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Sample records for cathode catalyst layer

  1. Anti-flooding cathode catalyst layer for high performance PEM fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Li, Aidan; Chan, Siew Hwa; Nguyen, Nam-trung [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

    2009-04-15

    Water management in cathode catalyst layer (CCL) plays an important role in the PEM fuel cell operation. A novel anti-flooding CCL is developed with the addition of oxygen permeable and hydrophobic dimethyl silicone oil (DSO) into the catalyst layer (CL) to improve the water balance and oxygen transport within the cathode. With the addition of 0.5 mg cm{sup -2} DSO in the CCL, the ability of water management has been enhanced greatly compared to that with a normal cathode. Electrochemical impedance spectroscopy has been employed to characterize the electrochemical behavior of the single fuel cell. The results show that the increased hydrophobicity of the CCL by DSO modification effectively expels water out of the voids of CCL. In addition, DSO in the CCL enhances oxygen accessibility to the CCL, thus improving the performance of the PEM fuel cell significantly. (author)

  2. 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...

  3. 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...

  4. 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.

  5. 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.

  6. 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 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.

  7. 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.

  8. Nitrogen-doped carbonaceous catalysts for gas-diffusion cathodes for alkaline aluminum-air batteries

    Science.gov (United States)

    Davydova, E. S.; Atamanyuk, I. N.; Ilyukhin, A. S.; Shkolnikov, E. I.; Zhuk, A. Z.

    2016-02-01

    Cobalt tetramethoxyphenyl porphyrin and polyacrylonitrile - based catalysts for oxygen reduction reaction were synthesized and characterized by means of SEM, TEM, XPS, BET, limited evaporation method, rotating disc and rotating ring-disc electrode methods. Half-cell and Al-air cell tests were carried out to determine the characteristics of gas-diffusion cathodes. Effect of active layer thickness and its composition on the characteristics of the gas-diffusion cathodes was investigated. Power density of 300 mW cm-2 was achieved for alkaline Al-air cell with an air-breathing polyacrylonitrile-based cathode.

  9. 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.

  10. 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.

  11. 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.)

  12. 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.

  13. 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.

  14. Microbial fuel cell performance with non-Pt cathode catalysts

    Science.gov (United States)

    HaoYu, Eileen; Cheng, Shaoan; Scott, Keith; Logan, Bruce

    Various cathode catalysts prepared from metal porphyrines and phthalocyanines were examined for their oxygen reduction activity in neutral pH media. Electrochemical studies were carried out with metal tetramethoxyphenylporphyrin (TMPP), CoTMPP and FeCoTMPP, and metal phthalocyanine (Pc), FePc, CoPc and FeCuPc, supported on Ketjenblack (KJB) carbon. Iron phthalocyanine supported on KJB (FePc-KJB) carbon demonstrated higher activity towards oxygen reduction than Pt in neutral media. The effect of carbon substrate was investigated by evaluating FePc on Vulcan XC carbon (FePcVC) versus Ketjenblack carbon. FePc-KJB showed higher activity than FePcVC suggesting the catalyst activity could be improved by using carbon substrate with a higher surface area. With FePc-KJB as the MFC cathode catalyst, a power density of 634 mW m -2 was achieved in 50 mM phosphate buffer medium at pH 7, which was higher than that obtained using the precious-metal Pt cathode (593 mW m -2). Under optimum operating conditions (i.e. using a high surface area carbon brush anode and 200 mM PBM as the supporting electrolyte with 1 g L -1 acetate as the substrate), the power density was increased to 2011 mW m -2. This high power output indicates that MFCs with low cost metal macrocycles catalysts is promising in further practical applications.

  15. Microbial fuel cell performance with non-Pt cathode catalysts

    Energy Technology Data Exchange (ETDEWEB)

    HaoYu, Eileen; Scott, Keith [School of Chemical Engineering and Advanced Materials, University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU (United Kingdom); Cheng, Shaoan; Logan, Bruce [Department of Civil and Environmental Engineering, The Penn State Hydrogen Energy (H{sub 2}E) Center, Penn State University, University Park, PA 16802 (United States)

    2007-09-27

    Various cathode catalysts prepared from metal porphyrines and phthalocyanines were examined for their oxygen reduction activity in neutral pH media. Electrochemical studies were carried out with metal tetramethoxyphenylporphyrin (TMPP), CoTMPP and FeCoTMPP, and metal phthalocyanine (Pc), FePc, CoPc and FeCuPc, supported on Ketjenblack (KJB) carbon. Iron phthalocyanine supported on KJB (FePc-KJB) carbon demonstrated higher activity towards oxygen reduction than Pt in neutral media. The effect of carbon substrate was investigated by evaluating FePc on Vulcan XC carbon (FePcVC) versus Ketjenblack carbon. FePc-KJB showed higher activity than FePcVC suggesting the catalyst activity could be improved by using carbon substrate with a higher surface area. With FePc-KJB as the MFC cathode catalyst, a power density of 634 mW m{sup -2} was achieved in 50 mM phosphate buffer medium at pH 7, which was higher than that obtained using the precious-metal Pt cathode (593 mW m{sup -2}). Under optimum operating conditions (i.e. using a high surface area carbon brush anode and 200 mM PBM as the supporting electrolyte with 1 g L{sup -1} acetate as the substrate), the power density was increased to 2011 mW m{sup -2}. This high power output indicates that MFCs with low cost metal macrocycles catalysts is promising in further practical applications. (author)

  16. 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.

  17. 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.

  18. 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.

  19. 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 ...

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. Monte Carlo simulation of the PEMFC catalyst layer

    Institute of Scientific and Technical Information of China (English)

    WANG Hongxing; CAO Pengzhen; WANG Yuxin

    2007-01-01

    The performance of the polymer electrolyte membrane fuel cell (PEMFC) is greatly controlled by the structure of the catalyst layer.Low catalyst utilization is still a significant obstacle to the commercialization of the PEMFC.In order to get a fundamental understanding of the electrode structure and to find the limiting factor in the low catalyst utilization,it is necessary to develop the mechanical model on the effect of catalyst layer structure on the catalyst utilization and the performance of the PEMFC.In this work,the structure of the catalyst layer is studied based on the lattice model with the Monte Carlo simulation.The model can predict the effects of some catalyst layer components,such as Pt/C catalyst,electrolyte and gas pores,on the utilization of the catalyst and the cell performance.The simulation result shows that the aggregation of conduction grains can greatly affect the degree of catalyst utilization.The better the dispersion of the conduction grains,the larger the total effective area of the catalyst is.To achieve higher utilization,catalyst layer components must be distributed by means of engineered design,which can prevent aggregation.

  7. 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)

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. Nonactivated and activated biochar derived from bananas as alternative cathode catalyst in microbial fuel cells.

    Science.gov (United States)

    Yuan, Haoran; Deng, Lifang; Qi, Yujie; Kobayashi, Noriyuki; Tang, Jiahuan

    2014-01-01

    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/m(2) 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.

  14. 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.

  15. 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...

  16. 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

  17. Optimization of Layered Cathode Materials for Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Christian Julien

    2016-07-01

    Full Text Available This review presents a survey of the literature on recent progress in lithium-ion batteries, with the active sub-micron-sized particles of the positive electrode chosen in the family of lamellar compounds LiMO2, where M stands for a mixture of Ni, Mn, Co elements, and in the family of yLi2MnO3•(1 − yLiNi½Mn½O2 layered-layered integrated materials. The structural, physical, and chemical properties of these cathode elements are reported and discussed as a function of all the synthesis parameters, which include the choice of the precursors and of the chelating agent, and as a function of the relative concentrations of the M cations and composition y. Their electrochemical properties are also reported and discussed to determine the optimum compositions in order to obtain the best electrochemical performance while maintaining the structural integrity of the electrode lattice during cycling.

  18. Hydrothermal Synthesis of Nanostructured Manganese Oxide as Cathodic Catalyst in a Microbial Fuel Cell Fed with Leachate

    Directory of Open Access Journals (Sweden)

    Yuan Haoran

    2014-01-01

    Full Text Available Much effort has been devoted to the synthesis of novel nanostructured MnO2 materials because of their unique properties and potential applications as cathode catalyst in Microbial fuel cell. Hybrid MnO2 nanostructures were fabricated by a simple hydrothermal method in this study. Their crystal structures, morphology, and electrochemical characters were carried out by FESEM, N2-adsorption-desorption, and CV, indicating that the hydrothermally synthesized MnO2 (HSM was structured by nanorods of high aspect ratio and multivalve nanoflowers and more positive than the naturally synthesized MnO2 (NSM, accompanied by a noticeable increase in oxygen reduction peak current. When the HSM was employed as the cathode catalyst in air-cathode MFC which fed with leachate, a maximum power density of 119.07 mW/m2 was delivered, 64.68% higher than that with the NSM as cathode catalyst. Furthermore, the HSM via a 4-e pathway, but the NSM via a 2-e pathway in alkaline solution, and as 4-e pathway is a more efficient oxygen reduction reaction, the HSM was more positive than NSM. Our study provides useful information on facile preparation of cost-effective cathodic catalyst in air-cathode MFC for wastewater treatment.

  19. Immobilization of a Metal-Nitrogen-Carbon Catalyst on Activated Carbon with Enhanced Cathode Performance in Microbial Fuel Cells.

    Science.gov (United States)

    Yang, Wulin; Logan, Bruce E

    2016-08-23

    Applications of microbial fuel cells (MFCs) are limited in part by low power densities mainly due to cathode performance. Successful immobilization of an Fe-N-C co-catalyst on activated carbon (Fe-N-C/AC) improved the oxygen reduction reaction to nearly a four-electron transfer, compared to a twoelectron transfer achieved using AC. With acetate as the fuel, the maximum power density was 4.7±0.2 W m(-2) , which is higher than any previous report for an air-cathode MFC. With domestic wastewater as a fuel, MFCs with the Fe-N-C/AC cathode produced up to 0.8±0.03 W m(-2) , which was twice that obtained with a Pt-catalyzed cathode. The use of this Fe-N-C/AC catalyst can therefore substantially increase power production, and enable broader applications of MFCs for renewable electricity generation using waste materials.

  20. Application of graphene-based nanomaterials as novel cathode catalysts for improving power generation in single chamber microbial fuel cells

    Science.gov (United States)

    Valipour, Alireza; Ayyaru, Sivasankaran; Ahn, Youngho

    2016-09-01

    The low catalytic activity, limited resources, complexity and costs, and non-environmentally friendly nature are key factors limiting the application of non-precious metals and their composites at the cathode in microbial fuel cells (MFCs). This study evaluated the feasibility of graphene-based nanomaterials (RGOHI-AcOH vs. RGO/Ni nanoparticle composite) as novel cathode catalysts in single chamber air-cathode MFCs. A series of MFCs with different catalyst loadings were produced. The electrochemical behavior of the MFCs were evaluated by cyclic voltammetry (CV) and impedance spectroscopy (EIS). As a result, the MFCs with the RGOHI-AcOH cathodes showed greater maximum power densities (>37%) than those with the RGO/Ni nanoparticle cathodes. In the MFCs, the highest maximum power density of 1683 ± 23 mW/m2 (CE = 72 ± 3%), which covers 77% of that estimated for Pt/C (2201 ± 45 mW/m2, CE = 81 ± 4%), was obtained from the double loading RGOHI-AcOH cathodes. Among the MFCs with the RGO/Ni nanoparticle composite cathodes, those loaded with a double catalyst (1015 ± 28 mW/m2, CE = 70 ± 2%) showed better power performance than the others. Both CV and EIS showed good agreement with the MFC results. This study suggests that the RGOHI-AcOH cathode, particularly with a double catalyst loading, is promising for sustainable low-cost green materials, stable power generation and the long-term operation of MFCs.

  1. 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

  2. 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).

  3. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

    Science.gov (United States)

    Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

    2016-01-01

    Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m−3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells. PMID:27734945

  4. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

    Science.gov (United States)

    Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

    2016-10-01

    Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m‑3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells.

  5. 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.

  6. Study of an unitised bidirectional vanadium/air redox flow battery comprising a two-layered cathode

    Science.gov (United States)

    grosse Austing, Jan; Nunes Kirchner, Carolina; Hammer, Eva-Maria; Komsiyska, Lidiya; Wittstock, Gunther

    2015-01-01

    The performance of a unitised bidirectional vanadium/air redox flow battery (VARFB) is described. It contains a two-layered cathode consisting of a gas diffusion electrode (GDE) with Pt/C catalyst for discharging and of an IrO2 modified graphite felt for charging. A simple routine is shown for the modification of a graphite felt with IrO2. A maximum energy efficiency of 41.7% at a current density of 20 mA cm-2 as well as an average discharge power density of 34.6 mW cm-2 at 40 mA cm-2 were obtained for VARFB operation at room temperature with the novel cathode setup. A dynamic hydrogen electrode was used to monitor half cell potentials during operation allowing to quantify the contribution of the cathode to the overall performance of the VARFB. Four consecutive cycles revealed that crossover of vanadium ions took place and irreversible degradation processes within the reaction unit lead to a performance decrease.

  7. Continuous flow membrane-less air cathode microbial fuel cell with spunbonded olefin diffusion layer.

    Science.gov (United States)

    Tugtas, Adile Evren; Cavdar, Pelin; Calli, Baris

    2011-11-01

    The power production performance of a membrane-less air-cathode microbial fuel cell was evaluated for 53 days. Anode and cathode electrodes and the micro-fiber cloth separator were configured by sandwiching the separator between two electrodes. In addition, the air-facing side of the cathode was covered with a spunbonded olefin sheet instead of polytetrafluoroethylene (PTFE) coating to control oxygen diffusion and water loss. The configuration resulted in a low resistance of about 4Ω and a maximum power density of 750 mW/m2. However, as a result of a gradual decrease in the cathode potential, maximum power density decreased to 280 mW/m2. The declining power output was attributed to loss of platinum catalyst (8.26%) and biomass growth (38.44%) on the cathode. Coulombic efficiencies over 55% and no water leakage showed that the spunbonded olefin sheet covering the air-facing side of the cathode can be a cost-effective alternative to PTFE coating.

  8. 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

    2016-10-01

    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.

  9. 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.

  10. 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.

  11. 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

  12. Evaluation of porous ceramic cathode layers for solid oxide fuel cells

    NARCIS (Netherlands)

    Haart, de L.G.J.; Vries, de K.J.; Carvalho, A.P.M.; Frade, J.R.; Marques, F.M.B.

    1991-01-01

    Sr0.15La0.85MnO3 layers with 2 and 10 u thickness, deposited on zirconia based electrolytes, were evaluated as cathodes for high temperature applications. Different electrode layers were characterized in terms of thickness, porosity, three phase boundary line per unit area (TPBL), and concentration

  13. 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.

  14. Highly stable precious metal-free cathode catalyst for fuel cell application

    Science.gov (United States)

    Serov, Alexey; Workman, Michael J.; Artyushkova, Kateryna; Atanassov, Plamen; McCool, Geoffrey; McKinney, Sam; Romero, Henry; Halevi, Barr; Stephenson, Thomas

    2016-09-01

    A platinum group metal-free (PGM-free) oxygen reduction reaction (ORR) catalyst engineered for stability has been synthesized using the sacrificial support method (SSM). This catalyst was comprehensively characterized by physiochemical analyses and tested for performance and durability in fuel cell membrane electrode assemblies (MEAs). This catalyst, belonging to the family of Fe-N-C materials, is easily scalable and can be manufactured in batches up to 200 g. The fuel cell durability tests were performed in a single cell configuration at realistic operating conditions of 0.65 V, 1.25 atmgauge air, and 90% RH for 100 h. In-depth characterization of surface chemistry and morphology of the catalyst layer before and after durability tests were performed. The failure modes of the PGM-free electrodes were derived from structure-to-property correlations. It is suggested that under constant voltage operation, the performance loss results from degradation of the electrode pore structure, while under carbon corrosion accelerated test protocols the failure mode is catalyst corrosion.

  15. Carbon corrosion of proton exchange membrane fuel cell catalyst layers studied by scanning transmission X-ray microscopy

    Science.gov (United States)

    Hitchcock, Adam P.; Berejnov, Viatcheslav; Lee, Vincent; West, Marcia; Colbow, Vesna; Dutta, Monica; Wessel, Silvia

    2014-11-01

    Scanning Transmission X-ray Microscopy (STXM) at the C 1s, F 1s and S 2p edges has been used to investigate degradation of proton exchange membrane fuel cell (PEM-FC) membrane electrode assemblies (MEA) subjected to accelerated testing protocols. Quantitative chemical maps of the catalyst, carbon support and ionomer in the cathode layer are reported for beginning-of-test (BOT), and end-of-test (EOT) samples for two types of carbon support, low surface area carbon (LSAC) and medium surface area carbon (MSAC), that were exposed to accelerated stress testing with upper potentials (UPL) of 1.0, 1.2, and 1.3 V. The results are compared in order to characterize catalyst layer degradation in terms of the amounts and spatial distributions of these species. Pt agglomeration, Pt migration and corrosion of the carbon support are all visualized, and contribute to differing degrees in these samples. It is found that there is formation of a distinct Pt-in-membrane (PTIM) band for all EOT samples. The cathode thickness shrinks due to loss of the carbon support for all MSAC samples that were exposed to the different upper potentials, but only for the most aggressive testing protocol for the LSAC support. The amount of ionomer per unit volume significantly increases indicating it is being concentrated in the cathode as the carbon corrosion takes place. S 2p spectra and mapping of the cathode catalyst layer indicates there are still sulfonate groups present, even in the most damaged material.

  16. 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.

  17. 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

  18. Atomic Layer Deposited Catalysts for Fuel Cell Applications

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta

    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 injected precursors...... for the realization of such tiny devices. It is a mature technology, suitable for mass production, where versatile structuring is available at the micro and nano regime. Carbon black supported catalysts synthesized by wet chemistry methods are not readily applicable for standard microfabrication techniques. Atomic...

  19. Investigation of Cathode Catalysts for Intermediate-temperature H2S-Air Fuel Cells%中温H2S-空气燃料电池阴极催化剂的研究

    Institute of Scientific and Technical Information of China (English)

    钟理; 罗京莉; K.Chuang

    2007-01-01

    Cathode catalysts comprising composite NiO, NiO-Pt, or LiNiO2 have been developed for electrochemical oxidation of hydrogen sulfide in intermediate-temperature solid oxide fuel cells (ITSOFCs).All catalysts exhibited good electrical conductivity and catalytic activity at operating temperature.Composite NiO catalysts were found to be more active and have lower over potential and higher current density than pure Pt although the electrical conductivity of NiO itself is lower than that of Pt.This problem has been overcome by either admixing as high as 10% (by mass) Ag powder into NiO cathode layer or using composite NiO catalysts such as NiO-Pt and LiNiO2 catalysts.Composite catalysts like NiO with Ag, electrolyte and starch admixed, NiO-Pt, which was prepared from a mixture of NiO and Pt powders, by admixing electrolyte and starch, and LiNiO2, which is derived from the reaction of LiOH-H2O and NiO with electrolyte and starch admixed have been shown to be feasible and effective in an intermediate-temperature H2S-air fuel cell.A fuel cell using Li2SO4-based proton-conducting membrane as electrolyte, metal sulfides as anode catalysts, and composite NiO as cathode catalysts produced a maximum current density about 300mA·cm-2 and maximum power density over 80mW·cm-2 at 680℃ .

  20. 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.

  1. 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....

  2. 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 contribution...

  3. 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.

  4. Formation of Ti-N graded bioceramic layer by DC hollow-cathode plasma nitriding

    Institute of Scientific and Technical Information of China (English)

    ZHENG Chuan-lin

    2004-01-01

    Ti-N graded ceramic layer was formed on titanium by using DC hollow-cathode plasma nitriding technique. The structure of Ti-N layer was analyzed using X-ray diffractometry(XRD) with Cu Kα radiation, and the microhardness( HV0.1) was measured from the surface to inner along the cross section of Ti-N layer. The results indicate that the Ti-N graded layer is composed of ε-Ti2 N, δ-TiN and α-Ti(N) phases. Mechanism discussion shows that hollow-cathode discharge can intensify gas ionization, increase current density and enhance the nitriding potential, which directly increases the thickness of the diffusion coatings compared with traditional nitriding methods.

  5. 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.

  6. PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design

    Science.gov (United States)

    Stariha, Sarah; Artyushkova, Kateryna; Workman, Michael J.; Serov, Alexey; Mckinney, Sam; Halevi, Barr; Atanassov, Plamen

    2016-09-01

    This work studies the morphology of platinum group metal-free (PGM-free) iron-nitrogen-carbon (Fe-N-C) catalyst layers for the oxygen reduction reaction (ORR) and compares catalytic performance via polarization curves. Three different nitrogen-rich organic precursors are used to prepare the catalysts. Using scanning electron microscopy (SEM) and focused ion beam (FIB) tomography, the porosity, Euler number (pore connectivity), overall roughness, solid phase size and pore size are calculated for catalyst surfaces and volumes. Catalytic activity is determined using membrane electrode assembly (MEA) testing. It is found that the dominant factor in MEA performance is transport limitations. Through the 2D and 3D metrics it is concluded that pore connectivity has the biggest effect on transport performance.

