lower activity of VONP-2 is evidently due to its higher impurity content. Natural vanadyl porphyrins promise to be useful as electrocatalysts of the oxygen reaction in alkaline media

  18. Cathodic Cage Plasma Nitriding: An Innovative Technique

    OpenAIRE

    de Sousa, R. R. M.; de Araújo, F. O.; da Costa, J. A. P.; A. de S. Brandim; de Brito, R. A.; Alves, C

    2012-01-01

    Cylindrical samples of AISI 1020, AISI 316, and AISI 420 steels, with different heights, were simultaneously treated by a new technique of ionic nitriding, entitled cathodic cage plasma nitriding (CCPN), in order to evaluate the efficiency of this technique to produce nitrided layers with better properties compared with those obtained using conventional ionic nitriding technique. This method is able to eliminate the edge effect in the samples, promoting a better uniformity of temperature, and...

  19. Erosion behavior of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Franz, Robert, E-mail: robert.franz@unileoben.ac.at; Mendez Martin, Francisca; Hawranek, Gerhard [Montanuniversität Leoben, Franz-Josef-Strasse 18, 8700 Leoben (Austria); Polcik, Peter [Plansee Composite Materials GmbH, Siebenbürgerstrasse 23, 86983 Lechbruck am See (Germany)

    2016-03-15

    Al{sub x}Cr{sub 1−x} composite cathodes with Al contents of x = 0.75, 0.5, and 0.25 were exposed to cathodic arc plasmas in Ar, N{sub 2}, and O{sub 2} atmospheres and their erosion behavior was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by x-ray diffraction analysis. Cathode poisoning effects in the reactive N{sub 2} and O{sub 2} atmospheres were nonuniform as a result of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded center region of the cathodes.

  20. Highly Efficient Micro Cathode Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Busek Company, Inc. proposes to develop a micro thermionic cathode that requires extremely low power and provides long lifetime. The basis for the cathode is a...

  1. Advanced Cathode Electrolyzer (ACE) Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The proposed innovation is a static, cathode-fed, 2000 psi, balanced-pressure Advanced Cathode Electrolyzer (ACE) based on PEM electrolysis technology. It...

  2. Atomic Layer Deposition of Al2O3-Ga2O3 Alloy Coatings for Li[Ni0.5Mn0.3Co0.2]O2 Cathode to Improve Rate Performance in Li-Ion Battery.

    Science.gov (United States)

    Laskar, Masihhur R; Jackson, David H K; Guan, Yingxin; Xu, Shenzhen; Fang, Shuyu; Dreibelbis, Mark; Mahanthappa, Mahesh K; Morgan, Dane; Hamers, Robert J; Kuech, Thomas F

    2016-04-27

    Metal oxide coatings can improve the electrochemical stability of cathodes and hence, their cycle-life in rechargeable batteries. However, such coatings often impose an additional electrical and ionic transport resistance to cathode surfaces leading to poor charge-discharge capacity at high C-rates. Here, a mixed oxide (Al2O3)1-x(Ga2O3)x alloy coating, prepared via atomic layer deposition (ALD), on Li[Ni0.5Mn0.3Co0.2]O2 (NMC) cathodes is developed that has increased electron conductivity and demonstrated an improved rate performance in comparison to uncoated NMC. A "co-pulsing" ALD technique was used which allows intimate and controlled ternary mixing of deposited film to obtain nanometer-thick mixed oxide coatings. Co-pulsing allows for independent control over film composition and thickness in contrast to separate sequential pulsing of the metal sources. (Al2O3)1-x(Ga2O3)x alloy coatings were demonstrated to improve the cycle life of the battery. Cycle tests show that increasing Al-content in alloy coatings increases capacity retention; whereas a mixture of compositions near (Al2O3)0.5(Ga2O3)0.5 was found to produce the optimal rate performance. PMID:27035035

  3. Cathode material for lithium batteries

    Science.gov (United States)

    Park, Sang-Ho; Amine, Khalil

    2013-07-23

    A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

  4. Power generation using an activated carbon fiber felt cathode in an upflow microbial fuel cell

    KAUST Repository

    Deng, Qian

    2010-02-01

    An activated carbon fiber felt (ACFF) cathode lacking metal catalysts is used in an upflow microbial fuel cell (UMFC). The maximum power density with the ACFF cathode is 315 mW m-2, compared to lower values with cathodes made of plain carbon paper (67 mW m-2), carbon felt (77 mW m-2), or platinum-coated carbon paper (124 mW m-2, 0.2 mg-Pt cm-2). The addition of platinum to the ACFF cathode (0.2 mg-Pt cm-2) increases the maximum power density to 391 mW m-2. Power production is further increased to 784 mW m-2 by increasing the cathode surface area and shaping it into a tubular form. With ACFF cutting into granules, the maximum power is 481 mW m-2 (0.5 cm granules), and 667 mW m-2 (1.0 cm granules). These results show that ACFF cathodes lacking metal catalysts can be used to substantially increase power production in UMFC compared to traditional materials lacking a precious metal catalyst. © 2009 Elsevier B.V.

  5. Smart cathodic protection systems

    NARCIS (Netherlands)

    Polder, R.B.; Leggedoor, J.; Schuten, G.; Sajna, S.; Kranjc, A.

    2010-01-01

    Cathodic protection delivers corrosion protection in concrete structures exposed to aggressive environments, e.g. in de-icing salt and marine climates. Working lives of a large number of CP systems are at least more than 13 years and probably more than 25 years, provided a minimum level of maintenan

  6. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  7. Pipeline integrity through cathodic protection

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, N. [Gas Authority India Ltd., New Delhi (India); Khanna, A.S. [Indian Inst. of Technology, Bombay (India)

    2008-07-01

    Pipeline integrity management is defined as a process for assessing and mitigating pipeline risks in an effort to reduce both the likelihood and consequences of incidents. Defects on pipelines result in production losses, environmental losses, as well as loss of goodwill and subsequent financial losses. This presentation addressed pipeline integrity through cathodic protection. It noted that pipeline integrity can be strengthened by successfully controlling, monitoring and mitigating corrosion strategies. It can also be achieved by avoiding external and internal corrosion failures. A good coating offers the advantages of low current density; lower power consumption; low wear of anodes; larger spacing between cathodic protection stations; and minimization of interference problems. The presentation reviewed cathodic protection of cross-country pipelines; a sacrificial cathodic protection system; and an impressed current cathodic protection system. The efficiency of a cathodic system was shown to depend on the use of reliable power sources; proper protection criterion; efficient and effective monitoring of cathodic protection; proper maintenance of the cathodic protection system; and effective remedial measures. Selection criteria, power sources, and a comparison of cathodic protection sources were also presented. Last, the presentation addressed protection criteria; current interruption circuits; monitoring of the cathodic protection system; use of corrosion coupons; advantages of weightless coupons; checking the insulating flanges for shorted bolts; insulated/short casings; anodic and cathodic interference; common corridor problems; and intelligent pigging. tabs., figs.

  8. Transition Metal Nitride Coated with Atomic Layers of Pt as a Low-Cost, Highly Stable Electrocatalyst for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Tian, Xinlong; Luo, Junming; Nan, Haoxiong; Zou, Haobin; Chen, Rong; Shu, Ting; Li, Xiuhua; Li, Yingwei; Song, Huiyu; Liao, Shijun; Adzic, Radoslav R

    2016-02-10

    The main challenges to the commercial viability of polymer electrolyte membrane fuel cells are (i) the high cost associated with using large amounts of Pt in fuel cell cathodes to compensate for the sluggish kinetics of the oxygen reduction reaction, (ii) catalyst degradation, and (iii) carbon-support corrosion. To address these obstacles, our group has focused on robust, carbon-free transition metal nitride materials with low Pt content that exhibit tunable physical and catalytic properties. Here, we report on the high performance of a novel catalyst with low Pt content, prepared by placing several layers of Pt atoms on nanoparticles of titanium nickel binary nitride. For the ORR, the catalyst exhibited a more than 400% and 200% increase in mass activity and specific activity, respectively, compared with the commercial Pt/C catalyst. It also showed excellent stability/durability, experiencing only a slight performance loss after 10 000 potential cycles, while TEM results showed its structure had remained intact. The catalyst's outstanding performance may have resulted from the ultrahigh dispersion of Pt (several atomic layers coated on the nitride nanoparticles), and the excellent stability/durability may have been due to the good stability of nitride and synergetic effects between ultrathin Pt layer and the robust TiNiN support. PMID:26796872

