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Sample records for solid electrolyte interface

  1. Electrolyte for batteries with regenerative solid electrolyte interface

    Xiao, Jie; Lu, Dongping; Shao, Yuyan; Bennett, Wendy D.; Graff, Gordon L.; Liu, Jun; Zhang, Ji-Guang

    2017-08-01

    An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

  2. Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

    Lu, Dongping; Tao, Jinhui; Yan, Pengfei; Henderson, Wesley A.; Li, Qiuyan; Shao, Yuyan; Helm, Monte L.; Borodin, Oleg; Graff, Gordon L.; Polzin, Bryant; Wang, Chong-Min; Engelhard, Mark; Zhang, Ji-Guang; De Yoreo, James J.; Liu, Jun; Xiao, Jie

    2017-02-10

    Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, in which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.

  3. Local Structure and Ionic Conduction at Interfaces of Electrode and Solid Electrolytes

    Yamada, Hirotsohi; Oga, Yusuke; Saruwatari, Isamu; Moriguchi, Isamu

    2012-01-01

    All solid state batteries are attracting interests as next generation energy storage devices. However, little is known on interfaces between active materials and solid electrolytes, which may affect performance of the devices. In this study, interfacial phenomena between electrodes and solid electrolytes of all solid state batteries were investigated by using nano-composites of Li 2SiO 3-TiO 2, Li 2SiO 3-LiTiO 2, and Li 2SiO 3-FePO 4. Studies on ionic conductivity of these composites revealed...

  4. Solid electrolytes

    Abraham, Kuzhikalail M.; Alamgir, Mohamed

    1993-06-15

    This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

  5. Point Electrode Studies of the Solid Electrolyte-Electrode Interface

    Jacobsen, Torben

    the equivalent capacity, $C^{1/\\alpha}$, plotted against the contact area during an experimental period of 2 weeks. The contact area is calculated from the electrolyte resistance as $A=1/(4\\pi(\\sigma R_{YSZ})^2)$. After the electrode has been allowed to touch the electrolyte an increasing capacity proportional......$C in air. The different perturbations are indicated on the graph by numbers. 1-2\\hfill\\parbox[t]{7.3cm}{Thermal cycle at equilibrium. Determination of activation energies.} 3-4\\hfill\\parbox[t]{7.3cm}{ Potential step to -0.150\\,V for 5 hours. Activation.} 5-6\\hfill\\parbox[t]{7.3cm}{ Potential staircase 0...... $\\rightarrow$ -0.150 $\\rightarrow$ 0.050$\\rightarrow$ -0.150 0V. Potential dependence of parameters.} 6-7\\hfill\\parbox[t]{7.3cm}{ Potential step to 0.050\\,V for 4 hours. Activation.} 8-9\\hfill\\parbox[t]{7.3cm}{ As 5-6.} 9-10\\hfill\\parbox[t]{7.3cm}{Thermal cycle at -0.150\\,V. Activation energies.} 11-12\\hfill...

  6. Weighted-density functional approach for the solid-liquid interfaces in electrolytes

    Cherepanova, T.A.; Stekolnikov, A.V.

    1991-09-01

    A weighted-density functional method is proposed to describe the atomic structure of the crystal-melt interface in electrolytes based on a charged-hard-sphere model of salt. The contribution of long-range Coulomb interaction is taken into account in the field formulation: the electrostatic field potential is determined from the Poisson equation. The ion density profiles and crystalline order parameter at the crystal-melt interface in the 1:1 symmetric electrolytes are calculated. The structurization of liquid near the solid surface is described. The results are compared to those for the neutral hard sphere system. The impurity distributions of extremely small concentrations are calculated both for the neutral and charged hard sphere systems. (author). 24 refs, 6 figs, 1 tab

  7. Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries

    Hayashi, Akitoshi, E-mail: hayashi@chem.osakafu-u.ac.jp [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka (Japan); Sakuda, Atsushi [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka (Japan); Department of Energy and Environment, Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka (Japan); Tatsumisago, Masahiro [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka (Japan)

    2016-07-15

    All-solid-state batteries with inorganic solid electrolytes (SEs) are recognized as an ultimate goal of rechargeable batteries because of their high safety, versatile geometry, and good cycle life. Compared with thin-film batteries, increasing the reversible capacity of bulk-type all-solid-state batteries using electrode active material particles is difficult because contact areas at solid–solid interfaces between the electrode and electrolyte particles are limited. Sulfide SEs have several advantages of high conductivity, wide electrochemical window, and appropriate mechanical properties, such as formability, processability, and elastic modulus. Sulfide electrolyte with Li{sub 7}P{sub 3}S{sub 11} crystal has a high Li{sup +} ion conductivity of 1.7 × 10{sup −2} S cm{sup −1} at 25°C. It is far beyond the Li{sup +} ion conductivity of conventional organic liquid electrolytes. The Na{sup +} ion conductivity of 7.4 × 10{sup −4} S cm{sup −1} is achieved for Na{sub 3.06}P{sub 0.94}Si{sub 0.06}S{sub 4} with cubic structure. Moreover, formation of favorable solid–solid interfaces between electrode and electrolyte is important for realizing solid-state batteries. Sulfide electrolytes have better formability than oxide electrolytes. Consequently, a dense electrolyte separator and closely attached interfaces with active material particles are achieved via “room-temperature sintering” of sulfides merely by cold pressing without heat treatment. Elastic moduli for sulfide electrolytes are smaller than that of oxide electrolytes, and Na{sub 2}S–P{sub 2}S{sub 5} glass electrolytes have smaller Young’s modulus than Li{sub 2}S–P{sub 2}S{sub 5} electrolytes. Cross-sectional SEM observations for a positive electrode layer reveal that sulfide electrolyte coating on active material particles increases interface areas even with a minimum volume of electrolyte, indicating that the energy density of bulk-type solid-state batteries is enhanced. Both surface coating

  8. Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

    Yu, C.; Ganapathy, S.; van Eck, Ernst R H; Wang, H.; Basak, S.; Li, Z.; Wagemaker, M.

    2017-01-01

    Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte

  9. Facilely solving cathode/electrolyte interfacial issue for high-voltage lithium ion batteries by constructing an effective solid electrolyte interface film

    Xu, Jingjing; Xia, Qingbo; Chen, Fangyuan; Liu, Tao; Li, Li; Cheng, Xueyuan; Lu, Wei; Wu, Xiaodong

    2016-01-01

    The cathode/electrolyte interface stability is the key factor for the cyclic performance and the safety performance of lithium ion batteries. Suppression of consuming key elements in the electrode materials is essential in this concern. In this purpose, we investigate a facile strategy to solve interfacial issue for high-voltage lithium ion batteries by adding an oxidable fluorinated phosphate, Bis(2,2,2-trifluoroethyl) Phosphite (BTFEP), as a sacrificial additive in electrolyte. We demonstrate that BTFEP additive could be oxidized at slightly above 4.28 V which is a relatively lower voltage than that of solvents, and the oxidative products facilitate in-situ forming a stable solid electrolyte interphase (SEI) film on the cathode surface. The results manifest the SEI film validly restrains the generation of HF and the interfacial side reaction between high-voltage charged LiNi 0.5 Mn 1.5 O 4 (LNMO) and electrolyte, hence, the dissolution of Mn and Ni is effectively suppressed. Finally, the cyclic performance of LNMO after 200 cycles was remarkably improved from 68.4% in blank electrolyte to 95% in 1 wt% BTFEP-adding electrolyte.

  10. Ceramic solid electrolytes

    Goodenough, John B. [Center for Materials Science and Engineering, University of Texas at Austin, Austin, TX (United States)

    1997-02-15

    Strategies for the design of ceramic solid electrolytes are reviewed. Problems associated with stoichiometric and doped compounds are compared. In the illustration of design principles, emphasis is given to oxide-ion electrolytes for use in solid-oxide fuel cells, oxygen pumps, and oxygen sensors

  11. Phenomenological theory of current-producing processes at the solid oxide electrolyte/gas electrode interface: steady-state polarization of fuel-cell electrodes

    Murygin, I.V.; Chebotin, V.N.

    1979-01-01

    The polarization of fuel-cell electrodes (mixtures CO + CO 2 and H 2 + H 2 O) in systems with solid oxide electrolytes is discussed. The theory is based upon a process model where the electrode reaction zone can spread along the line of three-phase contact by diffusion of reaction partners and products across the electrolyte/electrode and electrolyte/gas interface

  12. Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

    Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

    2017-04-15

    We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

  13. Beyond the continuum: how molecular solvent structure affects electrostatics and hydrodynamics at solid-electrolyte interfaces.

    Bonthuis, Douwe Jan; Netz, Roland R

    2013-10-03

    Standard continuum theory fails to predict several key experimental results of electrostatic and electrokinetic measurements at aqueous electrolyte interfaces. In order to extend the continuum theory to include the effects of molecular solvent structure, we generalize the equations for electrokinetic transport to incorporate a space dependent dielectric profile, viscosity profile, and non-electrostatic interaction potential. All necessary profiles are extracted from atomistic molecular dynamics (MD) simulations. We show that the MD results for the ion-specific distribution of counterions at charged hydrophilic and hydrophobic interfaces are accurately reproduced using the dielectric profile of pure water and a non-electrostatic repulsion in an extended Poisson-Boltzmann equation. The distributions of Na(+) at both surface types and Cl(-) at hydrophilic surfaces can be modeled using linear dielectric response theory, whereas for Cl(-) at hydrophobic surfaces it is necessary to apply nonlinear response theory. The extended Poisson-Boltzmann equation reproduces the experimental values of the double-layer capacitance for many different carbon-based surfaces. In conjunction with a generalized hydrodynamic theory that accounts for a space dependent viscosity, the model captures the experimentally observed saturation of the electrokinetic mobility as a function of the bare surface charge density and the so-called anomalous double-layer conductivity. The two-scale approach employed here-MD simulations and continuum theory-constitutes a successful modeling scheme, providing basic insight into the molecular origins of the static and kinetic properties of charged surfaces, and allowing quantitative modeling at low computational cost.

  14. Solid electrolyte fuel cells

    Isaacs, H. S.

    Progress in the development of functioning solid electrolyte fuel cells is summarized. The solid electrolyte cells perform at 1000 C, a temperature elevated enough to indicate high efficiencies are available, especially if the cell is combined with a steam generator/turbine system. The system is noted to be sulfur tolerant, so coal containing significant amounts of sulfur is expected to yield satisfactory performances with low parasitic losses for gasification and purification. Solid oxide systems are electrically reversible, and are usable in both fuel cell and electrolysis modes. Employing zirconium and yttrium in the electrolyte provides component stability with time, a feature not present with other fuel cells. The chemical reactions producing the cell current are reviewed, along with materials choices for the cathodes, anodes, and interconnections.

  15. Study of inhomogeneous solid adlayers at electrolyte-solid interfaces using differential reflectance spectroscopy. Progress report, July 1, 1977--February 28, 1978

    Sari, S.O.

    1978-03-01

    Differential reflectance spectroscopy has been used to study interactions at liquid-solid and air-solid interfaces. The aim is to examine a number of properties of adsorbed solid and molecular interlayers formed at such boundaries. Differential optical techniques have not previously been used to a large degree to investigate details of interfacial properties. However, in conjunction with x-ray and electron analysis these approaches are important for examining both electronic structure and adsorption-adhesion mechanics of surface coverings even if these are only a few atomic diameters in thickness. Such layers are induced in experiments by electronic circuitry devised to add or subtract controlled amounts of adlayer through reactions at electrolyte-solid interfaces. The purpose is to supply new information of a basic nature concerning interfacial properties. This can be important since crystal phases of some materials exist only in thin surface coverings. Thus, a connection of this work may well be important to new thin-layer technology. Moreover, an important relation seems well established to problems in solar energy. It is known, for example, that interfacial layers modify gas evolution at some electrolyte-oxide boundaries and thus their study is closely relevant to improvement of some new fuel production schemes

  16. Solid polymer electrolytes

    Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

    1995-01-01

    This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

  17. Bubble-Sheet-Like Interface Design with an Ultrastable Solid Electrolyte Layer for High-Performance Dual-Ion Batteries.

    Qin, Panpan; Wang, Meng; Li, Na; Zhu, Haili; Ding, Xuan; Tang, Yongbing

    2017-05-01

    In this work, a bubble-sheet-like hollow interface design on Al foil anode to improve the cycling stability and rate performance of aluminum anode based dual-ion battery is reported, in which, a carbon-coated hollow aluminum anode is used as both anode materials and current collector. This anode structure can guide the alloying position inside the hollow nanospheres, and also confine the alloy sizes within the hollow nanospheres, resulting in significantly restricted volumetric expansion and ultrastable solid electrolyte interface (SEI). As a result, the battery demonstrates an excellent long-term cycling stability within 1500 cycles with ≈99% capacity retention at 2 C. Moreover, this cell displays an energy density of 169 Wh kg -1 even at high power density of 2113 W kg -1 (10 C, charge and discharge within 6 min), which is much higher than most of conventional lithium ion batteries. The interfacial engineering strategy shown in this work to stabilize SEI layer and control the alloy forming position could be generalized to promote the research development of metal anodes based battery systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Solid state electrolyte systems

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R. [Pacific Northwest Lab., Richland, WA (United States)] [and others

    1997-12-01

    Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

  19. Asymmetric diffusion of Zr, Sc and Ce, Gd at the interface between zirconia electrolyte and ceria interlayer for solid oxide fuel cells

    Liang, Bo, E-mail: Liangbo@gdut.edu.cn; Tao, Tao; Zhang, Silong; Huang, Yongan; Cai, Zhihong; Lu, Shenguo, E-mail: sglu@gdut.edu.cn

    2016-09-15

    The microstructures of cathode interlayer and elemental diffusion behaviors across the interfacial region (electrolyte/interlayer) have been characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and scanning TEM combined with energy dispersive X-ray spectroscopy (STEM-EDS). A densified film about 100 nm is locally formed at the interface of electrolyte/interlayer as the interlayer using dip-coating method and being sintered at 1200 °C. It is observed that the compositional distribution curves across the interface are asymmetric. More amount of the Zr, Sc component is detected in gadolinium-doped ceria (GDC) than that of the Ce, Gd component is detected in scandia-stabilized-zirconia (SSZ). XRD and EDS results show that the densified layer might consist of (Zr, Ce)O{sub 2}-based solid solution. The high open circuit voltage of the cell is related to the dense structure of electrolyte, while the increased activation energy in overpotential resistance is attributed to the porous structure of interlayer as well as the high resistance phases locally formed at its interface. - Highlights: • The (Ce−Zr)O{sub 2} based solid solution was locally formed at 1200 °C. • More Zr, Sc elements were detected in GDC than Ce, Gd elements in SSZ. • Zirconia nanodomain was embedded in GDC beside grain boundary. • High OCVs were achieved due to the highly dense electrolyte layer.

  20. Electrolytic charge inversion at the liquid-solid interface in a nanopore in a doped semiconductor membrane

    Gracheva, Maria E [Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Leburton, Jean-Pierre [Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)

    2007-04-11

    The electrostatics of a nanopore in a doped semiconductor membrane immersed in an electrolyte is studied with a numerical model. Unlike dielectric membranes that always attract excess positive ion charges at the electrolyte/membrane interface whenever a negative surface charge is present, semiconductor membranes exhibit more versatility in controlling the double layer at the membrane surface. The presence of dopant charge in the semiconductor membrane, the shape of the nanopore and the negative surface charge resulting from the pore fabrication process have competing influences on the double layer formation. The inversion of the electrolyte surface charge from negative to positive is observed for n-Si membranes as a function of the membrane surface charge density, while no such inversion occurs for dielectric and p-Si membranes.

  1. A structural study of solid electrolyte interface on negative electrode of lithium-Ion battery by electron microscopy.

    Matsushita, Tadashi; Watanabe, Jiro; Nakao, Tatsuya; Yamashita, Seiichi

    2014-11-01

    For the last decades, the performance of the lithium-ion battery (LIB) has been significantly improved and its applications have been expanding rapidly. However, its performance has yet to be enhanced.In the lithium-ion battery development, it is important to elucidate the electrode structure change in detail during the charge and discharge cycling. In particular, solid electrolyte interface (SEI) formed by decomposition of the electrolytes on the graphite negative electrode surface should play an important role for battery properties. Therefore, it is essential to control the structure and composition of SEI to improve the battery performance. Here, we conducted a scanning electron microscope (SEM) and transmission electron microscope (TEM) study to elucidate the structures of the SEI during the charge and discharge process using LiNi1/3Co1/3Mn1/3O2 [1] cathode and graphite anode. [2] Since SEI is a lithium-containing compound with high activity, it was observed without being exposed to the atmosphere. The electrodes including SEI were sampled after dismantling batteries with cutoff voltages of 3V and 4.2V for the charge process and 3V for the discharge process. Fig.1 shows SEM images of the graphite electrode surface during the charge and discharge process. The change of the SEI structure during the process was clearly observed. Further, TEM images showed that the SEI grew thicker during the charge process and becomes thinner when discharged. These results with regard to the reversible SEI structure could give a new insight for the battery development.jmicro;63/suppl_1/i21/DFU056F1F1DFU056F1Fig. 1.SEM images of the graphite electrode surface:(a) before charge process;(b) with charge-cutoff voltage of 3.0V; (c) with charge-cutoff voltage of 4.2V; (d) with discharge-cutoff voltage of 3.0V. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  2. Lithium-ion transport in inorganic solid state electrolyte

    Gao Jian; Li Hong; Zhao Yu-Sheng; Shi Si-Qi

    2016-01-01

    An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and designing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell (to convey ions while isolate electrons), and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state electrolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes. (topical review)

  3. Solid polymer electrolyte lithium batteries

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  4. Tailoring the electrode-electrolyte interface of Solid Oxide Fuel Cells (SOFC) by laser micro-patterning to improve their electrochemical performance

    Cebollero, J. A.; Lahoz, R.; Laguna-Bercero, M. A.; Larrea, A.

    2017-08-01

    Cathode activation polarisation is one of the main contributions to the losses of a Solid Oxide Fuel Cell. To reduce this loss we use a pulsed laser to modify the surface of yttria stabilized zirconia (YSZ) electrolytes to make a corrugated micro-patterning in the mesoscale. The beam of the laser source, 5 ns pulse width and emitting at λ = 532 nm (green region), is computer-controlled to engrave the selected micro-pattern on the electrolyte surface. Several laser scanning procedures and geometries have been tested. Finally, we engrave a square array with 28 μm of lattice parameter and 7 μm in depth on YSZ plates. With these plates we prepare LSM-YSZ/YSZ/LSM-YSZ symmetrical cells (LSM: La1-xSrxMnO3) and determine their activation polarisation by Electrochemical Impedance Spectroscopy (EIS). To get good electrode-electrolyte contact after sintering it is necessary to use pressure-assisted sintering with low loads (about 5 kPa), which do not modify the electrode microstructure. The decrease in polarisation with respect to an unprocessed cell is about 30%. EIS analysis confirms that the reason for this decrease is an improvement in the activation processes at the electrode-electrolyte interface.

  5. 3D-Printing Electrolytes for Solid-State Batteries.

    McOwen, Dennis W; Xu, Shaomao; Gong, Yunhui; Wen, Yang; Godbey, Griffin L; Gritton, Jack E; Hamann, Tanner R; Dai, Jiaqi; Hitz, Gregory T; Hu, Liangbing; Wachsman, Eric D

    2018-05-01

    Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li 7 La 3 Zr 2 O 12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Solid electrolytes general principles, characterization, materials, applications

    Hagenmuller, Paul

    1978-01-01

    Solid Electrolytes: General Principles, Characterization, Materials, Applications presents specific theories and experimental methods in the field of superionic conductors. It discusses that high ionic conductivity in solids requires specific structural and energetic conditions. It addresses the problems involved in the study and use of solid electrolytes. Some of the topics covered in the book are the introduction to the theory of solid electrolytes; macroscopic evidence for liquid nature; structural models; kinetic models; crystal structures and fast ionic conduction; interstitial motion in

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

    Knibbe, Ruth; Hjelm, Johan; Menon, Mohan

    2010-01-01

    Electron microscopy characterization across the cathode–electrolyte interface of two different types of intermediate temperature solid oxide fuel cells (IT-SOFC) is performed to understand the origin of the cell performance disparity. One IT-SOFC cell had a sprayed-cosintered Ce0.90Gd0.01O1.95 (CGO...