  7. Function mechanism of carbide layer on surface of La2O3-Mo cathode

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The ion implanting method has been taken for implanting lanthanum ions into the surface layer of molybdenum wires in order to study the function of carbide layer on the surface of La2O3-Mo cathode in the emission. The function mechanism has been discussed by using XPS and AES methods. The results show that the carbide layer mainly acts as a reduction reagent to produce metallic lanthanum. Moreover, it can store the activator substance and carry them to the surface. Based on the research results, the carbonization technique has been changed. By applying the new technique, the lifetime of the La2O3-Mo cathode has been improved from 14  h to more than 1  000  h—the minimum lifetime for practical uses.

  8. 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

  9. 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)

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. Potential of porous Co3O4 nanorods as cathode catalyst for oxygen reduction reaction in microbial fuel cells.

    Science.gov (United States)

    Kumar, Ravinder; Singh, Lakhveer; Zularisam, A W; Hai, Faisal I

    2016-11-01

    This study aims to investigate the potential of porous Co3O4 nanorods as the cathode catalyst for oxygen reduction reaction (ORR) in aqueous air cathode microbial fuel cells (MFCs). The porous Co3O4 nanorods were synthesized by a facile and cost-effective hydrothermal method. Three different concentrations (0.5mg/cm(2), 1mg/cm(2), and 2mg/cm(2)) of Co3O4 nanorods coated on graphite electrodes were used to test its performance in MFCs. The results showed that the addition of porous Co3O4 nanorods enhanced the electrocatalytic activity and ORR kinetics significantly and the overall resistance of the system was greatly reduced. Moreover, the MFC with a higher concentration of the catalyst achieved a maximum power density of 503±16mW/m(2), which was approximately five times higher than the bare graphite electrode. The improved catalytic activity of the cathodes could be due to the porous properties of Co3O4 nanorods that provided the higher number of active sites for oxygen.

  16. Suppression of Cross Contamination in Multi-Layer Thin Film Prepared by Using Rotating Hexagonal Sputtering Cathode.

    Science.gov (United States)

    Park, Se Yeon; Choi, Bum Ho; Lee, Jong Ho

    2015-01-01

    In this study, single- and multi-layered thin films were prepared on a glass substrate using a newly developed rotating hexagonal sputtering cathode in a single chamber. The rotatinghexagonal sputtering cathode can install up to six different sputtering targets or six single targets in a cathode. Using the rotating hexagonal cathode, we prepared a single-layered AZO film and a multi-layer film to evaluate the performance of hexagonal gun. Cross-contamination, which is often observed in multi-layer thin film preparation, was suppressed to nearly zero by controlling process parameters and revising hardware. Energy-saving effects of five-layered glass were also verified by measuring the temperature.

  17. 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.

  18. Aqueous Solution Processed Photoconductive Cathode Interlayer for High Performance Polymer Solar Cells with Thick Interlayer and Thick Active Layer.

    Science.gov (United States)

    Nian, Li; Chen, Zhenhui; Herbst, Stefanie; Li, Qingyuan; Yu, Chengzhuo; Jiang, Xiaofang; Dong, Huanli; Li, Fenghong; Liu, Linlin; Würthner, Frank; Chen, Junwu; Xie, Zengqi; Ma, Yuguang

    2016-09-01

    An aqueous-solution-processed photoconductive cathode interlayer is developed, in which the photoinduced charge transfer brings multiple advantages such as increased conductivity and electron mobility, as well as reduced work function. Average power conversion efficiency over 10% is achieved even when the thickness of the cathode interlayer and active layer is up to 100 and 300 nm, respectively.

  19. 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)

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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...

  5. 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

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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.)

  11. 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.

  12. Modeling the cathode in a proton exchange membrane fuel cell using density functional theory How the carbon support can affect durability and activity of a platinum catalyst

    Science.gov (United States)

    Groves, Michael Nelson

    The current global energy and environmental challenges need to be addressed by developing a new portfolio of clean power producing devices. The proton exchange membrane fuel cell has the potential to be included and can fit into a variety of niches ranging from portable electronics to stationary residential applications. One of the many barriers to commercial viability is the cost of the cathode layer which requires too much platinum metal to achieve a comparable power output as well as would need to be replaced more frequently when compared to conventional sources for most applications. Using density functional theory, an ab initio modeling technique, these durability and activity issues are examined for platinum catalysts on graphene and carbon nanotube supports. The carbon supports were also doped by replacing individual carbon atoms with other second row elements (beryllium, boron, nitrogen, and oxygen) and the effect on the platinum-surface interaction along with the interaction between the platinum and the oxygen reduction reaction intermediates are discussed. Keywords: proton exchange membrane fuel cell, density functional theory, platinum catalyst, oxygen reduction reaction, doped carbon surfaces

  13. 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.

  14. 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.

  15. 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....

  16. 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.

  17. 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

    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....

  18. Electrochemical impedance study and performance of PdNi nanoparticles as cathode catalyst in a polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Ramos-Sanchez, G.; Santana-Salinas, A.; Vazquez-Huerta, G.; Solorza-Feria, O. [Inst. Politenico Nacional, Centro de Investigacion y de Estudios Avanzados, Mexico City (Mexico). Dept. de Quimica

    2010-07-15

    Polymer electrolyte membrane fuel cells (PEMFC) convert the energy stored in hydrogen and oxygen molecules directly into electricity. However, technical and economic challenges must be overcome to address cost, performance and stability issues associated with membrane electrode assemblies (MEA). The oxygen reduction reaction (ORR) which takes place in the cathode is the limiting reaction due to the slow kinetics of ORR on metals, including platinum (Pt). For that reason, much research has gone into finding catalyst materials with a similar or greater performance than Pt. Bimetallic palladium (Pd) based catalysts have been considered as alternative materials for ORR. In this study, a carbon-dispersed bimetallic PdNi was prepared by borohydride reduction using PdCl{sub 2} and NiCl{sub 2} as precursors in a tetrahydrofuran (THF) solution. The PdNi loading and weight percentage were optimized using the Simplex method. The MEA performance was evaluated at optimum conditions using the PdNi electrocatalyst as the cathode and a Pt-Etek carbon cloth as the anode. The maximum power density of 122 mW per cm{sup 2} was reached with 45 percent of PdNi wt percent at 30 psi and 80 degrees C. The catalytic activity and the mechanism of the ORR on PdNi, in 0.5M H{sub 2}SO{sub 4} was investigated using electrochemical impedance spectroscopy. The Tafel slope and the charge transfer coefficient were obtained from the impedance spectra at optimum condition of PdNi loading and PdNi wt percent. 24 refs., 2 tabs., 5 figs.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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. PMID:27479810

  4. Simulation of the atomic and ionic densities in the ionization layer of a plasma arc with a binary cathode

    Energy Technology Data Exchange (ETDEWEB)

    Ortega, D; Marin, J A Sillero; Munoz-Serrano, E; Casado, E, E-mail: f92orhed@uco.e [Departamento de Fisica, Universidad de Cordoba, 14071 Cordoba (Spain)

    2009-04-21

    A physical model was developed to study the behaviour of the cathode material evaporated from a thoriated tungsten cathode of an atmospheric-pressure argon plasma arc. The densities of tungsten and thorium atoms and ions in the ionization layer were obtained, and the influence of the different physical processes on the evaporated cathode material was established. It was found that almost all of the neutral atoms evaporated from the cathode are ionized near the beginning of the ionization layer, i.e. near the boundary between the sheath and the ionization layer. Thorium ions are concentrated in a 4 {mu}m region near the beginning of this layer, while tungsten ions are found in a region of 9 {mu}m. The contribution of the electric force to the velocity of ions is the dominant contribution only near the beginning of the ionization layer. At a distance from the interface between the sheath and the ionization layer greater than 3.8 {mu}m in the case of thorium ions, and greater than 5 {mu}m in the case of tungsten ions, the contributions of the density gradient forces and the frictional forces are more important than the electric force contribution.

  5. Performance of a Double Catalyst Fuel Cell Cathode with a Tubular Oxygen Breathing and Preliminary Reduction Zone

    Institute of Scientific and Technical Information of China (English)

    Lu(i)s A. Waack BAMBACE; Miriam NISHIMORI; Fernando M. RAMOS; Demétrio BASTOS -NETTO

    2005-01-01

    @@ This paper discusses a mathematical model for a liquid phase reacting flow occurring at the cathode of a patent pending novel fuel cell geometry, where a non homogeneous catalysis carried by gold and Prussian Blue, with the first reducing air O2 and the second the resulting H2O2. The breathing zone is porous walls microtubes, with three different types of pores in its walls. Inside the microtubes there is water solution of sulfuric acid. The microtubes possess an external layer of extremely porous polymer hydrophobic agent. A Prussian Blue thin porous layer is over the selective membrane. Appropriate porous and tubular connecting elements close the fluid loop. The asymmetry induces proper current and electric potential profiles, which leads to a mainly electrocapillary electrokinetic flow, which enhances the oxygen transport and assures the H2O2 flow to its reduction layer.

  6. 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)

  7. 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.

  8. 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.

  9. MnCo2O4 nanowires anchored on reduced graphene oxide sheets as effective bifunctional catalysts for Li-O2 battery cathodes.

    Science.gov (United States)

    Kim, Jong Guk; Kim, Youngmin; Noh, Yuseong; Kim, Won Bae

    2015-05-22

    A hybrid composite system of MnCo2 O4 nanowires (MCO NWs) anchored on reduced graphene oxide (RGO) nanosheets was prepared as the bifunctional catalyst of a Li-O2 battery cathode. The catalysts can be obtained from the hybridization of one-dimensional MCO NWs and two-dimensional RGO nanosheets. As O2 -cathode catalysts for Li-O2 cells, the MCO@RGO composites showed a high initial discharge capacity (ca. 11092.1 mAh gcarbon (-1) ) with a high rate performance. The Li-O2 cells could run for more than 35 cycles with high reversibility under a limited specific capacity of 1000 mAh gcarbon (-1) with a low potential polarization of 1.36 V, as compared with those of pure Ketjenblack and MCO NWs. The high cycling stability, low potential polarization, and rate capability suggest that the MCO@RGO composites prepared here are promising catalyst candidates for highly reversible Li-O2 battery cathodes.

  10. 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...

  11. 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

  12. 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

    2014-03-27

    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.

  13. 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.

  14. 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.

  15. 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.

  16. Effect of catalyst distribution in the active layers of proton exchange membrane fuel cells; Effet de la distribution du catalyseur dans les couches actives de piles a combustible de type PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Bultel, Y.; Durand, R.; Ozil, P. [Ecole Nationale Superieure d' Electrochimie et d' Electrometallurgie, Lab. d' Electrochimie et de Physico-chimie des Materiaux et des Interfaces, UMR 5631, 38 - Grenoble (France); Antoine, O. [Geneva Univ., Dept. de Chimie Minerale, Analytique et Appliquee, Sciences 2 (Switzerland)

    2000-07-01

    The aim of this work is to study the influence of the distribution of the platinum catalyst in the active layers on the performances of proton exchange membrane fuel cells (PEMFC) electrodes. In the one hand, the results predicted by the classical models and those in which the active layers is modified have been compared; these results have allowed to demonstrate theoretically the effect of the discrete distribution of the platinum catalyst in the form of nano-particles. On the other hand, the influence of a distribution gradient of the platinum catalyst for porous and non-porous active layers of PEMFC cathode has been experimentally demonstrated and predicted by numerical simulations. (O.M.)

  17. 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.

  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. 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.

  20. 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)

  1. 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.

  2. 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...

  3. 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.

  4. Layered SiC Sheets: A Potential Catalyst for Oxygen Reduction Reaction

    Science.gov (United States)

    Zhang, P.; Xiao, B. B.; Hou, X. L.; Zhu, Y. F.; Jiang, Q.

    2014-01-01

    The large-scale practical application of fuel cells cannot come true if the high-priced Pt-based electrocatalysts for oxygen reduction reaction (ORR) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, based on density functional theory (DFT), we exploited the potentials of layered SiC sheets as a novel catalyst for ORR. From our DFT results, it can be predicted that layered SiC sheets exhibit excellent ORR catalytic activity without CO poisoning, while the CO poisoning is the major drawback in conventional Pt-based catalysts. Furthermore, the layered SiC sheets in alkaline media has better catalytic activity than Pt(111) surface and have potential as a metal-free catalyst for ORR in fuel cells.

  5. 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.)

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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 Mn(2+) and Co(2+) 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. PMID:26894375

  13. 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.

  14. 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

  15. 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

  16. Nitrogen-Doped Carbon Nanoparticle-Carbon Nanofiber Composite as an Efficient Metal-Free Cathode Catalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Panomsuwan, Gasidit; Saito, Nagahiro; Ishizaki, Takahiro

    2016-03-23

    Metal-free nitrogen-doped carbon materials are currently considered at the forefront of potential alternative cathode catalysts for the oxygen reduction reaction (ORR) in fuel cell technology. Despite numerous efforts in this area over the past decade, rational design and development of a new catalyst system based on nitrogen-doped carbon materials via an innovative approach still present intriguing challenges in ORR catalysis research. Herein, a new kind of nitrogen-doped carbon nanoparticle-carbon nanofiber (NCNP-CNF) composite with highly efficient and stable ORR catalytic activity has been developed via a new approach assisted by a solution plasma process. The integration of NCNPs and CNFs by the solution plasma process can lead to a unique morphological feature and modify physicochemical properties. The NCNP-CNF composite exhibits a significantly enhanced ORR activity through a dominant four-electron pathway in an alkaline solution. The enhancement in ORR activity of NCNP-CNF composite can be attributed to the synergistic effects of good electron transport from highly graphitized CNFs as well as abundance of exposed catalytic sites and meso/macroporosity from NCNPs. More importantly, NCNP-CNF composite reveals excellent long-term durability and high tolerance to methanol crossover compared with those of a commercial 20 wt % supported on Vulcan XC-72. We expect that NCNP-CNF composite prepared by this synthetic approach can be a promising metal-free cathode catalyst candidate for ORR in fuel cells and metal-air batteries. PMID:26908214

  17. 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.)

  18. 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.

  19. 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)

  20. 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...

  1. 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...

  2. 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.

  3. 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)

  4. 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.

  5. 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

  6. 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

  7. Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Pengfei [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zheng, Jianming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lv, Dongping [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wei, Yi [Peking Univ., Beijing (China); Zheng, Jiaxin [Peking Univ., Beijing (China); Wang, Zhiguo [Univ. of Electronic Science and Technology of China, Chengdu (China); Kuppan, Saravanan [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Yu, Jianguo [Idaho National Lab. (INL), Idaho Falls, ID (United States); Luo, Langli [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Edwards, Danny J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Olszta, Matthew J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Amine, Khalil [Argonne National Lab. (ANL), Argonne, IL (United States); Liu, Jun [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Xiao, Jie [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pan, Feng [Peking Univ., Beijing (China); Chen, Guoying [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhang, Jiguang [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wang, Chong M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-07-06

    Capacity and voltage fading of layer structured cathode based on lithium transition metal oxide is closely related to the lattice position and migration behavior of the transition metal ions. However, it is scarcely clear about the behavior of each of these transition metal ions. We report direct atomic resolution visualization of interatomic layer mixing of transition metal (Ni, Co, Mn) and lithium ions in layer structured oxide cathodes for lithium ion batteries. Using chemical imaging with aberration corrected scanning transmission electron microscope (STEM) and DFT calculations, we discovered that in the layered cathodes, Mn and Co tend to reside almost exclusively at the lattice site of transition metal (TM) layer in the structure or little interlayer mixing with Li. In contrast, Ni shows high degree of interlayer mixing with Li. The fraction of Ni ions reside in the Li layer followed a near linear dependence on total Ni concentration before reaching saturation. The observed distinctively different behavior of Ni with respect to Co and Mn provides new insights on both capacity and voltage fade in this class of cathode materials based on lithium and TM oxides, therefore providing scientific basis for selective tailoring of oxide cathode materials for enhanced performance.

  8. 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.

  9. Growth of transition metals on cerium tungstate model catalyst layers

    Science.gov (United States)

    Skála, T.; Tsud, N.; Stetsovych, V.; Mysliveček, J.; Matolín, V.

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed.

  10. Atomic layer deposition overcoating: tuning catalyst selectivity for biomass conversion.

    Science.gov (United States)

    Zhang, Hongbo; Gu, Xiang-Kui; Canlas, Christian; Kropf, A Jeremy; Aich, Payoli; Greeley, Jeffrey P; Elam, Jeffrey W; Meyers, Randall J; Dumesic, James A; Stair, Peter C; Marshall, Christopher L

    2014-11-01

    The terraces, edges, and facets of nanoparticles are all active sites for heterogeneous catalysis. These different active sites may cause the formation of various products during the catalytic reaction. Here we report that the step sites of Pd nanoparticles (NPs) can be covered precisely by the atomic layer deposition (ALD) method, whereas the terrace sites remain as active component for the hydrogenation of furfural. Increasing the thickness of the ALD-generated overcoats restricts the adsorption of furfural onto the step sites of Pd NPs and increases the selectivity to furan. Furan selectivities and furfural conversions are linearly correlated for samples with or without an overcoating, though the slopes differ. The ALD technique can tune the selectivity of furfural hydrogenation over Pd NPs and has improved our understanding of the reaction mechanism. The above conclusions are further supported by density functional theory (DFT) calculations.

  11. 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

  12. 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.

  13. 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.

  14. Improvement of Energy Capacity with Vitamin C Treated Dual-Layered Graphene-Sulfur Cathodes in Lithium-Sulfur Batteries.

    Science.gov (United States)

    Kim, Jin Won; Ocon, Joey D; Kim, Ho-Sung; Lee, Jaeyoung

    2015-09-01

    A graphene-based cathode design for lithium-sulfur batteries (LSB) that shows excellent electrochemical performance is proposed. The dual-layered cathode is composed of a sulfur active layer and a polysulfide absorption layer, and both layers are based on vitamin C treated graphene oxide at various degrees of reduction. By controlling the degree of reduction of graphene, the dual-layered cathode can increase sulfur utilization dramatically owing to the uniform formation of nanosized sulfur particles, the chemical bonding of dissolved polysulfides on the oxygen-rich sulfur active layer, and the physisorption of free polysulfides on the absorption layer. This approach enables a LSB with a high specific capacity of over 600 mAh gsulfur (-1) after 100 cycles even under a high current rate of 1C (1675 mA gsulfur (-1) ). An intriguing aspect of our work is the synthesis of a high-performance dual-layered cathode by a green chemistry method, which could be a promising approach to LSBs with high energy and power densities.

  15. Improvement of Energy Capacity with Vitamin C Treated Dual-Layered Graphene-Sulfur Cathodes in Lithium-Sulfur Batteries.

    Science.gov (United States)

    Kim, Jin Won; Ocon, Joey D; Kim, Ho-Sung; Lee, Jaeyoung

    2015-09-01

    A graphene-based cathode design for lithium-sulfur batteries (LSB) that shows excellent electrochemical performance is proposed. The dual-layered cathode is composed of a sulfur active layer and a polysulfide absorption layer, and both layers are based on vitamin C treated graphene oxide at various degrees of reduction. By controlling the degree of reduction of graphene, the dual-layered cathode can increase sulfur utilization dramatically owing to the uniform formation of nanosized sulfur particles, the chemical bonding of dissolved polysulfides on the oxygen-rich sulfur active layer, and the physisorption of free polysulfides on the absorption layer. This approach enables a LSB with a high specific capacity of over 600 mAh gsulfur (-1) after 100 cycles even under a high current rate of 1C (1675 mA gsulfur (-1) ). An intriguing aspect of our work is the synthesis of a high-performance dual-layered cathode by a green chemistry method, which could be a promising approach to LSBs with high energy and power densities. PMID:25925659

  16. 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

  17. 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 ...