  9. Plasma characterization on carbon fiber cathode by spectroscopic diagnostics

    International Nuclear Information System (INIS)

    This paper mainly investigates plasma characterization on carbon fiber cathodes with and without cesium iodide (CsI) coating powered by a ∼300 ns, ∼200 kV accelerating pulse. It was found that the CsI layers can not only improve the diode voltage, but also maintain a stable perveance. This indicates a slowly changed diode gap or a low cathode plasma expansion velocity. By spectroscopic diagnostics, in the vicinity of the cathode surface the average plasma density and temperature were found to be ∼3 × 1014 cm−3 and ∼5 eV, respectively, for an electron current density of ∼40 A/cm2. Furthermore, there exists a multicomponent plasma expansion toward the anode. The plasma expansion velocity, corresponding to the carbon and hydrogen ions, is estimated to be ∼1.5 cm/μs. Most notably, Cs spectroscopic line was obtained only at the distance ≤ 0.5 mm from the cathode surface. Carbon and hydrogen ions are obtained up to the distance of 2.5 mm from the cathode surface. Cs ions almost remain at the vicinity of the cathode surface. These results show that the addition of CsI enables a slow cathode plasma expansion toward the anode, providing a positive prospect for developing long-pulse electron beam sources. (general)

  10. Copper oxide supported on platinum nanosheets array: High performance carbon-free cathode for lithium-oxygen cells

    Science.gov (United States)

    Ang, Huixiang; Zhang, Wenyu; Tan, Hui Teng; Chen, Hongyu; Yan, Qingyu

    2015-10-01

    In this study, we present a new strategy on controlling the interaction between the Li2O2-catalyst interfaces through improving the affinity of catalyst surface towards Li2O2 molecules. A seed-mediated growth approach has been developed to synthesize Pt nanosheets on the stainless steel mesh using Fe as the seed. We further grow a uniform layer of metallic Cu nanoparticles on Pt nanosheets surface through electrochemical deposition. The Cu is converted to CuO by exposing it to air under ambient condition. Such strategy has effectively solved the problem of non-uniform deposition of CuO on Pt surface that arises from the poor interaction of oxides on metals. By converting the oxide-on-metal to metal-on-metal system, a relatively uniform of CuO can be successfully deposited on Pt nanosheets. The CuO on Pt provides multiple nucleation sites on the surface of the cathode, which facilitates the formation of Li2O2 thin layer in the discharge cycle. This process plays a crucial role in achieving a high round-trip efficiency of 88%, reversible specific capacity of 1648 mAh g-1 (683 mAh g-1 with respect to the total electrode mass including Li2O2) at 100 mA g-1 and maintains capacity retention of 98% during the 60th cycle at a high current density of 1 A g-1.

  11. Controlled synthesis of lithium-rich layered Li1.2Mn0.56Ni0.12Co0.12O2 oxide with tunable morphology and structure as cathode material for lithium-ion batteries by solvo/hydrothermal methods

    International Nuclear Information System (INIS)

    Highlights: • Li1.2Mn0.56Ni0.12Co0.12O2 with different shapes was successfully prepared. • The solvent plays a key role in the formation of the product with various shapes. • The sample prepared by solvothermal method exhibits higher discharge capacity. • Its reversible capacity is approximately 306.9 mA h g−1 at 0.2 C. - Abstract: A Li-rich layered cathode material Li1.2Mn0.56Ni0.12Co0.12O2 (0.5Li2MnO3⋅0.5Li1.2Mn0.4Ni0.3Co0.3O2) with different morphologies has been successfully prepared by solvothermal and hydrothermal methods. The result demonstrates that the solvent plays a crucial role in the formation of the precursor and final product with various shapes and sizes. When tested as the cathode material for lithium ion batteries, the sample prepared by solvothermal method exhibits higher discharge capacity, better cycling performance, and more excellent rate capacity. It delivers a discharge capacity of 306.9 mA h g−1 at 0.2 C and 118.6 mA h g−1 even at a high rate of 5.0 C. The outstanding performance of the sample prepared by solvothermal method can be attributed to the well-ordered structure and well-defined morphology with smaller particle size and uniform distribution. The current study paves a new concept and applicable way to prepare high performance Li-rich layered cathode material for LIBs

  12. A CNT (carbon nanotube) paper as cathode gas diffusion electrode for water management of passive μ-DMFC (micro-direct methanol fuel cell) with highly concentrated methanol

    International Nuclear Information System (INIS)

    A novel MEA (membrane electrode assembly) structure of passive μ-DMFC (micro-direct methanol fuel cell) controls water management and decreases methanol crossover. The CNT (carbon nanotube) paper replacing CP (carbon paper) as GDL (gas diffusion paper) enhances water back diffusion which passively prevents flooding in the cathode and promotes low methanol crossover. Moreover, the unique structure of CNT paper can also enhance efficiency of oxygen mass transport and catalyst utilization. The passive μ-DMFC with CNT-MEA exhibits significantly higher performance than passive μ-DMFC with CP-MEA and can operate in high methanol concentration, showing the peak power density of 23.2 mW cm−2. The energy efficiency and fuel utilization efficiency are obviously improved from 11.54% to 22.7% and 36.61%–49.34%, respectively, and the water transport coefficient is 0.47 which is lower than previously reported passive μ-DMFC with CP. - Highlights: • This novel GDL (gas diffusion layer) solves water management and methanol crossover. • This GDL creates a hydraulic pressure in the cathode increasing water back diffusion. • This GDL improves the electrical conductivity and activity of catalyst

  13. High-performance lanthanum-ferrite-based cathode for SOFC

    DEFF Research Database (Denmark)

    Wang, W.G.; Mogensen, Mogens Bjerg

    2005-01-01

    LSCF/CGO on YSZ, the Rs was the same as that of our best LSM samples, which indicates good adhesion between LSCF/CGO cathode and YSZ electrolyte. Aging experiment at 800 'C for the cathode of LSCF/CGO on YSZ electrolyte shows a degradation rate of 5 x 10(-4) Omega CM2/h in R-p, while the R-s has no...... degreesC were achieved. These results are roughly six times better than our typical LSM cathodes. Slightly higher R-s was observed in the samples with LSCF/CGO cathode on the YSZ electrolyte with CGO coating due to extra contribution from the thin CGO layer and the CGO/YSZ interface. For the samples with...

  14. Verification of high efficient broad beam cold cathode ion source.

    Science.gov (United States)

    Abdel Reheem, A M; Ahmed, M M; Abdelhamid, M M; Ashour, A H

    2016-08-01

    An improved form of cold cathode ion source has been designed and constructed. It consists of stainless steel hollow cylinder anode and stainless steel cathode disc, which are separated by a Teflon flange. The electrical discharge and output characteristics have been measured at different pressures using argon, nitrogen, and oxygen gases. The ion exit aperture shape and optimum distance between ion collector plate and cathode disc are studied. The stable discharge current and maximum output ion beam current have been obtained using grid exit aperture. It was found that the optimum distance between ion collector plate and ion exit aperture is equal to 6.25 cm. The cold cathode ion source is used to deposit aluminum coating layer on AZ31 magnesium alloy using argon ion beam current which equals 600 μA. Scanning electron microscope and X-ray diffraction techniques used for characterizing samples before and after aluminum deposition. PMID:27587108

  15. Dynamic Aspects of Solid Solution Cathodes for Electrochemical Power Sources

    DEFF Research Database (Denmark)

    Atlung, Sven; West, Keld; Jacobsen, Torben

    1979-01-01

    Battery systems based on alkali metal anodes and solid solution cathodes,i.e., cathodes based on the insertion of the alkali cation in a "host lattice,"show considerable promise for high energy density storage batteries. Thispaper discusses the interaction between battery requirements, in...... particularfor vehicle propulsion, and electrochemical and constructional factors. It isargued that the energy obtainable at a given load is limited by saturation ofthe surface layers of cathode particles with cations, and that the time beforesaturation occurs is determined by diffusion of cations and electrons...... diffusioncoefficient in the solid exceeds 10–10 cm2 sec–1. On the basis of an approximaterelation between cathode thickness and electrode spacing the specificenergy for the Li/TiS2 system with organic electrolyte is estimated to be 120–150W-hr/kg in agreement with published values. ©1979 The Electrochemical Society...