  8. Estimation of current constriction losses via 3D tomography reconstructions in electrochemical devices: a case study of a solid oxide cell electrode/electrolyte interface

    Nielsen, Jimmi; Jørgensen, Peter Stanley

    2017-01-01

    In the present study, the methodology for accurate estimations of the current constriction resistance in solid state electrochemical devices via 3D tomography reconstructions is developed. The methodology is used to determine the current constriction resistances at the Ni:YSZ anode/YSZ electrolyte...... of the electrolyte thickness. The obtained results on current constriction resistances from numerical calculations on a 3D reconstruction of a Ni:YSZ anode/YSZ electrolyte assembly is compared with existing models with analytical expressions. The comparison shows, that the assumptions of existing models are by far...

  9. Charge regulation at semiconductor-electrolyte interfaces.

    Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

    2015-07-01

    The interface between a semiconductor material and an electrolyte solution has interesting and complex electrostatic properties. Its behavior will depend on the density of mobile charge carriers that are present in both phases as well as on the surface chemistry at the interface through local charge regulation. The latter is driven by chemical equilibria involving the immobile surface groups and the potential determining ions in the electrolyte solution. All these lead to an electrostatic potential distribution that propagate such that the electrolyte and the semiconductor are dependent on each other. Hence, any variation in the charge density in one phase will lead to a response in the other. This has significant implications on the physical properties of single semiconductor-electrolyte interfaces and on the electrostatic interactions between semiconductor particles suspended in electrolyte solutions. The present paper expands on our previous publication (Fleharty et al., 2014) and offers new results on the electrostatics of single semiconductor interfaces as well as on the interaction of charged semiconductor colloids suspended in electrolyte solution. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Comparative Study on the Solid Electrolyte Interface Formation by the Reduction of Alkyl Carbonates in Lithium ion Battery

    Haregewoin, Atetegeb Meazah; Leggesse, Ermias Girma; Jiang, Jyh-Chiang; Wang, Fu-Ming; Hwang, Bing-Joe; Lin, Shawn D.

    2014-01-01

    Mixed alkyl carbonates are widely used as solvent for a various lithium-ion battery applications. Understanding the behavior of each solvent in the mixed system is crucial for controlling the electrolyte composition. In this paper, we report a systematic electrochemical and spectroscopic comparison of the reduction of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC) when used as single (PC), binary (EC/PC, EC/DEC), and ternary (EC/PC/DEC) solvent systems. The reduction products are identified based on Fourier transform infrared spectroscopy (FTIR) after employing linear sweep voltammetry to certain potential regions and their possible formation mechanisms are discussed. FTIR analyses revealed that the reduction of EC and PC was not considerably influenced by the presence of other alkyl carbonates. However, DEC exhibited a different reduction product when used in EC/DEC and EC/PC/DEC solvent systems. The reduction of EC occurred before that of PC and DEC and produced a passivating surface film that prevented carbon exfoliation caused by PC. Battery performance test, cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscope is employed to study the surface films formed. The binary EC/DEC solvent system demonstrated more favorable performance, smaller impedance, and higher Li + ion diffusivity than did the other solvent systems used in this study

  11. Solid composite electrolytes for lithium batteries

    Kumar, Binod; Scanlon, Jr., Lawrence G.

    2000-01-01

    Solid composite electrolytes are provided for use in lithium batteries which exhibit moderate to high ionic conductivity at ambient temperatures and low activation energies. In one embodiment, a ceramic-ceramic composite electrolyte is provided containing lithium nitride and lithium phosphate. The ceramic-ceramic composite is also preferably annealed and exhibits an activation energy of about 0.1 eV.

  12. Response behaviour of oxygen sensing solid electrolytes

    Winnubst, Aloysius J.A.; Scharenborg, A.H.A.; Burggraaf, A.J.

    1985-01-01

    The response time (t r) after a step change in oxygen partial pressure was investigated for some solid electrolytes used in Nernst type oxygen sensors. The electrolyte as well as the (porous) electrode material affect the value oft r. Stabilized Bi2O3 materials exhibit slower response rates (largert

  13. Photoeffects of Semiconductor Electrolyte Interfaces

    1985-03-01

    effect of FeTiO3 had very’ little effect on the overall properties "of Fe 0? single crystals. On the other hand the effect on the Fe/Ti oxide thin...transfer alloy of Fe20 3 and FeTiO3 as an interesting candidate for use as a photoelectrode. a-iron oxide and iron titanate crystallize’in essentially...the same rhombohedral space group (RSC/R•) with similar lattice constants. Conse- quently Fe?( 3 and- FeTiO3 form a solid solution over the whole

  14. Secondary lithium solid polymer electrolyte cells

    Fix, K.A.; Sammells, A.F.

    1988-01-01

    A strategy for developing morphologically invariant lithium/solid polymer electrolyte interface is being investigated via the use of lithium intercalated electrodes. Emphasis is being placed upon the rutile material Li/sub x/WO/sub 2/ 0.1 < x < 1.0. An absence of shape change at this interface is expected to result in both long cycle life electrochemical cells and the simultaneous maintenance of small interelectrode spacing so that low IR losses can be maintained. During fabrication of cells investigated here both electrochemical and chemical lithium intercalation of WO/sub 2/ was pursued. In the case of larger WO/sub 2/ electrodes initially prepared for fully discharged state cells, electrochemical intercalation during cell charge was found to require significant time, and the reproducible achievement of complete uniform intercalation across the negative electrode became an issue. Emphasis was consequently placed upon cells fabricated using Li/sub x/WO/sub 2/ electrodes initially chemically intercalated by lithium prior to cell assembly. Previous work has demonstrated direct lithium intercalation of metal dichalcogenides using n-BuLi. Lithium activity in n-BuLi is, however, insufficient to achieve lithium intercalation of WO/sub 2//sup 4/. However, recent work has shown that WO/sub 2/ can be directly lithium intercalated upon immersion in lithium naphthalide. Li/sub x/WO/sub 2/ electrodes prepared in this work were intercalated using lithium naphthalide (0.8M) in 2MeTHF. Lithium intercalation was found to readily occur at room temperature, being initially rapid and slowing as bulk intercalation within the electrode proceeded. For electrodes intercalated in this manner, a relationship was identified between the degree of lithium intercalation and initial open-circuit potential in liquid non-aqueous electrolyte

  15. Electrolytes for solid oxide fuel cells

    Fergus, Jeffrey W.

    The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed.

  16. Electrolytes for solid oxide fuel cells

    Fergus, Jeffrey W. [Auburn University, Materials Research and Education Center, 275 Wilmore Laboratories, Auburn, AL 36849 (United States)

    2006-11-08

    The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed. (author)

  17. Solid polymer electrolyte from phosphorylated chitosan

    Fauzi, Iqbal, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Inorganic and Physical Chemistry Research Groups, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

    2014-03-24

    Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

  18. Impedance spectroscopy of ceramic solid electrolytes

    Muccillo, R.; Cosentino, I.C.; Florio, D.Z. de; Franca, Y.V.

    1996-01-01

    The Impedance Spectroscopy (IS) technique has been used to the study of Th O 2 :Y 2 O 3 , Zr O 2 :La 2 O 3 and Zr O 2 :Y 2 O 3 solid electrolytes. The results show that solid solution has been attained, grain boundaries act as oxygen-ion blockers, and the importance of the IS technique to study phase transformation in ceramics. (author)

  19. How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

    Suo, Liumin; Oh, Dahyun; Lin, Yuxiao; Zhuo, Zengqing; Borodin, Oleg; Gao, Tao; Wang, Fei; Kushima, Akihiro; Wang, Ziqiang; Kim, Ho-Cheol; Qi, Yue; Yang, Wanli; Pan, Feng; Li, Ju; Xu, Kang; Wang, Chunsheng

    2017-12-27

    Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

  20. Modeling the electrified solid-liquid interface

    Rossmeisl, Jan; Skulason, Egill; Björketun, Mårten

    2008-01-01

    function can be related directly to the potential scale of the normal hydrogen electrode. We also show how finite-size effects in common periodic slab-type calculations can be avoided in calculations of activation energies and reaction energies for charge transfer reactions, where we use the Heyrovsky......A detailed atomistic model based on density functional theory calculations is presented of the charged solid-electrolyte interface. Having protons solvated in a water bilayer outside a Pt(111) slab with excess electrons, we show how the interface capacitance is well described and how the work...

  1. Lithium-ion batteries having conformal solid electrolyte layers

    Kim, Gi-Heon; Jung, Yoon Seok

    2014-05-27

    Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

  2. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

    Lu, Yingying

    2014-08-10

    Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost-effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling at room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolyte/lithium interface and impedance analysis of the interface during different stages of cell operation. Our findings provide support for an important recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.

  3. Virus-Assembled Flexible Electrode-Electrolyte Interfaces for Enhanced Polymer-Based Battery Applications

    Ayan Ghosh

    2012-01-01

    Full Text Available High-aspect-ratio cobalt-oxide-coated Tobacco mosaic virus (TMV- assembled polytetrafluoroethylene (PTFE nonstick surfaces were integrated with a solvent-free polymer electrolyte to create an anode-electrolyte interface for use in lithium-ion batteries. The virus-assembled PTFE surfaces consisted primarily of cobalt oxide and were readily intercalated with a low-molecular-weight poly (ethylene oxide (PEO based diblock copolymer electrolyte to produce a solid anode-electrolyte system. The resulting polymer-coated virus-based system was then peeled from the PTFE backing to produce a flexible electrode-electrolyte component. Electrochemical studies indicated the virus-structured metal-oxide PEO-based interface was stable and displayed robust charge transfer kinetics. Combined, these studies demonstrate the development of a novel solid-state electrode architecture with a unique peelable and flexible processing attribute.

  4. Sulfide-conducting solid electrolytes

    Kalinina, L.A.; Shirokova, G.I.; Murin, I.V.; Ushakova, Yu.N.; Fominykh, E.G.; Lyalina, M.Yu.

    2000-01-01

    Feasibility of sulfide transfer in phases on the basis of BaZrS 3 and MLn 2 S 4 ( M = Ca, Ba; Ln = La, Y, Tm, Nd, Sm, Pr) is considered. Solid solution regions on the basis of ternary compounds are determined. Systematic study of the phases is carried out making use of the methods of conductometry, emf in chemical concentration chains without/with transfer, potentiostatic chronoamperometry. Possible mechanism of defect formation during successive alloying of ternary sulfides by binary ones in suggested [ru

  5. Anti-perovskite solid electrolyte compositions

    Zhao, Yusheng; Daemen, Luc Louis

    2015-12-26

    Solid electrolyte antiperovskite compositions for batteries, capacitors, and other electrochemical devices have chemical formula Li.sub.3OA, Li.sub.(3-x)M.sub.x/2OA, Li.sub.(3-x)N.sub.x/3OA, or LiCOX.sub.zY.sub.(1-z), wherein M and N are divalent and trivalent metals respectively and wherein A is a halide or mixture of halides, and X and Y are halides.

  6. Preparation of thoria calcia solid electrolytes

    Muccillo, R.

    1982-01-01

    The experimental procedures for the preparation of thoria-calcia solid electrolytes are described. Cold-pressed specimens pre-sintered at 1400 0 C and sintered at 2000 0 C have been used for thermally stimulated depolarization currents measurements in the temperature range 100 K - 300 K as well as for ionic conductivity measurements in the temperature range RT - 900 K. The detection of a relaxation peak probably due to the reorientation of the Ca'' sub(Th) - V sup(..) sub(O) complex shows that solid solution has been attained. Preliminary results of electrical conductivity are also reported. (Author) [pt

  7. Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

    Andrieu, X.; Boudin, F. [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

    1996-12-31

    The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

  8. Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

    Andrieu, X; Boudin, F [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

    1997-12-31

    The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

  9. Evaluation of apatite silicates as solid oxide fuel cell electrolytes

    Marrero-Lopez, D. [Dpto. de Fisica Aplicada I, Laboratorio de Materiales y Superficies (Unidad Asociada al C.S.I.C.), Universidad de Malaga, 29071 Malaga (Spain); Dpto. de Quimica Inorganica, Universidad de La Laguna, 38200 La Laguna, Tenerife (Spain); Martin-Sedeno, M.C.; Aranda, M.A.G. [Dpto. de Quimica Inorganica, Universidad Malaga, 29071 Malaga (Spain); Pena-Martinez, J. [Dpto. de Quimica Inorganica, Universidad de La Laguna, 38200 La Laguna, Tenerife (Spain); Instituto de Energias Renovables, Parque Tecnologico, Universidad de Castilla La Mancha, 02006 Albacete (Spain); Ruiz-Morales, J.C.; Nunez, P. [Dpto. de Quimica Inorganica, Universidad de La Laguna, 38200 La Laguna, Tenerife (Spain); Ramos-Barrado, J.R. [Dpto. de Fisica Aplicada I, Laboratorio de Materiales y Superficies (Unidad Asociada al C.S.I.C.), Universidad de Malaga, 29071 Malaga (Spain)

    2010-05-01

    Apatite-type silicates have been considered as promising electrolytes for Solid Oxide Fuel Cells (SOFC); however studies on the potential use of these materials in SOFC devices have received relatively little attention. The lanthanum silicate with composition La{sub 10}Si{sub 5.5}Al{sub 0.5}O{sub 26.75} has been evaluated as electrolyte with the electrode materials commonly used in SOFC, i.e. manganite, ferrite and cobaltite as cathode materials and NiO-CGO composite, chromium-manganite and Sr{sub 2}MgMoO{sub 6} as anode materials. Chemical compatibility, area-specific resistance and fuel cell studies have been performed. X-ray powder diffraction (XRPD) analysis did not reveal any trace of reaction products between the apatite electrolyte and most of the aforementioned electrode materials. However, the area-specific polarisation resistance (ASR) of these electrodes in contact with apatite electrolyte increased significantly with the sintering temperature, indicating reactivity at the electrolyte/electrode interface. On the other hand, the ASR values are significantly improved using a ceria buffer layer between the electrolyte and electrode materials to prevent reactivity. Maximum power densities of 195 and 65 mWcm{sup -2} were obtained at 850 and 700 C, respectively in H{sub 2} fuel, using an 1 mm-thick electrolyte, a NiO-Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9} composite as anode and La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} as cathode materials. This fuel cell was tested for 100 h in 5%H{sub 2}-Ar atmosphere showing stable performance. (author)

  10. Atomistic Simulation of Interfaces in Materials of Solid State Ionics

    Ivanov-Schitz, A. K.; Mazo, G. N.

    2018-01-01

    The possibilities of describing correctly interfaces of different types in solids within a computer experiment using molecular statics simulation, molecular dynamics simulation, and quantum chemical calculations are discussed. Heterophase boundaries of various types, including grain boundaries and solid electrolyte‒solid electrolyte and ionic conductor‒electrode material interfaces, are considered. Specific microstructural features and mechanisms of the ion transport in real heterophase structures (cationic conductor‒metal anode and anionic conductor‒cathode) existing in solid state ionics devices (such as solid-state batteries and fuel cells) are discussed.

  11. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

    Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.

    2014-01-01

    of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid

  12. Modeling of semiconductor nanostructures and semiconductor-electrolyte interfaces

    Birner, Stefan

    2011-01-01

    The main objective of Part I is to give an overview of some of the methods that have been implemented into the nextnano 3 software. Examples are discussed that give insight into doping, strain and mobility. Applications of the single-band Schroedinger equation include three-dimensional superlattices, and a qubit that is manipulated by a magnetic field. Results of the multi-band k.p method are presented for HgTe-CdTe and InAs-GaSb superlattices, and for a SiGe-Si quantum cascade structure. Particular focus is put on a detailed description of the contact block reduction (CBR) method that has been developed within our research group. By means of this approach, quantum transport in the ballistic limit in one, two and three dimensions can be calculated. I provide a very detailed description of the algorithm and present several well documented examples that highlight the key points of this method. Calculating quantum transport in three dimensions is a very challenging task where computationally efficient algorithms - apart from the CBR method - are not available yet. Part II describes the methods that I have implemented into the nextnano 3 software for calculating systems that consist of a combination of semiconductor materials and liquids. These biosensors have a solid-electrolyte interface, and the charges in the solid and in the electrolyte are coupled to each other through the Poisson-Boltzmann equation. I apply this model to a silicon based protein sensor, where I solve the Schroedinger equation together with the Poisson-Boltzmann equation self-consistently, and compare theoretical results with experiment. Furthermore, I have developed a novel approach to model the charge density profiles at semiconductor-electrolyte interfaces that allows us to distinguish hydrophobic and hydrophilic interfaces. Our approach extends previous work where ion specific potentials of mean force describe the distribution of ion species at the interface. I apply this new model to recently

  13. Modeling of semiconductor nanostructures and semiconductor-electrolyte interfaces

    Birner, Stefan

    2011-11-15

    The main objective of Part I is to give an overview of some of the methods that have been implemented into the nextnano{sup 3} software. Examples are discussed that give insight into doping, strain and mobility. Applications of the single-band Schroedinger equation include three-dimensional superlattices, and a qubit that is manipulated by a magnetic field. Results of the multi-band k.p method are presented for HgTe-CdTe and InAs-GaSb superlattices, and for a SiGe-Si quantum cascade structure. Particular focus is put on a detailed description of the contact block reduction (CBR) method that has been developed within our research group. By means of this approach, quantum transport in the ballistic limit in one, two and three dimensions can be calculated. I provide a very detailed description of the algorithm and present several well documented examples that highlight the key points of this method. Calculating quantum transport in three dimensions is a very challenging task where computationally efficient algorithms - apart from the CBR method - are not available yet. Part II describes the methods that I have implemented into the nextnano{sup 3} software for calculating systems that consist of a combination of semiconductor materials and liquids. These biosensors have a solid-electrolyte interface, and the charges in the solid and in the electrolyte are coupled to each other through the Poisson-Boltzmann equation. I apply this model to a silicon based protein sensor, where I solve the Schroedinger equation together with the Poisson-Boltzmann equation self-consistently, and compare theoretical results with experiment. Furthermore, I have developed a novel approach to model the charge density profiles at semiconductor-electrolyte interfaces that allows us to distinguish hydrophobic and hydrophilic interfaces. Our approach extends previous work where ion specific potentials of mean force describe the distribution of ion species at the interface. I apply this new model

  14. Neutron scattering studies of solid electrolytes

    Shapiro, S.M.

    1976-01-01

    The role which neutron scattering can play in determining the nature of the disorder and the conducting mechanism in the solid electrolytes is discussed. First, some of the general formalism for elastic and inelastic neutron scattering is reviewed, and the quantities which can be measured are pointed out. Then the application of neutron scattering to the studies of three different problems is examined; the anion disorder in the fluorite system, the dynamical behavior in beta-alumina, and the cation diffusion in αAgI are discussed. 8 figures

  15. Study of the carbon material / electrolyte interface; Etude de l`interface materiau carbone / electrolyte

    Genies, S.; Yazami, R. [Ecole Nationale Superieure d`Electrochimie et d`Electrometallurgie, 38 - Saint-Martin-d`Heres (France); Frison, J.C. [CNET, Centre de Recherches de Lannion, 22 (France); Ledran, J. [CNET, 92 - Issy-les-Moulineaux (France)

    1996-12-31

    The aim of this work is the comparative study of the properties of the natural graphite/liquid organic electrolyte interface by impedance spectroscopy with respect to different lithium salts (LiX with X = ClO{sub 4}{sup -}, BF{sub 4}{sup -}, CF{sub 3}SO{sub 3}{sup -}, N(CF{sub 3}SO{sub 2}){sub 2}{sup -}, PF{sub 6}{sup -}). The evolution of the interface properties during the first electrochemical reduction suggests different mechanisms of formation of passivation films. A more stable, thin and homogenous film seems to develop when the LiN(CF{sub 3}SO{sub 2}){sub 2} or LiPF{sub 6} lithium salts are used. The chemical diffusion coefficient of lithium in graphite has been determined by impedance spectroscopy. (J.S.) 16 refs.

  16. Study of the carbon material / electrolyte interface; Etude de l`interface materiau carbone / electrolyte

    Genies, S; Yazami, R [Ecole Nationale Superieure d` Electrochimie et d` Electrometallurgie, 38 - Saint-Martin-d` Heres (France); Frison, J C [CNET, Centre de Recherches de Lannion, 22 (France); Ledran, J [CNET, 92 - Issy-les-Moulineaux (France)

    1997-12-31

    The aim of this work is the comparative study of the properties of the natural graphite/liquid organic electrolyte interface by impedance spectroscopy with respect to different lithium salts (LiX with X = ClO{sub 4}{sup -}, BF{sub 4}{sup -}, CF{sub 3}SO{sub 3}{sup -}, N(CF{sub 3}SO{sub 2}){sub 2}{sup -}, PF{sub 6}{sup -}). The evolution of the interface properties during the first electrochemical reduction suggests different mechanisms of formation of passivation films. A more stable, thin and homogenous film seems to develop when the LiN(CF{sub 3}SO{sub 2}){sub 2} or LiPF{sub 6} lithium salts are used. The chemical diffusion coefficient of lithium in graphite has been determined by impedance spectroscopy. (J.S.) 16 refs.