  18. A facile cathode design combining Ni-rich layered oxides with Li-rich layered oxides for lithium-ion batteries

    Science.gov (United States)

    Song, Bohang; Li, Wangda; Yan, Pengfei; Oh, Seung-Min; Wang, Chong-Min; Manthiram, Arumugam

    2016-09-01

    A facile synthesis method has been developed to prepare xLi2MnO3·(1-x)LiNi0.7Co0.15Mn0.15O2 (x = 0, 0.03, 0.07, 0.10, 0.20, and 0.30) cathode materials, combining the advantages of the high specific capacity of the Ni-rich layered phase and the surface chemical stability of the Li-rich layered phase. X-ray diffraction (XRD), transmission electron microscopy (TEM), and electrochemical charge/discharge measurements confirm the formation of a Li-rich layered phase with C2/m symmetry. The high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) reveals a spatial relationship that the Li-rich nano-domain islands are integrated into the conventional Ni-rich layered matrix (R 3 bar m). Most importantly, this is the first time that Li-rich phase has been directly observed inside a particle at the nano-scale, when the overall composition of the layered oxide Li1+δNi1-y-z-δMnyMzO2 (M = metal) is Ni-rich (>0.5) rather than Mn-rich (>0.5). Remarkably, the xLi2MnO3·(1-x)LiNi0.7Co0.15Mn0.15O2 cathodes with optimized x value shows superior electrochemical performance at C/3 rate: an initial capacity of 190 mA h g-1 with 90% capacity retention after 400 cycles in a half cell and 73.5% capacity retention after 900 cycles in a pouch-type full cell.

  19. 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.

  20. Hydrocarbon oxidation over catalysts prepared by the molecular layer deposition technique

    Energy Technology Data Exchange (ETDEWEB)

    Koltsov, S.I.; Smirnov, V.M.; Postnov, V.N.; Postnova, A.M.; Aleskovskii, V.B.

    1980-01-01

    By depositing consecutive uniform monolayers of phosphorus pentoxide and vanadium pentoxide on a large-surface-area (240 sq m/g) silica gel, active and selective catalysts for hydrocarbon oxidation were obtained. Thus, in piperylene oxidation by air at 330/sup 0/-430/sup 0/C and 2000-18,000/hr space velocity, a productive capacity of 220 g/l./hr with 41 mole % each maleic anhydride yield and selectivity was achieved over a SiO/sub 2/-P/sub 2/O/sub 5//P/sub 2/O/sub 5//V/sub 2/O/sub 5/ catalyst (120 sq cm/g surface area), compared with 80 g/l./hr for a P/sub 2/O/sub 5/-V/sub 2/O/sub 5/ catalyst prepared by impregnation. In benzene oxidation, maleic anhydride yields of 52 and 60% and selectivities of 63 and 79% were achieved over SiO/sub 2/-P/sub 2/O/sub 5//V/sub 2/O/sub 5/ and SiO/sub 2/-P/sub 2/O/sub 5//P/sub 2/O/sub 5//P/sub 2/O/sub 5//V/sub 2/O/sub 5/ catalysts, respectively, compared with a 6% yield and very low selectivity over the impregnated P/sub 2/O/sub 5/-V/sub 2/O/sub 5/ catalyst. The molecular-layer catalysts retained their total activity for 100 hr on stream and permitted to reduce the oxidation temperature by 50/sup 0/-70/sup 0/C.

  1. Thin catalyst layers based on carbon nanotubes for PEM-fuel cell applications

    Science.gov (United States)

    Bohnenberger, T.; Matovic, J.; Schmid, U.

    2011-06-01

    In this study, two approaches are compared to develop thin, multifunctional films of carbon nanotubes (CNT) which are targeted to serve as a catalyst layer in fuel cells. The first is based on the direct deposition of mixed multi- and single-wall CNTs on metalized silicon wafers, using the metallization as a sacrificial layer to subsequently detach the CNT film from the substrate. It is a less time consuming and a straight forward method compared to the alternative under investigation, the layer-by-layer technique (LbL). The LbL uses bilayers of charged nanotubes to slowly build up a film with an exactly defined thickness. The process is well controlled, but the time constants for deposition of each bilayer are rather high (i.e. about 1 h). With additional annealing steps implemented during film generation this method, however, is regarded advantageous as membranes results with improved mechanical stability and a good homogeneity.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Lingyun [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Lin, Zekai [Department of Chemistry, University of Chicago, Chicago IL 60637 USA; Peng, Fei [Berzelii Center EXCELLENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, 10691 Stockholm Sweden; Wang, Weiwei [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Huang, Ruiyun [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Wang, Cheng [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Yan, Jiawei [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Liang, Jie [Berzelii Center EXCELLENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, 10691 Stockholm Sweden; Zhang, Zhiming [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Zhang, Teng [Department of Chemistry, University of Chicago, Chicago IL 60637 USA; Long, Lasheng [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Sun, Junliang [Berzelii Center EXCELLENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, 10691 Stockholm Sweden; College of Chemistry and Molecular Engineering, Peking University, 100871 Beijing China; Lin, Wenbin [College of Chemistry and Chemical Engineering, iCHEM, PCOSS, Xiamen University, Xiamen 361005 China; Department of Chemistry, University of Chicago, Chicago IL 60637 USA

    2016-03-08

    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 [Hf6O4(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.

  3. 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.

  4. 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).

  5. Ca/Alq3 hybrid cathode buffer layer for the optimization of organic solar cells based on a planar heterojunction

    Science.gov (United States)

    El Jouad, Z.; Barkat, L.; Stephant, N.; Cattin, L.; Hamzaoui, N.; Khelil, A.; Ghamnia, M.; Addou, M.; Morsli, M.; Béchu, S.; Cabanetos, C.; Richard-Plouet, M.; Blanchard, P.; Bernède, J. C.

    2016-11-01

    Use of efficient anode cathode buffer layer (CBL) is crucial to improve the efficiency of organic photovoltaic cells. Here we show that using a double CBL, Ca/Alq3, allows improving significantly cell performances. The insertion of Ca layer facilitates electron harvesting and blocks hole collection, leading to improved charge selectivity and reduced leakage current, whereas Alq3 blocks excitons. After optimisation of this Ca/Alq3 CBL using CuPc as electron donor, it is shown that it is also efficient when SubPc is substituted to CuPc in the cells. In that case we show that the morphology of the SubPc layer, and therefore the efficiency of the cells, strongly depends on the deposition rate of the SubPc film. It is necessary to deposit slowly (0.02 nm/s) the SubPc films because at higher deposition rate (0.06 nm/s) the films are porous, which induces leakage currents and deterioration of the cell performances. The SubPc layers whose formations are kinetically driven at low deposition rates are more uniform, whereas those deposited faster exhibit high densities of pinholes.

  6. High-Performanced Cathode with a Two-Layered R-P Structure for Intermediate Temperature Solid Oxide Fuel Cells.

    Science.gov (United States)

    Huan, Daoming; Wang, Zhiquan; Wang, Zhenbin; Peng, Ranran; Xia, Changrong; Lu, Yalin

    2016-02-01

    Driven by the mounting concerns on global warming and energy crisis, intermediate temperature solid-oxide fuel cells (IT-SOFCs) have attracted special attention for their high fuel efficiency, low toxic gas emission, and great fuel flexibility. A key obstacle to the practical operation of IT-SOFCs is their sluggish oxygen reduction reaction (ORR) kinetics. In this work, we applied a new two-layered Ruddlesden-Popper (R-P) oxide, Sr3Fe2O7-δ (SFO), as the material for oxygen ion conducting IT-SOFCs. Density functional theory calculation suggested that SFO has extremely low oxygen ion formation energy and considerable energy barrier for O(2-) diffusion. Unfortunately, the stable SrO surface of SFO was demonstrated to be inert to O2 adsorption and dissociation reaction, and thus restricts its catalytic activity toward ORR. Based on this observation, Co partially substituted SFO (SFCO) was then synthesized and applied to improve its surface vacancy concentration to accelerate the oxygen adsorptive reduction reaction rate. Electrochemical performance results suggested that the cell using the SFCO single phase cathode has a peak power density of 685 mW cm(-2) at 650 °C, about 15% higher than those when using LSCF cathode. Operating at 200 mA cm(-2), the new cell using SFCO is quite stable within the 100-h' test.

  7. 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.

  8. Sm1.5Sr0.5MO4 (M=Ni,Co,Fe) Cathode Catalysts for Ammonia Synthesis at Atmospheric Pressure and Low Temperature

    Institute of Scientific and Technical Information of China (English)

    XU,Gaochao; LIU,Ruiquan

    2009-01-01

    Sm1.5Sr0.5MO4 (M=Ni,Co,Fe) (SSM) catalysts were prepared by a sol-gel method and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).Ammonia was synthesized from wet hydrogen and dry nitrogen at atmospheric pressure and low temperature (25-100 ℃) with applied voltage,using SSM as a cathode,Ni-Ce0.5Sm0.2O2-δ(Ni-SDC) as an anode,and silver-platinum film as a current collector,Nation proton exchange membrane as a proton permeating membrane.Several important factors on ammonia synthesis were investigated and the optimal synthetic temperature was found,at which the highest rate of evolution of ammonia was up to 1.05×10-8 mol·cm- 2·S-1.

  9. 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

  10. 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.

  11. 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.

  12. Measurement of a new parameter representing the gas transport properties of the catalyst layers of polymer electrolyte fuel cells.

    Science.gov (United States)

    Iden, Hiroshi; Ohma, Atsushi; Tokunaga, Tomomi; Yokoyama, Kouji; Shinohara, Kazuhiko

    2016-05-14

    The optimization of the catalyst layers is necessary for obtaining a better fuel cell performance and reducing fuel cell cost. Although the ionomer coverage of the Pt catalyst is said to be a key parameter in this regard, the proportion of Pt either directly or indirectly covered by the ionomer is thought to be an important parameter with regard to gas transport (indirectly covered Pt: its gas transport paths are completely blocked by the ionomer even if it does not directly cover Pt). In this study, a new technique has been developed for evaluating the proportion of Pt covered indirectly or directly by the ionomer, which is defined as the "capped proportion", based on the carbon monoxide (CO) adsorption properties at different temperatures. The validity of the method was thoroughly examined by identifying the CO adsorption properties of the components of the catalyst layers. The capped proportion and oxygen transport resistance in the catalyst layers showed a good correlation, indicating that the capped proportion is a dominant factor of oxygen transport resistance. This technique thus enables the evaluation of the dominant factor of the gas transport properties of the catalyst layers. The method has another significant advantage in that it does not require a membrane electrode assembly, let alone electrochemical measurement, which should be helpful for catalyst layer optimization.

  13. 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

  14. 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℃.

  15. 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.

  16. 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.

  17. 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

  18. 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−

  19. 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.

  20. A Transient Model for Fuel Cell Cathode-Water Propagation Behavior inside a Cathode after a Step Potential

    Directory of Open Access Journals (Sweden)

    Der-Sheng Chan

    2010-04-01

    Full Text Available Most of the voltage losses of proton exchange membrane fuel cells (PEMFC are due to the sluggish kinetics of oxygen reduction on the cathode and the low oxygen diffusion rate inside the flooded cathode. To simulate the transient flooding in the cathode of a PEMFC, a transient model was developed. This model includes the material conservation of oxygen, vapor, water inside the gas diffusion layer (GDL and micro-porous layer (MPL, and the electrode kinetics in the cathode catalyst layer (CL. The variation of hydrophobicity of each layer generated a wicking effect that moves water from one layer to the other. Since the GDL, MPL, and CL are made of composite materials with different hydrophilic and hydrophobic properties, a linear function of saturation was used to calculate the wetting contact angle of these composite materials. The balance among capillary force, gas/liquid pressure, and velocity of water in each layer was considered. Therefore, the dynamic behavior of PEMFC, with saturation transportation taken into account, was obtained in this study. A step change of the cell voltage was used to illustrate the transient phenomena of output current, water movement, and diffusion of oxygen and water vapor across the entire cathode.

  1. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu; Ding, Dong; Wei, Tao; Liu, Meilin

    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 cathodes as

  3. Influence of hole injection layer and work function of cathode on the performance of light-emitting liquid crystal cells with fluorescent dye-doped nematic liquid crystal

    Science.gov (United States)

    Honma, Michinori; Horiuchi, Takao; Watanabe, Kyoko; Nose, Toshiaki

    2014-11-01

    We investigated the properties of rubrene-doped nematic-liquid-crystal cells to help determine the appropriate structure and material of electrodes for inducing light emission. In particular, we addressed the influence of the insertion of a hole injection layer (HIL) and the work function of the cathode on device performance. As a result, the employment of a HIL and a lower-work-function material was revealed to be effective in obtaining higher luminance and external quantum efficiency. We concluded that this improvement is caused by the facilitated carrier injection on the HIL and cathode surface, as is true for common organic light-emitting diodes.

  4. 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.

  5. 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.

  6. 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

  7. Evaluation of a cathode gas channel with a water absorption layer/waste channel in a PEFC by using visualization technique

    Energy Technology Data Exchange (ETDEWEB)

    Sugiura, Kimihiko; Nakata, Motoki; Yodo, Tadakatsu; Nishiguchi, Yusuke; Yamauchi, Makoto [Osaka Prefectural College of Technology, 26-12 Saiwai, Neyagawa, Osaka 572-8572 (Japan); Itoh, Yasuhiko [SANYO Electric Co., Ltd., 1-1-1 Sakata, Oizumi-machi, Ora-gun, Gunma 370-0596 (Japan)

    2005-08-18

    The polymer electrolyte fuel cell (PEFC) cathode is a performance-limiting component due to the slower oxygen reduction kinetics and mass transport limitations imposed by water generated in an electrochemical reaction. This water assists the performance of the PEFC by preventing drying of the polymer electrolyte. Conversely, the water hinders the transport of the reactant species by blocking the pores in the gas diffusion layer. Moreover, the effective electrode area is decreased, causing the cathode channel to become clogged with supersaturated water from the gas diffusion layer. This problem is overcome by separating the gas channel and the waste channel, and installing a water absorption layer (WAL). The new 'WAL type' gas channel has an installed WAL in which the designed waste channel is compared with the gas flow characteristics of a conventional cathode gas channel by using the visualization technique. Gas flowing into the WAL type separator is barely blocked before the WAL absorbs water condensed in the cathode gas channel. Therefore, the WAL type separator effectively improves the PEFC performance. (author)

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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%

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. Identifying active functionalities on few-layered graphene catalysts for oxidative dehydrogenation of isobutane.

    Science.gov (United States)

    Dathar, Gopi Krishna Phani; Tsai, Yu-Tung; Gierszal, Kamil; Xu, Ye; Liang, Chengdu; Rondinone, Adam J; Overbury, Steven H; Schwartz, Viviane

    2014-02-01

    The general consensus in the studies of nanostructured carbon catalysts for oxidative dehydrogenation (ODH) of alkanes to olefins is that the oxygen functionalities generated during synthesis and reaction are responsible for the catalytic activity of these nanostructured carbons. Identification of the highly active oxygen functionalities would enable engineering of nanocarbons for ODH of alkanes. Few-layered graphenes were used as model catalysts in experiments to synthesize reduced graphene oxide samples with varying oxygen concentrations, to characterize oxygen functionalities, and to measure the activation energies for ODH of isobutane. Periodic density functional theory calculations were performed on graphene nanoribbon models with a variety of oxygen functionalities at the edges to calculate their thermal stability and to model reaction mechanisms for ODH of isobutane. Comparing measured and calculated thermal stability and activation energies leads to the conclusion that dicarbonyls at the zigzag edges and quinones at armchair edges are appropriately balanced for high activity, relative to other model functionalities considered herein. In the ODH of isobutane, both dehydrogenation and regeneration of catalytic sites are relevant at the dicarbonyls, whereas regeneration is facile compared with dehydrogenation at quinones. The catalytic mechanism involves weakly adsorbed isobutane reducing functional oxygen and leaving as isobutene, and O2 in the feed, weakly adsorbed on the hydrogenated functionality, reacting with that hydrogen and regenerating the catalytic sites.

  19. 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.

  20. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries.

    Science.gov (United States)

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

    2016-01-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries. PMID:27363944

  1. Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

    Science.gov (United States)

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

    2016-01-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries. PMID:27363944

  2. 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.

  3. 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.

  4. 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.

  5. 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 −}.

  6. 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

  7. 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

  8. 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

  9. Binder free three-dimensional sulphur/few-layer graphene foam cathode with enhanced high-rate capability for rechargeable lithium sulphur batteries.

    Science.gov (United States)

    Xi, Kai; Kidambi, Piran R; Chen, Renjie; Gao, Chenlong; Peng, Xiaoyu; Ducati, Caterina; Hofmann, Stephan; Kumar, R Vasant

    2014-06-01

    A novel ultra-lightweight three-dimensional (3-D) cathode system for lithium sulphur (Li-S) batteries has been synthesised by loading sulphur on to an interconnected 3-D network of few-layered graphene (FLG) via a sulphur solution infiltration method. A free-standing FLG monolithic network foam was formed as a negative of a Ni metallic foam template by CVD followed by etching away of Ni. The FLG foam offers excellent electrical conductivity, an appropriate hierarchical pore structure for containing the electro-active sulphur and facilitates rapid electron/ion transport. This cathode system does not require any additional binding agents, conductive additives or a separate metallic current collector thus decreasing the weight of the cathode by typically ∼20-30 wt%. A Li-S battery with the sulphur-FLG foam cathode shows good electrochemical stability and high rate discharge capacity retention for up to 400 discharge/charge cycles at a high current density of 3200 mA g(-1). Even after 400 cycles the capacity decay is only ∼0.064% per cycle relative to the early (e.g. the 5th cycle) discharge capacity, while yielding an average columbic efficiency of ∼96.2%. Our results indicate the potential suitability of graphene foam for efficient, ultra-light and high-performance batteries.

  10. Mesoporous CuCo2O4 nanoparticles as an efficient cathode catalyst for Li-O2 batteries

    Science.gov (United States)

    Wang, Peng-Xiang; Shao, Lin; Zhang, Nai-Qing; Sun, Ke-Ning

    2016-09-01

    Extremely high energy density and environment friendly reaction make Li-O2 batteries a promising energy storage system. In order to improve the energy efficiency and cycle life of Li-O2 battery, spinel mesoporous CuCo2O4 was successfully synthesized by a facile hydrothermal method and investigated in Li-O2 batteries. The electrochemical measurements show that mesoporous CuCo2O4 possess higher oxygen reduction and oxygen evolution activity than bulk CuCo2O4 both in alkaline and non-aqueous solution. Owing to the inherent catalytic activity, high conductivity and facile mass transfer of mesoporous CuCo2O4, Li-O2 battery shows enhanced electrochemical performances, including much lower charge overpotential and a high capacity up to 5288 mAh g-1. When restricting the discharge capacity at 500 mAh g-1, it could operate over 80 cycles and exhibit superior cycle stability. These results indicate that mesoporous CuCo2O4 nanoparticles are appropriate bifunctional catalysts for Li-O2 batteries.

  11. 锂离子电池层状正极材料的研究进展%Research Process on Layer Cathode Material for Li-ion Batteries

    Institute of Scientific and Technical Information of China (English)

    杨世霞

    2012-01-01

    The paper mainly introduced the research process on layer cathode materials- LiCoO2, LiNiO2, Li MnO2 at present. The advantages and disadvantages of the three layer cathode materials were displayed, and also ways of the modification of LiCoO2 and LiNiO2: doping and coating. The structure and the properties of the layer cathode materials are prompted severely through modification which pointed out a way for the more widely apply of Li-ion batteries. What was more, I showed a prospect of apply of the cathode materials on Li-ion batteries.%文絮主要综述当前锂离子电池层状正极材料-LiCoO2、LiNiO2、LiMnO2的研究进展。阐述了三种层状盐结构正极材料的优缺点,对LiCoO2和LiNiO2正极材料的改性方法:掺杂和包覆处理。通过改性,层状正极材料豹结构和性能均有较大改善,为锂离子电池更为广泛的工业应用指明道路。对锂离子电池正极材料未来的应用前景做了一些展槊。

  12. 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.)

  13. 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...

  14. 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...

  15. Progress of non-precious metal oxide cathode catalysts microbial fuel cells%微生物燃料电池非贵金属氧化物阴极催化剂研究进展

    Institute of Scientific and Technical Information of China (English)

    邓丽芳; 袁浩然; 陈勇

    2012-01-01

    Microbial fue1 cell(MFC) is a device directly converting chemical energy in the organic matter into electricity with the microbial catalysts,which has been paid much attention because of its advantages of abundant resource,mild reaction condition and high theoretical efficiency.In order to clarify the research direction and development trend of non-precious metal oxide cathode catalysts,the research progress of two main non-precious metal oxide cathode catalysts(manganese dioxide and titanium dioxide) of MFC are summarized.The possible catalytic reaction mechanisms are analyzed also.Then,the application prospects of non-precious metal oxide cathode catalysts about MFC are discussed: 1) Cathode material modification,including replacement of metal oxides,doping,and morphological features change,etc.2) Cathode materials morphology modification: by hydrothermal synthesis,liquid phase deposition,sol gel method,etc.%微生物燃料电池(Microbial Fuel Cell,MFC)是一种利用微生物将底物中的化学能直接转化为电能的理想产电装置,具有产电与废弃物处置双重功效.为探究非贵金属氧化物作为微生物燃料电池阴极催化剂可能的研究方向和发展趋势,主要总结了近几年来两种主要非贵金属氧化物(二氧化锰、二氧化钛)作为微生物燃料电池阴极催化剂的最新研究进展,并分析了其可能的催化反应机制.随后,对其发展方向提出了自己的见解:1)阴极材料改性:包括金属氧化物替换、掺杂、形貌特征改变等;2)阴极材料结构形貌改性:水热合成、液相沉积、溶胶凝胶等方法.