  16. Joule heat generation in thermionic cathodes of high-pressure arc discharges

    Energy Technology Data Exchange (ETDEWEB)

    Benilov, M. S.; Cunha, M. D. [Departamento de Fisica, CCCEE, Universidade da Madeira, Largo do Municipio, 9000 Funchal (Portugal)

    2013-02-14

    The nonlinear surface heating model of plasma-cathode interaction in high-pressure arcs is extended to take into account the Joule effect inside the cathode body. Calculation results are given for different modes of current transfer to tungsten cathodes of different configurations in argon plasmas of atmospheric or higher pressures. Special attention is paid to analysis of energy balances of the cathode and the near-cathode plasma layer. In all the cases, the variation of potential inside the cathode is much smaller than the near-cathode voltage drop. However, this variation can be comparable to the volt equivalent of the energy flux from the plasma to the cathode and then the Joule effect is essential. Such is the case of the diffuse and mixed modes on rod cathodes at high currents, where the Joule heating causes a dramatic change of thermal and electrical regimes of the cathode. The Joule heating has virtually no effect over characteristics of spots on rod and infinite planar cathodes.

  17. Mechanisms of oxygen reduction reactions for carbon alloy catalysts via first principles molecular dynamics

    International Nuclear Information System (INIS)

    Carbon alloy catalysts (CACs) are one of promising candidates for platinum-substitute cathode catalysts for polymer electrolyte fuel cells. We have investigated possible mechanisms of oxygen reduction reactions (ORRs) for CACs via first-principles-based molecular dynamics simulations. In this contribution, we review possible ORRs at likely catalytic sites of CACs suggested from our simulations. (author)

  18. Arc cathode spots

    International Nuclear Information System (INIS)

    Arc spots are usually highly unstable and jump statistically over the cathode surface. In a magnetic field parallel to the surface, preferably they move in the retrograde direction; i.e., opposite to the Lorentzian rule. If the field is inclined with respect to the surface, the spots drift away at a certain angle with respect to the proper retrograde direction (Robson drift motion). These well-known phenomena are explained by one stability theory

  19. Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction.

    Science.gov (United States)

    Peera, S Gouse; Arunchander, A; Sahu, A K

    2016-08-14

    Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ∼110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the metallic species and greatly mitigates the leaching of Co and Fe during the long term cycling test. The high activity

  20. Membrane patterned by pulsed laser micromachining for proton exchange membrane fuel cell with sputtered ultra-low catalyst loadings

    Science.gov (United States)

    Cuynet, S.; Caillard, A.; Kaya-Boussougou, S.; Lecas, T.; Semmar, N.; Bigarré, J.; Buvat, P.; Brault, P.

    2015-12-01

    Proton exchange membranes were nano- and micro-patterned on their cathode side by pressing them against stainless steel molds previously irradiated by a Ti:Sapphire femtosecond laser. The membranes were associated to ultra-low loaded thin catalytic layers (25 μgPt cm-2) prepared by plasma magnetron sputtering. The Pt catalyst was sputtered either on the membrane or on the porous electrode. The fuel cell performance in dry conditions were found to be highly dependent on the morphology of the membrane surface. When nanometric ripples covered by a Pt catalyst were introduced on the surface of the membrane, the fuel cell outperformed the conventional one with a flat membrane. By combining nano- and micro-patterns (nanometric ripples and 11-24 μm deep craters), the performance of the cells was clearly enhanced. The maximum power density achieved by the fuel cell was multiplied by a factor of 3.6 (at 50 °C and 3 bar): 438 mW cm-2 vs 122 mW cm-2. This improvement is due to high catalyst utilization with a high membrane conductivity. When Pt is sputtered on the porous electrode (and not on the membrane), the contribution of the patterned membrane to the fuel cell efficiency was less significant, except in the presence of nanometric ripples. This result suggests that the patterning of the membrane must be consistent with the way the catalyst is synthesized, on the membrane or on the porous electrode.

  1. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    How can architecture promote the enriching experiences of the tolerant, the democratic, and the learning city - a city worth living in, worth supporting and worth investing in? Catalyst Architecture comprises architectural projects, which, by virtue of their location, context and their combination...... of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city...

  2. Efficient Oxygen Evolution Reaction Catalysts for Cell Reversal and Start/Stop Tolerance in Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Atanasoski, Radoslav [3M Industrial Mineral Products; Atanasoska, Liliana [3M Industrial Mineral Products; Cullen, David A [ORNL

    2013-01-01

    Minute amounts of ruthenium and iridium on platinum nanostructured thin films have been evaluated in an effort to reduce carbon corrosion and Pt dissolution during transient conditions in proton exchange membrane fuel cells. Electrochemical tests showed the catalysts had a remarkable oxygen evolution reaction (OER) activity, even greater than that of bulk, metallic thin films. Stability tests within a fuel cell environment showed that rapid Ru dissolution could be managed with the addition of Ir. Membrane electrode assemblies containing a Ru to Ir atomic ratio of 1:9 were evaluated under startup/shutdown and cell reversal conditions for OER catalyst loadings ranging from 1 to 10 g/cm2. These tests affirmed that electrode potentials can be controlled through the addition of OER catalysts without impacting the oxygen reduction reaction on the cathode or the hydrogen oxidation reaction on the anode. The morphology and chemical structure of the thin OER layers were characterized by scanning transmission electron microscopy and X-ray photoelectron spectroscopy in an effort to establish a correlation between interfacial properties and electrochemical behavior.

  3. Suitable alkaline for graphene peeling grown on metallic catalysts using chemical vapor deposition

    Science.gov (United States)

    Karamat, S.; Sonuşen, S.; Çelik, Ü.; Uysallı, Y.; Oral, A.

    2016-04-01

    In chemical vapor deposition, the higher growth temperature roughens the surface of the metal catalyst and a delicate method is necessary for the transfer of graphene from metal catalyst to the desired substrates. In this work, we grow graphene on Pt and Cu foil via ambient pressure chemical vapor deposition (AP-CVD) method and further alkaline water electrolysis was used to peel off graphene from the metallic catalyst. We used different electrolytes i.e., sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) and barium hydroxide Ba(OH)2 for electrolysis, hydrogen bubbles evolved at the Pt cathode (graphene/Pt/PMMA stack) and as a result graphene layer peeled off from the substrate without damage. The peeling time for KOH and LiOH was ∼6 min and for NaOH and Ba(OH)2 it was ∼15 min. KOH and LiOH peeled off graphene very efficiently as compared to NaOH and Ba(OH)2 from the Pt electrode. In case of copper, the peeling time is ∼3-5 min. Different characterizations like optical microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy were done to analyze the as grown and transferred graphene samples.

  4. Ceria catalyst for inert-substrate-supported tubular solid oxide fuel cells running on methane fuel

    Science.gov (United States)

    Zhao, Kai; Kim, Bok-Hee; Du, Yanhai; Xu, Qing; Ahn, Byung-Guk

    2016-05-01

    A ceria catalyst is applied to an inert-substrate supported tubular single cell for direct operation on methane fuel. The tubular single cell comprises a porous yttria-stabilized zirconia (YSZ) supporter, a Ni-Ce0.8Sm0.2O1.9 anode, a YSZ/Ce0.8Sm0.2O1.9 bi-layer electrolyte, and a La0.6Sr0.4Co0.2Fe0.8O3-δ cathode. The ceria catalyst is incorporated into the porous YSZ supporter layer by a cerium nitrate impregnation. The effects of ceria on the microstructure and electrochemical performance of the tubular single cell are investigated with respect to the number of impregnations. The optimum number of impregnations is determined to be four based on the maximum power density and polarization property of the tubular single cell in hydrogen and methane fuels. At 700 °C, the tubular single cell shows similar maximum power densities of ∼260 mW cm-2 in hydrogen and methane fuels, respectively. Moreover, the ceria catalyst significantly improves the performance stability of the cell running on methane fuel. At a current density of 350 mA cm-2, the single cell shows a low degradation rate of 2.5 mV h-1 during the 13 h test in methane fuel. These results suggest the feasibility of applying the ceria catalyst to the inert-substrate supported tubular single cell for direct operation on methane fuel.