  17. Interactions between lanthanum gallate based solid electrolyte and ceria

    Hrovat, M.; Ahmad-Khanlou, A.; Samardzija, Z.; Holc, J.

    1999-10-01

    Possible interactions between La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 2.85} and Gd{sub 2}O{sub 3}-doped CeO{sub 2} (solid electrolyte and anode binding materials, respectively, for solid oxide fuel cells (SOFC)) at 1,300 C were studied with diffusion couples and fired powder mixtures. The SrLaGa{sub 3}O{sub 7} compound was detected and its formation was attributed to the diffusion of La{sub 2}O{sub 3} from La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 2.85} into Ce{sub 1{minus}x}La{sub x}O{sub 2{minus}x/2} solid solution. As the resistivity of SrLaGa{sub 3}O{sub 7} is rather high, around 1 M{center_dot}ohm at 800 C, its presence in the solid electrolyte/anode interface could significantly increase the internal resistivity of an SOFC.

  18. Physicochemistry of the plasma-electrolyte solution interface

    Chen Qiang; Saito, Kenji; Takemura, Yu-ichiro; Shirai, Hajime

    2008-01-01

    The atmospheric rf plasma discharge was successfully investigated using NaOH or HCl electrolyte solutions as a counter electrode at different pH values. The emission intensities of solution components, self bias, and electron density strongly depend on the pH value of electrolyte. An addition of ethanol to the electrolyte solutions enhanced the dehydration, which markedly promoted the emissions of solution components as well as electrons from the solution. An acidification of the solution was always observed after the plasma exposure and two coexisting mechanisms were proposed to give a reasonable interpretation. The plasma-electrolyte interface was discussed based on a model of hydrogen cycle

  19. Investigation of a nanoconfined, ceramic composite, solid polymer electrolyte

    Jayasekara, Indumini; Poyner, Mark; Teeters, Dale

    2017-01-01

    The challenges for further development of lithium rechargeable batteries are finding electrolyte materials that are safe, have mechanical and thermal stability and have sufficiently high ionic conduction. Polymer electrolytes have many of these advantages, but suffer with low ionic conduction. This study involves the use of anodic aluminum oxide (AAO) membranes having nanochannels filled with polymer electrolyte to make composite solid electrolytes having ionic conductivity several orders of magnitude higher (10 −4 Ω ‐1 cm −1 ) than non-confined polymer. SEM, ac impedance spectroscopy, temperature dependence studies, XRD, ATR- FTIR and DSC studies were done in order to characterize and understand the behavior of nanoconfined polymer electrolytes. The composite polymer electrolyte was found to be more amorphous with polymer chains aligned in the direction of the nanochannels, which is felt to promote ion conduction. The electrolyte systems, confined in nanoporous membranes, can be used as electrolytes for the fabrication of a room temperature all solid state battery.

  20. Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

    West, William; Whitacre, Jay; Lim, James

    2008-01-01

    Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

  1. Cathode solid electrolyte interface’s function originated from salt type additives in lithium ion batteries

    Kaneko, Yu; Park, Juyeon; Yokotsuji, Hokuto; Odawara, Makoto; Takase, Hironari; Ue, Makoto; Lee, Maeng-Eun

    2016-01-01

    Highlights: • Our chemical analysis determines the important functional groups of cathode’s solid electrolyte interface originated from salt type additives. • Our quantum chemical calculation reveals the redox character of the additives and their candidate chemical components of the solid electrolyte interface. • Our molecular dynamics simulation reproduces the selective lithium ion translocation and protective layer formation as the solid electrolyte interface function. - Abstract: This is the study about the cathode’s solid electrolyte interface (SEI) formation mechanism of salt type additives (STAs) and its function. To address this issue, we performed several types of chemical analysis and computer simulation techniques. In order to reveal the redox nature and oxidative decomposition dynamics, the electrolyte (EL) solution dynamics by Quantum mechanics and Molecular mechanics (QM/MM) method was applied. The estimation of SEI chemical components agrees with our chemical analyses data and other group’s reports. The molecular dynamics simulation of sub micro second sampling indicates that the SEI phase induced from STAs functions as a lithium ion selective translocation media and protective coating layer against the degradation of the solvent molecules. The results give us an insight how to design additive’s chemical structure to improve longevity of the cell in the high voltage regime.

  2. Recent advances in solid polymer electrolytes for lithium batteries

    Qingqing Zhang; Kai Liu; Fei Ding; Xingjiang Liu

    2017-01-01

    Solid polymer electrolytes are light-weight,flexible,and non-flammable and provide a feasible solution to the safety issues facing lithium-ion batteries through the replacement of organic liquid electrolytes.Substantial research efforts have been devoted to achieving the next generation of solid-state polymer lithium batteries.Herein,we provide a review of the development of solid polymer electrolytes and provide comprehensive insights into emerging developments.In particular,we discuss the different molecular structures of the solid polymer matrices,including polyether,polyester,polyacrylonitrile,and polysiloxane,and their interfacial compatibility with lithium,as well as the factors that govern the properties of the polymer electrolytes.The discussion aims to give perspective to allow the strategic design of state-of-the-art solid polymer electrolytes,and we hope it will provide clear guidance for the exploration of high-performance lithium batteries.

  3. MultiLayer solid electrolyte for lithium thin film batteries

    Lee, Se -Hee; Tracy, C. Edwin; Pitts, John Roland; Liu, Ping

    2015-07-28

    A lithium metal thin-film battery composite structure is provided that includes a combination of a thin, stable, solid electrolyte layer [18] such as Lipon, designed in use to be in contact with a lithium metal anode layer; and a rapid-deposit solid electrolyte layer [16] such as LiAlF.sub.4 in contact with the thin, stable, solid electrolyte layer [18]. Batteries made up of or containing these structures are more efficient to produce than other lithium metal batteries that use only a single solid electrolyte. They are also more resistant to stress and strain than batteries made using layers of only the stable, solid electrolyte materials. Furthermore, lithium anode batteries as disclosed herein are useful as rechargeable batteries.

  4. Solid polymer electrolyte composite membrane comprising laser micromachined porous support

    Liu, Han [Waltham, MA; LaConti, Anthony B [Lynnfield, MA; Mittelsteadt, Cortney K [Natick, MA; McCallum, Thomas J [Ashland, MA

    2011-01-11

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  5. Microstructural studies on degradation of interface between LSM–YSZ cathode and YSZ electrolyte in SOFCs

    Liu, Yi-Lin; Hagen, Anke; Barfod, Rasmus

    2009-01-01

    The changes in the cathode/electrolyte interface microstructure have been studied on anode-supported technological solid oxide fuel cells (SOFCs) that were subjected to long-term (1500 h) testing at 750 °C under high electrical loading (a current density of 0.75 A/cm2). These cells exhibit...... different cathode degradation rates depending on, among others, the composition of the cathode gas, being significantly smaller in oxygen than in air. FE-SEM and high resolution analytical TEM were applied for characterization of the interface on a submicron- and nano-scale. The interface degradation has...... to decrease further due to the more pronounced formation of insulating zirconate phases that are present locally and preferably in LSM/YSZ electrolyte contact areas. The effects of the cathode gas on the interface degradation are discussed considering the change of oxygen activity at the interface, possible...

  6. Understanding and Overcoming the Challenges Posed by Electrode/Electrolyte Interfaces in Rechargeable Magnesium Batteries

    Mizuno, Fuminori, E-mail: fuminori.mizuno@tema.toyota.com; Singh, Nikhilendra; Arthur, Timothy S.; Fanson, Paul T. [Toyota Research Institute of North America, Ann Arbor, MI (United States); Ramanathan, Mayandi [Department of Chemical and Biological Engineering, Center for Electrochemical Science and Engineering, Illinois Institute of Technology, Chicago, IL (United States); Department of Chemical Engineering, University of Washington, Seattle, WA (United States); Benmayza, Aadil; Prakash, Jai [Department of Chemical and Biological Engineering, Center for Electrochemical Science and Engineering, Illinois Institute of Technology, Chicago, IL (United States); Liu, Yi-Sheng; Glans, Per-Anders; Guo, Jinghua [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA (United States)

    2014-11-11

    Magnesium (Mg) battery technologies have attracted attention as a high energy-density storage system due to the following advantages: (1) potentially high energy-density derived from a divalent nature, (2) low-cost due to the use of an earth-abundant metal, and (3) intrinsic safety aspect attributed to non-dendritic growth of Mg. However, these notable advantages are downplayed by undesirable battery reactions and related phenomena. As a result, there are only a few working rechargeable Mg battery systems. One of the root causes for undesirable behavior is the sluggish diffusion of Mg{sup 2+} inside a host lattice. Another root cause is the interfacial reaction at the electrode/electrolyte boundary. For the cathode/electrolyte interface, Mg{sup 2+} in the electrolyte needs a solvation–desolvation process prior to diffusion inside the cathode. Apart from the solid electrolyte interface (SEI) formed on the cathode, the divalent nature of Mg should cause kinetically slower solvation–desolvation processes than that of Li-ion systems. This would result in a high charge-transfer resistance and a larger overpotential. On the contrary, for the anode/electrolyte interface, the Mg deposition and dissolution process depends on the electrolyte nature and its compatibility with Mg metal. Also, the Mg metal/electrolyte interface tends to change over time, and with operating conditions, suggesting the presence of interfacial phenomena on the Mg metal. Hence, the solvation–desolvation process of Mg has to be considered with a possible SEI. Here, we focus on the anode/electrolyte interface in a Mg battery, and discuss the next steps to improve the battery performance.

  7. New Solid Polymer Electrolytes for Improved Lithium Batteries

    Hehemann, David G.

    2002-01-01

    The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

  8. Theory of bulk and interface constant phase elements in electrode- electrolyte systems

    Liu, S.H.

    1991-01-01

    This paper summarizes the progress gained in the last few years in our understanding of bulk and interface constant-phase-angle (CPA) behavior in electrode-electrolyte systems. It is now fairly well established that the interface constant-phase element originates from the fractal nature of the interface. The complex geometry gives rise to a fractal distribution of parallel current paths, and the competition between these paths results in the fractional power law behavior of the impedance across the interface. On the other hand, the early hope of relating the CPA exponent to the fractal dimension of the interface has been shown to be unattainable. Our understanding of the bulk CPA behavior, which is most prevalent in solid electrolytes, is only tentative. It is illustrated using a simple model that, under nonlinear dynamical laws that govern the flow of ions in the electrolyte, a current in the solid can generate a fractal distribution of vacancies which tend to impede the flow. The current is forced to negotiate a complex path through the solid, and the resulting fluctuation in path length and flow rate could be a source of the CPA behavior. 32 refs., 18 figs

  9. Solidification of liquid electrolyte with imidazole polymers for quasi-solid-state dye-sensitized solar cells

    Wang Miao; Lin Yuan; Zhou Xiaowen; Xiao Xurui; Yang Lei; Feng Shujing; Li Xueping

    2008-01-01

    Quasi-solid-state electrolytes were prepared by employing the imidazole polymers to solidify the liquid electrolyte containing lithium iodide, iodine and ethylene carbonate (EC)/propylene carbonate (PC) mixed solvent. The ionic conductivity and diffusion behavior of triiodide in the quasi-solid-state electrolytes were examined in terms of the polymer content. Application of the quasi-solid-state electrolytes to the dye-sensitized solar cells, the maximum energy conversion efficiency of 7.6% (AM 1.5, 100 mW cm -2 ) was achieved. The dependence of the photovoltaic performance on the polymer content and on the different anions of the imidazole polymers was studied by electrochemical impedance spectroscopy and cyclic voltammetry. The results indicate the charge transfer behaviors occurred at nanocrystalline TiO 2 /electrolyte and Pt/electrolyte interface play an important role in influencing the photovoltaic performance of quasi-solid-state dye-sensitized solar cells

  10. Crystalline structure and microstructural characteristics of the cathode/electrolyte solid oxide half-cells

    Chiba, Rubens; Vargas, Reinaldo Azevedo; Andreoli, Marco; Santoro, Thais Aranha de Barros; Seo, Emilia Satoshi Miyamaru

    2009-01-01

    The solid oxide fuel cell (SOFC) is an electrochemical device generating of electric energy, constituted of cathode, electrolyte and anode; that together they form a unity cell. The study of the solid oxide half-cells consisting of cathode and electrolyte it is very important, in way that is the responsible interface for the reduction reaction of the oxygen. These half-cells are ceramic materials constituted of strontium-doped lanthanum manganite (LSM) for the cathode and yttria-stabilized zirconia (YSZ) for the electrolyte. In this work, two solid oxide half-cells have been manufactured, one constituted of LSM cathode thin film on YSZ electrolyte substrate (LSM - YSZ half-cell), and another constituted of LSM cathode and LSM/YSZ composite cathode thin films on YSZ electrolyte substrate (LSM - LSM/YSZ - YSZ half cell). The cathode/electrolyte solid oxide half-cells were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results have been presented with good adherence between cathode and electrolyte and, LSM and YSZ phases were identified. (author)

  11. Direct observation of ionic structure at solid-liquid interfaces

    Siretanu, Igor; Ebeling, Daniel; Andersson, Martin Peter

    2014-01-01

    The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric...... double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered...

  12. PEO nanocomposite polymer electrolyte for solid state symmetric

    Physical and electrochemical properties of polyethylene oxide (PEO)-based nanocomposite solid polymer electrolytes (NPEs) were investigated for symmetric capacitor applications. Nanosize fillers, i.e., Al2O3 and SiO2 incorporated polymer electrolyte exhibited higher ionic conductivity than those with filler-free composites ...

  13. Potential-specific structure at the hematite-electrolyte interface

    McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter; Rosso, Kevin M.

    2018-02-21

    The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe2O3) (110$\\bar{2}$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.

  14. Solid polymer composite electrolytes for PEMFC

    Zaidi, S M.J.; Mikhailenko, S D; Kaliaguine, S

    1998-07-01

    Composite electrolyte membranes for fuel cell technology were prepared from solid state proton conductors and polymer binders. The polymers were partially sulfonated and non-sulfonated polysulfone (PS), porous polyetherimide (PEI) and polymethylmethacrylate (PMMA). As proton conductors H-chabazite, tungstophosphoric acid and its Na-salt and non-stoichiometric boron phosphate were employed. All membranes prepared using sulfonated PS as a binder with sulfonation degree higher than 50% were found to be mechanically unstable. They possess however reasonably high conductivity up to 6{times}10{sup {minus}3} S/cm. Introducing the tungstophosphoric acid (TPA) into the nonsulfonated porous PS makes possible to obtain strong and flexible membranes with s=4{times}10{sup {minus}3} S/cm, while use of boron phosphate in that case results in the conductivity of about 10{sup {minus}5} S/cm. Porous PEI impregnated with aqueous solution of TPA retains its original tensile strength and exhibited the conductivity s=2{times}10{sup {minus}4} S/cm. It however fell to 3{times}10{sup {minus}5} S/cm when the binder was modified with 2% of propionic acid, which caused a decrease in polymer pore size. Incorporation of the sodium acid salt of TPA into PEI allows one to obtain a composite with reasonably good mechanical properties and a conductivity of ca 10{sup {minus}5} S/cm for membranes prepared by the cast method. Using the phase inversion technique for preparation of the membranes of the same composition makes possible to increase their conductivity up to 10{sup {minus}4} S/cm. When boron phosphate was used in lieu of TPA salt the conductivity obtained is still higher reaching 3{times}10{sup {minus}5} and 3{times}10{sup {minus}4} S/cm for membranes prepared by cast and phase inversion techniques respectively. The PMMA based membranes were mechanically stable even when a solid content reached 55wt.%. Among PMMA membranes the highest conductivity of 10{sup {minus}3} S/cm was registered for

  15. A zwitterionic gel electrolyte for efficient solid-state supercapacitors

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-01-01

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

  16. Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

    Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

    2012-10-01

    The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

  17. Surface and interface sciences of Li-ion batteries. -Research progress in electrode-electrolyte interface-

    Minato, Taketoshi; Abe, Takeshi

    2017-12-01

    The application potential of Li-ion batteries is growing as demand increases in different fields at various stages in energy systems, in addition to their conventional role as power sources for portable devices. In particular, applications in electric vehicles and renewable energy storage are increasing for Li-ion batteries. For these applications, improvements in battery performance are necessary. The Li-ion battery produces and stores electric power from the electrochemical redox reactions between the electrode materials. The interface between the electrodes and electrolyte strongly affects the battery performance because the charge transfer causing the electrode redox reaction begins at this interface. Understanding of the surface structure, electronic structure, and chemical reactions at the electrode-electrolyte interface is necessary to improve battery performance. However, the interface is located between the electrode and electrolyte materials, hindering the experimental analysis of the interface; thus, the physical properties and chemical processes have remained poorly understood until recently. Investigations of the physical properties and chemical processes at the interface have been performed using advanced surface science techniques. In this review, current knowledge and future research prospects regarding the electrode-electrolyte interface are described for the further development of Li-ion batteries.

  18. Solid electrolyte material manufacturable by polymer processing methods

    Singh, Mohit; Gur, Ilan; Eitouni, Hany Basam; Balsara, Nitash Pervez

    2012-09-18

    The present invention relates generally to electrolyte materials. According to an embodiment, the present invention provides for a solid polymer electrolyte material that is ionically conductive, mechanically robust, and can be formed into desirable shapes using conventional polymer processing methods. An exemplary polymer electrolyte material has an elastic modulus in excess of 1.times.10.sup.6 Pa at 90 degrees C. and is characterized by an ionic conductivity of at least 1.times.10.sup.-5 Scm-1 at 90 degrees C. An exemplary material can be characterized by a two domain or three domain material system. An exemplary material can include material components made of diblock polymers or triblock polymers. Many uses are contemplated for the solid polymer electrolyte materials. For example, the present invention can be applied to improve Li-based batteries by means of enabling higher energy density, better thermal and environmental stability, lower rates of self-discharge, enhanced safety, lower manufacturing costs, and novel form factors.

  19. Solid polymer electrolyte composite membrane comprising plasma etched porous support

    Liu, Han; LaConti, Anthony B.

    2010-10-05

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  20. Design and Characterisation of Solid Electrolytes for All-Solid-State Lithium Batteries

    Sveinbjörnsson, Dadi Þorsteinn

    The development of all-solid-state lithium batteries, in which the currently used liquid electrolytes are substituted for solid electrolyte materials, could lead to safer batteries offering higher energy densities and longer cycle lifetimes. Designing suitable solid electrolytes with sufficient...... chemical and electrochemical stability, high lithium ion conduction and negligible electronic conduction remains a challenge. The highly lithium ion conducting LiBH4-LiI solid solution is a promising solid electrolyte material. Solid solutions with a LiI content of 6.25%-50% were synthesised by planetary......-rich microstructures during ball milling is found to significantly influence the conductivity of the samples. The long-range diffusion of lithium ions was measured using quasi-elastic neutron scattering. The solid solutions are found to exhibit two-dimensional conduction in the hexagonal plane of the crystal structure...

  1. Low temperature solid oxide electrolytes (LT-SOE): A review

    Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

    2017-01-01

    Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

  2. In-situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries

    Zhu, Zihua; Zhou, Yufan; Yan, Pengfei; Vemuri, Venkata Rama Ses; Xu, Wu; Zhao, Rui; Wang, Xuelin; Thevuthasan, Suntharampillai; Baer, Donald R.; Wang, Chong M.

    2015-08-19

    Dynamic molecular evolution at solid/liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe/observe the solid/liquid interface under reaction conditions, which in essence appears to be similarly true for all the fields involving solid/liquid phases, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization, We use in-situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid electrode/liquid electrolyte interface for a lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to deplete the salt anion and with low concentration of Li+ ions, which essentially leads to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributes to the overpotential of the cell. This unprecedented molecular level dynamic observation at the solid electrode/liquid electrolyte interface provides vital chemical information that is needed for designing of better battery chemistry for enhanced performance, and ultimately opens new avenues for using liquid SIMS to probe molecular evolution at solid/liquid interface in general.