  16. 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.

  17. 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

  18. Seed layer stimulated growth of crystalline high Al containing (Al,Cr){sub 2}O{sub 3} coatings deposited by cathodic arc evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Pohler, M., E-mail: markus.pohler@stud.unileoben.ac.at [Christian Doppler Laboratory for Advanced Hard Coatings at the Department of Physical Metallurgy and Materials Testing, Montanuniversität Leoben, Franz-Josef-Straße 18, A-8700 Leoben (Austria); Franz, R. [Christian Doppler Laboratory for Advanced Hard Coatings at the Department of Physical Metallurgy and Materials Testing, Montanuniversität Leoben, Franz-Josef-Straße 18, A-8700 Leoben (Austria); Ramm, J. [OC Oerlikon Balzers AG, Iramali 18, 9469 Balzers (Liechtenstein); Polcik, P. [PLANSEE Composite Materials GmbH, Siebenbürgerstraße 23, 86983 Lechbruck am See (Germany); Mitterer, C. [Christian Doppler Laboratory for Advanced Hard Coatings at the Department of Physical Metallurgy and Materials Testing, Montanuniversität Leoben, Franz-Josef-Straße 18, A-8700 Leoben (Austria)

    2014-01-01

    Single layer and dual layer (Al{sub x}Cr{sub 1−x}){sub 2}O{sub 3} coatings were synthesised by cathodic arc evaporation with different Al contents to study their growth characteristics. It was demonstrated that variations in the Al content, the energy of incident particles and the coating thickness control the crystallinity and the coating texture. Analysis by X-ray diffraction revealed a distinct (110) out of plane orientation after transition from a fine grained nucleation zone to a columnar growth mode. Furthermore, the impact of (Al{sub x}Cr{sub 1−x}){sub 2}O{sub 3} seed layers with x = 0.25 and 0.5 on the growth of (Al{sub x}Cr{sub 1−x}){sub 2}O{sub 3} top layers with x = 0.7 and 0.85 was evaluated in detail. According to X-ray diffraction and transmission electron microscopy, the development of the corundum-type crystal structure of the top layer was promoted by local epitaxy if the low Al containing seed layer exhibited a pronounced columnar structure. In this way, crystalline corundum-type coatings with an Al content up to x = 0.85 were obtained. - Highlights: • Industrial scale cathodic arc deposition of corundum type (Al{sub x}Cr{sub 1−x}){sub 2}O{sub 3} coatings • Discussion of the growth characteristics for different Al/Cr ratios • Characterisation of growth regimes in dual layer coatings • Template stimulated growth of crystalline corundum-type (Al{sub 0.85}Cr{sub 0.15}){sub 2}O{sub 3} coatings • Influence of bias voltage and seed layer thickness on the template effect.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Effect of ethylene glycol bis (propionitrile) ether (EGBE) on the performance and interfacial chemistry of lithium-rich layered oxide cathode

    Science.gov (United States)

    Hong, Pengbo; Xu, Mengqing; Zheng, Xiongwen; Zhu, Yunmin; Liao, Youhao; Xing, Lidan; Huang, Qiming; Wan, Huaping; Yang, Yongjun; Li, Weishan

    2016-10-01

    Ethylene glycol bis (propionitrile) ether (EGBE) is used as an electrolyte additive to improve the cycling stability and rate capability of Li/Li1.2Mn0.54Ni0.13Co0.13O2 cells at high operating voltage (4.8 V). After 150 cycles, cells with 1.0 wt% of EGBE containing electrolyte have remarkable cycling performance, 89.0% capacity retention; while the cells with baseline electrolyte only remain 67.4% capacity retention. Linear sweep voltammetry (LSV) and computation results demonstrate that EGBE preferably oxidizes on the cathode surface compared to the LiPF6/carbonate electrolyte. In order to further understand the effects of EGBE on Li1.2Mn0.54Ni0.13Co0.13O2 cathode upon cycling at high voltage, electrochemical behaviors and ex-situ surface analysis of Li1.2Mn0.54Ni0.13Co0.13O2 are investigated via electrochemical impedance spectroscopy (EIS), scanning electron spectroscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and inductive coupled plasma spectroscopy (ICP-MS). The improved cycling performance can be attributed to more stable and robust surface layer yield via incorporation of EGBE, which mitigates the oxidation of electrolyte on the cathode electrode, and also inhibits the dissolution of bulk transition metal ions as well upon cycling at high voltage.

  4. 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.

  5. 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

  6. 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).

  7. 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.

  8. 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

  9. 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.

  10. Metal-mediated Layer-by-layer Films of Multi-metalloporphyrin Arrays:a Novel Switchable Catalyst System

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    1 Results Metalloporphyrins as one kind of effective catalysts have received considerable attention in the past two decades,because of their selective oxidation of hydrocarbons and other organic compound under mild conditions.Great efforts have been made to oxidize or epoxidize the hydrocarbons and cycloparaffin with the oxidants such as PhIO,H2O2 catalyzed by the metalloporphyrins.However,the metalloporphyrins are normally dissolved in the reaction solution or immobilized on silica or other porous supp...

  11. 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.

  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. 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.

  14. 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

    Stabilizing efficient photoabsorbers for solar water splitting has recently shown significant progress with the development of various protection layers. Suitable protection layers for tandem devices should be conductive, transparent, and stable in strongly acidic or alkaline solutions. This paper...

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. 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...

  4. 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.

  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. 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

  7. 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...... of the novel catalyst material for synthesising hydrogen peroxide from oxygen and hydrogen, or from oxygen and water....

  8. High surface area graphite as alternative support for proton exchange membrane fuel cell catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira-Aparicio, P.; Folgado, M.A. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avda. Complutense 22, E-28040 Madrid (Spain); Daza, L. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avda. Complutense 22, E-28040 Madrid (Spain); Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie, 2 Campus de Cantoblanco, E-28049 Madrid (Spain)

    2009-07-01

    The suitability of a high surface area graphite (HSAG) as proton exchange membrane fuel cell (PEMFC) catalyst support has been evaluated and compared with that of the most popular carbon black: the Vulcan XC72. It has been observed that Pt is arranged on the graphite surface resulting in different structures which depend on the catalysts synthesis conditions. The influence that the metal particle size and the metal-support interaction exert on the catalysts degradation rate is analyzed. Temperature programmed oxidation (TPO) under oxygen containing streams has been shown to be a useful method to assess the resistance of PEMFC catalysts to carbon corrosion. The synthesized Pt/HSAG catalysts have been evaluated in single cell tests in the cathode catalytic layer. The obtained results show that HSAG can be a promising alternative to the traditionally used Vulcan XC72 carbon black when suitable catalysts synthesis conditions are used. (author)

  9. 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

  10. 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

  11. 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

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

    Science.gov (United States)

    Kim, Tae Gun; Lee, Hyunbok; Yi, Yeonjin; Lee, Seung Mi; Kim, Jeong Won

    2015-07-01

    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.

  13. 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.

  14. 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.)

  15. α,α'-Diarylacenaphtho[1,2-c]phosphole P-oxides: divergent synthesis and application to cathode buffer layers in organic photovoltaics.

    Science.gov (United States)

    Matano, Yoshihiro; Saito, Arihiro; Suzuki, Yuto; Miyajima, Tooru; Akiyama, Seiji; Otsubo, Saika; Nakamoto, Emi; Aramaki, Shinji; Imahori, Hiroshi

    2012-10-01

    A divergent method for the synthesis of α,α'-diarylacenaphtho[1,2-c]phosphole P-oxides has been established; α,α'-dibromoacenaphtho[c]phosphole P-oxide, which was prepared through a Ti(II)-mediated cyclization of 1,8-bis(trimethylsilylethynyl)naphthalene, underwent a Stille coupling with three different kinds of aryltributylstannanes to afford the α,α'-diarylacenaphtho[c]phosphole P-oxides in moderate to good yields. X-ray crystallographic analyses and UV/Vis absorption/fluorescence measurements have revealed that the degree of π-conjugation, the packing motif, the electron-accepting ability, and the thermal stability of the acenaphtho[c]phosphole π-systems are finely tunable with the α-aryl substituents. All the P=O and P=S derivatives exhibited high stability in their electrochemically reduced state. To use this class of arene-fused phosphole π-systems as n-type semiconducting materials, we evaluated device performances of the bulk heterojunction organic photovoltaics (OPV) that consist of poly(3-hexylthiophene), an indene-C(70) bisadduct, and a cathode buffer layer. The insertion of the diarylacenaphtho[c]phosphole P-oxides as the buffer layer was found to improve the power conversion efficiency of the polymer-based OPV devices.

  16. 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.

  17. 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

  18. 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)

  19. 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.

  20. 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

  1. 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...

  2. 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.

  3. 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.

  4. 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...

  5. 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.

  6. Electrochemical Kinetics and Performance of Layered Composite Cathode Material Li[Li0.2Ni0.2Mn0.6]O2

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Shi, Wei; Gu, Meng; Xiao, Jie; Zuo, Pengjian; Wang, Chong M.; Zhang, Jiguang

    2013-10-10

    Lithium-rich, manganese-rich (LMR) layered composite cathode material Li[Li0.2Ni0.2Mn0.6]O2 has been successfully prepared by a co-precipitation method and its structure is confirmed by XRD characterization. The material delivers a high discharge capacity of 281 mAh g-1, when charged and discharged at a low current density of 10 mA g-1. However, significant increase of cell polarization and decrease of discharge capacity are observed at voltages below 3.5 V with increasing current densities. Galvanostatic intermittent titration technique (GITT) analysis demonstrates that lithium ion intercalation/de-intercalation reactions in this material are kinetically controlled by Li2MnO3 and its activated MnO2 component. The relationship between the electrochemical kinetics and rate performance as well as cycling stability has been systematically investigated. High discharge capacity of 149 mAh g-1 can be achieved at 10 C charge rate and C/10 discharge rate. The result demonstrates that the Li2MnO3 based material could withstand high charge rate (except initial activation process), which is very promising for practical applications. A lower discharge current density is preferred to overcome the kinetic barrier of lithium ion intercalation into MnO2 component, in order to achieve higher discharge capacity even at high charge rates.

  7. Layered Lithium-Rich Oxide Nanoparticles Doped with Spinel Phase: Acidic Sucrose-Assistant Synthesis and Excellent Performance as Cathode of Lithium Ion Battery.

    Science.gov (United States)

    Chen, Min; Chen, Dongrui; Liao, Youhao; Zhong, Xiaoxin; Li, Weishan; Zhang, Yuegang

    2016-02-01

    Nanolayered lithium-rich oxide doped with spinel phase is synthesized by acidic sucrose-assistant sol-gel combustion and evaluated as the cathode of a high-energy-density lithium ion battery. Physical characterizations indicate that the as-synthesized oxide (LR-SN) is composed of uniform and separated nanoparticles of about 200 nm, which are doped with about 7% spinel phase, compared to the large aggregated ones of the product (LR) synthesized under the same condition but without any assistance. Charge/discharge demonstrates that LR-SN exhibits excellent rate capability and cyclic stability: delivering an average discharge capacity of 246 mAh g(-1) at 0.2 C (1C = 250 mA g(-1)) and earning a capacity retention of 92% after 100 cycles at 4 C in the lithium anode-based half cell, compared to the 227 mA g(-1) and the 63% of LR, respectively. Even in the graphite anode-based full cell, LR-SN still delivers a capacity of as high as 253 mAh g(-1) at 0.1 C, corresponding to a specific energy density of 801 Wh kg(-1), which are the best among those that have been reported in the literature. The separated nanoparticles of the LR-SN provide large sites for charge transfer, while the spinel phase doped in the nanoparticles facilitates lithium ion diffusion and maintains the stability of the layered structure during cycling.

  8. 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

  9. 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.

  10. 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...

  11. 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

  12. 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.

  13. 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...

  14. 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...

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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...

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. Stochastic reconstruction and a scaling method to determine effective transport coefficients of a proton exchange membrane fuel cell catalyst layer

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, R. [Centro de Investigacion en Energia, UNAM, Privada Xochicalco S/N, 62580 Temixco (Mexico); Andaverde, J. [Centro de Investigacion en Ingenieria y Ciencias Aplicadas, UAEM, Av. Universidad 1001, Col. Chamilpa, 62210 Cuernavaca (Mexico); Escobar, B. [Instituto Tecnologico de Cancun, Av. Kabah 3, 77515 Cancun (Mexico); Cano, U. [Instituto de Investigaciones Electricas, Av. Reforma 113, col. Palmira, 62490 Cuernavaca (Mexico)

    2011-02-01

    This work uses a method for the stochastic reconstruction of catalyst layers (CLs) proposing a scaling method to determine effective transport properties in proton exchange membrane fuel cell (PEMFC). The algorithm that generates the numerical grid makes use of available information before and after manufacturing the CL. The structures so generated are characterized statistically by two-point correlation functions and by the resultant pore size distribution. As an example of this method, the continuity equation for charge transport is solved directly on the three-dimensional grid of finite control volumes (FCVs), to determine effective electrical and proton conductivities of different structures. The stochastic reconstruction and the electrical and proton conductivity of a 45 {mu}m side size cubic sample of a CL, represented by more than 3.3 x 10{sup 12} FVCs were realized in a much shorter time compared with non-scaling methods. Variables studied in an example of CL structure were: (i) volume fraction of dispersed electrolyte, (ii) total CL porosity and (iii) pore size distribution. Results for the conduction efficiency for this example are also presented. (author)

  7. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.

    Science.gov (United States)

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit; Baranova, Elena A; Santinacci, Lionel

    2014-01-01

    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.

  8. 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.

  9. A durable PtRu/C catalyst with a thin protective layer for direct methanol fuel cells.

    Science.gov (United States)

    Shimazaki, Yuzuru; Hayasaka, Sho; Koyama, Tsubasa; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

    2010-11-15

    A methanol oxidation catalyst with improved durability in acidic environments is reported. The catalyst consists of PtRu alloy nanoparticles on a carbon support that were stabilized with a silane-coupling agent. The catalyst was prepared by reducing ions of Pt and Ru in the presence of a carbon support and the silane-coupling agent. The careful choice of preparatory conditions such as the concentration of the silane-coupling agent and solution pH resulted in the preparation of catalyst in which the PtRu nanoparticles were dispersively adsorbed onto the carbon support. The catalytic activity was similar to that of a commercial catalyst and was unchanged after immersion in sulfuric acid solution for 1000 h, suggesting the high durability of the PtRu catalyst for the anode of direct methanol fuel cells.

  10. 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.

    2016-09-01

    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.

  11. 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

  12. 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.

  13. 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.

  14. Structural integrity--Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yahong; Hu, Enyuan; Yang, Feifei; Corbett, Jeff; Sun, Zhihong; Lyu, Yingchun; Yu, Xiqian; Liu, Yijin; Yang, Xiao-Qing; Li, Hong (BNL); (SLAC); (UCSF); (Donghua); (Chinese Aca. Sci.)

    2016-10-24

    Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. Here, our study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li2Ru0.5Mn0.5O3 cathode particles at the meso to nano scale. We performed combined X-ray spectroscopy, diffraction and microscopy experiments to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scale morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. It also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.

  15. Photoelectrochemical Carbon Dioxide Reduction Using a Nanoporous Ag Cathode.

    Science.gov (United States)

    Zhang, Yan; Luc, Wesley; Hutchings, Gregory S; Jiao, Feng

    2016-09-21

    Solar fuel production from abundant sources using photoelectrochemical (PEC) systems is an attractive approach to address the challenges associated with the intermittence of solar energy. In comparison to electrochemical systems, PEC cells directly utilize solar energy as the energy input, and if necessary, then an additional external bias can be applied to drive the desired reaction. In this work, a PEC cell composing of a Ni-coated Si photoanode and a nanoporous Ag cathode was developed for CO2 conversion to CO. The thin Ni layer not only protected the Si wafer from photocorrosion but also served as the oxygen evolution catalyst. At an external bias of 2.0 V, the PEC cell delivered a current density of 10 mA cm(-2) with a CO Faradaic efficiency of ∼70%. More importantly, a stable performance up to 3 h was achieved under photoelectrolysis conditions, which is among the best literature-reported performances for PEC CO2 reduction cells. The photovoltage of the PEC cell was estimated to be ∼0.4 V, which corresponded to a 17% energy saving by solar energy utilization. Postreaction structural analysis showed the corrosion of the Ni layer at the Si photoanode/catalyst interface, which caused performance degradation under prolonged operations. A stable oxygen evolution catalyst with a robust interface is crucial to the long-term stability of PEC CO2 reduction cells. PMID:27588723

  16. 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

  17. 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

  18. 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.)

  19. Control of thickness and chemical properties of atomic layer deposition overcoats for stabilizing Cu/γ-Al2 O3 catalysts.

    Science.gov (United States)

    O'Neill, Brandon J; Sener, Canan; Jackson, David H K; Kuech, Thomas F; Dumesic, James A

    2014-12-01

    Whereas sintering and leaching of copper nanoparticles during liquid-phase catalytic processing can be prevented by using atomic layer deposition (ALD) to overcoat the nanoparticles with AlOx , this acidic overcoat leads to reversible deactivation of the catalyst by resinification and blocking of the pores within the overcoat during hydrogenation of furfural. We demonstrate that decreasing the overcoat thickness from 45 to 5 ALD cycles is an effective method to increase the rate per gram of catalyst and to decrease the rate of deactivation for catalysts pretreated at 673 K, and a fully regenerable copper catalyst can be produced with only five ALD cycles of AlOx . Moreover, although an overcoat of MgOx does not lead to stabilization of copper nanoparticles against sintering and leaching during liquid-phase hydrogenation reactions, the AlOx overcoat can be chemically modified to decrease acidity and deactivation through the addition of MgOx , while maintaining stability of the copper nanoparticles.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. Development of advanced catalytic layer based on vertically aligned conductive polymer arrays for thin-film fuel cell electrodes

    Science.gov (United States)

    Jiang, Shangfeng; Yi, Baolian; Cao, Longsheng; Song, Wei; Zhao, Qing; Yu, Hongmei; Shao, Zhigang

    2016-10-01

    The degradation of carbon supports significantly influences the performance of proton exchange membrane fuel cells (PEMFCs), particularly in the cathode, which must be overcome for the wide application of fuel cells. In this study, advanced catalytic layer with electronic conductive polymer-polypyrrole (PPy) nanowire as ordered catalyst supports for PEMFCs is prepared. A platinum-palladium (PtPd) catalyst thin layer with whiskerette shapes forms along the long axis of the PPy nanowires. The resulting arrays are hot-pressed on both sides of a Nafion® membrane to construct a membrane electrode assembly (without additional ionomer). The ordered thin catalyst layer (approximately 1.1 μm) is applied in a single cell as the anode and the cathode without additional Nafion® ionomer. The single cell yields a maximum performance of 762.1 mW cm-2 with a low Pt loading (0.241 mg Pt cm-2, anode + cathode). The advanced catalyst layer indicates better mass transfer in high current density than that of commercial Pt/C-based electrode. The mass activity is 1.08-fold greater than that of DOE 2017 target. Thus, the as-prepared electrodes have the potential for application in fuel cells.

  7. 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.

  8. Influence of lithium content on high rate cycleability of layered Li 1+ xNi 0.30Co 0.30Mn 0.40O 2 cathodes for high power lithium-ion batteries

    Science.gov (United States)

    Santhanam, R.; Jones, Philip; Sumana, Adusumilli; Rambabu, B.

    Layered Li 1+ xNi 0.30Co 0.30Mn 0.40O 2 (x = 0, 0.05, 0.10, 0.15) materials have been synthesized using citric acid assisted sol-gel method. The materials with excess lithium showed distinct differences in the structure and the charge and discharge characteristics. The rate capability tests were performed and compared on Li 1+ xNi 0.30Co 0.30Mn 0.40O 2 (x = 0, 0.05, 0.10, 0.15) cathode materials. Among these materials, Li 1.10Ni 0.30Co 0.30Mn 0.40O 2 cathode demonstrated higher discharge capacity than that of the other cathodes. Upon extended cycling at 1C and 8C, Li 1.10Ni 0.30Co 0.30Mn 0.40O 2 showed better capacity retention when compared to other materials with different lithium content. Li 1.10Ni 0.30Co 0.30Mn 0.40O 2 exhibited 93 and 90% capacity retention where as Li 1.05Ni 0.30Co 0.30Mn 0.40O 2, Li 1.15Ni 0.30Co 0.30Mn 0.40O 2, and Li 1.00Ni 0.30Co 0.30Mn 0.40O 2 exhibited only 84, 71, and 63% (at 1C), and 79, 66 and 40% (at 10C) capacity retention, respectively, after 40 cycles. The enhanced high rate cycleability of Li 1.10Ni 0.30Co 0.30Mn 0.40O 2 cathode is attributed to the improved structural stability due to the formation of appropriate amount of Li 2MnO 3-like domains in the transition metal layer and decreased Li/Ni disorder (i.e., Ni content in the Li layer).