  5. Oxidation-resistant catalyst supports for proton exchange membrane fuel cells

    Science.gov (United States)

    Chhina, Harmeet

    In automotive applications, when proton exchange membrane fuel cells (PEMFCs) are subjected to frequent startup-shutdown cycles, a significant drop in performance is observed. One reason for this drop in performance is oxidation of the carbon in the catalyst layer when cathode potential excursions as high as 1.5V are observed. In this work, non-carbon based catalyst support materials were studied. The materials investigated include: tungsten carbide (WC), tungsten oxide (WOx), and niobium (Nb) or tungsten (W) doped titania. Platinum was dispersed on commercial samples of WC and WO x. Stability tests were performed by stepping the materials between 0.6 to 1.8V. Higher stability of both WC and WOx was observed compared to carbon based commercial catalyst (HiSpec 4000). The performance of Pt supported on WC or WOx was found to be lower than that of Pt/C due to poor dispersion of Pt on these low surface area commercial powders. High surface area Nb and W doped titania materials synthesized using sol-gel techniques were subjected to several heat treatments and atmospheres, and their resulting physical properties characterized. The materials' phase changes and their impact on electrical conductivity were evaluated. W doped titania was found to be resistive, and for Nb doped titania, the rutile phase was found to be more conductive than the anatase phase. Conventionally, 10-50 wt% Pt is supported on carbon, but as the non-carbon catalyst support materials have different densities, similar mass ratios of catalyst to support will not result in directly comparable performances. It is recommended that the ratio of Pt surface area to the support surface area should be similar when comparing Pt supported on carbon to Pt supported on a non-carbon support. A normalization approach was investigated in this work, and the ORR performance of 40wt.%Pt/C was found to be similar to that of 10wt.%Pt/Nb-TiO2. Fuel cell performance tests showed significantly higher stability of Pt on Nb

  6. Iron-rich nanoparticle encapsulated, nitrogen doped porous carbon materials as efficient cathode electrocatalyst for microbial fuel cells

    Science.gov (United States)

    Lu, Guolong; Zhu, Youlong; Lu, Lu; Xu, Kongliang; Wang, Heming; Jin, Yinghua; Jason Ren, Zhiyong; Liu, Zhenning; Zhang, Wei

    2016-05-01

    Developing efficient, readily available, and sustainable electrocatalysts for oxygen reduction reaction (ORR) in neutral medium is of great importance to practical applications of microbial fuel cells (MFCs). Herein, a porous nitrogen-doped carbon material with encapsulated Fe-based nanoparticles (Fe-Nx/C) has been developed and utilized as an efficient ORR catalyst in MFCs. The material was obtained through pyrolysis of a highly porous organic polymer containing iron(II) porphyrins. The characterizations of morphology, crystalline structure and elemental composition reveal that Fe-Nx/C consists of well-dispersed Fe-based nanoparticles coated by N-doped graphitic carbon layer. ORR catalytic performance of Fe-Nx/C has been evaluated through cyclic voltammetry and rotating ring-disk electrode measurements, and its application as a cathode electrocatalyst in an air-cathode single-chamber MFC has been investigated. Fe-Nx/C exhibits comparable or better performance in MFCs than 20% Pt/C, displaying higher cell voltage (601 mV vs. 591 mV), maximum power density (1227 mW m-2 vs. 1031 mW m-2) and Coulombic efficiency (50% vs. 31%). These findings indicate that Fe-Nx/C is more tolerant and durable than Pt/C in a system with bacteria metabolism and thus holds great potential for practical MFC applications.

  7. Dynamic behavior of thermionic dispenser cathodes under ion bombardment

    Science.gov (United States)

    Cortenraad, R.; van der Gon, A. W. Denier; Brongersma, H. H.; Gärtner, G.; Raasch, D.; Manenschijn, A.

    2001-04-01

    We have investigated the surface coverage and electron emission of thermionic dispenser cathodes during 3 keV Ar+ ion bombardment, thereby simulating the bombardment of the cathodes by residual gases that takes place in cathode-ray tubes as used in television sets. During the ion bombardment at the operating temperature of 1030 °C, a dynamic equilibrium is established between the sputter removal and resupply mechanisms of the Ba and O atoms that form the dipole layer on the cathode substrate. We demonstrated that the performance of the cathodes under ion bombardment is governed by the O removal and resupply rates. It was found that the Ba resupply rate is almost an order of magnitude higher than the O resupply rate, but that the Ba can only be present on the surface bound to O atoms. Therefore, the Ba/O ratio is approximately equal to unity during the ion bombardment. Based on the investigations of the removal and resupply processes, we proposed a model that accurately describes the surface coverage and electron emission during the ion bombardment, including the dependence of the ion flux and cathode temperature.

  8. Study of Poly (3,4-ethylenedioxythiophene)/MnO2 as Composite Cathode Materials for Aluminum-Air Battery

    International Nuclear Information System (INIS)

    Highlights: • Open-tunnel structure of MnO2 catalysts were prepared by the hydrothermal method. • PEDOT was deposited on MnO2/carbon paper by oxidative chemical vapor deposition. • PEDOT/α-MnO2/10AA composite cathode shows the highest discharge performance. • The enhancement on discharge performance was due to the clear charge transfer. - Abstract: This study focuses on the development of the composite electrode materials for an aluminum-air battery and improving the oxygen reduction reaction (ORR) of the air electrode by matching alpha- and beta- manganese dioxide (MnO2) with poly-(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer. The catalyst powders of α-MnO2 and β-MnO2 are prepared by hydrothermal method with different precursors, while PEDOT conducting polymer is subsequently deposited on the screen-printed electrodes (MnO2/carbon paper) by oxidative chemical vapor deposition (oCVD). Material characteristics of prepared MnO2 powder and PEDOT layer are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman scattering spectroscopy. The half-cell polarization curve test is found to be strongly depended on the crystalline phases of MnO2. From experimental observations and a density functional theory (DFT) study, the conductivity of PEDOT/α-MnO2 is found to be higher than PEDOT/β-MnO2 contributed to structural effect mediated improvements in charge transfer. As a result, integrating the deposition of PEDOT on α-MnO2/carbon paper as composite cathode is suitable for the use in aluminum-air battery

  9. High Performance and Durable Low PGM Cathode Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Liu, Jun [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shao, Yuyan [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cheng, Yingwen [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Borup, Rodney L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rockward, Tommy [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Brosha, Eric Lanich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-08-17

    There is a strong need to decrease the amount of Pt electrocatalyst used in fuel cells and increase its durability for transportation application. Conventional strategies include Pt nanocrystals and Pt alloy with well-controlled structures, durable carbon support, non-carbon support, etc. We have developed the so-called “metal-metal oxide-carbon” triple junction concept to stabilize Pt and protect carbon from corrosion. It also improved the activity of Pt. The good performance was not achieved in fuel cell test mainly because of the transport issue due to the use of 2D graphene. In this project, our main goal is to demonstrate the concept in fuel cell device test using 3D porous graphene as support so that the transport issue could be addressed.

  10. Thin films of aluminum nitride and aluminum gallium nitride for cold cathode applications

    Science.gov (United States)

    Sowers, A. T.; Christman, J. A.; Bremser, M. D.; Ward, B. L.; Davis, R. F.; Nemanich, R. J.

    1997-10-01

    Cold cathode structures have been fabricated using AlN and graded AlGaN structures (deposited on n-type 6H-SiC) as the thin film emitting layer. The cathodes consist of an aluminum grid layer separated from the nitride layer by a SiO2 layer and etched to form arrays of either 1, 3, or 5 μm holes through which the emitting nitride surface is exposed. After fabrication, a hydrogen plasma exposure was employed to activate the cathodes. Cathode devices with 5 μm holes displayed emission for up to 30 min before failing. Maximum emission currents ranged from 10-100 nA and required grid voltages ranging from 20-110 V. The grid currents were typically 1 to 104 times the collector currents.