  3. Solid-state electrolyte for supercapacitors

    K.C., Sabin

    2016-01-01

    Renewable energy has become a primary focus for scientific community since last decade. Great interesting investigations and creative works have been carried out to develop technology for powering our society, including disrupt technology for efficient energy storage and power manage. Supercapacitors (SP) also known as electrochemical double layer capacitors uses high surface area active electrode materials and various electrolytes to achieve capacitance of several order magnitude greater tha...

  4. Graphene quantum dots as the electrolyte for solid state supercapacitors

    Zhang, Su; Li, Yutong; Song, Huaihe; Chen, Xiaohong; Zhou, Jisheng; Hong, Song; Huang, Minglu

    2016-01-01

    We propose that graphene quantum dots (GQDs) with a sufficient number of acidic oxygen-bearing functional groups such as -COOH and -OH can serve as solution- and solid- type electrolytes for supercapacitors. Moreover, we found that the ionic conductivity and ion-donating ability of the GQDs could be markedly improved by simply neutralizing their acidic functional groups by using KOH. These neutralized GQDs as the solution- or solid-type electrolytes greatly enhanced the capacitive performance and rate capability of the supercapacitors. The reason for the enhancement can be ascribed to the fully ionization of the weak acidic oxygen-bearing functional groups after neutralization. PMID:26763275

  5. Fuel cells with solid polymer electrolyte and their application on vehicles

    Fateev, V.

    1996-04-01

    In Russia, solid polymer electrolyte MF-4-SK has been developed for fuel cells. This electrolyte is based on perfluorinated polymer with functional sulfogroups. Investigations on electrolyte properties and electrocatalysts have been carried out.

  6. Solid oxide fuel cells with bi-layered electrolyte structure

    Zhang, Xinge; Robertson, Mark; Deces-Petit, Cyrille; Xie, Yongsong; Hui, Rob; Qu, Wei; Kesler, Olivera; Maric, Radenka; Ghosh, Dave [Institute for Fuel Cell Innovation, National Research Council Canada, 4250 Wesbrook Mall, Vancouver, B.C. V6T 1W5 (Canada)

    2008-01-10

    In this work, we have developed solid oxide fuel cells with a bi-layered electrolyte of 2 {mu}m SSZ and 4 {mu}m SDC using tape casting, screen printing, and co-firing processes. The cell reached power densities of 0.54 W cm{sup -2} at 650 C and 0.85 W cm{sup -2} at 700 C, with open circuit voltage (OCV) values larger than 1.02 V. The electrical leaking between anode and cathode through an SDC electrolyte has been blocked in the bi-layered electrolyte structure. However, both the electrolyte resistance (R{sub el}) and electrode polarization resistance (R{sub p,a+c}) increased in comparison to cells with single-layered SDC electrolytes. The formation of a solid solution of (Ce, Zr)O{sub 2-x} during sintering process and the flaws in the bi-layered electrolyte structure seem to be the main causes for the increase in the R{sub el} value (0.32 {omega} cm{sup 2}) at 650 C, which is almost one order of magnitude higher than the calculated value. (author)

  7. Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

    Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

    2018-04-25

    Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

  8. Polarization behavior of lithium electrode in polymetric solid electrolytes

    Matsuda, Yoshiharu (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan)); Morita, Masayuki (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan)); Tsutsumi, Hiromori (Dept. of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi Univ., Ube (Japan))

    1993-04-15

    Complexes of novel polymer matrices and lithium salts have been prepared as polymeric solid electrolytes for lithium batteries. Poly(ethylene oxide)-grafted poly(methylmethacrylate) (PEO-PMMA) and poly(methylsiloxane) (PMS) were used as the matrices. The conductance behavior of the complexes and the basic polarization characteristics of the lithium electrode in the polymeric electrolytes were studied. As high conductivities as 10[sup -3] S cm[sup -1] were obtained at room temperature for the PMMA-based electrolytes containing some liquid plasticizer. Limiting current densities of 3 to 5 mA cm[sup -2] were observed for the anodic and cathodic polarization of the lithium electrode. The transport number of Li[sup +] was approximately unity in 'single-ion type' PMS-based electrolyte, in which the polarization curve of the lithium electrode showed no current hysteresis. (orig.)

  9. A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

    Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

    2005-05-01

    The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

  10. Electrochemical Synthesis of Ammonia in Solid Electrolyte Cells

    Garagounis, Ioannis; Kyriakou, Vasileios; Skodra, Aglaia; Vasileiou, Eirini; Stoukides, Michael

    2014-01-01

    Developed in the early 1900s, the “Haber–Bosch” synthesis is the dominant NH 3 synthesis process. Parallel to catalyst optimization, current research efforts are also focused on the investigation of new methods for ammonia synthesis, including the electrochemical synthesis with the use of solid electrolyte cells. Since the first report on Solid State Ammonia Synthesis (SSAS), more than 30 solid electrolyte materials were tested and at least 15 catalysts were used as working electrodes. Thus far, the highest rate of ammonia formation reported is 1.13 × 10 -8 mol s -1 cm -2 , obtained at 80°C with a Nafion solid electrolyte and a mixed oxide, SmFe 0.7 Cu 0.1 Ni 0.2 O 3 , cathode. At high temperatures (>500°C), the maximum rate was 9.5 × 10 −9 mol s -1 cm -2 using Ce 0.8 Y 0.2 O 2-δ –[Ca 3 (PO 4 ) 2 –K 3 PO 4 ] as electrolyte and Ag–Pd as cathode. In this paper, the advantages and the disadvantages of SSAS vs. the conventional process and the requirements that must be met in order to promote the electrochemical process into an industrial level are discussed.

  11. Zinc composite anode for batteries with solid electrolyte

    Tedjar, F.; Melki, T.; Zerroual, L.

    A new negative composite anode for batteries with a solid electrolyte is studied. Using a complex of zinc ammonium chloride mixed with zinc metal powder, the advantage of the Zn/Zn 2+ electrode ( e = -760 mV) is kept while the energy density and the shelf-life of the battery are increased.

  12. Zinc composite anode for batteries with solid electrolyte

    Tedjar, F.; Melki, T.; Zerroual, L. (Setif Univ. (Algeria). Unite de Recherche Electrochimie)

    1992-05-01

    A new negative composite anode for batteries with a solid electrolyte is studied. Using a complex of zinc ammonium chloride mixed with zinc metal powder, the advantage of the Zn/Zn[sup 2+] electrode (e = -760 mV) is kept while the energy density and the shelf-life of the battery are increased. (orig.).

  13. PEO nanocomposite polymer electrolyte for solid state symmetric ...

    cells/supercapacitors) to electro-chromic displays, smart windows and ... electrolytes and their usage in lithium ion rechargeable solid state batteries are well .... the experimental plot using the Arrhenius relationship σ = σ0exp(−Ea/kT) where ...

  14. Electrochemical Synthesis of Ammonia in Solid Electrolyte Cells

    Garagounis, Ioannis; Kyriakou, Vasileios [Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki (Greece); Chemical Processes and Energy Resources Institute, Center for Research and Technology Hellas, Thessaloniki (Greece); Skodra, Aglaia [Chemical Processes and Energy Resources Institute, Center for Research and Technology Hellas, Thessaloniki (Greece); Vasileiou, Eirini; Stoukides, Michael, E-mail: stoukidi@cperi.certh.gr [Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki (Greece); Chemical Processes and Energy Resources Institute, Center for Research and Technology Hellas, Thessaloniki (Greece)

    2014-01-17

    Developed in the early 1900s, the “Haber–Bosch” synthesis is the dominant NH{sub 3} synthesis process. Parallel to catalyst optimization, current research efforts are also focused on the investigation of new methods for ammonia synthesis, including the electrochemical synthesis with the use of solid electrolyte cells. Since the first report on Solid State Ammonia Synthesis (SSAS), more than 30 solid electrolyte materials were tested and at least 15 catalysts were used as working electrodes. Thus far, the highest rate of ammonia formation reported is 1.13 × 10{sup -8} mol s{sup -1} cm{sup -2}, obtained at 80°C with a Nafion solid electrolyte and a mixed oxide, SmFe{sub 0.7}Cu{sub 0.1}Ni{sub 0.2}O{sub 3}, cathode. At high temperatures (>500°C), the maximum rate was 9.5 × 10{sup −9} mol s{sup -1} cm{sup -2} using Ce{sub 0.8}Y{sub 0.2}O{sub 2-δ}–[Ca{sub 3}(PO{sub 4}){sub 2}–K{sub 3}PO{sub 4}] as electrolyte and Ag–Pd as cathode. In this paper, the advantages and the disadvantages of SSAS vs. the conventional process and the requirements that must be met in order to promote the electrochemical process into an industrial level are discussed.

  15. Electrochemical Synthesis of Ammonia in Solid Electrolyte Cells

    Ioannis eGaragounis

    2014-01-01

    Full Text Available Developed in the early 1900's, the Haber-Bosch synthesis is the dominant NH3 synthesis process. Parallel to catalyst optimization, current research efforts are also focused on the investigation of new methods for ammonia synthesis, including the electrochemical synthesis with the use of solid electrolyte cells. Since the first report on Solid State Ammonia Synthesis (SSAS, more than 30 solid electrolyte materials were tested and at least 15 catalysts were used as working electrodes. Thus far, the highest rate of ammonia formation reported is 1.13×10−8 mol s−1 cm−2, obtained at 80°C with a Nafion solid electrolyte and a mixed oxide, SmFe0.7Cu0.1Ni0.2O3, cathode. At high temperatures (>500oC the maximum rate was 9.5*10-9 mol s−1 cm−2 using Ce0.8Y0.2O2-δ -[Ca3(PO42 -K3PO4] as electrolyte and Ag-Pd as cathode. In this paper, the advantages and the disadvantages of SSAS vs the conventional process and the requirements that must be met in order to promote the electrochemical process into an industrial level, are discussed.

  16. Solid-state graft copolymer electrolytes for lithium battery applications.

    Hu, Qichao; Caputo, Antonio; Sadoway, Donald R

    2013-08-12

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

  17. Current limit diagrams for dendrite formation in solid-state electrolytes for Li-ion batteries

    Raj, R.; Wolfenstine, J.

    2017-03-01

    We build upon the concept that nucleation of lithium dendrites at the lithium anode-solid state electrolyte interface is instigated by the higher resistance of grain boundaries that raises the local electro-chemical potential of lithium, near the lithium-electrode. This excess electro-chemo-mechanical potential, however, is reduced by the mechanical back stress generated when the dendrite is formed within the electrolyte. These parameters are coalesced into an analytical model that prescribes a specific criterion for dendrite formation. The results are presented in the form of current limit diagrams that show the "safe" and "fail" regimes for battery function. A higher conductivity of the electrolyte can reduce dendrite formation.

  18. Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

    Wang, Aiping; Kadam, Sanket; Li, Hong; Shi, Siqi; Qi, Yue

    2018-03-01

    A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li+ transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multi-scale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

  19. Improving cyclic stability of lithium nickel manganese oxide cathode for high voltage lithium ion battery by modifying electrode/electrolyte interface with electrolyte additive

    Li, Bin; Wang, Yaqiong; Tu, Wenqiang; Wang, Zaisheng; Xu, Mengqing; Xing, Lidan; Li, Weishan

    2014-01-01

    Highlights: • Cyclic stability of LiNi 0.5 Mn 1.5 O 4 is improved significantly by using PES as additive. • A protective SEI is formed on LiNi 0.5 Mn 1.5 O 4 due to the preferential oxidation of PES. • The SEI suppresses electrolyte decomposition and structure destruction of LiNi 0.5 Mn 1.5 O 4 . - Abstract: We report a new approach to improve the cyclic stability of lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ) cathode, in which the cathode/electrolyte interface is modified by using prop-1-ene-1, 3-sultone (PES) as an electrolyte additive. The interfacial properties of LiNi 0.5 Mn 1.5 O 4 cathode in PES-containing electrolyte have been investigated by scanning electron spectroscopy (SEM), transmission electron microscopy (TEM), thermal gravimetry (TG), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammometry (CV), chronoamperometry (CA), and constant current charge/discharge test. It is found that the application of PES improves significantly the cyclic stability of LiNi 0.5 Mn 1.5 O 4 . After 400 cycles at 1C rate (1C=147 mA g −1 ), the capacity retention of LiNi 0.5 Mn 1.5 O 4 is 90% for the cell using 1.0 wt% PES, while only 49% for the cell without the additive. The characterizations from SEM, TEM, TG, XRD, and XPS confirm that the LiNi 0.5 Mn 1.5 O 4 /electrolyte interface is modified and a protective solid electrolyte interface film is formed on LiNi 0.5 Mn 1.5 O 4 particles, which prevents LiNi 0.5 Mn 1.5 O 4 from destruction and suppresses the electrolyte decomposition

  20. On the theory of the electroreduction of solid oxide electrolytes

    Chebotin, V.N.; Brajnin, M.I.; Solov'eva, L.M.; Pakhnutov, I.A.; Lukach, Yu.S.

    1986-01-01

    The process of direct current passage through the cell with MOsub(2)+MeOsub(r) solid electrolyte (M-Zr, Hf, Ce, Th; Me-Ca, Sr, Sc, Y, lanthanides), a blockage cathode and a reversible anode is considered; it leads to electrolyte deviation from stoichiometric composition to insufficient oxygen content. The degree of this deviation and n-type electron conductivity proportional to it, depending on coordinate and time, is described by the nonlinear differential equation of the diffusion type. Electron conductivity of the electrolyte near the cathode increases in time approximating to the limiting value proportional to current conducted. As the distance to the cathode increases electron conductivity reduces by the exponential law, which transforms to a linear one in due course

  1. Alkaline solid polymer electrolytes and their application to rechargeable batteries; Electrolytes solides polymeres alcalins application aux generateurs electrochimiques rechargeables

    Guinot, S

    1996-03-15

    A new family of solid polymer electrolytes (SPE) based on polyoxyethylene (POE), KOH and water is investigated in view of its use in rechargeable batteries. After a short review on rechargeable batteries, the preparation of various electrolyte compositions is described. Their characterization by differential scanning calorimetry (DSC), thermogravimetric analysis, X-ray diffraction and microscopy confirm a multi-phasic structure. Conductivity measurements give values up to 10 sup -3 S cm sup -1 at room temperature. Their use in cells with nickel as negative electrode and cadmium or zinc as positive electrode has been tested; cycling possibility has been shown to be satisfactory. (C.B.) 113 refs.

  2. High-temperature solid electrolyte interphases (SEI) in graphite electrodes

    Rodrigues, Marco-Tulio F.; Sayed, Farheen N.; Gullapalli, Hemtej; Ajayan, Pulickel M.

    2018-03-01

    Thermal fragility of the solid electrolyte interphase (SEI) is a major source of performance decay in graphite anodes, and efforts to overcome the issues offered by extreme environments to Li-ion batteries have had limited success. Here, we demonstrate that the SEI can be extensively reinforced by carrying the formation cycles at elevated temperatures. Under these conditions, decomposition of the ionic liquid present in the electrolyte favored the formation of a thicker and more protective layer. Cells in which the solid electrolyte interphase was cast at 90 °C were significantly less prone to self-discharge when exposed to high temperature, with no obvious damages to the formed SEI. This additional resilience was accomplished at the expense of rate capability, as charge transfer became growingly inefficient in these systems. At slower rates, however, cells that underwent SEI formation at 90 °C presented superior performances, as a result of improved Li+ transport through the SEI, and optimal wetting of graphite by the electrolyte. This work analyzes different graphite hosts and ionic liquids, showing that this effect is more pervasive than anticipated, and offering the unique perspective that, for certain systems, temperature can actually be an asset for passivation.

  3. Modeling of ionic transport in solid polymer electrolytes

    Cheang, P L; Teo, L L; Lim, T L

    2010-01-01

    A Monte Carlo model describing the ionic trans port in solid polyme relectrolyte is developed. Single cation simulation is carried out using hopping rate to study the transport mechanism of a thermally activated ion in solid polymer electrolyte. In our model, the ion is able to hop along a polymer chain and to jump between different chains, surmounting energy barriers that consist of polymer's activation energy and the externally applied electric field. The model is able to trace the motion of ion across polymer electrolyte. The mean hopping distance is calculated based on the available open bond in the next nearest side. Random numbers are used to determine the hopping distances, free flight times, final energy and direction of the cation after successful hop. Drift velocity and energy of cation are simulated in our work. The model is expected to be able to simulate the lithium-polymer battery in future.

  4. Faradic resistance of the electrode/electrolyte interface.

    Mayer, S; Geddes, L A; Bourland, J D; Ogborn, L

    1992-09-01

    A new method is used to measure the direct-current (Faradic) resistance of a single electrode/electrolyte interface. The method employs a constant-current pulse and a potential-sensing electrode. By choosing a sufficiently long pulse duration, the voltage between the test and potential-sensing electrode exhibits a three-phase response. In the steady-state phase, the voltage measured is equal to the current flowing through the electrode Faradic resistance and the resistance of the electrolyte between the test and potential-sensing electrode. By measuring this latter resistance with a high-frequency sinusoidal alternating current, the voltage drop in the electrolyte is calculated and subtracted from the voltage measured between the test and potential-sensing electrode, thereby allowing calculation of the Faradic resistance. By plotting the reciprocal of the Faradic resistance against current density and fitting the data points to a third-order polynomial, it is possible to determine the zero-current density (Faradic) resistance. This technique was used to determine the Faradic resistance of electrodes (0.1 cm2) of stainless-steel, platinum, platinum-iridium and rhodium in 0.9 per cent NaCl at 25 degrees. The zero current Faradic resistance is lowest for platinum (30.3 k omega), slightly higher for platinum-iridium (47.6k omega), much higher for rhodium (111k omega) and highest for type 316 stainless-steel (345k omega). In all cases, the Faradic resistance decreases dramatically with increasing current density.

  5. Nanoscale heterogeneity at the aqueous electrolyte-electrode interface

    Limmer, David T.; Willard, Adam P.

    2015-01-01

    Using molecular dynamics simulations, we reveal emergent properties of hydrated electrode interfaces that while molecular in origin are integral to the behavior of the system across long times scales and large length scales. Specifically, we describe the impact of a disordered and slowly evolving adsorbed layer of water on the molecular structure and dynamics of the electrolyte solution adjacent to it. Generically, we find that densities and mobilities of both water and dissolved ions are spatially heterogeneous in the plane parallel to the electrode over nanosecond timescales. These and other recent results are analyzed in the context of available experimental literature from surface science and electrochemistry. We speculate on the implications of this emerging microscopic picture on the catalytic proficiency of hydrated electrodes, offering a new direction for study in heterogeneous catalysis at the nanoscale.

  6. Moessbauer studies of microscopic disorder in solid electrolytes

    Pasternak, M.

    1987-01-01

    We implement for the first time Moessbauer spectroscopy (MS) to investigate short-range properties of disorder in solid electrolytes. MS in 129 I and 119 Sn was carried out in RbAg 4 I 5 and as impurity in Ag 2 Se, respectively. Measurements were performed both in the superionic and the normal phases. It is shown that localized cation hopping is an inherent feature of the α-AgI-type solid electrolytes. In RbAg 4 I 5 , at temperatures far below T c , a small fraction of Ag is still locally mobile and at T>T c , its concentration increases exponentially. A strong linear temperature dependence of the point-charge electric field gradient is observed and explained in terms of local hopping. With 119 Sn in Ag 2 Se we observe the onset of 'local melting' of the Ag surroundingt the SnSe 4 cluster at 50 K below the bulk superionic phase transition. The characteristic features of MS related to microscopic studies of solid electrolytes are fully described. (orig.)

  7. Internal-reference solid-electrolyte oxygen sensor

    Haaland, D.M.

    1977-01-01

    A new solid-electrolyte oxygen sensor has been developed that eliminates the conventional oxygen reference in previous solid-electrolyte oxygen sensor designs and is, therefore, ideally suited as an insertion device for remote oxygen monitoring applications. It is constructed with two cells of stabilized zirconia sealed into a small unit using a new high-temperature platinum-zirconia seal. One electrochemical cell monitors the ratio of oxygen partial pressures inside and outside the sensor while the other solid-electrolyte cell is used for quantitative electrochemical pumping of oxygen. The internal oxygen reference is generated by initially pumping all oxygen out of the known internal volume of the sensor and then quantitatively pumping oxygen back in until oxygen partial pressures are equal inside and out. This information is used with the ideal gas law to calculate oxygen partial pressures. Tests were conducted from 400 to 1000 0 C in mixtures of oxygen and nitrogen spanning approximately 0.2 to 21 percent oxygen concentration range. Sensors with sputtered platinum and porous platinum paste electrodes were compared

  8. Fabrication of All-Solid-State Lithium-Ion Cells Using Three-Dimensionally Structured Solid Electrolyte Li7La3Zr2O12 Pellets

    Shoji, Mao; Munakata, Hirokazu; Kanamura, Kiyoshi

    2016-01-01

    All-solid-state lithium-ion batteries using Li + -ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of the promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D) structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZAl), which is a Al-doped Li 7 La 3 Zr 2 O 12 (LLZ) with Li + -ion conductivity of ~10 –4 S ⋅cm −1 at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 μm depth holes in 700 μm × 700 μm area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO 2 /LLZAl/lithium-metal configuration. It is expected that the LiCoO 2 –LLZAl interface is formed by point-to-point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, Li 3 BO 3 , which is a mechanically soft solid electrolyte with a low melting point at around 700

  9. Review on solid electrolytes for all-solid-state lithium-ion batteries

    Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li

    2018-06-01

    All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy density. One of key components in the ASS battery (ASSB) is solid electrolyte that determines performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.