  9. 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

  10. 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)

  11. Efficient indium-tin-oxide free inverted organic solar cells based on aluminum-doped zinc oxide cathode and low-temperature aqueous solution processed zinc oxide electron extraction layer

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dazheng; Zhang, Chunfu, E-mail: cfzhang@xidian.edu.cn; Wang, Zhizhe; Zhang, Jincheng; Tang, Shi; Wei, Wei; Sun, Li; Hao, Yue, E-mail: yhao@xidian.edu.cn [State Key Discipline Laboratory of Wide Band Gap Semiconductor Technology, School of Microelectronics, Xidian University, No. 2 South Taibai Road, Xi' an 710071 (China)

    2014-06-16

    Indium-tin-oxide (ITO) free inverted organic solar cells (IOSCs) based on aluminum-doped zinc oxide (AZO) cathode, low-temperature aqueous solution processed zinc oxide (ZnO) electron extraction layer, and poly(3-hexylthiophene-2, 5-diyl):[6, 6]-phenyl C{sub 61} butyric acid methyl ester blend were realized in this work. The resulted IOSC with ZnO annealed at 150 °C shows the superior power conversion efficiency (PCE) of 3.01%, if decreasing the ZnO annealing temperature to 100 °C, the obtained IOSC also shows a PCE of 2.76%, and no light soaking issue is observed. It is found that this ZnO film not only acts as an effective buffer layer but also slightly improves the optical transmittance of AZO substrates. Further, despite the relatively inferior air-stability, these un-encapsulated AZO/ZnO IOSCs show comparable PCEs to the referenced ITO/ZnO IOSCs, which demonstrates that the AZO cathode is a potential alternative to ITO in IOSCs. Meanwhile, this simple ZnO process is compatible with large area deposition and plastic substrates, and is promising to be widely used in IOSCs and other relative fields.

  12. Lithium-Rich Layered Oxide Li1.18 Ni0.15 Co0.15 Mn0.52 O2 as the Cathode Material for Hybrid Sodium-Ion Batteries.

    Science.gov (United States)

    Wei, Zhixuan; Gao, Yu; Wang, Lei; Zhang, Chaoyang; Bian, Xiaofei; Fu, Qiang; Wang, Chunzhong; Wei, Yingjin; Du, Fei; Chen, Gang

    2016-08-01

    Li-rich layered oxide Li1.18 Ni0.15 Co0.15 Mn0.52 O2 (LNCM) is, for the first time, examined as the positive electrode for hybrid sodium-ion battery and its Na(+) storage properties are comprehensively studied in terms of galvanostatic charge-discharge curves, cyclic voltammetry and rate capability. LNCM in the proposed sodium-ion battery demonstrates good rate capability whose discharge capacity reaches about 90 mA h g(-1) at 10 C rate and excellent cycle stability with specific capacity of about 105 mA h g(-1) for 200 cycles at 5 C rate. Moreover, ex situ ICP-OES suggests interesting mixed-ions migration processes: In the initial two cycles, only Li(+) can intercalate into the LNCM cathode, whereas both Li(+) and Na(+) work together as the electrochemical cycles increase. Also the structural evolution of LNCM is examined in terms of ex situ XRD pattern at the end of various charge-discharge scans. The strong insight obtained from this study could be beneficial to the design of new layered cathode materials for future rechargeable sodium-ion batteries. PMID:27320123

  13. Ca3Co4O9+δ, a growing potential SOFC cathode material: impact of the layer composition and thickness on the electrochemical properties

    NARCIS (Netherlands)

    Rolle, A.; Abbas, H.A.A.; Huo, D.; Capoen, E.; Mentré, O.; Vannier, R.N.; Daviero-Minaud, S.; Boukamp, B.A.

    2016-01-01

    The thermoelectric material Ca3Co4O9 + δ (CCO), with an electronic conductivity of σe = 240 S·cm− 1 at 650 °C and a good chemical and mechanical compatibility with the standard Ce0.9Gd0.1O1.95 electrolyte (CGO, TEC: 9–10 · 10− 6 K− 1), was recently identified as a potential cathode material for soli

  14. Preparation, structure study and electrochemistry of layered H2V3O8 materials: High capacity lithium-ion battery cathode

    Science.gov (United States)

    Sarkar, Sudeep; Bhowmik, Arghya; Pan, Jaysree; Bharadwaj, Mridula Dixit; Mitra, Sagar

    2016-10-01

    The present study explores H2V3O8 as high capacity cathode material for lithium-ion batteries (LIB's). Despite having high discharge capacity, H2V3O8 material suffers from poor electrochemical stability for prolonged cycle life. Ultra-long H2V3O8 nanobelts with ordered crystallographic patterns are synthesized via a hydrothermal process to mitigate this problem. The growth of the crystal is facile along [001] direction, and the most common surface is (001) as suggested by Wulff construction study. Electrochemical performance of H2V3O8 cathode is tested against Li/Li+ at various current rates. At 50 mA g-1current rate, it delivers a discharge capacity of 308 mAh g-1, whereas, at 3000 mA g-1, an initial discharge capacity of 144 mAh g-1 is observed and stabilized at 100 mAh g-1 till 500 cycles. Further, the density functional theory (DFT) based simulations study of both the pristine and lithiated phase of H2V3O8 cathode materials is undertaken. DFT study reveals the presence of hydrogen as hydroxyl unit in the framework of the host. In correlation, the magnetic property of vanadium atoms is examined in detail with through partial density of states (PDOS) calculation during three stage lithiation processes and evaluating various potential steps involved in lithium insertion.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. Investigation on the origin of diffusion impedance in the porous cathode of a proton exchange membrane fuel cell (PEMFC) via electrochemical impedance spectroscopy (EIS)

    Energy Technology Data Exchange (ETDEWEB)

    Mainka, J.; Maranzana, G.; Dillet, J.; Didierjean, S.; Lottin, O. [Nancy Univ., Centre national de la recherche scientifique, Vandoeuvre les Nancy (France). Laboratoire d' Energetique et de Mecanique Theorique et Appliquee

    2009-07-01

    This study provided a preliminary examination of the impact of gas flow rate on the impedance characteristics of a proton exchange membrane fuel cell (PEMFC). The mass transport phenomena within the porous cathode of PEMFCs can be analyzed through electrochemical impedance spectroscopy (EIS). The geometrical description of the electrodes chosen to complete the EIS interpretations is a form of the agglomerate model, where the agglomerates are a mixture of carbon powder and catalyst particles, whereas the electrolyte is assumed to cover only the pore surfaces. Therefore, the reactants access the active catalyst sites by passing successively through the gas diffusion layer (GDL), the pores of the electrode, and finally through a thin electrolyte layer. The fuel cell equivalent electrical circuit is based on a Butler-Volmer formalism that takes into consideration oxygen diffusion in the pores of the GDL and/or the active layer through a Warburg element. The results reveal that in the cathode, the mass transfer limiting layer is most likely the active layer, provided liquid water is present within the pores. Under normal operating conditions, the mass transport resistance of the gas diffusion layer is negligible, as is the fine electrolyte layer coating the agglomerate.

  3. 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.

  4. 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.

  5. Prevention of the water flooding by micronizing the pore structure of gas diffusion layer for polymer electrolyte fuel cell

    Science.gov (United States)

    Hiramitsu, Yusuke; Sato, Hitoshi; Hori, Michio

    In polymer electrolyte fuel cells, high humidity must be established to maintain high proton conductivity in the polymer electrolyte. However, the water that is produced electrochemically at the cathode catalyst layer can condense in the cell and cause an obstruction to the diffusion of reaction gas in the gas diffusion layer and the gas channel. This leads to a sudden decrease of the cell voltage. To combat this, strict water management techniques are required, which usually focus on the gas diffusion layer. In this study, the use of specially treated carbon paper as a flood-proof gas diffusion layer under extremely high humidity conditions was investigated experimentally. The results indicated that flooding originates at the interface between the gas diffusion layer and the catalyst layer, and that such flooding could be eliminated by control of the pore size in the gas diffusion layer at this interface.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. Influence of Ti(4+) on the electrochemical performance of Li-rich layered oxides - high power and long cycle life of Li2Ru1-xTixO3 cathodes.

    Science.gov (United States)

    Kalathil, Abdul Kareem; Arunkumar, Paulraj; Kim, Da Hye; Lee, Jong-Won; Im, Won Bin

    2015-04-01

    Li-rich layered oxides are the most attractive cathodes for lithium-ion batteries due to their high capacity (>250 mAh g(-1)). However, their application in electric vehicles is hampered by low power density and poor cycle life. To address these, layered Li2Ru0.75Ti0.25O3 (LRTO) was synthesized and the influence of electroinactive Ti(4+) on the electrochemical performance of Li2RuO3 was investigated. LRTO exhibited a reversible capacity of 240 mAh g(-1) under 14.3 mA g(-1) with 0.11 mol of Li loss after 100 cycles compared to 0.22 mol of Li for Li2Ru0.75Sn0.25O3. More Li(+) can be extracted from LRTO (0.96 mol of Li) even after 250 cycles at 143 mA g(-1) than Li2RuO3 (0.79 mol of Li). High reversible Li extraction and long cycle life were attributed to structural stability of the LiM2 layer in the presence of Ti(4+), facilitating the lithium diffusion kinetics. The versatility of the Li2MO3 structure may initiate exploration of Ti-based Li-rich layered oxides for vehicular applications.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. The Effect of Inhomogeneous Compression on Water Transport in the Cathode of a Proton Exchange Membrane Fuel Cell

    DEFF Research Database (Denmark)

    Olesen, Anders Christian; Berning, Torsten; Kær, Søren Knudsen

    2012-01-01

    A three-dimensional, multicomponent, two-fluid model developed in the commercial CFD package CFX 13 (ANSYS Inc.) is used to investigate the effect of porous media compression on water transport in a proton exchange membrane fuel cell (PEMFC). The PEMFC model only consist of the cathode channel, gas...... diffusion layer, microporous layer, and catalyst layer, excluding the membrane and anode. In the porous media liquid water transport is described by the capillary pressure gradient, momentum loss via the Darcy-Forchheimer equation, and mass transfer between phases by a nonequilibrium phase change model....... Furthermore, the presence of irreducible liquid water is taken into account. In order to account for compression, porous media morphology variations are specified based on the gas diffusion layer (GDL) through-plane strain and intrusion which are stated as a function of compression. These morphology...

  20. Utilization of Active Ni to Fabricate Pt-Ni Nanoframe/NiAl Layered Double Hydroxide Multifunctional Catalyst through In Situ Precipitation.

    Science.gov (United States)

    Ren, Fumin; Wang, Zheng; Luo, Liangfeng; Lu, Haiyuan; Zhou, Gang; Huang, Weixin; Hong, Xun; Wu, Yuen; Li, Yadong

    2015-09-14

    Integration of different active sites into metallic catalysts, which may impart new properties and functionalities, is desirable yet challenging. Herein, a novel dealloying strategy is demonstrated to decorate nickel-aluminum layered double hydroxide (NiAl-LDH) onto a Pt-Ni alloy surface. The incorporation of chemical etching of Pt-Ni alloy and in situ precipitation of LDH are studied by joint experimental and theoretical efforts. The initial Ni-rich Pt-Ni octahedra transform by interior erosion into Pt3 Ni nanoframes with enlarged surface areas. Furthermore, owing to the basic active sites of the decorated LDH together with the metallic sites of Pt3 Ni, the resulting Pt-Ni nanoframe/NiAl-LDH composites exhibit excellent catalytic activity and selectivity in the dehydrogenation of benzylamine and hydrogenation of furfural. PMID:26241390

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  9. 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

  10. Carbon-Based Air-Breathing Cathodes for Microbial Fuel Cells

    Directory of Open Access Journals (Sweden)

    Irene Merino-Jimenez

    2016-08-01

    Full Text Available A comparison between different carbon-based gas-diffusion air-breathing cathodes for microbial fuel cells (MFCs is presented in this work. A micro-porous layer (MPL based on carbon black (CB and an activated carbon (AC layer were used as catalysts and applied on different supporting materials, including carbon cloth (CC, carbon felt (CF, and stainless steel (SS forming cathode electrodes for MFCs treating urine. Rotating ring disk electrode (RRDE analyses were done on CB and AC to: (i understand the kinetics of the carbonaceous catalysts; (ii evaluate the hydrogen peroxide production; and (iii estimate the electron transfer. CB and AC were then used to fabricate electrodes. Half-cell electrochemical analysis, as well as MFCs continuous power performance, have been monitored. Generally, the current generated was higher from the MFCs with AC electrodes compared to the MPL electrodes, showing an increase between 34% and 61% in power with the AC layer comparing to the MPL. When the MPL was used, the supporting material showed a slight effect in the power performance, being that the CF is more powerful than the CC and the SS. These differences also agree with the electrochemical analysis performed. However, the different supporting materials showed a bigger effect in the power density when the AC layer was used, being the SS the most efficient, with a power generation of 65.6 mW·m−2, followed by the CC (54 mW·m−2 and the CF (44 mW·m−2.

  11. 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

  12. 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...

  13. 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. 

  14. Highly stable Na2/3 (Mn0.54 Ni0.13 Co0.13 )O2 cathode modified by atomic layer deposition for sodium-ion batteries.

    Science.gov (United States)

    Kaliyappan, Karthikeyan; Liu, Jian; Lushington, Andrew; Li, Ruying; Sun, Xueliang

    2015-08-10

    For the first time, atomic layer deposition (ALD) of Al2 O3 was adopted to enhance the cyclic stability of layered P2-type Na2/3 (Mn0.54 Ni0.13 Co0.13 )O2 (MNC) cathodes for use in sodium-ion batteries (SIBs). Discharge capacities of approximately 120, 123, 113, and 105 mA h g(-1) were obtained for the pristine electrode and electrodes coated with 2, 5, and 10 ALD cycles, respectively. All electrodes were cycled at the 1C discharge current rate for voltages between 2 and 4.5 V in 1 M NaClO4 electrolyte. Among the electrodes tested, the Al2 O3 coating from 2 ALD cycles (MNC-2) exhibited the best electrochemical stability and rate capability, whereas the electrode coated by 10 ALD cycles (MNC-10) displayed the highest columbic efficiency (CE), which exceeded 97 % after 100 cycles. The enhanced electrochemical stability observed for ALD-coated electrodes could be a result of the protection effects and high band-gap energy (Eg =9.00 eV) of the Al2 O3 coating layer. Additionally, the metal-oxide coating provides structural stability against mechanical stresses occurring during the cycling process. The capacity, cyclic stability, and rate performance achieved for the MNC electrode coated with 2 ALD cycles of Al2 O3 reveal the best results for SIBs. This study provides a promising route toward increasing the stability and CE of electrode materials for SIB application.

  15. 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.)

  16. 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.

  17. 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.

  18. 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...

  19. 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.

  20. 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.)

  1. Effect of cathode gas humidification on performance and durability of Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Hagen, Anke; Liu, Yi-Lin

    2010-01-01

    The effect of cathode inlet gas humidification was studied on single anode supported Solid Oxide Fuel Cells (SOFC's). The studied cells were Risø 2 G and 2.5 G. The former consists of a LSM:YSZ composite cathode, while the latter consists of a LSCF:CGO composite cathode on a CGO protection layer...

  2. Synthesis and characterization of multi-layer core-shell structural LiFeBO3/C as a novel Li-battery cathode material

    Science.gov (United States)

    Zhang, Bao; Ming, Lei; Zheng, Jun-chao; Zhang, Jia-feng; Shen, Chao; Han, Ya-dong; Wang, Jian-long; Qin, Shan-e.

    2014-09-01

    A multi-layer core-shell structural LiFeBO3/C has been successfully synthesized via spray-drying and carbothermal method using LiBO2·8H2O, Fe(NO3)3·9H2O, and citric acid as starting materials. The Rietveld refinement results indicate the sample consists of two phases: LiFeBO3 [94(6)% w/w], and LiFeO2 [6(4)% w/w]. SEM images show that the LiFeBO3 powders consist of rough similar-spherical particles with a size distribution ranging from 1 μm to 5 μm. TEM results present that the LiFeBO3 spherical particles are well coated by nano-carbon webs and form a multi-layer core-shell structure. The amount of carbon was determined to be 6.50% by C/S analysis. The prepared LiFeBO3-LiFeO2/C presents an initial discharge capacity of 196.5 mAh g-1 at the current density of 10 mA g-1 between 1.5 and 4.5 V, and it can deliver a discharge capacity of 136.1 mAh g-1 after 30 cycles, presents excellent electrochemical properties, indicating the surface sensitivity in the air was restrained.

  3. 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

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst.

    Science.gov (United States)

    Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

    2015-01-01

    Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

  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.

  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. Ion exchange membrane cathodes for scalable microbial fuel cells.

    Science.gov (United States)

    Zuo, Yi; Cheng, Shaoan; Logan, Bruce E

    2008-09-15

    One of the main challenges for using microbial fuel cells (MFCs) is developing materials and architectures that are economical and generate high power densities. The performance of two cathodes constructed from two low-cost anion (AEM) and cation (CEM) exchange membranes was compared to that achieved using an ultrafiltration (UF) cathode, when the membranes were made electrically conductive using graphite paint and a nonprecious metal catalyst (CoTMPP). The best performance in single-chamber MFCs using graphite fiber brush anodes was achieved using an AEM cathode with the conductive coating facing the solution, at a catalyst loading of 0.5 mg/cm2 CoTMPP. The maximum power densitywas 449 mW/ m2 (normalized to the projected cathode surface area) or 13.1 W/m3 (total reactor volume), with a Coulombic efficiency up to 70% in a 50 mM phosphate buffer solution (PBS) using acetate. Decreasing the CoTMPP loading by 40-80% reduced power by 28-56%, with only 16% of the power (72 mW/m2) generated using an AEM cathode lacking a catalyst. Using a current collector (a stainless steel mesh) pressed against the inside surface of the AEM cathode and 200 mM PBS, the maximum power produced was further increased to 728 mW/m2 (21.2 W/m3). The use of AEM cathodes and brush anodes provides comparable performance to similar systems that use materials costing nearly an order of magnitude more (carbon paper electrodes) and thus represent more useful materials for reducing the costs of MFCs for wastewater treatment applications. PMID:18853817

  12. 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)

  13. 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.

  14. High efficiency solution processed fluorescent yellow organic light-emitting diode through fluorinated alcohol treatment at the emissive layer/cathode interface

    Science.gov (United States)

    Ng, Calvin Yi Bin; Yeoh, Keat Hoe; Whitcher, Thomas J.; Azrina Talik, Noor; Woon, Kai Lin; Saisopa, Thanit; Nakajima, Hideki; Supruangnet, Ratchadaporn; Songsiriritthigul, Prayoon

    2014-01-01

    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.

  15. 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.

  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. 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.

  18. 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)

  19. 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

  20. Interaction between Nafion ionomer and noble metal catalyst for PEMFCs

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma

    The implement of polymer impregnation in electrode structure (catalyst layer) decreasing the noble metal catalyst loading by a factor of ten , , is one of the essential mile stones in the evolution of Proton Exchange Membrane Fuel Cells’ development among the application of catalyst support...... and electrode deposition etc. In fuel cell reactions, both electrons and protons are involved. Impregnation of Nafion ionomer in catalyst layer effectively increases the proton-electron contact, enlarge the reaction zone, extend the reaction from the surface to the entire electrode. Therefore, the entire...... catalyst layer conducts both electrons and protons so that catalyst utilization in the layer is improved dramatically. The catalyst layer will in turn generate and sustain a higher current density. One of the generally adapted methods to impregnate Nafion into the catalyst layer is to mix the catalysts...