  11. Emission from ferroelectric cathodes

    International Nuclear Information System (INIS)

    The authors have recently initiated an investigation of electron emission from ferroelectric cathodes. The experimental apparatus consisted of an electron diode and a 250 kV, 12 ohm, 70 ns pulsed high voltage power source. A planar triode modulator driven by a synthesized waveform generator initiates the polarization inversion and allows inversion pulse tailoring. The pulsed high voltage power source is capable of delivering two high voltage pulses within 50 μs of each other and is capable of operating at a sustained repetition rate of 5 Hz. The initial measurements indicate that emission current densities above the Child-Langmuir Space Charge Limit, JCL, are possible. They explain this effect to be based on a non-zero initial energy of the emitted electrons. They also determined that this effect is strongly coupled to relative timing between the inversion pulse and application of the main anode-cathode pulse. They also have initiated brightness measurements of the emitted beam and estimate a preliminary lower bound to be on the order of 109 A/m2-rad2 for currents close to JCL and factor of two less at currents over 4JCL. As in previous measurements at this Laboratory, they performed the measurement using a pepper pot technique. Beamlet profiles are recorded with a fast phosphor and gated cameras. They describe their apparatus and preliminary measurements

  12. Nanostructured lanthanum manganate composite cathode

    DEFF Research Database (Denmark)

    Wang, Wei Guo; Liu, Yi-Lin; Barfod, Rasmus;

    2005-01-01

    that the (La1-xSrx)(y)MnO3 +/-delta (LSM) composite cathodes consist of a network of homogenously distributed LSM, yttria-stabilized zirconia (YSZ), and pores. The individual grain size of LSM or YSZ is approximately 100 nm. The degree of contact between cathode and electrolyte is 39% on average. (c...

  13. Virtual cathode microwave devices -- Basics

    Energy Technology Data Exchange (ETDEWEB)

    Thode, L.E.; Snell, C.M.

    1991-01-01

    Unlike a conventional microwave tube, a virtual-cathode device operates above the space-charge limit where the depth of the space-charge potential can cause electron reflection. The region associated with this electron reflection is referred to as a virtual cathode. Microwaves can be generated through oscillations in the position of the virtual cathode and through the bunching of electrons trapped in a potential well between the real and virtual cathodes. These two mechanisms are competitive. There are three basic classes of virtual cathode devices: (1) reflex triode; (2) reditron and side-shoot vircator; and (3) reflex diode or vircator. The reflex diode is the highest power virtual-cathode device. For the reflex diode the energy exchange between the beam and electromagnetic wave occurs in both the axial and radial directions. In some designs the oscillating-virtual-cathode frequency exceeds the reflexing-electron frequency exceeds the oscillating-virtual-cathode frequency. For the flex diode a periodic disruption in magnetic insulation can modulate the high- frequency microwave power. Overall, particle-in-cell simulation predictions and axial reflex diode experiments are in good agreement. Although frequency stability and phase locking of the reflex diode have been demonstrated, little progress has been made in efficiency enhancement. 58 refs., 11 figs.

  14. Virtual cathode microwave devices: Basics

    Science.gov (United States)

    Thode, L. E.; Snell, C. M.

    Unlike a conventional microwave tube, a virtual-cathode device operates above the space-charge limit where the depth of the space-charge potential can cause electron reflection. The region associated with this electron reflection is referred to as a virtual cathode. Microwaves can be generated through oscillations in the position of the virtual cathode and through the bunching of electrons trapped in a potential well between the real and virtual cathodes. These two mechanisms are competitive. There are three basic classes of virtual cathode devices: (1) reflex triode; (2) reditron and side-shoot vircator; and (3) reflex diode or vircator. The reflex diode is the highest power virtual-cathode device. For the reflex diode the energy exchange between the beam and electromagnetic wave occurs in both the axial and radial directions. In some designs the oscillating virtual-cathode frequency exceeds the reflexing-electron frequency while in other designs the reflexing-electron frequency exceeds the oscillating virtual-cathode frequency. For the flex diode, a periodic disruption in magnetic insulation can modulate the high-frequency microwave power. Overall, particle-in-cell simulation predictions and axial reflex diode experiments are in good agreement. Although frequency stability and phase locking of the reflex diode have been demonstrated, little progress has been made in efficiency enhancement.

  15. Lowering of the cathode fall voltage by laser exposure of the cathode in a high-pressure mercury discharge

    International Nuclear Information System (INIS)

    The effect of an additional electrode heating by laser light exposure of one electrode has been studied in a high-pressure mercury discharge. The exposed electrode operates as cathode or anode during the corresponding half-cycles of a square-wave current which has been used for driving the discharge. The additional heating influences the discharge voltage and the electrode tip temperatures in different ways during the cathode and anode phases. Only during the cathode phase is there a noticeable decrease in the discharge voltage connected with a moderate increase in the cathode tip temperature. The maximum absorbed laser power of 6.2 W causes a voltage decrease of about 3.5 V for a discharge current of 1.8 A. The exposure during the anode phase is characterized by a strong increase in the electrode tip temperature and a nearly unchanged discharge voltage. Theoretically determined parameters of the cathode boundary layer are given. For a constant discharge current the power balance at the cathode surface suggests a nearly linear dependence of the discharge voltage lowering on the laser input power, which has been verified experimentally

  16. Methods for batch fabrication of cold cathode vacuum switch tubes

    Science.gov (United States)

    Walker, Charles A.; Trowbridge, Frank R.

    2011-05-10

    Methods are disclosed for batch fabrication of vacuum switch tubes that reduce manufacturing costs and improve tube to tube uniformity. The disclosed methods comprise creating a stacked assembly of layers containing a plurality of adjacently spaced switch tube sub-assemblies aligned and registered through common layers. The layers include trigger electrode layer, cathode layer including a metallic support/contact with graphite cathode inserts, trigger probe sub-assembly layer, ceramic (e.g. tube body) insulator layer, and metallic anode sub-assembly layer. Braze alloy layers are incorporated into the stacked assembly of layers, and can include active metal braze alloys or direct braze alloys, to eliminate costs associated with traditional metallization of the ceramic insulator layers. The entire stacked assembly is then heated to braze/join/bond the stack-up into a cohesive body, after which individual switch tubes are singulated by methods such as sawing. The inventive methods provide for simultaneously fabricating a plurality of devices as opposed to traditional methods that rely on skilled craftsman to essentially hand build individual devices.

  17. Miniature Reservoir Cathode: An Update

    Science.gov (United States)

    Vancil, Bernard K.; Wintucky, Edwin G.

    2002-01-01

    We report on recent work to produce a small low power, low cost reservoir cathode capable of long life (more than 100,000 hours) at high loading (> 5 A/sq cm). Our objective is a highly manufacturable, commercial device costing less than $30. Small highly loaded cathodes are needed, especially for millimeter wave tubes, where focusing becomes difficult when area convergence ratios are too high. We currently have 3 models ranging from .060-inch diameter to. 125-inch diameter. Reservoir type barium dispenser cathodes have a demonstrated capability for simultaneous high emission density and long life. Seven reservoir cathodes continue to operate on the cathode life test facility at NSWC, Crane, Indiana at 2 and 4 amps/sq cm. They have accumulated nearly 100,000 hours with practically no change in emission levels or knee temperature.

  18. Surface electron–hydronium ion-pair bound to silver and gold cathodes: A density functional theoretical study of photocatalytic hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Noble metal catalysts, such as silver and gold, play a significant role in photocatalytic water splitting to hydrogen for their high efficiency and environmentally-friendly nature. In this paper, a surface electron–hydronium ion-pair (EHIP) was proposed as an intermediate for photocatalytic hydrogen evolution reaction (HER) on silver and gold cathodes based on density functional theory (DFT) calculations. The EHIP is in the configuration of H3O+(H2O)ne−, where the hydronium H3O+ and the electron is separated by water layers. The electron bound in the EHIP can first be excited under light irradiation, subsequently inducing a structural relaxation into a hydrated hydrogen atom. Eventually, two hydrogen atoms recombine into a hydrogen molecule in the thin layer close to the electrode surface, e.g. at the outer Helmholtz plane (OHP). Additionally, Raman spectra of the interfacial EHIP species are calculated, which is in support of the presence of EHIP intermediates in the process of photocatalytic HER on silver and gold cathodes

  19. Graphene supported heterogeneous catalysts for Li-O2 batteries

    Science.gov (United States)

    Alaf, M.; Tocoglu, U.; Kartal, M.; Akbulut, H.

    2016-09-01

    In this study production and characterization of free-standing and flexible (i) graphene, (ii) α-MnO2/graphene, (iii) Pt/graphene (iv) α-MnO2/Pt/graphene composite cathodes for Li-air batteries were reported. Graphene supported heterogeneous catalysts were produced by a facile method. In order to prevent aggregation of graphene sheets and increase not only interlayer distance but also surface area, a trace amount multi-wall carbon nano tube (MWCNT) was introduced to the composite structure. The obtained composite catalysts were characterized by SEM, X-ray diffraction, N2 adsorption-desorption analyze and Raman spectroscopy. The electrochemical characterization tests including galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) measurement of catalyst were carried out by using an ECC-Air test cell. These highly active graphene supported heterogeneous composite catalysts provide competitive properties relative to other catalyst materials for Li-air batteries.