  10. Ceramic membrane fuel cells based on solid proton electrolytes

    Meng, Guangyao; Ma, Qianli; Peng, Ranran; Liu, Xingqin [USTC Lab. for Solid State Chemistry and Inorganic Membranes, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026 (China); Ma, Guilin [School of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123 (China)

    2007-04-15

    The development of solid oxide fuel cells (SOFCs) has reached its new stage characterized with thin electrolytes on porous electrode support, and the most important fabrication techniques developed in which almost all are concerned with inorganic membranes, and so can be named as ceramic membrane fuel cells (CMFCs). CMFCs based on proton electrolytes (CMFC-H) may exhibit more advantages than CMFCs based on oxygen-ion electrolytes (CMFC-O) in many respects, such as energy efficiency and avoiding carbon deposit. Ammonia fuelled CMFC with proton-conducting BaCe{sub 0.8}Gd{sub 0.2}O{sub 2.9} (BCGO) electrolyte (50 {mu}m in thickness) is reported in this works, which showed the open current voltage (OCV) values close to theoretical ones and rather high power density. And also, we have found that the well known super oxide ion conductor, La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{alpha}} (LSGM), is a pure proton conductor in H{sub 2} and mixed proton and oxide ion conductor in wet air, while it is a pure oxide ion conductor in oxygen or dry air. To demonstrate the CMFC-H concept to get high performance fuel cells the techniques for thin membranes, chemical vapor deposition (CVD), particularly novel CVD techniques, should be given more attention because of their many advantages. (author)

  11. SXPS study of model GaAs(100)/electrolyte interface

    Lebedev, Mikhail V. [A.F. Ioffe Physico-Technical Institute, Russian Academy of Sciences, St. Petersburg (Russian Federation); Mankel, Eric; Mayer, Thomas; Jaegermann, Wolfram [Institute of Material Sciences, Darmstadt University of Technology, Darmstadt (Germany)

    2010-02-15

    Model GaAs(100)/electrolyte interfaces are prepared in vacuum by co-adsorption of Cl{sub 2} and 2-propanol molecules at LN{sub 2} temperature. On adsorption of Cl{sub 2} molecules gallium chlorides, elemental arsenic and arsenic chlorides are formed. Co-adsorption of 2-propanol causes formation of additional GaCl{sub 3} and AsCl, as well as soluble/volatile As-based complexes, which are released from the surface depleting the sur- face by arsenic. Comparison of the As 3d and Ga 3d spectra obtained after heating the model interface to room temperature with the corresponding spectra obtained after emersion of the GaAs(100) surface from HCl/2-propanol solution allows to conclude that in HCl solution Cl{sup -} ions attack gallium sites and H{sup +} ions mostly attack arsenic sites. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Electrochemical hydrogen isotope sensor based on solid electrolytes

    Matsumoto, Hiroshige; Hayashi, Hiroyuki; Iwahara, Hiroyasu

    2002-01-01

    An electrochemical sensor of hydrogen isotopes based on solid electrolytes for determining the hydrogen isotope ratios and/or total hydrogen pressures in gases has been developed. This paper describes the methodology of the hydrogen isotope sensing together with experimental results. When hydrogen isotope gases are introduced to an electrochemical cell using a proton-conducting electrolyte (hydrogen isotope cell), the electromotive force (EMF) of the cell agrees with that theoretically estimated. The EMF signals can be used for the determination of the hydrogen isotope ratio in gases if the total hydrogen pressure is predetermined. By supplementary use of an oxide ion conductor cell, both the ratio and total pressure of the hydrogen isotopes can be simultaneously determined. (author)

  13. Failure analysis of electrolyte-supported solid oxide fuel cells

    Fleischhauer, Felix; Tiefenauer, Andreas; Graule, Thomas; Danzer, Robert; Mai, Andreas; Kuebler, Jakob

    2014-07-01

    For solid oxide fuel cells (SOFCs) one key aspect is the structural integrity of the cell and hence its thermo mechanical long term behaviour. The present study investigates the failure mechanisms and the actual causes for fracture of electrolyte supported SOFCs which were run using the current μ-CHP system of Hexis AG, Winterthur - Switzerland under lab conditions or at customer sites for up to 40,000 h. In a first step several operated stacks were demounted for post-mortem inspection, followed by a fractographic evaluation of the failed cells. The respective findings are then set into a larger picture including an analysis of the present stresses acting on the cell like thermal and residual stresses and the measurements regarding the temperature dependent electrolyte strength. For all investigated stacks, the mechanical failure of individual cells can be attributed to locally acting bending loads, which rise due to an inhomogeneous and uneven contact between the metallic interconnect and the cell.

  14. Electrode-electrolyte interface model of tripolar concentric ring electrode and electrode paste.

    Nasrollaholhosseini, Seyed Hadi; Steele, Preston; Besio, Walter G

    2016-08-01

    Electrodes are used to transform ionic currents to electrical currents in biological systems. Modeling the electrode-electrolyte interface could help to optimize the performance of the electrode interface to achieve higher signal to noise ratios. There are previous reports of accurate models for single-element biomedical electrodes. In this paper we develop a model for the electrode-electrolyte interface for tripolar concentric ring electrodes (TCRE) that are used to record brain signals.

  15. Materials Development for All-Solid-State Battery Electrolytes

    Wang, Weimin

    Solid electrolytes in all solid-state batteries, provide higher attainable energy density and improved safety. Ideal solid electrolytes require high ionic conductivity, a high elastic modulus to prevent dendrite growth, chemical compatibility with electrodes, and ease of fabrication into thin films. Although various materials types, including polymers, ceramics, and composites, are under intense investigation, unifying design principles have not been identified. In this thesis, we study the key ion transport mechanisms in relation to the structural characteristics of polymers and glassy solids, and apply derived material design strategies to develop polymer-silica hybrid materials with improved electrolyte performance characteristics. Poly(ethylene) oxide-based solid electrolytes containing ceramic nanoparticles are attractive alternatives to liquid electrolytes for high-energy density Li batteries. We compare the effect of Li1.3Al0.3Ti 1.7(PO4)3 active nanoparticles, passive TiO 2 nanoparticles and fumed silica. Up to two orders of magnitude enhancement in ionic conductivity is observed for composites with active nanoparticles, attributed to cation migration through a percolating interphase region that develops around the active nanoparticles, even at low nanoparticle loading. We investigate the structural origin of elastic properties and ionic migration mechanisms in sodium borosilicate and sodium borogermanate glass electrolyte system. A new statistical thermodynamic reaction equilibrium model is used in combination with data from nuclear magnetic resonance and Brillouin light scattering measurements to determine network structural unit fractions. The highly coordinated structural units are found to be predominantly responsible for effective mechanical load transmission, by establishing three-dimensional covalent connectivity. A strong correlation exists between bulk modulus and the activation energy for ion conduction. We describe the activated process in

  16. Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

    Jongh, P. E. de; Blanchard, D.; Matsuo, M.

    2016-01-01

    A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible...... electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries....

  17. Thin film galvanic cell with RbAg4I5 solid electrolyte

    Bodnaruk, L.I.; Danilov, A.V.; Kulinkovich, V.E.; Aleskovskij, V.B.

    1975-01-01

    In order to decrease the size and weight and to increase the specific capacity and energy of galvanic cells, some solid electrolytes in the form of thin films are proposed. The galvanic cells were prepared by a combined method: the cathodic and anodic materials (Te and Ag) were evaporated under vacuo to cover an electrolyte layer, the latter being obtained by impregnating the porous materials with RbAg 4 I 5 acetonic solution. The most specific charge curves of the galvanic cells at various current densities are given: specific energy of the samples was 0.2 to 0.7 watt-h/kg, their capacity being 0.1 to 0.2 mah. Behaviour of the cells when stored (that of Ag(RbAg 4 I 5 ) interface in particular) was investigated, namely, the effect of the storage time on the capacity and internal resistance of the galvanic cell

  18. Solid electrolyte batteries and fast ion conducting glasses, factors affecting a proposed merger

    Uhlmann, D R; Tuller, H L; Button, D P; Valez, M [Massachusetts Inst. of Tech., Cambridge (USA). Dept. of Materials Science and Engineering

    1983-01-01

    The present paper is concerned with advanced battery systems employing glass as a solid electrolyte. After an initial discussion of battery systems employing solid electrolytes, and of the attractive features offered by glass electrolytes, consideration is given to batteries fabricated with such electrolytes and to their performance characteristics. Subsequent discussion is directed to the two principal characteristics of glasses which are critical to their use as solid electrolytes - viz., their electrical conductivity and resistance to corrosive attack. The present state of knowledge in each of these areas is summarized, with particular focus on glasses with exceptionally high ionic conductivities - so-called fast ion conductors or FIC's.

  19. Towards High-Performance Aqueous Sodium-Ion Batteries: Stabilizing the Solid/Liquid Interface for NASICON-Type Na2 VTi(PO4 )3 using Concentrated Electrolytes.

    Zhang, Huang; Jeong, Sangsik; Qin, Bingsheng; Vieira Carvalho, Diogo; Buchholz, Daniel; Passerini, Stefano

    2018-02-22

    Aqueous Na-ion batteries may offer a solution to the cost and safety issues of high-energy batteries. However, substantial challenges remain in the development of electrode materials and electrolytes enabling high performance and long cycle life. Herein, we report the characterization of a symmetric Na-ion battery with a NASICON-type Na 2 VTi(PO 4 ) 3 electrode material in conventional aqueous and "water-in-salt" electrolytes. Extremely stable cycling performance for 1000 cycles at a high rate (20 C) is found with the highly concentrated aqueous electrolytes owing to the formation of a resistive but protective interphase between the electrode and electrolyte. These results provide important insight for the development of aqueous Na-ion batteries with stable long-term cycling performance for large-scale energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. High temperature fuel cell with ceria-based solid electrolyte

    Arai, H.; Eguchi, K.; Yahiro, H.; Baba, Y.

    1987-01-01

    Cation-doped ceria is investigated as an electrolyte for the solid oxide fuel cell. As for application to the fuel cells, the electrolyte are desired to have high ionic conductivity in deriving a large electrical power. A series of cation-doped ceria has higher ionic conductivity than zirconia-based oxides. In the present study, the basic electrochemical properties of cation-doped ceria were studied in relation to the application of fuel cells. The performance of fuel cell with yttria-doped ceria electrolyte was evaluated. Ceria-based oxides were prepared by calcination of oxide mixtures of the components or calcination of co-precipitated hydroxide mixtures from the metal nitrate solution. The oxide mixtures thus obtained were sintered at 1650 0 C for 15 hr in air into disks. Ionic transference number, t/sub i/, was estimated from emf of oxygen concentration cell. Electrical conductivities were measured by dc-4 probe method by varying the oxygen partial pressure. The fuel cell was operated by oxygen and hydrogen

  1. Solid-State NMR Study of New Copolymers as Solid Polymer Electrolytes

    Jean-Christophe Daigle

    2018-01-01

    Full Text Available We report the analysis of comb-like polymers by solid-state NMR. The polymers were previously evaluated as solid-polymer-electrolytes (SPE for lithium-polymer-metal batteries that have suitable ionic conductivity at 60 °C. We propose to develop a correlation between 13C solid-state NMR measurements and phase segregation. 13C solid-state NMR is a perfect tool for differentiating polymer phases with fast or slow motions. 7Li was used to monitor the motion of lithium ions in the polymer, and activation energies were calculated.

  2. Degradation of the solid electrolyte interphase induced by the deposition of manganese ions

    Shin, Hosop; Park, Jonghyun; Sastry, Ann Marie; Lu, Wei

    2015-06-01

    The deposition of manganese ions dissolved from the cathode onto the interface between the solid electrolyte interphase (SEI) and graphite causes severe capacity fading in manganese oxide-based cells. The evolution of the SEI layer containing these Mn compounds and the corresponding instability of the layer are thoroughly investigated by artificially introducing soluble Mn ions into a 1 mol L-1 LiPF6 electrolyte solution. Deposition of dissolved Mn ions induces an oxygen-rich SEI layer that results from increased electrolyte decomposition, accelerating SEI growth. The spatial distribution of Mn shows that dissolved Mn ions diffuse through the porous layer and are deposited mostly at the inorganic layer/graphite interface. The Mn compound deposited on the anode, identified as MnF2, originates from a metathesis reaction between LiF and dissolved Mn ion. It is confirmed that ion-exchange reaction occurs in the inorganic layer, converting SEI species to Mn compounds. Some of the Mn is observed inside the graphite; this may cause surface structural disordering in the graphite, limiting lithium-ion intercalation. The continuous reaction that occurs at the inorganic layer/graphite interfacial regions and the modification of the original SEI layer in the presence of Mn ions are critically related to capacity fade and impedance rise currently plaguing Li-ion cells.

  3. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    Kartini, Evvy; Manawan, Maykel

    2016-01-01

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  4. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    Kartini, Evvy [Center for Science and Technology of Advanced Materials – National Nuclear Energy Agency, Kawasan Puspiptek Serpong, Tangerang Selatan15314, Banten (Indonesia); Manawan, Maykel [Post Graduate Program of Materials Science, University of Indonesia, Jl.Salemba Raya No.4, Jakarta 10430 (Indonesia)

    2016-02-08

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  5. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    Kartini, Evvy; Manawan, Maykel

    2016-02-01

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say "the most important emerging energy technology" is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner's cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  6. An induced current method for measuring zeta potential of electrolyte solution-air interface.

    Song, Yongxin; Zhao, Kai; Wang, Junsheng; Wu, Xudong; Pan, Xinxiang; Sun, Yeqing; Li, Dongqing

    2014-02-15

    This paper reports a novel and very simple method for measuring the zeta potential of electrolyte solution-air interface. When a measuring electrode contacts the electrolyte solution-air interface, an electrical current will be generated due to the potential difference between the electrode-air surface and the electrolyte solution-air interface. The amplitude of the measured electric signal is linearly proportional to this potential difference; and depends only on the zeta potential at the electrolyte solution-air interface, regardless of the types and concentrations of the electrolyte. A correlation between the zeta potential and the measured voltage signal is obtained based on the experimental data. Using this equation, the zeta potential of any electrolyte solution-air interface can be evaluated quickly and easily by inserting an electrode through the electrolyte solution-air interface and measuring the electrical signal amplitude. This method was verified by comparing the obtained results of NaCl, MgCl2 and CaCl2 solutions of different pH values and concentrations with the zeta potential data reported in the published journal papers. Copyright © 2013 Elsevier Inc. All rights reserved.

  7. Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

    Gao, Han [Chemical; Maglia, Filippo [BMW Group, Munich 80788, Germany; Lamp, Peter [BMW Group, Munich 80788, Germany; Amine, Khalil [Chemical; Chen, Zonghai [Chemical

    2017-12-13

    Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.

  8. An interface-reconstruction effect for rechargeable aluminum battery in ionic liquid electrolyte to enhance cycling performances

    Feng Wu

    2018-01-01

    Full Text Available Aluminum (Al metal has been regarded as a promising anode for rechargeable batteries because of its natural abundance and high theoretical specific capacity. However, rechargeable aluminum batteries (RABs using Al metal as anode display poor cycling performances owing to interface problems between anode and electrolyte. The solid-electrolyte interphase (SEI layer on the anode has been confirmed to be essential for improving cycling performances of rechargeable batteries. Therefore, we immerse the Al metal in ionic liquid electrolyte for some time before it is used as anode to remove the passive film and expose fresh Al to the electrolyte. Then the reactions of exposed Al, acid, oxygen and water in electrolyte are occurred to form an SEI layer in the cycle. Al/electrolyte/V2O5 full batteries with the thin, uniform and stable SEI layer on Al metal anode perform high discharge capacity and coulombic efficiency (CE. This work illustrates that an SEI layer is formed on Al metal anode in the cycle using a simple and effective pretreatment process and results in superior cycling performances for RABs.

  9. Low temperature electrochemistry at normal conductor/frozen electrolyte interface

    Borkowska, Z.; Stimming, U.

    1991-01-01

    The frozen electrolyte technique (FREECE = FRozen Electrolyte ElectroChEmistry) is based on the experimental result that frozen electrolytes are suitable for electrochemical studies. This technique has been used in our laboratory and also by others to investigate interfacial electrochemical behavior. An argument will be given as to why the FREECE technique is advantageous in a number of respects and what kind of electrolyte systems can be used. Reference is made to electrochemical results such as interfacial reactions and double layer properties. 26 refs

  10. Electron states at electrolyte/n-GaN and electrolyte/n-InGaN interfaces

    Rudinsky, M. E., E-mail: rudinskym@mail.ru; Gutkin, A. A.; Brunkov, P. N. [Russian Academy of Sciences, Ioffe Physical-Technical Institute (Russian Federation)

    2012-06-15

    The differential capacitance and differential active conductance of rectifying contacts of n-GaN and n-In{sub x}Ga{sub 1-x}N (x Almost-Equal-To 0.15) with an electrolyte (0.2 M aqueous solutions of NaOH, NaCl, or HCl) have been studied. It was found that electron states with energies corresponding to the upper half of the energy gap of a semiconductor exist at the interface between these semiconductors and a NaOH solution. The density and characteristic recharging time of states noticeably contributing to the differential capacitance and differential active conductance at probe-voltage frequencies of 0.3-1 kHz grow with their binding energy and, for states lying at 0.15-0.3 eV below the conduction-band bottom of n-GaN, fall within the ranges 10{sup 12}-2 Multiplication-Sign 10{sup 13} cm{sup -2} eV{sup -1} and 10{sup -4}-10{sup -2} s, respectively. For contacts with NaCl and HCl solutions, there are no states of this kind. It is assumed that the observed states are related to the adsorption of hydroxyl groups.

  11. Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

    Shinagawa, Tatsuya; Cao, Zhen; Cavallo, Luigi; Takanabe, Kazuhiro

    2016-01-01

    Direct photon to chemical energy conversion using semiconductor-electrocatalyst-electrolyte interfaces has been extensively investigated for more than a half century. Many studies have focused on screening materials for efficient photocatalysis

  12. Systems and methods for monitoring a solid-liquid interface

    Stoddard, Nathan G; Lewis, Monte A.; Clark, Roger F

    2013-06-11

    Systems and methods are provided for monitoring a solid-liquid interface during a casting process. The systems and methods enable determination of the location of a solid-liquid interface during the casting process.

  13. PREPARATION AND CHARACTERIZATION OF SOLID ELECTROLYTES: FUEL CELL APPLICATIONS

    Rambabu Bobba; Josef Hormes; T. Wang; Jaymes A. Baker; Donald G. Prier; Tommy Rockwood; Dinesha Hawkins; Saleem Hasan; V. Rayanki

    1997-12-31

    Electrolytes. Ionically conducting solid electrolytes are successfully used for battery, fuel cell and sensor applications.

  14. The potential for ionic liquid electrolytes to stabilise the magnesium interface for magnesium/air batteries

    Khoo, Timothy; Howlett, Patrick C.; Tsagouria, Maureen; MacFarlane, Douglas R.; Forsyth, Maria

    2011-01-01

    Magnesium/air batteries are a possible high-energy density power source that, to date, have not received strong commercial interest due to issues with the corrosion of the magnesium and evaporation of the electrolyte. In this work we report on the use of ionic liquid based electrolytes to stabilise the metal/electrolyte interface and their impact on the electrochemical performance. Galvanostatic measurements indicate that the water content of the ionic liquid electrolyte plays an important role in the cell discharge characteristics. Surface characterisation using EIS, ATR-FTIR and powder diffraction examined the unique properties of the surface film formed on the magnesium anode.