  1. Cathode materials: A personal perspective

    Energy Technology Data Exchange (ETDEWEB)

    Goodenough, John B. [Texas Materials Institute, University of Texas at Austin, ETC 9.102, 1 University Station, Austin, TX 78712-1063 (United States)

    2007-12-06

    A thermodynamically stable rechargeable battery has a voltage limited by the window of the electrolyte. An aqueous electrolyte has a window of 1.2 eV, which prevents achieving the high energy density desired for many applications. A non-aqueous electrolyte with a window of 5 eV requires Li{sup +} rather than H{sup +} as the working ion. Early experiments with Li{sub x}TiS{sub 2} cathodes showed competitive capacity and rate capability, but problems with a lithium anode made the voltage of a safe cell based on a sulfide cathode too low to be competitive with a nickel/metal-hydride battery. Transition-metal oxides can give voltages of 4.5 V versus Li{sup +}/Li{sup 0}. However, the challenge with oxides has been to obtain a competitive capacity and rate capability while retaining a high voltage with low-cost, environmentally friendly cathode materials. Comparisons will be made between layered Li{sub 1-x}MO{sub 2}, spinels Li{sub 1-x}[M{sub 2}]O{sub 4}, and olivines Li{sub 1-x}MPO{sub 4} having 0 < x < 1. Although higher capacities can be obtained with layered Li{sub 1-x}MO{sub 2} compounds, which have enabled the wireless revolution, their metastability makes them unlikely to be used in power applications. The spinel and olivine framework structures have been shown to be capable of charge/discharge rates of over 10C with a suitable temperature range for plug-in hybrid vehicles. (author)

  2. 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.

  3. Cathodes - Technological review

    Energy Technology Data Exchange (ETDEWEB)

    Cherkouk, Charaf; Nestler, Tina [Institut für Experimentelle Physik, Technische Universität Bergakademie Freiberg, Leipziger Straße 23, 09596 Freiberg (Germany)

    2014-06-16

    Lithium cobalt oxide (LiCoO{sub 2}) 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, LiCoO{sub 2} 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 LiCoO{sub 2}. 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. 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.

  5. 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

  6. 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.

  7. 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

  8. Organic photovoltaic solar cells with cathode modified by ZnO.

    Science.gov (United States)

    Kim, Hyeong Pil; Yusoff, Abd Rashid Bin Mohd; Jang, Jin

    2013-07-01

    Solution processed cathode organic photovoltaic cells (OPVs) utilizing thin layer of ZnO with 27% increase in power conversion efficiency (PCE) to control devices have been demonstrated. Devices without the presence of ZnO layer have much lower PCE than the ones with ZnO layer. Cathode modification layer can be used to reduce photogenerated excitions and finally improve the performance of the OPVs. The successful demonstrations of OPVs with an introduction of ZnO cathode layer give promise of further device progresses.

  9. 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

  10. 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

  11. 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.

  12. Cathode materials review

    Energy Technology Data Exchange (ETDEWEB)

    Daniel, Claus, E-mail: danielc@ornl.gov; Mohanty, Debasish, E-mail: danielc@ornl.gov; Li, Jianlin, E-mail: danielc@ornl.gov; Wood, David L., E-mail: danielc@ornl.gov [Oak Ridge National Laboratory, 1 Bethel Valley Road, MS6472 Oak Ridge, TN 37831-6472 (United States)

    2014-06-16

    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 LiCoO{sub 2} 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.

  13. Cathode materials review

    Science.gov (United States)

    Daniel, Claus; Mohanty, Debasish; Li, Jianlin; Wood, David L.

    2014-06-01

    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.

  14. 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

  15. 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)

  16. 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.

  17. 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.

  18. 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...

  19. 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...

  20. 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.

  1. 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.

  2. Tests of Cathode Strip Chamber Prototypes

    CERN Document Server

    Bonushkin, Yuri; Chrisman, David; Durkin, S; Ferguson, Thomas; Giacomelli, Paolo; Gorn, William; Hauser, Jay; Hirschfelder, J; Hoftiezer, John; Hoorani, Hafeez R; Kisselev, Oleg; Klem, Daniel; Korytov, Andrey; Layter, John G; Lennous, Paul; Ling, Ta-Yung; Matthey, Christina; Medved, Serguei; Minor, C; Mitselmakher, Guenakh; Müller, Thomas; Otwinowski, Stanislaw; Preston, L; Prokofiev, O E; Rush, Chuck J; Schenk, P; Sedykh, Yu; Smirnov, Igor; Soulimov, V; Vaniachine, A; Vercelli, T; Wuest, Craig R; Zeng, Ji-Yang; von Goeler, Eberhard

    1997-01-01

    We report on the results of testing two six-layer 0.6 x 0.6 cm^2 cathode strip chamber ( CSC) prototypes in a muon beam at CERN. The prototypes were designed to simulate sections of the end-cap muon system of the Compact Muon Solenoid ( CMS) detector which will be installed at the Large Hadron Collider ( LHC). We measured the spatial and time resolutions of each chamber for different gains, different orientations with respect to the beam direction and different strength magnetic fields. The single-layer spatial resolution of a prototype with a strip pitch of 15.88 mm ranged from 78 micron to 468 micron, depending on whether the particle passed between two cathode strips or through the center of a strip; its six-layer resolution was found to be 44 micron. The single-layer spatial resolution of a prototype with a strip pitch of 6.35 mm ranged from 54 to 66 micron; its six-layer resolution w as found to be 23 micron. The efficiency for collecting an anode wire signal from one of six layers within a 20 ns time wi...

  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. Bottom-up catalytic approach towards nitrogen-enriched mesoporous carbons/sulfur composites for superior Li-S cathodes.

    Science.gov (United States)

    Sun, Fugen; Wang, Jitong; Chen, Huichao; Qiao, Wenming; Ling, Licheng; Long, Donghui

    2013-01-01

    We demonstrate a sustainable and efficient approach to produce high performance sulfur/carbon composite cathodes via a bottom-up catalytic approach. The selective oxidation of H2S by a nitrogen-enriched mesoporous carbon catalyst can produce elemental sulfur as a by-product which in-situ deposit onto the carbon framework. Due to the metal-free catalytic characteristic and high catalytic selectivity, the resulting sulfur/carbon composites have almost no impurities that thus can be used as cathode materials with compromising battery performance. The layer-by-layer sulfur deposition allows atomic sulfur binding strongly with carbon framework, providing efficient immobilization of sulfur. The nitrogen atoms doped on the carbon framework can increase the surface interactions with polysulfides, leading to the improvement in the trapping of polysulfides. Thus, the composites exhibit a reversible capacity of 939 mAh g(-1) after 100 cycles at 0.2 C and an excellent rate capability of 527 mAh g(-1) at 5 C after 70 cycles.

  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. 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.

  7. Carbon Nanohorn-Derived Graphene Nanotubes as a Platinum-Free Fuel Cell Cathode.

    Science.gov (United States)

    Unni, Sreekuttan M; Illathvalappil, Rajith; Bhange, Siddheshwar N; Puthenpediakkal, Hasna; Kurungot, Sreekumar

    2015-11-01

    Current low-temperature fuel cell research mainly focuses on the development of efficient nonprecious electrocatalysts for the reduction of dioxygen molecule due to the reasons like exorbitant cost and scarcity of the current state-of-the-art Pt-based catalysts. As a potential alternative to such costly electrocatalysts, we report here the preparation of an efficient graphene nanotube based oxygen reduction electrocatalyst which has been derived from single walled nanohorns, comprising a thin layer of graphene nanotubes and encapsulated iron oxide nanoparticles (FeGNT). FeGNT shows a surface area of 750 m(2)/g, which is the highest ever reported among the metal encapsulated nanotubes. Moreover, the graphene protected iron oxide nanoparticles assist the system to attain efficient distribution of Fe-Nx and quaternary nitrogen based active reaction centers, which provides better activity and stability toward the oxygen reduction reaction (ORR) in acidic as well as alkaline conditions. Single cell performance of a proton exchange membrane fuel cell by using FeGNT as the cathode catalyst delivered a maximum power density of 200 mW cm(-2) with Nafion as the proton exchange membrane at 60 °C. The facile synthesis strategy with iron oxide encapsulated graphitic carbon morphology opens up a new horizon of hope toward developing Pt-free fuel cells and metal-air batteries along with its applicability in other energy conversion and storage devices. PMID:26458554

  8. 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

  9. 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…

  10. 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.

  11. Plasma characterization on carbon fiber cathode by spectroscopic diagnostics

    Institute of Scientific and Technical Information of China (English)

    Liu Lie; Li Li-Min; Xu Qi-Fu; Chang Lei; Wen Jian-Chun

    2009-01-01

    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 Cal enables a slow cathode plasma expansion toward the anode,providing a positive prospect for developing long-pulse electron beam sources.

  12. High surface area stainless steel brushes as cathodes in microbial electrolysis cells.

    Science.gov (United States)

    Call, Douglas F; Merrill, Matthew D; Logan, Bruce E

    2009-03-15

    Microbial electrolysis cells (MECs) are an efficient technology for generating hydrogen gas from organic matter, but alternatives to precious metals are needed for cathode catalysts. We show here that high surface area stainless steel brush cathodes produce hydrogen at rates and efficiencies similar to those achieved with platinum-catalyzed carbon cloth cathodes in single-chamber MECs. Using a stainless steel brush cathode with a specific surface area of 810 m2/m3, hydrogen was produced at a rate of 1.7 +/- 0.1 m3-H2/m3-d (current density of 188 +/- 10 A/m3) at an applied voltage of 0.6 V. The energy efficiency relative to the electrical energy input was 221 +/- 8%, and the overall energy efficiency was 78 +/- 5% based on both electrical energy and substrate utilization. These values compare well to previous results obtained using platinum on flat carbon cathodes in a similar system. Reducing the cathode surface area by 75% decreased performance from 91 +/- 3 A/m3 to 78 +/- 4 A/m3. A brush cathode with graphite instead of stainless steel and a specific surface area of 4600 m2/m3 generated substantially less current (1.7 +/- 0.0 A/m3), and a flat stainless steel cathode (25 m2/m3) produced 64 +/- 1 A/m3, demonstrating that both the stainless steel and the large surface area contributed to high current densities. Linear sweep voltammetry showed that the stainless steel brush cathodes both reduced the overpotential needed for hydrogen evolution and exhibited a decrease in overpotential over time as a result of activation. These results demonstrate for the first time that hydrogen production can be achieved at rates comparable to those with precious metal catalysts in MECs without the need for expensive cathodes. PMID:19368232

  13. 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.

  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. 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

  16. Surface Carbonization of Mo-La2O3 Cathode

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The carbonized structures of Mo-La2O3 cathode specimens have been investigated by means of FE SEM and XRD, respectively. The substructure of carbonized layer in the Mo-La2O3 cathode has been found for the first time. The results showed that the carbonized layer with uniform Mo2C was helpful to emission,while the demixing carbonized layer with a compact MoC outside layer was harmful to emission. The uniform Mo2C layer consists of coarse particles with lots of grain boundary crevices as well as holes arranging perpendic ular to the wire axle and up to surface, which was beneficial to the migration of activated rare-earth in activa tion and operating.

  17. The cathode plasma simulation

    Science.gov (United States)

    Suksila, Thada

    Since its invention at the University of Stuttgart, Germany in the mid-1960, scientists have been trying to understand and explain the mechanism of the plasma interaction inside the magnetoplasmadynamics (MPD) thruster. Because this thruster creates a larger level of efficiency than combustion thrusters, this MPD thruster is the primary cadidate thruster for a long duration (planetary) spacecraft. However, the complexity of this thruster make it difficult to fully understand the plasma interaction in an MPD thruster while operating the device. That is, there is a great deal of physics involved: the fluid dynamics, the electromagnetics, the plasma dynamics, and the thermodynamics. All of these physics must be included when an MPD thruster operates. In recent years, a computer simulation helped scientists to simulate the experiments by programing the physics theories and comparing the simulation results with the experimental data. Many MPD thruster simulations have been conducted: E. Niewood et al.[5], C. K. J. Hulston et al.[6], K. D. Goodfellow[3], J Rossignol et al.[7]. All of these MPD computer simulations helped the scientists to see how quickly the system responds to the new design parameters. For this work, a 1D MPD thruster simulation was developed to find the voltage drop between the cathode and the plasma regions. Also, the properties such as thermal conductivity, electrical conductivity and heat capacity are temperature and pressure dependent. These two conductivity and heat capacity are usually definded as constant values in many other models. However, this 1D and 2D cylindrical symmetry MPD thruster simulations include both temperature and pressure effects to the electrical, thermal conductivities and heat capacity values interpolated from W. F. Ahtye [4]. Eventhough, the pressure effect is also significant; however, in this study the pressure at 66 Pa was set as a baseline. The 1D MPD thruster simulation includes the sheath region, which is the

  18. 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.

  19. Layered double hydroxide and related catalysts for hydrogen production and a biorefinery%水滑石类催化剂催化制氢及生物炼制

    Institute of Scientific and Technical Information of China (English)

    王伟; 徐振新; 郭章龙; 江成发; 储伟

    2015-01-01

    近年来,水滑石由于其独特的性质受到越来越多的关注。作为非均相固体催化剂,水滑石及其衍生物具有优良的催化性能,因此得到了广泛研究和应用。本文简述了水滑石的几种合成方法,重点介绍了水滑石类催化剂在催化制氢和生物炼制方面的应用,并预测了水滑石类材料在新材料合成及环境友好催化体系中的应用前景。%Layered double hydroxides (LDHs) have received much attention for their unique properties. As solid catalysts, LDHs and their derivates have been widely studied and applied for their excellent catalytic performance. Several synthesis methods of LDHs were briefly introduced, and the applica‐tions of LDHs and related catalysts for hydrogen production and a biorefinery were emphasized in this article. The prospects for LDH related compounds in the synthesis of new materials and their catalytic application in green catalysis systems were also presented.

  20. 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)

  1. Performance of metal alloys as hydrogen evolution reaction catalysts in a microbial electrolysis cell

    NARCIS (Netherlands)

    Jeremiasse, A.W.; Bergsma, J.; Kleijn, J.M.; Saakes, M.; Buisman, C.J.N.; Cohen Stuart, M.A.; Hamelers, H.V.M.

    2011-01-01

    H2 can be produced from organic matter with a microbial electrolysis cell (MEC). To decrease the energy input and increase the H2 production rate of an MEC, a catalyst is used at the cathode. Platinum is an effective catalyst, but its high costs stimulate searching for alternatives, such as non-nobl

  2. Exfoliation and reassembly of cobalt oxide nanosheets into a reversible lithium-ion battery cathode.

    Science.gov (United States)

    Compton, Owen C; Abouimrane, Ali; An, Zhi; Palmeri, Marc J; Brinson, L Catherine; Amine, Khalil; Nguyen, SonBinh T

    2012-04-10

    An exfoliation-reassembly-activation (ERA) approach to lithium-ion battery cathode fabrication is introduced, demonstrating that inactive HCoO(2) powder can be converted into a reversible Li(1-x) H(x) CoO(2) thin-film cathode. This strategy circumvents the inherent difficulties often associated with the powder processing of the layered solids typically employed as cathode materials. The delamination of HCoO(2) via a combination of chemical and mechanical exfoliation generates a highly processable aqueous dispersion of [CoO(2) ](-) nanosheets that is critical to the ERA approach. Following vacuum-assisted self-assembly to yield a thin-film cathode and ion exchange to activate this material, the generated cathodes exhibit excellent cyclability and discharge capacities approaching that of low-temperature-prepared LiCoO(2) (~83 mAh g(-1) ), with this good electrochemical performance attributable to the high degree of order in the reassembled cathode.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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) 2005...

  12. 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.

  13. 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.

  14. Catalyst composition

    Energy Technology Data Exchange (ETDEWEB)

    Onodera, T.; Sakai, T.; Sumitani, K.; Yamasaki, Y.

    1984-11-27

    A catalyst composition comprising a crystalline aluminosilicate selected from the group consisting of zeolite ZSM-5, zeolite ZSM-11, zeolite ZSM-12, zeolite ZSM-35 and zeolite ZSM-38 and having a silica/alumina mole ratio of 20 to 1,000; and at least two metals which are platinum and at least one other metal selected from the group consisting of titanium, chromium, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, palladium, tin, barium, cerium, tungsten, osmium, lead, cadmium, mercury, indium, lanthanum and beryllium. This catalyst composition is useful particularly for the isomerization of aromatic hydrocarbons and reforming of naphtha.

  15. 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

  16. Model of Cathode Catalyst Layer and Analysis on Performance of PEM Fuel Cells%PEM燃料电池阴极催化剂层的模型及性能分析

    Institute of Scientific and Technical Information of China (English)

    吴玉厚; 孙红; Lin Hong-tan

    2001-01-01

    以物质和电流平衡为基础,建立了PEM燃料电池阴极催化剂层的数学模型,并运用逐次近似法求解此数学模型·比较发现,数值计算结果和实验结果吻合很好.同时分析了孔隙率和催化剂表面积对催化剂层性能的影响.

  17. Fabrication and performance of La0.8Sr0.2MnO3/YSZ graded composite cathodes for SOFC

    Institute of Scientific and Technical Information of China (English)

    SUN Kening; PIAO Jinhua; ZHANG Naiqing; CHEN Xinbing; XU Shen; ZHOU Derui

    2008-01-01

    The performance of multi-layer (1-x)La0.8Sr0.2MnO3/xYSZ graded composite cathodes was studied as electrode materials for intermediate solid oxide fuel cells (SOFC). The thermal expansion coefficient, electrical conductivity, and electrochemical performance of multi-layer composite cathodes were investigated. The thermal expansion coefficient and electrical conductivity decreased with the increase in YSZ content. The (1-x)La0.8Sr0.2MnO3/xYSZ composite cathode greatly increased the length of the active triple phase boundary line (TPBL) among electrode, electrolyte, and gas phase, leading to a decrease in polarization resistance and an increase in polarization current density. The polarization current density of the triple-layer graded composite cathode (0.77 A/cm2) was the highest and that of the monolayer cathode (0.13 A/cm2) was the lowest. The polarization resistance (Rp) of the triple-layer graded composite cathode was only 0.182Ω·cm2 and that of the monolayer composite cathode was 0.323Ω·cm2. The power density of the triple-layer graded composite cathode was the highest and that of the monolayer composite cathode was the lowest. The triple-layer graded composite cathode had superior performance.

  18. 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.

  19. 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.

  20. Dynamic Aspects of Solid Solution Cathodes for Electrochemical Power Sources

    DEFF Research Database (Denmark)

    Atlung, Sven; West, Keld; Jacobsen, Torben

    1979-01-01

    , 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......–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, Inc....

  1. 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.

  2. 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.

  3. Aqueous cathode for next-generation alkali-ion batteries.

    Science.gov (United States)

    Lu, Yuhao; Goodenough, John B; Kim, Youngsik

    2011-04-20

    The lithium-ion batteries that ushered in the wireless revolution rely on electrode strategies that are being stretched to power electric vehicles. Low-cost, safe electrical-energy storage that enables better use of alternative energy sources (e.g., wind, solar, and nuclear) requires an alternative strategy. We report a demonstration of the feasibility of a battery having a thin, solid alkali-ion electrolyte separating a water-soluble redox couple as the cathode and lithium or sodium in a nonaqueous electrolyte as the anode. The cell operates without a catalyst and has high storage efficiency. The possibility of a flow-through mode for the cathode allows flexibility of the cell design for safe, large-capacity electrical-energy storage at an acceptable cost. PMID:21443190

  4. An Improved Blue Polymer Light-Emitting Diode by Using Sodium Hydroxide/Ca/Al Cathode

    Institute of Scientific and Technical Information of China (English)

    MA Liang; XIE Zhi-Yuan; LIU Jun; YANG Jun-Wei; CHENG Yan-Xiang; WANG Li-Xiang; WANG Fo-Song

    2005-01-01

    @@ The performance of blue polymer light-emitting diodes (PLEDs) based on poly(9,9-dioctylfluorene) (PFO) is improved by introducing a thin layer of sodium hydroxide (NaOH) between the calcium cathode and the PFO emissive layer. By replacing the commonly used Ca/Al cathode by a NaOH (2.5nm)/Ca (10 nm)/Al cathode,the driving voltage is reduced from 8.3 V to 5.4 V and the light-emitting efficiency is enhanced from 0.46cd/A to 0. 72 cd/A for achieving a luminance of 500 cd/m2, respectively. Moreover, the device with NaOH/Ca/Al cathode shows a pure blue emission of (0.17, 0. 12) at high brightnesses. These improvements are attributed to introduction of a thin layer of NaOH that can lower the interfacial barrier and facilitate electron injection.

  5. 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.

  6. 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).

  7. Electronic modification of Pt via Ti and Se as tolerant cathodes in air-breathing methanol microfluidic fuel cells.

    Science.gov (United States)

    Ma, Jiwei; Habrioux, Aurélien; Morais, Cláudia; Alonso-Vante, Nicolas

    2014-07-21

    We reported herein on the use of tolerant cathode catalysts such as carbon supported Pt(x)Ti(y) and/or Pt(x)Se(y) nanomaterials in an air-breathing methanol microfluidic fuel cell. In order to show the improvement of mixed-reactant fuel cell (MRFC) performances obtained with the developed tolerant catalysts, a classical Pt/C nanomaterial was used for comparison. Using 5 M methanol concentration in a situation where the fuel crossover is 100% (MRFC-mixed reactant fuel cell application), the maximum power density of the fuel cell with a Pt/C cathodic catalyst decreased by 80% in comparison with what is observed in the laminar flow fuel cell (LFFC) configuration. With Pt(x)Ti(y)/C and Pt(x)Se(y)/C cathode nanomaterials, the performance loss was only 55% and 20%, respectively. The evaluation of the tolerant cathode catalysts in an air-breathing microfluidic fuel cell suggests the development of a novel nanometric system that will not be size restricted. These interesting results are the consequence of the high methanol tolerance of these advanced electrocatalysts via surface electronic modification of Pt. Herein we used X-ray photoelectron and in situ FTIR spectroscopies to investigate the origin of the high methanol tolerance on modified Pt catalysts.