  20. Central tracking chamber with inflated cathode-strip foils

    International Nuclear Information System (INIS)

    A new cylindrical low-mass central drift chamber has been constructed for the K+ → π+νν experiment at BNL (E787). The chamber consists of 12 layers of axial wire cells and 6 layers of thin cathode-strip foils, four of which are supported by differential gas pressure. The momentum resolution (RMS) for muons and pions in the range 150 to 250 MeV is found to be about 0.9%. (authors)

  1. Study on the TiN Modified Layer on the Surface of 20CrNiMo Steel by Needle-shape Cathode Glow Discharging%20CrNiMo表面针状空心阴极辉光放电制备TiN研究

    Institute of Scientific and Technical Information of China (English)

    陈飞; 赫单; 陈家庆; 周海

    2011-01-01

    在真空炉内以针状钛丝为溅射源极,以氩气和氮气为放电气体,利用辉光放电现象、尖端放电和空心阴极效应在 20CrNiMo 表面复合渗镀合成TiN 改性层,目的是提高 20CrNiMo 表面的耐磨性能.利用扫描电子显微镜(SEM)观察了改性层的截面形貌;测量了改性层的显微硬度并用 XRD 观察分析了改性层的相结构;采用 MFT-4000 型高速往复磨损试验机对渗镀改性层的摩擦磨损性能进行了研究.结果表明:在试验工艺条件下 20CrNiMo 试样表面制备的TiN 改性层厚度约为 40μm.改性后表面摩擦因数为 0.169,较 20CrNiMo 基体的摩擦因数 0.324 明显减小,耐磨性能提高.%The multiple structures made of alloying and coating layers of TiN was achieved on the surface of 20CrNiMo steel by the needle-shape cathode glow discharging. It is aimed to reduce the friction coefficient of the 20CrNiMo and to improve the property of the wear-resistance. The morphology of TiN modified layer at the cross section was observed by Scanning Electron Microscope (SEM). The friction and wear behavior of the TiN/ZrN films under dry sliding against GCrl5 steel was evaluated on a MFT-4000 high speed to-and-fro wear test rig. The results showed that it was feasible to prepare TiN layer of 40 μm thickness by the needle-shape cathode glow discharging. It has been found that the TiN modified layer has excellent friction and wear-resistant behaviors. The friction coefficient of the 20CrNiMo substrate was about 0.324 under dry sliding,while the TiN modified layer experienced much abated friction coefficient to 0.169 under the same testing condition.

  2. Water transport through a PEM (proton exchange membrane) fuel cell in a seven-layer model

    International Nuclear Information System (INIS)

    The most critical problems to overcome in the PEM (proton exchange membrane) fuel cell technology are the water management. In this work, a seven-layer theoretical model is proposed that includes anode and cathode inlet channels, anode and cathode GDLs (gas diffusion layers), CLs (catalyst layers), and the 117 Nation proton exchange membrane. The mathematical model is a one-dimensional, steady-state, isothermal and isobar to describe the water transport phenomena in PEMFC (proton exchange membrane fuel cell). A rationally chosen set of parameters are considered such as the humidity and the stoichiometry of the inlet gases, the porosity of GDL, and the membrane thickness. The results show that with sufficient levels of humidity, the water management would improve for larger porosities of GDLs or a thinner membrane, and the resistance and over voltage of the membrane can be reduced significantly as well. This model will help to select system parameters so that the fuel cell would not suffer from dehydration and flooding. Also, model predictions were successfully compared to theoretical I–V polarization curves presented by Chen et al. (2007) and Springer et al. (1991). - Highlights: ► A model to describe the water transport phenomena in a PEMFC with a seven-layer structure is proposed. ► Parameters such as humidity of reactant gases, membrane thickness, porosity of GDL and stoichiometric ratio are considered. ► This model will help to select parameters so that the fuel cell would not suffer from dehydration and flooding

  3. Growth of single and bilayer graphene by filtered cathodic vacuum arc technique

    Energy Technology Data Exchange (ETDEWEB)

    Kesarwani, A. K.; Panwar, O. S., E-mail: ospanwar@mail.nplindia.ernet.in; Bisht, Atul [Polymorphic Carbon Thin Films Group, Physics of Energy Harvesting Division, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012, India and Academy of Scientific and Innovative Research (AcSIR), CSIR Campus, New Delhi 110012 (India); Dhakate, S. R. [Physics and Engineering of Carbon Materials, Division of Materials Physics and Engineering, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012, India and Academy of Scientific and Innovative Research (AcSIR), CSIR Campus, New Delhi 110012 (India); Rakshit, R. K. [Quantum Phenomena and Applications Group, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012, India and Academy of Scientific and Innovative Research (AcSIR), CSIR Campus, New Delhi 110012 (India); Singh, V. N. [Electron and Ion Microscopy, Sophisticated and Analytical Instruments, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012, India and Academy of Scientific and Innovative Research (AcSIR), CSIR Campus, New Delhi 110012 (India); Kumar, Ashish [Polymorphic Carbon Thin Films Group, Physics of Energy Harvesting Division, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012 (India)

    2016-03-15

    The authors present a viable process to grow the high quality graphene films with control over number of layers by the filtered cathodic vacuum arc (FCVA) technique. In the FCVA process, the different carbon concentrations can be controlled by precisely tuning the arc time (1–4 s). The arc generated carbon was deposited on the nickel catalyst at 800 °C, annealed for 10 min, and cooled down to room temperature in the presence of hydrogen gas, resulting in the graphene films with control over number of layers. Prior to arcing, hydrogen etching of nickel was carried out to clean the surface of the substrate. A growth model to prepare the high quality graphene has also been proposed. The as-grown graphene films were transferred to different substrates and are characterized by Raman spectroscopy, optical microscopy, high resolution transmission electron microscopy, and atomic force microscopy to determine the number of layers present in these films. Raman spectra of the prepared graphene films exhibit change in the G peak position from 1582.4 to 1578.1 cm{sup −1}, two-dimensional (2D) peak shifts from 2688.5 to 2703.8 cm{sup −1}, the value of I{sub 2D}/I{sub G} increased from 0.38 to 3.82, and the full width at half maxima of 2D peak changed from 41 to 70 cm{sup −1}, for different layers of graphene films. The high resolution transmission electron microscopy image revealed that the graphene films prepared for 1 and 2 s arc times have single and bi- or trilayered structures, respectively.

  4. Growth of single and bilayer graphene by filtered cathodic vacuum arc technique

    International Nuclear Information System (INIS)

    The authors present a viable process to grow the high quality graphene films with control over number of layers by the filtered cathodic vacuum arc (FCVA) technique. In the FCVA process, the different carbon concentrations can be controlled by precisely tuning the arc time (1–4 s). The arc generated carbon was deposited on the nickel catalyst at 800 °C, annealed for 10 min, and cooled down to room temperature in the presence of hydrogen gas, resulting in the graphene films with control over number of layers. Prior to arcing, hydrogen etching of nickel was carried out to clean the surface of the substrate. A growth model to prepare the high quality graphene has also been proposed. The as-grown graphene films were transferred to different substrates and are characterized by Raman spectroscopy, optical microscopy, high resolution transmission electron microscopy, and atomic force microscopy to determine the number of layers present in these films. Raman spectra of the prepared graphene films exhibit change in the G peak position from 1582.4 to 1578.1 cm−1, two-dimensional (2D) peak shifts from 2688.5 to 2703.8 cm−1, the value of I2D/IG increased from 0.38 to 3.82, and the full width at half maxima of 2D peak changed from 41 to 70 cm−1, for different layers of graphene films. The high resolution transmission electron microscopy image revealed that the graphene films prepared for 1 and 2 s arc times have single and bi- or trilayered structures, respectively

  5. Considerations of the Role of the Cathodic Region in Localized Corrosion

    International Nuclear Information System (INIS)