  15. Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

    Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

    2015-02-24

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

  16. Improved ceramic anodes for SOFCs with modified electrode/electrolyte interface

    Abdul Jabbar, Mohammed Hussain; Høgh, Jens Valdemar Thorvald; Zhang, Wei

    2012-01-01

    The electrode performance of solid oxide fuel cell anode with Pd nanoparticles at the interface of ScYSZ electrolyte and Sr0.94Ti0.9Nb0.1O3 (STN) electrode introduced in the form of metal functional layer have been investigated at temperatures below 600 °C. A metal functional layer consisting of Pd...... was deposited by magnetron sputtering. Effecting from heat treatments, Pd nanoparticles with particle sizes in the range of 5–20 nm were distributed at the interface, and throughout the backbone. The polarization resistance of the modified STN reduced to 30 Ωcm2 at 600 °C, which is three times less than...... an unmodified STN backbone. In order to improve the anode performance further, Pd and Gd-doped CeO2 electrocatalysts were infiltrated into the STN backbone. The modified interface with Pd nanoparticles in combination with nanostructured electrocatalyst by infiltration resulted in polarisation resistances of 0...

  17. A model problem concerning ionic transport in microstructured solid electrolytes

    Curto Sillamoni, Ignacio J.; Idiart, Martín I.

    2015-11-01

    We consider ionic transport by diffusion and migration through microstructured solid electrolytes. The assumed constitutive relations for the constituent phases follow from convex energy and dissipation potentials which guarantee thermodynamic consistency. The effective response is determined by homogenizing the relevant field equations via the notion ofmulti-scale convergence. The resulting homogenized response involves several effective tensors, but they all require the solution of just one standard conductivity problem over the representative volume element. A multi-scale model for semicrystalline polymer electrolytes with spherulitic morphologies is derived by applying the theory to a specific class of two-dimensional microgeometries for which the effective response can be computed exactly. An enriched model accounting for a random dispersion of filler particles with interphases is also derived. In both cases, explicit expressions for the effective material parameters are provided. The models are used to explore the effect of crystallinity and filler content on the overall response. Predictions support recent experimental observations on doped poly-ethylene-oxide systems which suggest that the anisotropic crystalline phase can actually support faster ion transport than the amorphous phase along certain directions dictated by the morphology of the polymeric chains. Predictions also support the viewpoint that ceramic fillers improve ionic conductivity and cation transport number via interphasial effects.

  18. Robust solid polymer electrolyte for conducting IPN actuators

    Festin, Nicolas; Maziz, Ali; Plesse, Cédric; Teyssié, Dominique; Chevrot, Claude; Vidal, Frédéric

    2013-01-01

    Interpenetrating polymer networks (IPNs) based on nitrile butadiene rubber (NBR) as first component and poly(ethylene oxide) (PEO) as second component were synthesized and used as a solid polymer electrolyte film in the design of a mechanically robust conducting IPN actuator. IPN mechanical properties and morphologies were mainly investigated by dynamic mechanical analysis and transmission electron microscopy. For 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) swollen IPNs, conductivity values are close to 1 × 10 −3 S cm −1 at 25 ° C. Conducting IPN actuators have been synthesized by chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) within the PEO/NBR IPN. A pseudo-trilayer configuration has been obtained with PEO/NBR IPN sandwiched between two interpenetrated PEDOT electrodes. The robust conducting IPN actuators showed a free strain of 2.4% and a blocking force of 30 mN for a low applied potential of ±2 V. (paper)

  19. Robust solid polymer electrolyte for conducting IPN actuators

    Festin, Nicolas; Maziz, Ali; Plesse, Cédric; Teyssié, Dominique; Chevrot, Claude; Vidal, Frédéric

    2013-10-01

    Interpenetrating polymer networks (IPNs) based on nitrile butadiene rubber (NBR) as first component and poly(ethylene oxide) (PEO) as second component were synthesized and used as a solid polymer electrolyte film in the design of a mechanically robust conducting IPN actuator. IPN mechanical properties and morphologies were mainly investigated by dynamic mechanical analysis and transmission electron microscopy. For 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) swollen IPNs, conductivity values are close to 1 × 10-3 S cm-1 at 25 ° C. Conducting IPN actuators have been synthesized by chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) within the PEO/NBR IPN. A pseudo-trilayer configuration has been obtained with PEO/NBR IPN sandwiched between two interpenetrated PEDOT electrodes. The robust conducting IPN actuators showed a free strain of 2.4% and a blocking force of 30 mN for a low applied potential of ±2 V.

  20. Development of solid electrolytes for water electrolysis at higher temperature

    Linkous, C.A. [Florida Solar Energy Center, Cocoa, FL (United States)

    1996-10-01

    This report describes efforts in developing new solid polymer electrolytes that will enable operation of proton exchange membrane electrolyzers at higher temperatures than are currently possible. Several ionomers have been prepared from polyetheretherketone (PEEK), polyethersulfone (PES), and polyphenylquinoxaline (PPQ) by employing various sulfonation procedures. By controlling the extent of sulfonation, a range of proton conductivities could be achieved, whose upper limit actually exceeded that of commercially available perfluoralkyl sulfonates. Thermoconductimetric analysis of samples at various degrees of sulfonation showed an inverse relationship between conductivity and maximum operating temperature. This was attributed to the dual effect of adding sulfonate groups to the polymer: more acid groups produce more protons for increased conductivity, but they also increase water uptake, which mechanically weakens the membrane. This situation was exacerbated by the limited acidity of the aromatic sulfonic acids (pK{sub A} {approx} 2-3). The possibility of using partial fluorination to raise the acid dissociation constant is discussed.

  1. Raman spectral and electrochemical studies of lithium/electrolyte interfaces

    Odziemkowski, M

    1922-01-01

    Cyclic voltammetry, corrosion potential-time transients and Normal Raman spectroscopy have been employed to characterize the lithium-lithium salt, organic solvent, interfacial region. An in-situ cutting technique was developed to expose lithium metal. In-situ optical and ex-situ scanning electron microscopy (SEM) have been used to examine the morphology of the lithium electrode surface during exposure at open circuit and after anodic polarization. The main reaction product detected by in-situ Raman spectroscopy in the system/lithium/LiAsF[sub 6], tetrahydrofuran (THF) electrolyte was polytetrahydrofuran (PTHF). The conditions for the polymerization reaction in the presence of lithium metal have been determined. Tetrahydrofuran (THF) decomposition reaction mechanisms are discussed. Decomposition reaction products have been determined as arsenic (II) oxide, As[sub 2]O[sub 3] (arsenolite) and arsenious oxyfluoride AsF[sub 2]-O-AsF[sub 2]. Potentiodynamic polarization measurements revealed a substantial shift of the corrosion potential towards positive values and only a moderate increase of anodic dissolution current for in-situ cut lithium metal. Corrosion potential-time merits have been measured. The following electrolytes have been investigated: LiAsF[sub 6], LiPF[sub 6], LiClO[sub 4], and Li(CF[sub 3]SO[sub 2])[sub 2]N in THF, 2Me-THF, and propylene carbonate (PC). The transients permit the ranking of the reactivity of the electrolytes. These measurements have shed light on understanding the stability of various stability and and solvents in contact with lithium. Compared to purified electrolytes, small amounts of water shift the corrosion potential towards even more positive values. Intensive anodic cycling of a Li electrode in unpurified LiAsF[sub 6]/THF electrolyte leads to the breakdown of a surface film/films. While at the open circuit potential (OCP), water in this same electrolyte leads to crack formation in the bulk lithium electrode.

  2. CVD Graphene/Ni Interface Evolution in Sulfuric Electrolyte

    Yivlialin, Rossella; Bussetti, Gianlorenzo; Duò, Lamberto

    2018-01-01

    Systems comprising single and multilayer graphene deposited on metals and immersed in acid environments have been investigated, with the aim of elucidating the mechanisms involved, for instance, in hydrogen production or metal protection from corrosion. In this work, a relevant system, namely...... chemical vapor deposited (CVD) multilayer graphene/Ni (MLGr/Ni), is studied when immersed in a diluted sulfuric electrolyte. The MLGr/Ni electrochemical and morphological properties are studied in situ and interpreted in light of the highly oriented pyrolytic graphite (HOPG) electrode behavior, when...... immersed in the same electrolyte. Following this interpretative framework, the dominant role of the Ni substrate in hydrogen production is clarified....

  3. An insight into intrinsic interfacial properties between Li metals and Li10GeP2S12 solid electrolytes.

    Chen, Bingbing; Ju, Jiangwei; Ma, Jun; Zhang, Jianjun; Xiao, Ruijuan; Cui, Guanglei; Chen, Liquan

    2017-11-29

    Density functional theory simulations and experimental studies were performed to investigate the interfacial properties, including lithium ion migration kinetics, between lithium metal anode and solid electrolyte Li 10 GeP 2 S 12 (LGPS). The LGPS[001] plane was chosen as the studied surface because the easiest Li + migration pathway is along this direction. The electronic structure of the surface states indicated that the electrochemical stability was reduced at both the PS 4 - and GeS 4 -teminated surfaces. For the interface cases, the equilibrium interfacial structures of lithium metal against the PS 4 -terminated LGPS[001] surface (Li/PS 4 -LGPS) and the GeS 4 -terminated LGPS[001] surface (Li/GeS 4 -LGPS) were revealed based on the structural relaxation and adhesion energy analysis. Solid electrolyte interphases were expected to be formed at both Li/PS 4 -LGPS and Li/GeS 4 -LGPS interfaces, resulting in an unstable state of interface and large interfacial resistance, which was verified by the EIS results of the Li/LGPS/Li cell. In addition, the simulations of the migration kinetics show that the energy barriers for Li + crossing the Li/GeS 4 -LGPS interface were relatively low compared with the Li/PS 4 -LGPS interface. This may contribute to the formation of Ge-rich phases at the Li/LGPS interface, which can tune the interfacial structures to improve the ionic conductivity for future all-solid-state batteries. This work will offer a thorough understanding of the Li/LGPS interface, including local structures, electronic states and Li + diffusion behaviors in all-solid-state batteries.

  4. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S.

    2016-01-01

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  5. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp [Nagoya Institute of Technology, Gokiso, Showa, Nagoya, Aichi (Japan)

    2016-07-06

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  6. Cross-Linked Solid Polymer Electrolyte for All-Solid-State Rechargeable Lithium Batteries

    Ben youcef, Hicham; Garcia-Calvo, Oihane; Lago, Nerea; Devaraj, Shanmukaraj; Armand, Michel

    2016-01-01

    Semi-interpenetrated network Solid Polymer Electrolytes (SPEs) were fabricated by UV-induced cross-linking of poly(ethyleneglycol) diacrylate (PEGDA) and divinylbenzene (DVB) within a poly(ethyleneoxide) (PEO) matrix (M v = 5 × 10 6 g mol −1 ), comprising lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI), at a molar ratio of EO:Li ∼ 30:1. The influence of the DVB content on the final SPE properties was investigated in detail. An increase of DVB concentration resulted in self-standing polymer electrolytes. The DVB cross-linker incorporation was found to decrease the crystallinity of the PEO matrix from 34% to 23%, with a decrease in the melting temperature (T m ) of the membrane from 50 °C to 34 °C. Moreover, the influence of the DVB concentration on the ionic conductivity was determined for polymer electrolytes with 0, 10, 20 and 45% DVB from room temperature (RT) to 80 °C. The resulting SPEs showed a high electrochemical stability of 4.3 V as well as practical conductivity values exceeding 10 −4 S cm −1 at 70 °C. Cycling performance of these semi-interpenetrated SPE’s have been shown with a Li metal polymer battery and all solid -state Li sulphur battery.

  7. Electrospinning of Ceramic Solid Electrolyte Nanowires for Lithium-Ion Batteries with Enhanced Ionic Conductivity

    Yang, Ting

    Solid electrolytes have great potential to address the safety issues of Li-ion batteries, but better synthesis methods are still required for ceramics electrolytes such as lithium lanthanum titanate (LLTO) and lithium lanthanum zirconate (LLZO). Pellets made from ceramic nanopowders using conventional sintering can be porous due to the agglomeration of nanoparticles (NPs). Electrospinning is a simple and versatile technique for preparing oxide ceramic nanowires (NWs) and was used to prepare electrospun LLTO and LLZO NWs. Pellets prepared from the electrospun LLTO NWs had higher density, less void space, and higher Li+ conductivity compared to those comprised of LLTO prepared with conventional sol-gel methods, which demonstrated the potential that electrospinning can provide towards improving the properties of sol-gel derived ceramics. Cubic phase LLZO was stabilized at room temperature in the form of electrospun NWs without extrinsic dopants. Bulk LLZO with tetragonal structure was transformed to the cubic phase using particle size reduction via ball milling. Heating conditions that promoted particle coalescence and grain growth induced a transformation from the cubic to tetragonal phase in both types of nanostructured LLZO. Composite polymer solid electrolyte was fabricated using LLZO NWs as the filler and showed an improved ionic conductivity at room temperature. Nuclear magnetic resonance studies show that LLZO NWs partially modify the polymer matrix and create preferential pathways for Li+ conduction through the modified polymer regions. Doping did not have significant effect on improving the overall conductivity as the interfaces played a predominant role. By comparing fillers with different morphologies and intrinsic conductivities, it was found that both NW morphology and high intrinsic conductivity are desired.

  8. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Teran, Alexander Andrew

    -like environment around the ion while the second mechanism of ion conduction is attributed to diffusion of the entire polymer chain with coordinated ions. Equilibrated block copolymer electrolytes exhibit a non-monotonic dependence on molecular weight, decreasing with increasing molecular weight in the small molecular weight limit before increasing when molecular weight exceeds about 10 kg mol-1. Conductivity in annealed electrolytes was shown to be affected by two competing factors: the glass transition temperature of the insulating polystyrene block and the width of the conducting poly(ethylene oxide) (PEO) channel. In the low molecular weight limit, all ions are in contact with both polystyrene (PS) and PEO segments. The intermixing between PS and PEO segments is restricted to an interfacial zone of width of about 5 nm. The fraction of ions affected by the interfacial zone decreases as the conducting channel width increases. Furthermore, the effect of thermal history on the conductivity of the block copolymer electrolytes was examined. Results suggest that long-range order impedes ion transport, and consequently decreases in conductivity of up to 80% were seen upon annealing. The effect of morphology on ion transport was studied by conducting simultaneous impedance and X-ray scattering experiments as the block copolymer electrolyte transitioned from an ordered lamellar structure to a disordered phase. The ionic conductivity increased discontinuously through the transition from order to disorder. A simple framework for quantifying the magnitude of the discontinuity was presented. Finally, block copolymer electrolytes were examined specifically for use in high energy density solid state lithium/sulfur batteries. Such materials have been shown to form a stable interface with lithium metal anodes, maintain intimate contact upon cycling, and have sufficiently high shear moduli to retard dendrite formation. Having previously satisfied the concerns associated with the lithium metal

  9. Photoelectrical stimulation of neuronal cells by an organic semiconductor-electrolyte Interface

    Abdullaeva, Oliya S.; Schulz, Matthias; Balzer, Frank

    2016-01-01

    As a step toward the realization of neuroprosthetics for vision restoration, we follow an electrophysiological patch-clamp approach to study the fundamental photoelectrical stimulation mechanism of neuronal model cells by an organic semiconductor–electrolyte interface. Our photoactive layer...... consisting of an anilino-squaraine donor blended with a fullerene acceptor is supporting the growth of the neuronal model cell line (N2A cells) without an adhesion layer on it and is not impairing cell viability. The transient photocurrent signal upon illumination from the semiconductor–electrolyte layer....... Furthermore, we characterize the morphology of the semiconductor–electrolyte interface by atomic force microscopy and study the stability of the interface in dark and under illuminated conditions....

  10. Fermi Potential across Working Solid Oxide Cells with Zirconia or Ceria Electrolytes

    Jacobsen, Torben; Chatzichristodoulou, Christodoulos; Mogensen, Mogens Bjerg

    2014-01-01

    A solid electrolyte will always possess a finite electronic conductivity, in particular electrolytes like doped ceria that easily get reduced and become mixed ionic and electronic conductors. This given rise too high leak currents through the solid oxide cell (SOC). Especially, problems have been...... driving the O2-ions is not the Fermi potential, which is the potential of the electrons, but the Galvani potential (or inner potential) (1). The concepts of potentials describing the electrical situation of a solid electrolyte is shown i Fig. 1, and an example of the Fermi potential (π) and Galvani...

  11. Challenges and perspectives of garnet solid electrolytes for all solid-state lithium batteries

    Liu, Qi; Geng, Zhen; Han, Cuiping; Fu, Yongzhu; Li, Song; He, Yan-bing; Kang, Feiyu; Li, Baohua

    2018-06-01

    Garnet Li7La3Zr2O12 (LLZO) solid electrolytes recently have attracted tremendous interest as they have the potential to enable all solid-state lithium batteries (ASSLBs) owing to high ionic conductivity (10-3 to 10-4 S cm-1), negligible electronic transport, wide potential window (up to 9 V), and good chemical stability. Here we present the key issues and challenges of LLZO in the aspects of ion conduction property, interfacial compatibility, and stability in air. First, different preparation methods of LLZO are reviewed. Then, recent progress about the improvement of ionic conductivity and interfacial property between LLZO and electrodes are presented. Finally, we list some emerging LLZO-based solid-state batteries and provide perspectives for further research. The aim of this review is to summarize the up-to-date developments of LLZO and lead the direction for future development which could enable LLZO-based ASSLBs.

  12. Nonlinear ionic transport through microstructured solid electrolytes: homogenization estimates

    Curto Sillamoni, Ignacio J.; Idiart, Martín I.

    2016-10-01

    We consider the transport of multiple ionic species by diffusion and migration through microstructured solid electrolytes in the presence of strong electric fields. The assumed constitutive relations for the constituent phases follow from convex energy and dissipation potentials which guarantee thermodynamic consistency. The effective response is heuristically deduced from a multi-scale convergence analysis of the relevant field equations. The resulting homogenized response involves an effective dissipation potential per species. Each potential is mathematically akin to that of a standard nonlinear heterogeneous conductor. A ‘linear-comparison’ homogenization technique is then used to generate estimates for these nonlinear potentials in terms of available estimates for corresponding linear conductors. By way of example, use is made of the Maxwell-Garnett and effective-medium linear approximations to generate estimates for two-phase systems with power-law dissipation. Explicit formulas are given for some limiting cases. In the case of threshold-type behavior, the estimates exhibit non-analytical dilute limits and seem to be consistent with fields localized in low energy paths.

  13. Zirconium oxide based ceramic solid electrolytes for oxygen detection

    Caproni, Erica

    2007-01-01

    Taking advantage of the high thermal shock resistance of zirconia-magnesia ceramics and the high oxide ion conductivity of zirconia-yttria ceramics, composites of these ceramics were prepared by mixing, pressing and sintering different relative concentrations of ZrO 2 : 8.6 mol% MgO and ZrO 2 : 3 mol% Y 2 O 3 solid electrolytes. Microstructural analysis of the composites was carried out by X-ray diffraction and scanning electron microscopy analyses. The thermal behavior was studied by dilatometric analysis. The electrical behavior was evaluated by the impedance spectroscopy technique. An experimental setup was designed for measurement the electrical signal generated as a function of the amount of oxygen at high temperatures. The main results show that these composites are partially stabilized (monoclinic, cubic and tetragonal) and the thermal behavior is similar to that of ZrO 2 : 8.6 mol% MgO materials used in disposable high temperature oxygen sensors. Moreover, the results of analysis of impedance spectroscopy show that the electrical conductivity of zirconia:magnesia is improved with zirconia-yttria addition and that the electrical signal depends on the amount of oxygen at 1000 deg C, showing that the ceramic composites can be used in oxygen sensors. (author)

  14. Chitosan-gold-Lithium nanocomposites as solid polymer electrolyte.

    Begum, S N Suraiya; Pandian, Ramanathaswamy; Aswal, Vinod K; Ramasamy, Radha Perumal

    2014-08-01

    Lithium micro batteries are emerging field of research. For environmental safety biodegradable films are preferred. Recently biodegradable polymers have gained wide application in the field of solid polymer electrolytes. To make biodegradable polymers films plasticizers are usually used. However, use of plasticizers has disadvantages such as inhomogenities in phases and mechanical instability that will affect the performance of Lithium micro batteries. We have in this research used gold nanoparticles that are environmentally friendly, instead of plasticizers. Gold nanoparticles were directly template upon chitosan membranes by reduction process so as to enhance the interactions of Lithium with the polymer. In this article, for the first time the characteristics of Chitosan-gold-Lithium nanocomposite films are investigated. The films were prepared using simple solution casting technique. We have used various characterization tools such as Small Angle Neutron Scattering (SANS), XRD, FTIR, Raman, FESEM, and AFM, Light scattering, Dielectric and electrical conductivity measurements. Our investigations show that incorporation of gold results in enhancement of conductivity in Lithium containing Chitosan films. Also it affects the dielectric characteristics of the films. We conclude through various characterization tools that the enhancement in the conductivity was due to the retardation of crystal growth of lithium salt in the presence of gold nanoparticles. A model is proposed regarding the formation of the new nanocomposite. The conductivity of these biodegradable films is comparable to those of the current inorganic Lithium micro batteries. This new chitosan-Au-Li nanocomposite has potential applications in the field of Lithium micro batteries.