  8. Modeling and validation of single-chamber microbial fuel cell cathode biofilm growth and response to oxidant gas composition

    Science.gov (United States)

    Ou, Shiqi; Zhao, Yi; Aaron, Douglas S.; Regan, John M.; Mench, Matthew M.

    2016-10-01

    This work describes experiments and computational simulations to analyze single-chamber, air-cathode microbial fuel cell (MFC) performance and cathodic limitations in terms of current generation, power output, mass transport, biomass competition, and biofilm growth. Steady-state and transient cathode models were developed and experimentally validated. Two cathode gas mixtures were used to explore oxygen transport in the cathode: the MFCs exposed to a helium-oxygen mixture (heliox) produced higher current and power output than the group of MFCs exposed to air or a nitrogen-oxygen mixture (nitrox), indicating a dependence on gas-phase transport in the cathode. Multi-substance transport, biological reactions, and electrochemical reactions in a multi-layer and multi-biomass cathode biofilm were also simulated in a transient model. The transient model described biofilm growth over 15 days while providing insight into mass transport and cathodic dissolved species concentration profiles during biofilm growth. Simulation results predict that the dissolved oxygen content and diffusion in the cathode are key parameters affecting the power output of the air-cathode MFC system, with greater oxygen content in the cathode resulting in increased power output and fully-matured biomass.

  9. 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.

  10. 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 combinatio...... meaningful for everyone. The exhibited works are designed by SANAA, Diller Scofidio + Renfro, James Corner Field Operation, JBMC Arquitetura e Urbanismo, Atelier Bow-Wow, Ateliers Jean Nouvel, COBE, Transform, BIG, Topotek1, Superflex, and by visual artist Jane Maria Petersen....

  11. 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.

  12. Effect of various cathode modifying layers on the performances of SubPc/C60 based inverted organic solar cells∗%阴极修饰层对SubPc/C60倒置型有机太阳能电池性能的影响*

    Institute of Scientific and Technical Information of China (English)

    李青; 李海强; 赵娟; 黄江; 于军胜

    2013-01-01

      采用Cs2CO3,石墨烯(graphene):Cs2CO3混合材料和ZnO纳米颗粒作为阴极修饰材料,研究了不同阴极界面修饰层对基于SubPc/C60的倒置结构的有机太阳能电池性能的影响.结果表明:引入适当厚度的阴极修饰层,可以提高器件的性能和稳定性;尤其是基于Cs2CO3以及graphene:Cs2CO3混合阴极修饰层的光伏器件,能量转换效率(PCE)提高了2倍;同时,采用ZnO纳米颗粒作为阴极修饰层的器件,开路电压(VOC)达到0.89 V,并且器件的PCE提高了4倍多.此外,不同电极修饰材料和倒置结构的引入可以有效防止器件串连电阻的升高,从而提高器件的稳定性.%  Organic solar cell (OSC) with an inverted structure based on subphthalocyanine (SubPc)/C60 is fabricated by using Cs2CO3, graphene:Cs2CO3 mixed system and ZnO nanoparticles as cathode modifying materials, and its influences on the performance and stability of OSC are investigated. The results show that the OSC with an appropriate thickness of cathode modifying layer exhibits higher performance and it is more stable than those unmodified ones. The power conversion efficiency (PCE) of the Cs2CO3 and graphene:Cs2CO3 mixed material modified device is enhanced by a factor of two. Meanwhile, the ZnO nanoparticle modified device shows a highest open-circuit voltage (VOC) of 0.89 V, and the PCE increases more than 4 times. Besides, the adoptions of different cathode modifying materials and the inverted structures can effectively prevent the series resistance of the device from increasing, thereby improving the stability of the device.

  13. 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.

  14. 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%.

  15. Diffuse and spot mode of cathode arc attachments in an atmospheric magnetically rotating argon arc

    International Nuclear Information System (INIS)

    A model including the cathode, near-cathode region, and arc column was constructed. Specifically, a thermal perturbation layer at the arc fringe was calculated in order to couple sheath/presheath modelling with typical arc column modelling. Comparative investigation of two modes of attachment of a dc (100, 150, 200 A) atmospheric-pressure arc in argon to a thermionic cathode made of pure tungsten was conducted. Computational data revealed that there exists two modes of arc discharge: the spot mode, which has an obvious cathode surface temperature peak in the arc attachment centre; and the diffuse mode, which has a flat cathode surface temperature distribution and a larger arc attachment area. The modelling results of the arc attachment agree with previous experimental observations for the diffuse mode. A further 3D simulation is obviously needed to investigate the non-axisymmetrical features, especially for the spot mode. (paper)

  16. 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.

  17. 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

  18. Cathode material for lithium ion accumulators prepared by screen printing for Smart Textile applications

    Science.gov (United States)

    Syrový, T.; Kazda, T.; Syrová, L.; Vondrák, J.; Kubáč, L.; Sedlaříková, M.

    2016-03-01

    The presented study is focused on the development of LiFePO4 based cathode for thin and flexible screen printed secondary lithium based accumulators. An ink formulation was developed for the screen printing technique, which enabled mass production of accumulator's cathode for Smart Label and Smart Textile applications. The screen printed cathode was compared with an electrode prepared by the bar coating technique using an ink formulation based on the standard approach of ink composition. Obtained LiFePO4 cathode layers were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and galvanostatic charge/discharge measurements at different loads. The discharge capacity, capacity retention and stability at a high C rate of the LiFePO4 cathode were improved when Super P and PVDF were replaced by conductive polymers PEDOT:PSS. The achieved capacity during cycling at various C rates was approximately the same at the beginning and at the end, and it was about 151 mAh/g for cycling under 1C. The obtained results of this novelty electrode layer exceed the parameters of several electrode layers based on LiFePO4 published in literature in terms of capacity, cycling stability and overcomes them in terms of simplicity/industrial process ability of cathode layer fabrication and electrode material preparation.

  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. Oxide diffusion in innovative SOFC cathode materials.

    Science.gov (United States)

    Hu, Y; Thoréton, V; Pirovano, C; Capoen, E; Bogicevic, C; Nuns, N; Mamede, A-S; Dezanneau, G; Vannier, R N

    2014-01-01

    Oxide diffusion was studied in two innovative SOFC cathode materials, Ba(2)Co(9)O(14) and Ca(3)Co(4)O(9)+δ derivatives. Although oxygen diffusion was confirmed in the promising material Ba(2)Co(9)O(14), it was not possible to derive accurate transport parameters because of an oxidation process at the sample surface which has still to be clarified. In contrast, oxygen diffusion in the well-known Ca(3)Co(4)O(9)+δ thermoelectric material was improved when calcium was partly substituted with strontium, likely due to an increase of the volume of the rock salt layers in which the conduction process takes place. Although the diffusion coefficient remains low, interestingly, fast kinetics towards the oxygen molecule dissociation reaction were shown with surface exchange coefficients higher than those reported for the best cathode materials in the field. They increased with the strontium content; the Sr atoms potentially play a key role in the mechanism of oxygen molecule dissociation at the solid surface. PMID:25407246

  1. 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)

  2. Methanol Tolerant PWA-Pt/C Catalyst with Excellent Electrocatalytic Activity for Oxygen Reduction in Direct Methanol Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    It was reported for the first time that phosphorictungstenic acid (PWA) could promote the oxygen reduction reaction (ORR) and inhibit the methanol oxidation reaction at the cathodic Pt/C catalyst in the direct methanol fuel cell (DMFC). When the weight ratio of PWA to Pt/C is 1,the composite catalyst increases the reduction current of oxygen by about 38% and decreases the oxidation current of methanol by about 76% compared with that of the Pt/C catalyst.

  3. Outcoupling efficiency of OLEDs with 2D periodical corrugation at the cathode

    International Nuclear Information System (INIS)

    We study theoretically the optical performance of organic light-emitting diodes (OLEDs) with 2D periodical corrugation at the cathode. We show how emergence of radiative surface plasmon resonances at the 2D corrugated cathode leads to the enhancement of the outcoupling efficiency of the OLED, which is primarily due to the outcoupling of emission generated by vertically oriented emitting excitons in the emission layer. We analyze the outcoupling efficiency of the OLED as a function of geometrical parameters of the corrugation and establish design rules for optimal outcoupling enhancement with the 2D corrugation at the cathode. (paper)

  4. Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

    Science.gov (United States)

    Manthiram, Arumugam; Choi, Wongchang

    2014-05-13

    The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn.sub.2-y-zLi.sub.yM.sub.zO.sub.4 oxide with NH.sub.4HF.sub.2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

  5. Lanthanum Manganate Based Cathodes for Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Jørgensen, Mette Juhl

    Composite cathodes for solid oxide fuel cells were investigated using electrochemical impedance spectroscopy and scanning electron microscopy. The aim was to study the oxygen reduction process in the electrode in order to minimise the voltage drop in the cathode. The electrodes contained...... a composite layer made from lanthanum strontium manganate (LSM) and yttria stabilised zirconia (YSZ) and a layer of pure LSM aimed for current collection. The performance of the composite electrodes was sensitive to microstructure and thickness. Further, the interface between the composite and the current...... five processes were found to affect the impedance of LSM/YSZ composite electrodes. Two high frequency processes were ascribed to transport of oxide ions/oxygen intermediates across LSM/YSZ interfaces and through YSZ in the composite. Several competitive elementary reaction steps, which appear as one...

  6. Heterogeneous electrocatalysis in porous cathodes of solid oxide fuel cells

    CERN Document Server

    Fu, Y; Bertei, A; Qi, C; Mohanram, A; Pietras, J D; Bazant, M Z

    2014-01-01

    A general physics-based model is developed for heterogeneous electrocatalysis in porous electrodes and used to predict and interpret the impedance of solid oxide fuel cells. This model describes the coupled processes of oxygen gas dissociative adsorption and surface diffusion of the oxygen intermediate to the triple phase boundary, where charge transfer occurs. The model accurately captures the Gerischer-like frequency dependence and the oxygen partial pressure dependence of the impedance of symmetric cathode cells. Digital image analysis of the microstructure of the cathode functional layer in four different cells directly confirms the predicted connection between geometrical properties and the impedance response. As in classical catalysis, the electrocatalytic activity is controlled by an effective Thiele modulus, which is the ratio of the surface diffusion length (mean distance from an adsorption site to the triple phase boundary) to the surface boundary layer length (square root of surface diffusivity div...

  7. Metal Nanoparticles and Carbon-Based Nanostructures as Advanced Materials for Cathode Application in Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Pietro Calandra

    2010-01-01

    Full Text Available We review the most advanced methods for the fabrication of cathodes for dye-sensitized solar cells employing nanostructured materials. The attention is focused on metal nanoparticles and nanostructured carbon, among which nanotubes and graphene, whose good catalytic properties make them ideal for the development of counter electrode substrates, transparent conducting oxide, and advanced catalyst materials.

  8. Double electrical layer in the cathode spot / Двойной электрический слой в катодном пятне / Dvostruki električni sloj u katodnom spotu

    Directory of Open Access Journals (Sweden)

    Leonid I. Gretchikhin

    2016-07-01

    Full Text Available The paper describes a new phenomenon of the generation of the double electrical layer above the cathode spot surface. The neutralization of this layer leads to the reverse current of free electrons, generated due to negative ions ionization. The negatively charged flame of the cathode spot periodically ignites and attenuates, so the duration of the cathode spot existence is defined by this oscillating process. The reverse motion of the cathode spot in the longitudinal magnetic field takes place owing to the generation of the reverse high-power neutralization current of the double electrical layer by the electrons appearing during the negative ions ionization in the cathode flame. / Установлено новое явление, заключающееся в образовании над поверхностью катодного пятна двойного электрического слоя, нейтрализация которого приводит к обратному току свободными электронами, образующихся вследствие ионизации отрицательных ионов. Отрицательно заряженный факел из катодного пятна периодически пропадает и возникает. Этот колебательный процесс определяет длительность существования катодного пятна. Обратное движение катодного пятна в продольном магнитном поле происходит вследствие образования обратного мощного тока нейтрализации двойного электрического слоя электронами, возникающих при ионизации отрицательных ионов в катодном факеле. / U radu se opisuje novootkrivena pojava stvaranja dvostrukog

  9. Reservoir Cathode for Electric Space Propulsion Project

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose a reservoir cathode to improve performance in both ion and Hall-effect thrusters. We propose to adapt our existing reservoir cathode technology to this...

  10. Reservoir Cathode for Electric Space Propulsion Project

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose a hollow reservoir cathode to improve performance in ion and Hall thrusters. We will adapt our existing reservoir cathode technology to this purpose....

  11. Novel catalysts and photoelectrochemical system for solar fuel production

    Science.gov (United States)

    Zhang, Yan

    spectroscopy (XAS). The photocatalytic activities of as-made nanoparticles were investigated using a well-studied visible light driven [Ru(bpy)3]2+-persulfate system. In both Clark electrode and reactor/gas chromatography (GC) systems, Mn-substituted Co3O 4 nanoparticles exhibited the highest turnover frequency (TOF) among all the three kinds of catalysts. The data presented in this paper suggest that the photocatalytic oxygen evolution activity of Co3O 4 spinel catalyst can be further enhanced by Mn3+ substitution at the octahedral sites. The second part of this piece of work was carried out to further investigate cobalt oxide based photocatalytic oxygen evolution catalyst. A new strategy was developed to synthesize nonsupported cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO 3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.0023 per second per cobalt in photocatalytic oxygen evolution reaction. X-ray absorption results suggested that a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen atoms and hydroxide groups in an octahedral arrangement to form 8 Co4O4 cubanes, may be responsible for the exceptionally high oxygen evolution catalysis activity. This thesis work is completed with the development of a photoanode-driven photoelectrochemical cell for CO2 reduction. A NiOx decorated Si photoanode and nanoporous Ag cathode were employed. With an external bias of 2.0 V, a current density at cathode of 10 mA/cm2 and Faradaic efficiency of 70% for CO2 to CO was achieved. Compared to a normal electrochemical cell, the photoelectrochemical cell saves 0.4 V electrical energy by absorbing photo-energy. In addition, post-test photoanodes were carefully characterized by SEM, XAS, and XPS

  12. High-Capacity, High-Voltage Composite Oxide Cathode Materials

    Science.gov (United States)

    Hagh, Nader M.

    2015-01-01

    This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

  13. Hollow cathode arc: effect of the cathode material on the internal plasma

    International Nuclear Information System (INIS)

    In discharges with hollow cathodes functioning in the arc regime, the cathode emits thermionic electrons which ionize the gas. To reduce the electrical power consumed by these discharges, cathodes made of thoriated tungsten and lathanum hexaboride have been used. The parameters of the plasma generated into the cathode have been measured with electrostatic probes. (Auth.)

  14. Tungsten imido catalysts for selective ethylene dimerisation.

    Science.gov (United States)

    Wright, Christopher M R; Turner, Zoë R; Buffet, Jean-Charles; O'Hare, Dermot

    2016-02-14

    A tungsten imido complex W(NDipp)Me3Cl (Dipp = 2,6-(i)Pr-C6H3) is active for the selective dimerisation of ethylene to yield 1-butene under mild conditions. Immobilisation and activation of W(NDipp)Cl4(THF) on layered double hydroxides, silica or polymethylaluminoxane yields active solid state catalysts for the selective dimerisation of ethylene. The polymethylaluminoxane-based catalyst displays a turnover frequency (4.0 molC2H4 molW(-1) h(-1)) almost 7 times that of the homogeneous catalyst. PMID:26779579

  15. Tungsten imido catalysts for selective ethylene dimerisation.

    Science.gov (United States)

    Wright, Christopher M R; Turner, Zoë R; Buffet, Jean-Charles; O'Hare, Dermot

    2016-02-14

    A tungsten imido complex W(NDipp)Me3Cl (Dipp = 2,6-(i)Pr-C6H3) is active for the selective dimerisation of ethylene to yield 1-butene under mild conditions. Immobilisation and activation of W(NDipp)Cl4(THF) on layered double hydroxides, silica or polymethylaluminoxane yields active solid state catalysts for the selective dimerisation of ethylene. The polymethylaluminoxane-based catalyst displays a turnover frequency (4.0 molC2H4 molW(-1) h(-1)) almost 7 times that of the homogeneous catalyst.

  16. Mechanistic Enhancement of SOFC Cathode Durability

    Energy Technology Data Exchange (ETDEWEB)

    Wachsman, Eric [Univ. of Maryland, College Park, MD (United States)

    2016-02-01

    Durability of solid oxide fuel cells (SOFC) under “real world” conditions is an issue for commercial deployment. In particular cathode exposure to moisture, CO2, Cr vapor (from interconnects and BOP), and particulates results in long-term performance degradation issues. Here, we have conducted a multi-faceted fundamental investigation of the effect of these contaminants on cathode performance degradation mechanisms in order to establish cathode composition/structures and operational conditions to enhance cathode durability.

  17. Fe-Mo alloy coatings as cathodes in chlorate production process

    Directory of Open Access Journals (Sweden)

    Gajić-Krstajić Ljiljana M.

    2016-01-01

    Full Text Available The aim of this study was to gain a better understanding of the feasibility of partial replacement of dichromate, Cr(VI, with phosphate buffer, focusing on the cathode reaction selectivity for hydrogen evolution on mild steel and Fe-Mo cathodes in undivided cell for chlorate production. To evaluate the ability of phosphate and Cr(VI additions to hinder hypochlorite and chlorate reduction, overall current efficiency (CE measurements in laboratory cell for chlorate production on stationary electrodes were performed. The concentration of hypochlorite was determined by a conventional potentiometric titration method using 0.01 mol dm-3 As2O3 solution as a titrant. The chlorate concentration was determined by excess of 1.0 mol dm-3 As2O3 solution and excess of arsenic oxide was titrated with 0.1 mol dm-3 KBrO3 solution in a strong acidic solution. Cathodic hypochlorite and chlorate reduction were suppressed efficiently by addition of 3 g dm-3 dichromate at both cathodes, except that Fe-Mo cathode exhibited higher catalytic activity for hydrogen evolution reaction (HER. The overvoltage for the HER was around 0.17 V lower on Fe-Mo cathode than on mild steel at the current density of 3 kA m-2. It was found that a dichromate content as low as 0.1 g dm-3 is sufficient for complete suppression of cathodic hypochlorite and chlorate reduction onto Fe-Mo catalyst in phosphate buffering system (3 g dm-3 Na2HPO4 + NaH2PO4. The overall current efficiency was practically the same as in the case of the presence of 3 g dm-3 dichromate buffer (98 %. However, for the mild steel cathode, the overall current efficiency for the chlorate production was somewhat lower in the above mentioned mixed phosphate + dichromate buffering system (95% than in the pure dichromate buffering solution (97.5%.

  18. Effects of composition of the micro porous layer and the substrate on performance in the electrochemical reduction of CO2 to CO

    Science.gov (United States)

    Kim, Byoungsu; Hillman, Febrian; Ariyoshi, Miho; Fujikawa, Shigenori; Kenis, Paul J. A.

    2016-04-01

    With the development of better catalysts, mass transport limitations are becoming a challenge to high throughput electrochemical reduction of CO2 to CO. In contrast to optimization of electrodes for fuel cells, optimization of gas diffusion electrodes (GDE) - consisting of a carbon fiber substrate (CFS), a micro porous layer (MPL), and a catalyst layer (CL) - for CO2 reduction has not received a lot of attention. Here, we studied the effect of the MPL and CFS composition on cathode performance in electroreduction of CO2 to CO. In a flow reactor, optimized GDEs exhibited a higher partial current density for CO production than Sigracet 35BC, a commercially available GDE. By performing electrochemical impedance spectroscopy in a CO2 flow reactor we determined that a loading of 20 wt% PTFE in the MPL resulted in the best performance. We also investigated the influence of the thickness and wet proof level of CFS with two different feeds, 100% CO2 and the mixture of 50% CO2 and N2, determining that thinner and lower wet proofing of the CFS yields better cathode performance than when using a thicker and higher wet proof level of CFS.

  19. Novel Cathodes Prepared by Impregnation Procedures

    Energy Technology Data Exchange (ETDEWEB)

    Eduardo Paz

    2006-09-30

    (1) We showed that similar results were obtained when using various LSM precursors to produce LSM-YSZ cathodes. (2) We showed that enhanced performance could be achieved by adding LSCo to LSMYSZ cathodes. (3) We have preliminary results showing that there is a slow deactivation with LSFYSZ cathodes.