    The ability of wetted cathodes of limited area to support localized corrosion sites on passive materials exposed to atmospheric conditions was studied computationally. The analysis pertains to conditions where metal surfaces are covered by thin layers of moisture in contrast to conditions of full immersion. The moisture may be a continuous layer or in patches with and without particulate on the surface. These conditions are of interest for the surfaces of the waste packages at the proposed Yucca Mountain Repository where waste packages are supported in air. The cathode capacity was characterized by the total net cathodic current, Inet, which the surface surrounding a localized corrosion site (i.e., a pit or crevice) could supply. The cathode capacity increases with increasing cathode area, but it saturates at finite cathode sizes due to the resistance of the thin electrolyte layer. The magnitude of the capacity depends on the water layer thickness, the solution conductivity, and the electrochemical reaction kinetics. The presence of particulates is treated by considering both volume and surface coverage effects. The limited electrolyte volume under thin film conditions can lead to rapid pH changes which decrease the cathode capacity due to the slower electrochemical kinetics at elevated pH. These effects can make localized corrosion less likely to be sustained

  6. QE data for Pb/Nb deposited photo cathode samples

    CERN Document Server

    Sekutowicz, J

    2010-01-01

    This report outlines progress in the development of photo-cathodes for a hybrid lead/niobium (Pb/Nb) superconducting SRF electron injector. We have coated eight Nb samples with lead to study and determine deposition conditions leading to high quality emitting area. The results show that the oxide layer significantly influences the quantum efficiency (QE) of all measured cathodes. In addition, we learned that although the laser cleaning enhanced the QE substantially, the film morphology was strongly modified. That observation convinced us to make the coatings thicker and therefore more robust.

  7. Titanium Dioxide as a Cathode Material in a Dry Cell

    OpenAIRE

    Duncan ALOKO; Eyitayo Amos AFOLABI

    2007-01-01

    Titanium dioxide was proposed as an alternative cathode material in place of Manganesse (IV) oxide. TiO2 was found to be highly polarized when in an electric field and its surface area of adsorption of solution determined to be 1070.32 m2/g. The adsorption of alkaline anions (i.e. SO42- , NO3-, Cl- and Br-) were investigated. The anions were adsorbed between the layers of the cathode material thereby altering its surface texture for a better performance. Increase in concentration of the anion...

  8. Fuel Cells Catalyst for Start-up and Shutdown Conditions: Electrochemical, XPS, and TEM Evaluation of Sputter-Deposited Ru, Ir, and Ti on Pt-Nano-Structured Thin Film (NSTF) Support

    Energy Technology Data Exchange (ETDEWEB)

    Atanasoski, Radoslav [3M Industrial Mineral Products; Atanasoska, Liliana [3M Industrial Mineral Products; Cullen, David A [ORNL; Vernstrom, George [3M Industrial Mineral Products; More, Karren Leslie [ORNL; Haugen, Gregory [3M Industrial Mineral Products

    2012-01-01

    Minute amounts of Ru, Ir and Ti (2 and 10 g/cm2) sputter-deposited over 3M Pt-coated nano-structured thin film (NSTF) substrate were evaluated as oxygen evolution reaction (OER) catalysts in a polymer electrolyte membrane (PEM) environment. The purpose of the study was to explore the suitability of these elements for modifying both the anode and the cathode catalysts in order to lower the overpotential for the oxidation of water during transient conditions. By keeping the electrode potential as close as possible to the thermodynamic potential for OER, other components in the fuel cell, such as platinum, the gas diffusion layer and the bipolar plates, will be less prone to degradation. While Ru and Ir were chosen due to their high OER activity in aqueous environment, Ti was also included due to its ability to stabilize the OER catalysts. The 3M Pt-NSTF was selected as a stable, carbon-free substrate. The surface chemistry and the morphology of OER catalysts on Pt-NSTF were examined by x-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The OER catalytic activity of Ru and Ir in PEMs compares well with their behavior in aqueous environment. It was found that Ru is more active than Ir, that Ir is considerably more stable, while the mass activity of both is higher in comparison with similar OER catalyst.

  9. Cathodic Cage Plasma Nitriding: An Innovative Technique

    Directory of Open Access Journals (Sweden)

    R. R. M. de Sousa

    2012-01-01

    Full Text Available Cylindrical samples of AISI 1020, AISI 316, and AISI 420 steels, with different heights, were simultaneously treated by a new technique of ionic nitriding, entitled cathodic cage plasma nitriding (CCPN, in order to evaluate the efficiency of this technique to produce nitrided layers with better properties compared with those obtained using conventional ionic nitriding technique. This method is able to eliminate the edge effect in the samples, promoting a better uniformity of temperature, and consequently, a smaller variation of the thickness/height relation can be obtained. The compound layers were characterized by X-ray diffraction, optical microscopy, and microhardness test profile. The results were compared with the properties of samples obtained with the conventional nitriding, for the three steel types. It was verified that samples treated by CCPN process presented, at the same temperature, a better uniformity in the thickness and absence of the edge effect.

  10. Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction

    Science.gov (United States)

    Peera, S. Gouse; Arunchander, A.; Sahu, A. K.

    2016-07-01

    long term durability of the Fe-Co/NF-GNF catalyst make it a promising ORR electrocatalyst for the fuel cell cathode reaction.Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ~110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the

  11. Organic photovoltaic device with interfacial layer and method of fabricating same

    Science.gov (United States)

    Marks, Tobin J.; Hains, Alexander W.

    2013-03-19

    An organic photovoltaic device and method of forming same. In one embodiment, the organic photovoltaic device has an anode, a cathode, an active layer disposed between the anode and the cathode; and an interfacial layer disposed between the anode and the active layer, the interfacial layer comprising 5,5'-bis[(p-trichlorosilylpropylphenyl)phenylamino]-2,2'-bithiophene (PABTSi.sub.2).

  12. Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

    Science.gov (United States)

    Strom, Matthew James

    Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms. Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR. Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms. A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled

  13. Hollow Cathode With Multiple Radial Orifices

    Science.gov (United States)

    Brophy, John R.

    1992-01-01

    Improved hollow cathode serving as source of electrons has multiple radial orifices instead of single axial orifice. Distributes ion current more smoothly, over larger area. Prototype of high-current cathodes for ion engines in spacecraft. On Earth, cathodes used in large-diameter ion sources for industrial processing of materials. Radial orientation of orifices in new design causes current to be dispersed radially in vicinity of cathode. Advantageous where desireable to produce plasma more nearly uniform over wider region around cathode.

  14. Micro-hollow cathode dischargers

    International Nuclear Information System (INIS)

    In order to develop a hollow cathode discharge (HCD) with its increased current over planar electrode glow discharges, the cathode fall, which is on the order of the mean free path for ionization, must be comparable in length to the hole diameter. This indicates that the discharge parameters vary with pressure, p, times hole diameter, D. The pD product for stable operation of a hollow cathosde discharge was quoted to be on the order of one to ten Torr cm for noble gases, less for molecular gases. White (1959) observed the hollow cathode effect in a neon discharge at a pressure of 100 Torr when the hole dimensions were less than 1 mm. The cathode hole in his experiments changed from a cylindrical into a spherical cavity due to sputtering. The anode consisted in White's experiment of a pin on the axis of the discharge geometry. We have studied micro-hollow (submillimeter) cathode discharges between two electrodes with aligned cylindrical holes by determining the current-voltage characteristics and the visual appearance of the discharge in argon over a wide range of pressure and voltage. The cross-section of the discharge geometry. The cathode is made of molybdenum or barium oxide inserted into a tungsten matrix (dispenser-cathode), the anode of molybdenum, and the dielectric spacer is mica. The discharge was operated under dc conditions, with half-wave rectified ac voltage applied, and pulsed with a 400 μs rectangular voltage pulse. The lower limit in pressure was determined by the maximum voltage which could be applied to the discharge geometry without breakdown along insulators. The upper limit, in this study, is determined by the transition from cathode electrode emission due to ion-impact to thermal emission of electrons, which causes a dramatic increase in current and a drop in forward voltage to values on the order of 20 V

  15. Study and development of membrane electrode assemblies for Proton Exchange Membrane Fuel Cell (PEMFC) with palladium based catalysts

    International Nuclear Information System (INIS)