  15. Diffusion welding of ZrO2 solid electrolyte cells

    Schaefer, W.; Schmidberger, R.

    1980-01-01

    Zirconia based solid-electrolyte-cells can be applied as electrolysis-cells or fuel cells at high temperatures. Scaling up to technical aggregates must be realized by a gastight electrical series-connection of many tubular single cells. A suitable process for connecting single cells is diffusion welding. Starting materials were sintered zirconia-tubes (16 mm diameter, 10 mm length) and gastight interconnecting rings (16 mm diameter, 0.5-2mm length) from gold, platinum or electrically conducting mixed oxides. ZrO 2 -tubes and interconnecting rings were mounted in alternating sequence and diffusion welded under axial pressure at high temperatures. From economic reasons noble metals cannot be used for technical aggregates. The developments were therefore concentrated on the connection with mixed oxides. Optimized welding parameters are: 1400-1500 0 C welding temperature, 2 hours welding time and an axial pressure of approximately 1 Nmm 2 . Up to now gastight tubes consisting of 20 single cells were preparated by diffusion-welding in one step. The process will be further developed for the production of 50-cell-tubes with a total length of about 60 cm. (orig.) [de

  16. Towards first principles modeling of electrochemical electrode-electrolyte interfaces

    Nielsen, Malte; Björketun, Mårten; Hansen, Martin Hangaard

    2015-01-01

    We present a mini-perspective on the development of first principles modeling of electrochemical interfaces. We show that none of the existing methods deal with all the thermodynamic constraints that the electrochemical environment imposes on the structure of the interface. We present two...

  17. New electrodes for hydrogen/oxygen solid polymer electrolyte fuel cell

    Mosdale, R [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Recherche Fondamentale sur la Matiere Condensee; Stevens, P [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Thermohydraulique et de Physique

    1993-12-31

    A new method of preparation of Electrode/Membrane/Electrode (EME) assemblies for Proton Exchange Membrane Fuel Cells (PEMFC) has been developed. The electrodes are deposited directly onto a Nafion electrolyte membrane from a mixture of platinized carbon, Nafion solution, and PTFE by using a spray technique. By this technique, porous electrodes are obtained with an optimized gas/electrolyte/catalyst interface, and electrode/membrane interface.

  18. Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes

    Gómez-Marín, Ana M.; Hernández-Ortíz, Juan P.

    2014-01-01

    Highlights: • Discretized model for an interface of covered electrodes. • Two limiting behaviors are capture: double-layer and conductive interfaces. • Additional phenomena are included easily: acid/base equilibrium, ion mobility. • The model provides explanations to observed phenomena that is vaguely explained in the literature. • Implications on electrodes in fuel cells are given and it opens avenues to understand and design such systems. - Abstract: A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott–Schottky or Gouy–Chapman–Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments

  19. Quantum dot doped solid polymer electrolyte for device application

    Singh, Pramod K.; Kim, Kang Wook; Rhee, Hee-Woo [Department of Chemical and Biomolecular Engineering, Sogang University, Mapo-Gu, Seoul 121-742 (Korea)

    2009-06-15

    ZnS capped CdSe quantum dots embedded in PEO:KI:I{sub 2} polymer electrolyte matrix have been synthesized and characterized for dye sensitized solar cell (DSSC) application. The complex impedance spectroscopy shows enhance in ionic conductivity ({sigma}) due to charges provide by quantum dots (QD) while AFM affirm the uniform distribution of QD into polymer electrolyte matrix. Cyclic voltammetry revealed the possible interaction between polymer electrolyte, QD and iodide/iodine. The photovoltaic performances of the DSSC containing quantum dots doped polymer electrolyte was also found to improve. (author)

  20. Bifurcation of elastic solids with sliding interfaces

    Bigoni, D.; Bordignon, N.; Piccolroaz, A.; Stupkiewicz, S.

    2018-01-01

    Lubricated sliding contact between soft solids is an interesting topic in biomechanics and for the design of small-scale engineering devices. As a model of this mechanical set-up, two elastic nonlinear solids are considered jointed through a frictionless and bilateral surface, so that continuity of the normal component of the Cauchy traction holds across the surface, but the tangential component is null. Moreover, the displacement can develop only in a way that the bodies in contact do neither detach, nor overlap. Surprisingly, this finite strain problem has not been correctly formulated until now, so this formulation is the objective of the present paper. The incremental equations are shown to be non-trivial and different from previously (and erroneously) employed conditions. In particular, an exclusion condition for bifurcation is derived to show that previous formulations based on frictionless contact or `spring-type' interfacial conditions are not able to predict bifurcations in tension, while experiments-one of which, ad hoc designed, is reported-show that these bifurcations are a reality and become possible when the correct sliding interface model is used. The presented results introduce a methodology for the determination of bifurcations and instabilities occurring during lubricated sliding between soft bodies in contact.

  1. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

    2013-10-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

  2. Recent progress in sulfide-based solid electrolytes for Li-ion batteries

    Liu, D., E-mail: liu.dongqiang@ireq.ca; Zhu, W.; Feng, Z.; Guerfi, A.; Vijh, A.; Zaghib, K.

    2016-11-15

    Graphical abstract: Li{sub 2}S-GeS{sub 2}-P{sub 2}S{sub 5} ternary diagram showing various sulphide compounds as solid electrolytes for Li-ion batteries. - Highlights: • Recent progress of sulfide-based solid electrolytes is described from point of view of structure. • Thio-LISICON type electrolytes exhibited high ionic conductivity due to their bcc sublattice and unique Li{sup +} diffusion pathway. • “Mixed-anion effect” is also an effective way to modify the energy landscape as well as the ionic conductivity. - Abstract: Sulfide-based ionic conductors are one of most attractive solid electrolyte candidates for all-solid-state batteries. In this review, recent progress of sulfide-based solid electrolytes is described from point of view of structure. In particular, lithium thio-phosphates such as Li{sub 7}P{sub 3}S{sub 11}, Li{sub 10}GeP{sub 2}S{sub 12} and Li{sub 11}Si{sub 2}PS{sub 12} etc. exhibit extremely high ionic conductivity of over 10{sup −2} S cm{sup −1} at room temperature, even higher than those of commercial organic carbonate electrolytes. The relationship between structure and unprecedented high ionic conductivity is delineated; some potential drawbacks of these electrolytes are also outlined.

  3. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Chiu, K.-F.; Su, S.-H.

    2013-01-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

  4. Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

    Xu, Ruochen; Zhang, Shengzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Wu, Jianbo; Gu, Changdong; Tu, Jiangping

    2018-04-20

    Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Truly quasi-solid-state lithium cells utilizing carbonate free polymer electrolytes on engineered LiFePO_4

    Nair, Jijeesh R.; Cíntora-Juárez, Daniel; Pérez-Vicente, Carlos; Tirado, José L.; Ahmad, Shahzada; Gerbaldi, Claudio

    2016-01-01

    Highlights: • Carbonate free truly quasi-solid-state polymer electrolytes for lithium batteries. • Simple and easy up scalable preparation by solvent free thermal curing. • LiFePO_4 cathode engineered by PEDOT:PSS interphase at the current collector. • Direct polymerization over the engineered electrode surface in one pot. • Stable lithium polymer cells operating in a wide temperature range. - Abstract: Stable and safe functioning of a Li-ion battery is the demand of modern generation. Herein, we are demonstrating the application of an in-situ free radical polymerisation process (thermal curing) to fabricate a polymer electrolyte that possesses mechanical robustness, high thermal stability, improved interfacial and ion transport characteristics along with stable cycling at ambient conditions. The polymer electrolyte is obtained by direct polymerization over the electrode surface in one pot starting from a reactive mixture comprising an ethylene oxide-based dimethacrylic oligomer (BDM), dimethyl polyethylene glycol (DPG) and lithium salt. Furthermore, an engineered cathode is used, comprising a LiFePO_4/PEDOT:PSS interface at the current collector that improves the material utilization at high rates and mitigates the corrosive effects of LiTFSI on aluminium current collector. The lithium cell resulting from the newly elaborated multiphase assembly of the composite cathode with the DPG-based carbonate-free polymer electrolyte film exhibits excellent reversibility upon prolonged cycling at ambient as well as elevated temperatures, which is found to be superior compared to previous reports on uncoated electrodes with polymer electrolytes.

  6. Sodium-ion transfer at the interface between ceramic and organic electrolytes

    Sagane, Fumihiro; Abe, Takeshi; Ogumi, Zempachi [Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2010-11-01

    Sodium-ion transfer through the interface between ceramic and organic electrolytes was studied by AC impedance spectroscopy. Na{sub 3}Zr{sub 1.88}Y{sub 0.12}Si{sub 2}PO{sub 12} (NASICON) and Na-{beta}''-alumina were used as ceramic electrolytes, and propylene carbonate (PC) and dimethyl sulfoxide (DMSO) containing 0.05 mol dm{sup -3} NaCF{sub 3}SO{sub 3} were used as organic electrolytes. The semi-circle ascribed to interfacial charge transfer resistance (R{sub ct}) was observed. The activation energies for sodium-ion transfer at the interface between ceramic and organic electrolytes were evaluated by the temperature dependency of R{sub ct}. As a result, the activation energies depended on the ceramic electrolytes but not on the solvents. These results suggest that sodium-ion transfer from ceramic to organic electrolytes should be responsible for the activation energies, which is contrary to the case in a lithium-ion transfer system. Based on these results, the mechanism of interfacial sodium-ion transfer was discussed. (author)

  7. Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes.

    Gómez-Marín, Ana M; Hernández-Ortíz, Juan P

    2014-09-24

    A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott-Schottky or Gouy-Chapman-Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Modifying zirconia solid electrolyte surface property to enhance oxide transport

    Liaw, B.Y.; Song, S.Y. [Univ. of Hawaii, Honolulu, HI (United States)

    1996-12-31

    Bismuth-strontium-calcium-copper oxide (Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}, BSCCO) is known for its high T{sub c} superconducting behavior and mixed conducting property. The applicability of similar high T{sub c} cuprates for intermediate-temperature solid oxide fuel cell (SOFC) application has been studied recently. We investigated the electrochemical behavior of several Ag{vert_bar}BSCCO{vert_bar}10 mol% yttria-stabilized zirconia (YSZ){vert_bar}Ag and Ag{vert_bar}YSZ{vert_bar}Ag cells using complex impedance spectroscopy. A highly uniform and porous microstructure was observed at the interface of the YSZ and BSCCO. The ionic conductivity determined from the Nyquest plots in the temperature range of 200-700{degrees}C agrees with the values reported in the literature. The specific resistance of the BSCCO{vert_bar}YSZ interface was also determined to be lower than those of the conventional manganite electrode, suggesting that BSCCO seems attractive for cathode applications in SOFC.

  9. Thermal transport across solid-solid interfaces enhanced by pre-interface isotope-phonon scattering

    Lee, Eungkyu; Luo, Tengfei

    2018-01-01

    Thermal transport across solid interfaces can play critical roles in the thermal management of electronics. In this letter, we use non-equilibrium molecular dynamics simulations to investigate the isotope effect on the thermal transport across SiC/GaN interfaces. It is found that engineered isotopes (e.g., 10% 15N or 71Ga) in the GaN layer can increase the interfacial thermal conductance compared to the isotopically pure case by as much as 23%. Different isotope doping features, such as the isotope concentration, skin depth of the isotope region, and its distance from the interface, are investigated, and all of them lead to increases in thermal conductance. Studies of spectral temperatures of phonon modes indicate that interfacial thermal transport due to low-frequency phonons (transport. This work may provide insights into interfacial thermal transport and useful guidance to practical material design.

  10. Low energy electron diffraction (LEED) and sum frequency generation (SFG) vibrational spectroscopy studies of solid-vacuum, solid-air and solid-liquid interfaces

    Hoffer, Saskia [Univ. of California, Berkeley, CA (United States)

    2002-01-01

    Electron based surface probing techniques can provide detailed information about surface structure or chemical composition in vacuum environments. The development of new surface techniques has made possible in situ molecular level studies of solid-gas interfaces and more recently, solid-liquid interfaces. The aim of this dissertation is two-fold. First, by using novel sample preparation, Low Energy Electron Diffraction (LEED) and other traditional ultra high vacuum (UHV) techniques are shown to provide new information on the insulator/vacuum interface. The surface structure of the classic insulator NaCl has been determined using these methods. Second, using sum frequency generation (SFG) surface specific vibrational spectroscopy studies were performed on both the biopolymer/air and electrode/electrolyte interfaces. The surface structure and composition of polyetherurethane-silicone copolymers were determined in air using SFG, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). SFG studies of the electrode (platinum, gold and copper)/electrolyte interface were performed as a function of applied potential in an electrochemical cell.

  11. Modulation of solid electrolyte interphase of lithium-ion batteries by LiDFOB and LiBOB electrolyte additives

    Huang, Shiqiang; Wang, Shuwei; Hu, Guohong; Cheong, Ling-Zhi; Shen, Cai

    2018-05-01

    Solid-electrolyte interphase (SEI) layer is an organic-inorganic composite layer that allows Li+ transport across but blocks electron flow across and prevents solvent diffusing to electrode surface. Morphology, thickness, mechanical and chemical properties of SEI are important for safety and cycling performance of lithium-ion batteries. Herein, we employ a combination of in-situ AFM and XPS to investigate the effects of two electrolyte additives namely lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalato)borate (LiBOB) on SEI layer. LiDFOB is found to result in a thin but hard SEI layer containing more inorganic species (LiF and LiCO3); meanwhile LiBOB promotes formation of a thick but soft SEI layer containing more organic species such as ROCO2Li. Findings from present study will help development of electrolyte additives that promote formation of good SEI layer.

  12. Characterization of solid-solution interface by potentiometric titration and electrophoretic mobility

    Lindecker, C.; Drot, R.; Fourest, B.; Simoni, E.

    1999-01-01

    The study of nuclear waste storage in deep geological sites involves the understanding of processes which could produce a possible dispersion or retention of radioelements. The dispersion of solid particles in aqueous solution is consequently important to be characterized. In this bi-phased system it is necessary to determine the characteristics of the solid-solution interface. The method used of this study is the techniques of potentiometric titration applied to heterogeneous systems. The material studied were phosphate matrices which were synthesized in the laboratory. The dependence of their surface change upon the nature of the electrolytes was investigated

  13. A note on the standard electron transfer potential at the interface between two immiscible electrolyte solutions

    Samec, Zdeněk

    2009-01-01

    Roč. 55, č. 2 (2009), s. 75-81 ISSN 0034-6691 R&D Projects: GA ČR(CZ) GA203/07/1257 Institutional research plan: CEZ:AV0Z40400503 Keywords : interface between two immiscible electrolyte solutions * interfacial electron transfer * standard electron trasfer potential * homogeneous electron transfer Subject RIV: CG - Electrochemistry

  14. Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

    DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

    2012-01-01

    Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

  15. CONDUCTIVITY STUDIES OF (PEO +KHCO3 SOLID ELECTROLYTE SYSTEM AND ITS APPLICATION AS AN ELECTROCHEMICAL CELL

    K. VIJAY KUMAR

    2010-06-01

    Full Text Available Solid polymer electrolyte system, polyethylene oxide (PEO complexed with potassium bicarbonate (KHCO3 salt was prepared by solution-cast technique. Several experimental techniques such as infrared radiation (IR, differential scanning calorimeter (DSC, and composition dependence conductivity, temperature dependence conductivity in the temperature range of 308–368 K and transport number measurements were employed to characterize this polymer electrolyte system. The conductivity of the (PEO+KHCO3 electrolyte was found to be about 3 times larger than that of pure PEO at room temperature. The transference data indicated that the charge transport in these polymer electrolyte systems is predominantly due to K+ ions. Using this polymer electrolyte an electrochemical cell with configuration K+/(PEO+KHCO3/(I2+C+electrolyte was fabricated and its discharge characteristics are studied. A number of other cell parameters associated with the cell were evaluated and are reported in this paper.

  16. Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3-δ Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

    Ravella, Uday K; Liu, Jingjing; Corbel, Gwenaël; Skinner, Stephen J; Lacorre, Philippe

    2016-08-23

    Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 μm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Transire, a Program for Generating Solid-State Interface Structures

    2017-09-14

    ARL-TR-8134 ● SEP 2017 US Army Research Laboratory Transire, a Program for Generating Solid-State Interface Structures by...Program for Generating Solid-State Interface Structures by Caleb M Carlin and Berend C Rinderspacher Weapons and Materials Research Directorate, ARL...

  18. Enzyme Activity and Biomolecule Templating at Liquid and Solid Interfaces

    Harvey W. Blanch

    2004-12-01

    There are two main components of this research program. The first involves studies of the adsorption and catalytic activity of proteins at fluid-fluid and fluid-solid interfaces; the second employs biological macromolecules as templates at the solid-liquid interface for controlled crystallization of inorganic materials, to provide materials with specific functionality.

  19. Engineering the Membrane/Electrode Interface To Improve the Performance of Solid-State Supercapacitors.

    Huang, Chun; Zhang, Jin; Snaith, Henry J; Grant, Patrick S

    2016-08-17

    This paper investigates the effect of adding a 450 nm layer based on porous TiO2 at the interface between a 4.5 μm carbon/TiO2 nanoparticle-based electrode and a polymer electrolyte membrane as a route to improve energy storage performance in solid-state supercapacitors. Electrochemical characterization showed that adding the interface layer reduced charge transfer resistance, promoted more efficient ion transfer across the interface, and significantly improved charge/discharge dynamics in a solid-state supercapacitor, resulting in an increased areal capacitance from 45.3 to 111.1 mF cm(-2) per electrode at 0.4 mA cm(-2).

  20. Fabrication of All-Solid-State Lithium-Ion Cells Using Three-Dimensionally Structured Solid Electrolyte Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} Pellets

    Shoji, Mao; Munakata, Hirokazu; Kanamura, Kiyoshi, E-mail: kanamura@tmu.ac.jp [Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Tokyo (Japan)

    2016-08-30

    All-solid-state lithium-ion batteries using Li{sup +}-ion conducting ceramic electrolytes have been focused on as attractive future batteries for electric vehicles and renewable energy conversion systems because high safety can be realized due to non-flammability of ceramic electrolytes. In addition, a higher volumetric energy density than that of current lithium-ion batteries is expected since the all-solid-state lithium-ion batteries can be made in bipolar cell configurations. However, the special ideas and techniques based on ceramic processing are required to construct the electrochemical interface for all-solid-state lithium-ion batteries since the battery development has been done so far based on liquid electrolyte system over 100 years. As one of the promising approaches to develop practical all-solid-state batteries, we have been focusing on three-dimensionally (3D) structured cell configurations such as an interdigitated combination of 3D pillars of cathode and anode, which can be realized by using solid electrolyte membranes with hole-array structures. The application of such kinds of 3D structures effectively increases the interface between solid electrode and solid electrolyte per unit volume, lowering the internal resistance of all-solid-state lithium-ion batteries. In this study, Li{sub 6.25}Al{sub 0.25}La{sub 3}Zr{sub 2}O{sub 12} (LLZAl), which is a Al-doped Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} (LLZ) with Li{sup +}-ion conductivity of ~10{sup –4} S ⋅cm{sup −1} at room temperature and high stability against lithium-metal, was used as a solid electrolyte, and its pellets with 700 μm depth holes in 700 μm × 700 μm area were fabricated to construct 3D-structured all-solid-state batteries with LiCoO{sub 2}/LLZAl/lithium-metal configuration. It is expected that the LiCoO{sub 2}–LLZAl interface is formed by point-to-point contact even when the LLZAl pellet with 3D hole-array structure is applied. Therefore, Li{sub 3}BO{sub 3}, which is a

  1. Solid State Polymer Electrolytes for Dye-sensitized Solar Cell

    2007-01-01

    1 Introduction Over the past decade,Dye-sensitized solar cells (DSSCs) have been intensively investigated as potential alternatives to conventional inorganic photovoltaic devices due to their low production cost and high energy conversion[1-4]. This type of solar cell has achieved an impressive energy conversion efficiency of over 10%,whose electrolyte is a voltaic organic liquid solvent containing iodide/triiodide as redox couple.However,the use of a liquid electrolyte brings difficulties in the practi...