  20. Direct observation of the dealloying process of a platinum–yttrium nanoparticle fuel cell cathode and its oxygenated species during the oxygen reduction reaction

    OpenAIRE

    Kaya, Sarp; Malacrida, Paolo; Casalongue, Hernan G. Sanchez; Masini, Federico; Hernandez-Fernandez, Patricia; Deiana, Davide; Ogasawara, Hirohito; Stephens, Ifan E. L.; Nilsson, Anders; Chorkendorff, Ib

    2015-01-01

    Size-selected 9 nm PtxY nanoparticles have recently shown an outstanding catalytic activity for the oxygen reduction reaction, representing a promising cathode catalyst for proton exchange membrane fuel cells (PEMFCs). Studying their electrochemical dealloying is a fundamental step towards the understanding of both their activity and stability. Herein, size-selected 9 nm PtxY nanoparticles have been deposited on the cathode side of a PEMFC specifically designed for in situ ambient pressure X-...

  1. Electrochemical catalyst recovery method

    Science.gov (United States)

    Silva, Laura J.; Bray, Lane A.

    1995-01-01

    A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

  2. Air-cathode structure optimization in separator-coupled microbial fuel cells

    KAUST Repository

    Zhang, Xiaoyuan

    2011-12-01

    Microbial fuel cells (MFC) with 30% wet-proofed air cathodes have previously been optimized to have 4 diffusion layers (DLs) in order to limit oxygen transfer into the anode chamber and optimize performance. Newer MFC designs that allow close electrode spacing have a separator that can also reduce oxygen transfer into the anode chamber, and there are many types of carbon wet-proofed materials available. Additional analysis of conditions that optimize performance is therefore needed for separator-coupled MFCs in terms of the number of DLs and the percent of wet proofing used for the cathode. The number of DLs on a 50% wet-proofed carbon cloth cathode significantly affected MFC performance, with the maximum power density decreasing from 1427 to 855mW/m 2 for 1-4 DLs. A commonly used cathode (30% wet-proofed, 4 DLs) produced a maximum power density (988mW/m 2) that was 31% less than that produced by the 50% wet-proofed cathode (1 DL). It was shown that the cathode performance with different materials and numbers of DLs was directly related to conditions that increased oxygen transfer. The coulombic efficiency (CE) was more affected by the current density than the oxygen transfer coefficient for the cathode. MFCs with the 50% wet-proofed cathode (2 DLs) had a CE of >84% (6.8A/m 2), which was substantially larger than that previously obtained using carbon cloth air-cathodes lacking separators. These results demonstrate that MFCs constructed with separators should have the minimum number of DLs that prevent water leakage and maximize oxygen transfer to the cathode. © 2011 Elsevier B.V.

  3. The fractal nature of vacuum arc cathode spots

    Energy Technology Data Exchange (ETDEWEB)

    Anders, Andre

    2005-05-27

    Cathode spot phenomena show many features of fractals, for example self-similar patterns in the emitted light and arc erosion traces. Although there have been hints on the fractal nature of cathode spots in the literature, the fractal approach to spot interpretation is underutilized. In this work, a brief review of spot properties is given, touching the differences between spot type 1 (on cathodes surfaces with dielectric layers) and spot type 2 (on metallic, clean surfaces) as well as the known spot fragment or cell structure. The basic properties of self-similarity, power laws, random colored noise, and fractals are introduced. Several points of evidence for the fractal nature of spots are provided. Specifically power laws are identified as signature of fractal properties, such as spectral power of noisy arc parameters (ion current, arc voltage, etc) obtained by fast Fourier transform. It is shown that fractal properties can be observed down to the cutoff by measurement resolution or occurrence of elementary steps in physical processes. Random walk models of cathode spot motion are well established: they go asymptotically to Brownian motion for infinitesimal step width. The power spectrum of the arc voltage noise falls as 1/f {sup 2}, where f is frequency, supporting a fractal spot model associated with Brownian motion.

  4. Enhanced Activated Carbon Cathode Performance for Microbial Fuel Cell by Blending Carbon Black

    KAUST Repository

    Zhang, Xiaoyuan

    2014-02-04

    Activated carbon (AC) is a useful and environmentally sustainable catalyst for oxygen reduction in air-cathode microbial fuel cells (MFCs), but there is great interest in improving its performance and longevity. To enhance the performance of AC cathodes, carbon black (CB) was added into AC at CB:AC ratios of 0, 2, 5, 10, and 15 wt % to increase electrical conductivity and facilitate electron transfer. AC cathodes were then evaluated in both MFCs and electrochemical cells and compared to reactors with cathodes made with Pt. Maximum power densities of MFCs were increased by 9-16% with CB compared to the plain AC in the first week. The optimal CB:AC ratio was 10% based on both MFC polarization tests and three electrode electrochemical tests. The maximum power density of the 10% CB cathode was initially 1560 ± 40 mW/m2 and decreased by only 7% after 5 months of operation compared to a 61% decrease for the control (Pt catalyst, 570 ± 30 mW/m2 after 5 months). The catalytic activities of Pt and AC (plain or with 10% CB) were further examined in rotating disk electrode (RDE) tests that minimized mass transfer limitations. The RDE tests showed that the limiting current of the AC with 10% CB was improved by up to 21% primarily due to a decrease in charge transfer resistance (25%). These results show that blending CB in AC is a simple and effective strategy to enhance AC cathode performance in MFCs and that further improvement in performance could be obtained by reducing mass transfer limitations. © 2014 American Chemical Society.

  5. Materials characterization of impregnated W and W–Ir cathodes after oxygen poisoning

    International Nuclear Information System (INIS)

    Highlights: • Impregnated W and W–Ir cathodes were operated with 100 ppm of oxygen in Xe gas. • High concentrations of oxygen accelerated the formation of tungstate layers. • The W–Ir emitter exhibited less erosion and redeposition at the upstream end. • Tungsten was preferentially transported in the insert plasma of the W–Ir cathode. - Abstract: Electric thrusters use hollow cathodes as the electron source for generating the plasma discharge and for beam neutralization. These cathodes contain porous tungsten emitters impregnated with BaO material to achieve a lower surface work function and are operated with xenon propellant. Oxygen contaminants in the xenon plasma can poison the emitter surface, resulting in a higher work function and increased operating temperature. This could lead directly to cathode failure by preventing discharge ignition or could accelerate evaporation of the BaO material. Exposures over hundreds of hours to very high levels of oxygen can result in increased temperatures, oxidation of the tungsten substrate, and the formation of surface layers of barium tungstates. In this work, we present results of a cathode test in which impregnated tungsten and tungsten–iridium emitters were operated with 100 ppm of oxygen in the xenon plasma for several hundred hours. The chemical and morphological changes were studied using scanning electron microscopy, energy dispersive spectroscopy, and laser profilometry. The results provide strong evidence that high concentrations of oxygen accelerate the formation of tungstate layers in both types of emitters, a phenomenon not inherent to normal cathode operation. Deposits of pure tungsten were observed on the W–Ir emitter, indicating that tungsten is preferentially removed from the surface and transported in the insert plasma. A W–Ir cathode surface will therefore evolve to a pure W composition, eliminating the work function benefit of W–Ir. However, the W–Ir emitter exhibited less erosion

  6. Materials characterization of impregnated W and W–Ir cathodes after oxygen poisoning

    Energy Technology Data Exchange (ETDEWEB)

    Polk, James E., E-mail: james.e.polk@jpl.nasa.gov [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109 (United States); Capece, Angela M. [California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (United States)

    2015-05-30

    Highlights: • Impregnated W and W–Ir cathodes were operated with 100 ppm of oxygen in Xe gas. • High concentrations of oxygen accelerated the formation of tungstate layers. • The W–Ir emitter exhibited less erosion and redeposition at the upstream end. • Tungsten was preferentially transported in the insert plasma of the W–Ir cathode. - Abstract: Electric thrusters use hollow cathodes as the electron source for generating the plasma discharge and for beam neutralization. These cathodes contain porous tungsten emitters impregnated with BaO material to achieve a lower surface work function and are operated with xenon propellant. Oxygen contaminants in the xenon plasma can poison the emitter surface, resulting in a higher work function and increased operating temperature. This could lead directly to cathode failure by preventing discharge ignition or could accelerate evaporation of the BaO material. Exposures over hundreds of hours to very high levels of oxygen can result in increased temperatures, oxidation of the tungsten substrate, and the formation of surface layers of barium tungstates. In this work, we present results of a cathode test in which impregnated tungsten and tungsten–iridium emitters were operated with 100 ppm of oxygen in the xenon plasma for several hundred hours. The chemical and morphological changes were studied using scanning electron microscopy, energy dispersive spectroscopy, and laser profilometry. The results provide strong evidence that high concentrations of oxygen accelerate the formation of tungstate layers in both types of emitters, a phenomenon not inherent to normal cathode operation. Deposits of pure tungsten were observed on the W–Ir emitter, indicating that tungsten is preferentially removed from the surface and transported in the insert plasma. A W–Ir cathode surface will therefore evolve to a pure W composition, eliminating the work function benefit of W–Ir. However, the W–Ir emitter exhibited less erosion

  7. Cathodic protection to control microbiologically influenced corrosion

    International Nuclear Information System (INIS)

    Information about the cathodic protection performance in environments with microbiologically influenced corrosion (MIC) effects is very fragmented and often contradictory. Not enough is known about the microbial effects on cathodic protection effectiveness, criteria, calcareous deposits, corrosion rates and possible hydrogen embrittlement of titanium and some stainless steel condenser tubes. This paper presents a review of cathodic protection systems, describes several examples of cathodic protection in environments with MIC effects and provides preliminary conclusions about cathodic protection design parameters, criteria and effectiveness in MIC environments. 30 refs

  8. Cathodes for molten-salt batteries

    Science.gov (United States)

    Argade, Shyam D.

    1993-02-01

    Viewgraphs of the discussion on cathodes for molten-salt batteries are presented. For the cathode reactions in molten-salt cells, chlorine-based and sulfur-based cathodes reactants have relatively high exchange current densities. Sulfur-based cathodes, metal sulfides, and disulfides have been extensively investigated. Primary thermal batteries of the Li-alloy/FeS2 variety have been available for a number of years. Chlorine based rechargable cathodes were investigated for the pulse power application. A brief introduction is followed by the experimental aspects of research, and the results obtained. Performance projections to the battery system level are discussed and the presentation is summarized with conclusions.

  9. Synopsis of Cathode No.4 Activation

    International Nuclear Information System (INIS)

    The purpose of this report is to describe the activation of the fourth cathode installed in the DARHT-II Injector. Appendices have been used so that an extensive amount of data could be included without danger of obscuring important information contained in the body of the report. The cathode was a 612 M type cathode purchased from Spectra-Mat. Section II describes the handling and installation of the cathode. Section III is a narrative of the activation based on information located in the Control Room Log Book supplemented with time plots of pertinent operating parameters. Activation of the cathode was performed in accordance with the procedure listed in Appendix A. The following sections provide more details on the total pressure and constituent partial pressures in the vacuum vessel, cathode heater power/filament current, and cathode temperature

  10. Hybrid microwave oscillators with a virtual cathode

    International Nuclear Information System (INIS)

    A review is given of the developments and theoretical investigations of a fundamentally new class of microwave devices, namely, hybrid microwave oscillators with a virtual cathode, which combine the useful properties of virtual cathodes with the advantages of those traditional microwave oscillators that operate with subcritical-current beams and have a high efficiency in generating ultrarelativistic electron beams. Among such devices are the following: a hybrid diffractional microwave oscillator with a virtual cathode, a hybrid gyro-device with a virtual cathode, a hybrid beam-plasma vircator, a hybrid gyrocon with a virtual cathode, a hybrid Cherenkov oscillator with a virtual cathode, a hybrid microwave oscillator of the 'vircator + traveling-wave tube' type, an original two-beam tube with a virtual cathode, and a klystron-like vircator

  11. Synthesis and electrochemical properties of layered structure Li[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} cathode material

    Energy Technology Data Exchange (ETDEWEB)

    Prathibha, G.; Rosaiah, P.; Reddy, B. Purusottam; Ganesh, K. Sivajee; Hussain, O. M., E-mail: hussainsvu@gmail.com [Thin Films laboratory, Department of Physics, Sri Venkateswara University, Tirupati – 517502 (India)

    2015-06-24

    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[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} from the precursors and analyze qualitatively and studied the electrochemical properties. The XRD spectrum exhibited predominant (003) orientation at 2θ =18.39{sup o} 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{sup −1} with good cyclic stability was observed for the prepared sample in the potential range 0.0 −1.0V in aqueous medium.

  12. Application of a mixed metal oxide catalyst to a metallic substrate

    Science.gov (United States)

    Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

    2009-01-01

    A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

  13. High-performance lanthanum-ferrite-based cathode for SOFC

    DEFF Research Database (Denmark)

    Wang, W.G.; Mogensen, Mogens Bjerg

    2005-01-01

    (La0.6Sr0.4)(1-x)Co0.2Fe0.8O3/Ce0.9Gd0.1O3 (LSCF/CGO) composite cathodes were investigated for SOFC application at intermediate temperature, i.e., 500-700 degreesC. The LSCF/CGO cathodes have been studied on three types of tape-casted electrolyte substrates including CGO electrolyte, Yttrium......-stabilized Zirconia (YSZ) electrolyte coated with a thin layer of CGO, and YSZ electrolyte. Impedance spectra were measured to determine the polarization resistance (R,) and series resistance (R-s) on cells in a symmetric configuration. R-p of 0.19 Omega cm(2) at 600 degreesC and 0.026 Omega cm(2) at 700 degrees......C were obtained using LSCF/CGO cathode on CGO electrolyte. On the YSZ electrolyte with thin layer CGO coating, R-p of 0.6 Omega cm(2) at 600 degreesC and 0.12 Omega cm(2) at 700 degreesC were obtained. On the YSZ electrolyte directly, R-p of 1.0 Omega cm(2) at 600 degreesC and 0.13 Omega cm(2) at 700...

  14. Foundation Flash Catalyst

    CERN Document Server

    Goralski, Greg

    2010-01-01

    This book offers an introduction to Flash Catalyst for designers with intermediate to advanced skills. It discusses where Catalyst sits within the production process and how it communicates with other programs. It covers all of the features of the Flash Catalyst workspace, teaching you how to create designs from scratch, how to build application designs and add functionality, and how to master the Catalyst/Flex workflow. * Introduces Flash Catalyst * Focuses on production process * Covers the interrelation between Flash Catalyst and Photoshop/Illustrator/Flex/Flash What you'll learn Starting f

  15. Research on the effect of cathode plasma expansion on x-band relativistic backward wave oscillator using moving-boundary conformal PIC method

    Science.gov (United States)

    Chen, Zaigao; Wang, Jianguo; Wang, Yue

    2016-09-01

    The cathode plasma expansion has been widely investigated and is recognized as impedance collapse in a relativistic backward wave oscillator (RBWO). However, the process of formation and expansion of cathode plasma is very complicated, and the thickness of plasma is only several millimeters, so the simulation of cathode plasma requires high temporal and spatial resolutions. Only the scaled-down diode model and the thin gas layer model are considered in the previous hybrid simulation, and there are few numerical studies on the effect of cathode plasma expansion on the RBWO. In this paper, the moving-boundary conformal particle-in-cell method is proposed; the cathode plasma front is treated in this novel method as the actual cathode surface, and the explosive electron emission boundary moves as the expansion of cathode plasma. Moreover, in order to accurately simulate the electromagnetic field near the cathode surface, the conformal finite-difference time-domain method based on the enlarged cell technique is adopted. The numerical simulation indicates that the diode voltage decreases and the beam current increases as cathode plasma expands; when the cathode plasma velocity is 10 cm/μs, the pulse duration of the generated microwave decreases from 30 ns to 10 ns, the working frequency decreases from 9.83 GHz to 9.64 GHz, and the output power decreases 30% in the course of cathode plasma expansion.

  16. The Effect of Humidity and Oxygen Partial Pressure on LSM–YSZ Cathode

    DEFF Research Database (Denmark)

    Knöfel, Christina; Chen, Ming; Mogensen, Mogens Bjerg

    2011-01-01

    Two series of anode supported solid oxide fuel cells (SOFC) were prepared, one with a composite cathode layer of lanthanum strontium manganite (LSM) and yttria stabilized zirconia (YSZ) on top and the other further has a LSM current collector layer on top. The fuel cells were heat treated at 1...... of manganese concentration and strontium enrichment on the surface of the materials. Formation of monoclinic zirconia and zirconate phases was also observed. These results give a closer insight into possible degradation mechanisms of SOFC composite cathode materials in dependence of humidity and oxygen partial...

  17. Composite Cathodes for Dual-Rate Li-Ion Batteries

    Science.gov (United States)

    Whitacre, Jay; West, William; Bugga, Ratnakumar

    2008-01-01

    Composite-material cathodes that enable Li-ion electrochemical cells and batteries to function at both high energy densities and high discharge rates are undergoing development. Until now, using commercially available cathode materials, it has been possible to construct cells that have either capability for high-rate discharge or capability to store energy at average or high density, but not both capabilities. However, both capabilities are needed in robotic, standby-power, and other applications that involve duty cycles that include long-duration, low-power portions and short-duration, high-power portions. The electrochemically active ingredients of the present developmental composite cathode materials are: carbon-coated LiFePO4, which has a specific charge capacity of about 160 mA h/g and has been used as a high-discharge-rate cathode material and Li[Li(0.17)Mn(0.58)Ni(0.25)]O2, which has a specific charge capacity of about 240 mA h/g and has been used as a high-energy-density cathode material. In preparation for fabricating the composite material cathode described, these electrochemically active ingredients are incorporated into two sub-composites: a mixture comprising 10 weight percent of poly(vinylidine fluoride); 10 weight percent of carbon and 80 weight percent of carbon coated LiFePO4; and, a mixture comprising 10 weight percent of PVDF, and 80 weight percent of Li[Li(0.17)Mn(0.58)Ni(0.25)]O2. In the fabrication process, these mixtures are spray-deposited onto an aluminum current collector. Electrochemical tests performed thus far have shown that better charge/discharge performance is obtained when either 1) each mixture is sprayed on a separate area of the current collector or (2) the mixtures are deposited sequentially (in contradistinction to simultaneously) on the same current-collector area so that the resulting composite cathode material consists of two different sub-composite layers.

  18. Highly redox-resistant solid oxide fuel cell anode materials based on La-doped SrTiO3 by catalyst impregnation strategy

    Science.gov (United States)

    Shen, X.; Sasaki, K.

    2016-07-01

    An anode backbone using 40 wt% (ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 (SSZ)-Sr0.9La0.1TiO3 (SLT) cermet was prepared for SSZ electrolyte-supported SOFC single cells. 15 mgcm-2 Ce0.9Gd0.1O2 (GDC) was impregnated to totally cover the SSZ-SLT anode backbone surface acting as a catalyst, and the cell voltage achieved 0.865 V at 200 mAcm-2 using (La0.75Sr0.25)0.98MnO3 (LSM)-SSZ cathode in 3%-humidified hydrogen fuel at 800 °C. Cell performance was substantially improved from 0.865 V to >0.97 V when 0.03 mgcm-2 Pd or Ni was further incorporated as a secondary catalyst into the anode layer. 50 redox cycles were performed to investigate redox stability of this high performance anode. It was found that even after the 50 redox cycle long-term degradation test, cell voltage at 200 mAcm-2 was retained around 0.94 V, higher than the cell performance using the conventional Ni-SSZ cermet anode. The catalytically-active reaction sites at ceria-Pd or ceria-Ni may account for the excellent performance, and the extremely low metal catalyst concentration prevent serious metal aggregation in achieving excellent redox stability.

  19. Titanium Dioxide as a Cathode Material in a Dry Cell

    Directory of Open Access Journals (Sweden)

    Duncan ALOKO

    2007-09-01

    Full Text Available 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 anions solution enhances greater electric surface charge. Thus, sulphate ion is having the best result as compared to other anions because of its highest electric charge and adsorption at 1M concentration of solution. This is in agreement with the relative position of ions in the electrochemical series in the decreasing order of electro- negativity as well as in the increasing order of preference for discharge.

  20. Pt–Au/C cathode with enhanced oxygen-reduction activity in PEFCs

    Indian Academy of Sciences (India)

    G Selvarani; S Vinod Selvaganesh; P Sridhar; S Pitchumani; A K Shukla

    2011-04-01

    Carbon-supported Pt–Au (Pt–Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt–Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt–Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt–Au/C catalysts, (3:1) Pt–Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt–Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0.6 V with (3:1) Pt–Au/C cathode delivers a maximum power-density of 0.65 W/cm2 in relation to 0.53 W/cm2 delivered by the PEFC with pristine carbon-supported Pt cathode.