    PEMFC systems are capable of generating electricity with high efficiency and low or no emissions, but durability and cost issues prevent its large commercialization. In this work MEA with palladium based catalysts were developed, Pd/C, Pt/C and alloys PdPt/C catalysts with different ratios between metals and carbon were synthesized and characterized. A study of the ratio between catalyst and Nafion Ionomer for formation of high performance triple-phase reaction was carried out, a mathematical model to implement this adjustment to catalysts with different relations between metal and support taking into account the volumetric aspects of the catalyst layer was developed and then a study of the catalyst layer thickness was performed. X-ray diffraction, Transmission and Scanning Electron Microscopy, X-ray Energy Dispersive, Gas Pycnometry, Mercury Intrusion Porosimetry, Gas adsorption according to the BET and BJH equations, and Thermo Gravimetric Analysis techniques were used for characterization and particle size, specific surface areas and lattice parameters determinations were also carried out. All catalysts were used on MEAs preparation and evaluated in 5 cm2 single cell from 25 to 100 °C at 1 atm and the best composition was also evaluated at 3 atm. In the study of metals for reactions, to reduce the platinum applied to the electrodes without performance losses, Pd/C and PdPt/C 1:1 were selected for anodes and cathodes, respectively. The developed MEA structure used 0,25 mgPt.cm-2, showing power densities up to 550 mW.cm-2 and power of 2.2 kWnet per gram of platinum. The estimated costs showed that there was a reduction of up to 64.5 %, compared to the MEA structures previously known. Depending on the temperature and operating pressure, values from US$ 1,475.30 to prepare MEAs for each installed kilowatt were obtained. Taking into account recent studies, it was concluded that the cost of the developed MEA is compatible with PEMFC stationary application. (author)

  16. Hollow cathode hydrogen ion source

    International Nuclear Information System (INIS)

    High current density ion sources have been used to heat plasmas in controlled thermonuclear reaction experiments. High beam currents imply relatively high emission currents from cathodes which have generally taken the form of tungsten filaments. This paper describes a hydrogen ion source which was primarily developed to assess the emission current capability and design requirements for hollow cathodes for application in neutral injection devices. The hydrogen source produced ions by electron bombardment via a single hollow cathode. Source design followed mercury ion thruster technology, using a weak magnetic field to enhance ionization efficiency. A 1.3-cm diameter hollow cathode using a low work function material dispenser performed satisfactorily over a discharge current range of 10 to 90 A. Cylindrical probe measurements taken without ion extraction indicate maximum ion number densities on the order of 1012 cm-3. Discharge durations ranged from 30 seconds to continuous operation. Tests with beam extraction at 2.5 keV and 30 A discharge current yield average ion beam current densities of 0.1 A cm-2 over a 5-cm extraction diameter. Results of this study can be used to supply the baseline information needed to scale hollow cathodes for operation at discharge currents of hundreds of amperes using distributed cathodes

  17. Inserting various cathodic buffer layers to enhance the performance of Pentacene/C60 based organic solar cells%利用不同阴极缓冲层来改善Pentacene/C60太阳能电池的性能

    Institute of Scientific and Technical Information of China (English)

    刘瑞; 徐征; 赵谡玲; 张福俊; 曹晓宁; 孔超; 曹文喆; 龚伟

    2011-01-01

    制备了结构为ITO/Pentacene/C60/Al的双层光伏电池器件,在C60/Al界面插入了常用的缓冲层材料bathocuproine(BCP)作为阴极缓冲层,通过优化BCP层的厚度来提高电池的性能并研究了阴极缓冲层的作用机理.实验发现,BCP厚度为10 nm时器件的效率最高,为0.46%.在此基础上,利用bathophenanthroline(Bphen)和3,4,9,10-Perylenetetracarb-oxylicdianhydride(PTCDA)材料取代BCP,分别研究了缓冲层材料电子迁移率以及光吸收特性对器件性能的影响.在使用电子迁移率比BCP高两个数量级的Bphen材料作为缓冲层后,电池效率提高到了0.56%.而当使用在可见光区有较强光吸收的PTCDA材料作为缓冲层时,可以起到增加电池光吸收的作用,电池短路电流提高至5.97 mA/cm2,效率达0.87%.%Devices with the structure of ITO/Pentacene/C60/Al were prepared. Then, in order to enhance the performance of these cells and study the mechanism of the cathodic buffer layer, bathocuproine (BCP) of different thickness were inserted between C60 and Al. When inserting 10 nm BCP, the power conversion effciency of the cell is as high as 0.46%. On this basis, bathophenanthroline (Bphen) and 3, 4, 9, 10-Perylenetetracarb-oxylicdianhydride (PTCDA) are used instead of BCP, so as to compare and discuss the effects on the performance of the solar cells caused by the electron mobility and optical absorption properties of the cathodic buffer layers. As the electron mobility of Bphen is two orders of magnitude higher than that of BCP, the efficiency of devices with Bphen as the buffer layer was improved to 0. 56%. Furthermore,the absorption spectrum of devices was obviously enhanced by inserting PTCDA material which has large absorption in visible light region, and the highest current density of such device was enhanced to 5.97 mA/cm2 and the efficiency was 0. 87%.

  18. Li-Rich Layered Cathode Material Li[Li0.157Ni0.138Co0.134Mn0.571]O2 Synthesized with Solid-State Coordination Method

    Science.gov (United States)

    Liao, Da-qian; Xia, Chao-yang; Xi, Xiao-ming; Zhou, Chun-xian; Xiao, Ke-song; Chen, Xiao-qing; Qin, Shi-biao

    2016-06-01

    Lithium-rich layered material Li[Li0.157Ni0.138Co0.134Mn0.571]O2 was prepared with the solid-state coordination method. Lithium nitrate, nickel acetate, cobalt acetate, and manganese acetate were used as raw materials, and citric acid as solid complexing agent. The lithium-rich layered material was prepared by heat-treating the precursors of the solid-phase complex compound. The prepared materials exhibited typical layer structure, nanosize distribution, and excellent electrochemical performance, and the preparation process has the advantages of low cost and simplicity. The initial discharge capacity of the prepared material reached as high as 270 mAh/g, and the charge-transfer resistance of the electrode was about 165 Ω at 4.0 V.

  19. Evaluation of low cost cathode materials for treatment of industrial and food processing wastewater using microbial electrolysis cells

    KAUST Repository

    Tenca, Alberto

    2013-02-01

    Microbial electrolysis cells (MECs) can be used to treat wastewater and produce hydrogen gas, but low cost cathode catalysts are needed to make this approach economical. Molybdenum disulfide (MoS2) and stainless steel (SS) were evaluated as alternative cathode catalysts to platinum (Pt) in terms of treatment efficiency and energy recovery using actual wastewaters. Two different types of wastewaters were examined, a methanol-rich industrial (IN) wastewater and a food processing (FP) wastewater. The use of the MoS2 catalyst generally resulted in better performance than the SS cathodes for both wastewaters, although the use of the Pt catalyst provided the best performance in terms of biogas production, current density, and TCOD removal. Overall, the wastewater composition was more of a factor than catalyst type for accomplishing overall treatment. The IN wastewater had higher biogas production rates (0.8-1.8 m3/m3-d), and COD removal rates (1.8-2.8 kg-COD/m3-d) than the FP wastewater. The overall energy recoveries were positive for the IN wastewater (3.1-3.8 kWh/kg-COD removed), while the FP wastewater required a net energy input of -0.7 - 1.2 kWh/kg-COD using MoS 2 or Pt cathodes, and -3.1 kWh/kg-COD with SS. These results suggest that MoS2 is the most suitable alternative to Pt as a cathode catalyst for wastewater treatment using MECs, but that net energy recovery will be highly dependent on the specific wastewater. © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  20. Carbon nanotube growth on nanozirconia under strong cathodic polarization in steam and carbon dioxide

    DEFF Research Database (Denmark)

    Tao, Youkun; Ebbesen, Sune Dalgaard; Zhang, Wei;

    2014-01-01

    nanozirconia acting as a catalyst for the growth of carbon nanotubes (CNTs) during electrochemical conversion of carbon dioxide and water in a nickel-yttria- stabilized zirconia cermet under strong cathodic polarization. An electrocatalytic mechanism is proposed for the growth of the CNTs. ${{{\\rm {\\rm V......Growth of carbon nanotubes (CNTs) catalyzed by zirconia nanoparticles was observed in the Ni-yttria doped zirconia (YSZ) composite cathode of a solid oxide electrolysis cell (SOEC) at approximately 875 °C during co-electrolysis of CO2 and H2O to produce CO and H 2. CNT was observed to grow under...