  2. In-situ Plasticized Cross-linked Polymer Composite Electrolyte Enhanced with Lithium-ion Conducting Nanofibers for Ambient All-Solid-State Lithium-ion Batteries

    Yan, Chaoyi; Zhu, Pei; Jia, Hao; Zhu, Jiadeng; Selvan, R. Kalai; Li, Ya; Dong, Xia; Du, Zhuang; Angunawela, Indunil; Wu, Nianqiang; Dirican, Mahmut

    2018-04-29

    Solid electrolytes have been gaining attention recently for the development of next-generation Li-ion batteries due to the substantial improvements in stability and safety. Among various types of solid electrolytes, composite solid electrolytes (CSEs) exhibit both high ionic conductivity and excellent interfacial contact with the electrodes. Incorporating active nanofibers into the polymer matrix demonstrates an effective method to fabricate CSEs. However, current CSEs based on traditional poly(ethylene oxide) (PEO) polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations, which limit further improvements in Li+ conductivity and electrochemical stability. Herein, we synthesize a novel PEO based cross-linked polymer (CLP) as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40 × 10-4 S cm-1. Li0.3La0.557TiO3 (LLTO) nanofibers incorporated composite solid electrolytes (L-CLPCSE) exhibit enhanced ionic conductivity without showing filler agglomeration. The high content of Li-conductive nanofibers improves the mechanical strength, ensures the conductive networks, and increases the total Li+ conductivity to 3.31 × 10-4 S cm-1. The all-solid-state Li|LiFePO4 batteries with L-CLPCSE are able to deliver attractive specific capacity of 147 mAh g-1 at room temperature, and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.

  3. Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

    Pandey, G. P.; Hashmi, S. A.

    2013-12-01

    Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

  4. A novel perspective on the formation of the solid electrolyte interphase on the graphite electrode for lithium-ion batteries

    Yan Jian; Zhang Jian; Su Yuchang; Zhang Xigui; Xia Baojia

    2010-01-01

    In this paper, we describe how the mechanism of formation of a protective film [the solid electrolyte interphase (or interface) (SEI)] on a graphite electrode for Li-ion batteries was investigated from the novel perspective of precipitation of the final decomposition products that arise from the reduction of a nonaqueous electrolyte solution in contact with the graphite electrode. Within the framework of this new perspective, we can elegantly account for the compositional and structural differences between the basal-plane and edge-plane SEIs and for the origins of the multi-layer structure and the parabolic growth law of the SEIs on both the edge-plane and basal-plane surfaces of the graphite electrode.

  5. Electrophoretic deposition of 9-YSZ solid electrolyte on Ni- YSZ composite

    Santos, F.S.; Yoshito, W.K.; Lazar, D.R.R.; Ussui, V.

    2010-01-01

    9-YSZ ceramic and Ni-YSZ metal/ceramic composite are the more commonly used materials for the fabrication of solid oxide fuel cell electrolyte and anode, respectively. The main challenges for these applications are the forming of both materials as superposed double thin layers. In the present work ceramic powder of 9- YSZ was synthesized by a coprecipitation technique and the Ni O-YSZ composite by a combustion technique. The later was formed by uniaxial pressing as cylindrical pellets of 15 mm diameter. Thin ceramic layers of 9-YSZ were deposited on composite pellets from a suspension with 10% solid content by an Electrophoretic Deposition technique. Applied voltage varied in the range of 30 to 200 V and deposition time from 15 to 90 seconds, evaluating the deposited mass, porosity on the interface and adhesion of layers. Resulted ceramics were characterized by X-ray diffraction and were observed in a scanning electron microscope. Results showed that deposited layers are thin (∼20μm), dense and have good adhesion on the surface of composite substrate. (author)

  6. Electrochemical testing of suspension plasma sprayed solid oxide fuel cell electrolytes

    Waldbillig, D.; Kesler, O.

    Electrochemical performance of metal-supported plasma sprayed (PS) solid oxide fuel cells (SOFCs) was tested for three nominal electrolyte thicknesses and three electrolyte fabrication conditions to determine the effects of electrolyte thickness and microstructure on open circuit voltage (OCV) and series resistance (R s). The measured OCV values were approximately 90% of the Nernst voltages, and electrolyte area specific resistances below 0.1 Ω cm 2 were obtained at 750 °C for electrolyte thicknesses below 20 μm. Least-squares fitting was used to estimate the contributions to R s of the YSZ bulk material, its microstructure, and the contact resistance between the current collectors and the cells. It was found that the 96% dense electrolyte layers produced from high plasma gas flow rate conditions had the lowest permeation rates, the highest OCV values, and the smallest electrolyte-related voltage losses. Optimal electrolyte thicknesses were determined for each electrolyte microstructure that would result in the lowest combination of OCV loss and voltage loss due to series resistance for operating voltages of 0.8 V and 0.7 V.

  7. The effects of functional ionic liquid on properties of solid polymer electrolyte

    An Yongxin; Cheng Xinqun; Zuo Pengjian; Liao Lixia; Yin Geping

    2011-01-01

    Highlights: → The functional ionic liquid(IL)-polymer electrolytes were successfully prepared. → The ionic conductivity of PEO electrolytes was raised to above 10-4 S.cm-1 at room temperature by functional IL. → The cells using functional IL-PEO electrolyte show higher reversible capacity and long cycle life. - Abstract: Polyethylene oxide (PEO) based solid state electrolytes have been thought as promising electrolytes to replace the organic liquid electrolyte for lithium ion batteries. But the lower ionic conductivities at room temperature restrict their application. In this paper, functional ionic liquid and polymer mixed electrolytes are prepared from N-methyoxymethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (PP1.1O1TFSI) and polyethylene oxide. The PP1.1O1TFSI, a kind of room-temperature molten salt, was added to the conventional P(EO) 20 LiTFSI polymer electrolyte and resulted in a significant improvement of the ionic conductivity at room temperature. LiFePO 4 /Li and Li 4 Ti 5 O 12 /Li cells using this kind of electrolyte show high reversible capacity and stable cycle performance.

  8. Study of lithium glassy solid electrolyte/electrode interface by ...

    Unknown

    Institut de Chimie de la Matière Condensée de Bordeaux – C.N.R.S. et Ecole Nationale Supérieure de Chimie et de ... chemically very stable with the different types of electrodes studied here. ... tigated to improve the battery performance.

  9. A novel thermosetting gel electrolyte for stable quasi-solid-state dye-sensitized solar cells

    Lan, Z.; Lin, J.M.; Huang, M.L.; Hao, S.C. [Institute of Materials Physical Chemistry, Huaqiao University, Quanzhou, 362021 (China); Sato, T.; Yin, S. [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 1-1 Katahira 2-Chome, Aoba-ku, Sendai 980-8577 (Japan); Wu, J.H.

    2007-11-19

    Using poly(acrylic acid)-poly(ethylene glycol) hybrid-absorbing liquid electrolyte, we prepare a novel thermosetting gel electrolyte (TSGE) with ionic conductivity of 6.12 mS cm{sup -1}. Based on the TSGE, a quasi-solid-state dye-sensitized solar cell with a good long-term stability and light-to-electricity conversion efficiency of 6.10 % is attained under AM 1.5 irradiation. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  10. Functional Polymer Electrolytes for Multidimensional All-Solid-State Lithium Batteries

    Sun, Bing

    2015-01-01

    Pressing demands for high power and high energy densities in novel electrical energy storage units have caused reconsiderations regarding both the choice of battery chemistry and design. Practical concerns originating in the conventional use of flammable liquid electrolytes have renewed the interests of using solvent-free polymer electrolytes (SPEs) as solid ionic conductors for safer batteries. In this thesis work, SPEs developed from two polymer host structures, polyethers and polycarbonate...

  11. Preparation and Characterization of PVA Alkaline Solid Polymer Electrolyte with Addition of Bamboo Charcoal

    Lidan Fan; Mengyue Wang; Zhen Zhang; Gang Qin; Xiaoyi Hu; Qiang Chen

    2018-01-01

    Natural bamboo charcoal (BC) powder has been developed as a novel filler in order to further improve performances of the polyvinyl alcohol (PVA)-based alkaline solid polymer electrolyte (ASPE) by solution casting method. X-ray diffraction patterns of composite polymer electrolyte with BC revealed the decrease in the degree of crystallinity with increasing content of BC. Scanning electron microscopy images showed pores on a micrometer scale (average diameter about 2 μm) distributed inside a...

  12. Study of Surface States at the Semiconductor/electrolyte Interface of Liquid-Junction Solar Cells.

    Siripala, Withana P.

    The existence of surface states at the semiconductor electrolyte interface of photoelectrochemical (PEC) cells plays a major role in determining the performance of the device in regard to the potential distribution and transport mechanisms of photogenerated carriers at the interface. We have investigated the n-TiO(,2)/electrolyte interface using three experimental techniques: relaxation spectrum analysis, photocurrent spectroscopy, and electrolyte electroreflectance (EER) spectroscopy. The effect of Fermi level pinning at the CdIn(,2)SE(,4)/aqueous-polysulfide interface was also studied using EER. Three distinct surface states were observed at the n-TiO(,2)/aqueous-electrolyte interface. The dominant state, which tails from the conduction band edge, is primarily responsible for the surface recombination of photocarriers at the interface. The second surface state, observed at 0.8 eV below the conduction band of TiO(,2), originates in the dark charge transfer intermediates (TiO(,2)-H). It is proposed that the sub-bandgap (SBG) photocurrent-potential behavior is a result of the mechanism of dynamic formation and annihilation of these surface states. The third surface state was at 1.3 eV below the conduction band of TiO(,2), and the SBG EER measurements show this state is "intrinsic" to the surface. These states were detected with SBG EER and impedance measurements in the presence of electrolytes that can adsorb on the surface of TiO(,2). Surface concentration of these states was evaluated with impedance measurements. EER measurements on a CdIn(,2)Se(,4)/polysulfide system have shown that the EER spectrum is sensitive to the surface preparation of the sample. The EER signal was quenched as the surface was driven to strong depletion, owing to Fermi level pinning at the interface in the presence of a high density of surface states. The full analysis of this effect enables us to measure the change in the flatband potential, as a function of the electrode potential, and

  13. Microwave assisted sintering of gadolinium doped barium cerate electrolyte for intermediate temperature solid oxide fuel cells

    Kumar, Arumugam Senthil, E-mail: senthu.ramp@gmail.com [Department of Physics, PSG College of Technology, Coimbatore, 641 004, Tamilnadu (India); Balaji, Ramamoorthy [Department of Physics, PSG College of Technology, Coimbatore, 641 004, Tamilnadu (India); Jayakumar, Srinivasalu [Department of Physics, PSG Institute of Technology and Applied Research, Coimbatore, 641 062, Tamilnadu (India); Pradeep, Chandran [Department of Physics, Indian Institute of Technology, Madras, 600 036, Tamilnadu (India)

    2016-10-01

    In Solid Oxide Fuel Cell (SOFC), electrolyte plays a vital role to increase the energy conversion efficiency. The main hurdle of such electrolyte in fuel cell is its higher operating temperature (1000 °C) which results in design limitation and higher fabrication cost. In order to reduce the operating temperature of SOFC, a suitable electrolyte has been prepared through co-precipitation method followed by microwave sintering of solid ceramic. The calcination temperature for the as-prepared powder was identified using Differential Scanning Calorimetry. The crystal structure of the sample was found to exhibit its orthorhombic perovskite structure. The particle size was determined using High-Resolution Transmission Electron Microscope with uniform in shape and size, match with XRD results and confirmed from structural analysis. Thus, the sample prepared via co-precipitation method and the solid ceramic sintered through microwave can be a promising electrolyte for fuel cells operated at intermediate temperature. - Highlights: • To synthesis the composite electrolyte by chemical method and sinter using microwave. • To reduce the operating temperature of electrolyte for high ionic conductivity in SOFC's. • To study the phase purity and to develop nanocomposite at reduced temperature.

  14. Non-linear response of electrode-electrolyte interface at high current density

    Ruiz, G.A.; Felice, C.J.; Valentinuzzi, M.E.

    2005-01-01

    A distributed parameter non-linear circuit is presented as fractal model of an electrode-electrolyte interface. It includes the charge transfer resistance and the double layer capacitance at each fractal level. The circuit explains the linear behavior of its series equivalent resistance R eq with signals of amplitudes eq Fourier spectrum. As a consequence, both the equivalent resistance and reactance drop with voltage, facts reported experimentally by other authors

  15. In situ scanning probe spectroscopy at nanoscale solid/liquid interfaces

    Schindler, W.; Hugelmann, M.; Hugelmann, Ph.

    2005-01-01

    Electrochemistry provides unique features for the preparation of low-dimensional structures, but in situ spectroscopy with atomic/molecular resolution at such structures is at present not well established yet. This paper shows that in situ scanning probe spectroscopy at solid/liquid interfaces can be utilized to study electronic properties at nanoscale, if appropriate conditions are applied. Tunneling spectroscopy provides information about tunneling barrier heights and electronic states in the tunneling gap, as shown on Au(1 1 1) substrates, contact spectroscopy allows for transport measurements at single nanostructures, as shown at Au/n-Si(1 1 1) nanodiodes. The influence of the electrolytic environment on spectroscopic investigations is not a principal limitation, but offers additional degrees of freedom, which allow, for example, spectroscopic studies of potential dependent surface phenomena at solid/liquid interfaces

  16. Kinetics of aging of metastable, zirconium-dioxide-based solid electrolytes

    Vlasov, A.N.; Inozemtsev, M.V.

    1985-01-01

    The kinetics of aging of zirconium-dioxide-based metastable solid oxide electrolytes stabilized with 8 to 10 mole % of yttrium, holmium, or scandium oxide were studied over the temperature range from 1200 to 1373 0 K. Kinetic equations were proposed which describe the conduction behavior of two-phase solid electrolytes in a wide time range. The processes were found to occur independently at the initial stage of aging in the cubic solution, viz., an increase in the number of nuclei of the new phase, and a growth in volume of nuclei of the new phase. After a long time the former process ceases, and the kinetics of aging of the electrolyte only are determined by the kinetics of volume growth of the inclusions of new phase. The time-dependent behavior of two-phase solid solutions is discussed theoretically and examined experimentally

  17. Kinetics of aging of metastable solid electrolytes based on zirconium dioxide

    Vlasov, A.N.; Inozemtsev, M.V.

    1985-01-01

    Kinetics of aging of metastable solid electrolytes on the base of zirconium dioxide stabilized with 8-10 mol.%of yttrium, holmium, and scandium oxides has been studied within the 1200-1373 K temperature range. Kinetic equations describibg behaviour of electric conductivity of two-phase solid electrolytes within a wide temperature interval have been suggested. It has been established that at the initial stage of ageing in cubic solid solution two processes proceed independently of one another: growth of a number of new phase centres and of a volume of new phase centres. At large times growth of a number of new phase centres stops, and kinetics of electrolyte aging is defined only by the growth kinetics of a volume of new phase inclusions

  18. Polarization characteristics of composite electrodes in electrochemical cells with solid electrolytes based on CeO2 and LaGaO3

    Yaroslavtsev, I. Yu.; Kuzin, B. L.; Bronin, D. I.; Bogdanovich, N. M.

    2005-01-01

    For two types of electrochemical cells with oxygen-conducting solid electrolytes based on lanthanum gallate (LSGM) and cerium oxide (SDC) studied are the temperature dependences of the polarization conductivity of air electrodes prepared from lanthanum strontium manganite (LSM) and composites LSM-LSGM, LSM-SDC, and LSM-SSZ (SSZ is zirconium dioxide-based electrolyte). Effect of praseodymium oxide, added into these electrodes as a modifier, on their electrochemical properties is examined. Electrochemical systems with an LSM/LSGM interface exhibit low electrochemical activity toward the oxygen reaction, because during the formation of electrodes, LSM interacts with LSGM to form a poorly conducting product [ru

  19. Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

    Shinagawa, Tatsuya

    2016-08-04

    Direct photon to chemical energy conversion using semiconductor-electrocatalyst-electrolyte interfaces has been extensively investigated for more than a half century. Many studies have focused on screening materials for efficient photocatalysis. Photocatalytic efficiency has been improved during this period but is not sufficient for industrial commercialization. Detailed elucidation on the photocatalytic water splitting process leads to consecutive six reaction steps with the fundamental parameters involved: The photocatalysis is initiated involving photophysics derived from various semiconductor properties (1: photon absorption, 2: exciton separation). The generated charge carriers need to be transferred to surfaces effectively utilizing the interfaces (3: carrier diffusion, 4: carrier transport). Consequently, electrocatalysis finishes the process by producing products on the surface (5: catalytic efficiency, 6: mass transfer of reactants and products). Successful photocatalytic water splitting requires the enhancement of efficiency at each stage. Most critically, a fundamental understanding of the interfacial phenomena is highly desired for establishing "photocatalysis by design" concepts, where the kinetic bottleneck within a process is identified by further improving the specific properties of photocatalytic materials as opposed to blind material screening. Theoretical modeling using the identified quantitative parameters can effectively predict the theoretically attainable photon-conversion yields. This article provides an overview of the state-of-the-art theoretical understanding of interfacial problems mainly developed in our laboratory. Photocatalytic water splitting (especially hydrogen evolution on metal surfaces) was selected as a topic, and the photophysical and electrochemical processes that occur at semiconductor-metal, semiconductor-electrolyte and metal-electrolyte interfaces are discussed.

  20. Photoelectrical Stimulation of Neuronal Cells by an Organic Semiconductor-Electrolyte Interface.

    Abdullaeva, Oliya S; Schulz, Matthias; Balzer, Frank; Parisi, Jürgen; Lützen, Arne; Dedek, Karin; Schiek, Manuela

    2016-08-23

    As a step toward the realization of neuroprosthetics for vision restoration, we follow an electrophysiological patch-clamp approach to study the fundamental photoelectrical stimulation mechanism of neuronal model cells by an organic semiconductor-electrolyte interface. Our photoactive layer consisting of an anilino-squaraine donor blended with a fullerene acceptor is supporting the growth of the neuronal model cell line (N2A cells) without an adhesion layer on it and is not impairing cell viability. The transient photocurrent signal upon illumination from the semiconductor-electrolyte layer is able to trigger a passive response of the neuronal cells under physiological conditions via a capacitive coupling mechanism. We study the dynamics of the capacitive transmembrane currents by patch-clamp recordings and compare them to the dynamics of the photocurrent signal and its spectral responsivity. Furthermore, we characterize the morphology of the semiconductor-electrolyte interface by atomic force microscopy and study the stability of the interface in dark and under illuminated conditions.

  1. Screening possible solid electrolytes by calculating the conduction pathways using Bond Valence method

    Gao, Jian; Chu, Geng; He, Meng; Zhang, Shu; Xiao, RuiJuan; Li, Hong; Chen, LiQuan

    2014-08-01

    Inorganic solid electrolytes have distinguished advantages in terms of safety and stability, and are promising to substitute for conventional organic liquid electrolytes. However, low ionic conductivity of typical candidates is the key problem. As connective diffusion path is the prerequisite for high performance, we screen for possible solid electrolytes from the 2004 International Centre for Diffraction Data (ICDD) database by calculating conduction pathways using Bond Valence (BV) method. There are 109846 inorganic crystals in the 2004 ICDD database, and 5295 of them contain lithium. Except for those with toxic, radioactive, rare, or variable valence elements, 1380 materials are candidates for solid electrolytes. The rationality of the BV method is approved by comparing the existing solid electrolytes' conduction pathways we had calculated with those from experiments or first principle calculations. The implication for doping and substitution, two important ways to improve the conductivity, is also discussed. Among them Li2CO3 is selected for a detailed comparison, and the pathway is reproduced well with that based on the density functional studies. To reveal the correlation between connectivity of pathways and conductivity, α/ γ-LiAlO2 and Li2CO3 are investigated by the impedance spectrum as an example, and many experimental and theoretical studies are in process to indicate the relationship between property and structure. The BV method can calculate one material within a few minutes, providing an efficient way to lock onto targets from abundant data, and to investigate the structure-property relationship systematically.

  2. Development status of oxygen solid electrolyte sensors in HLMC in respect to monoblock reactor facilities

    Martynov, P.N.; Askhadullin, R.Sh.; Storozhenko, A.N.; Shelemet'ev, V.M.; Sadovnichij, R.P.; Ivanov, I.I.

    2014-01-01

    The results of developing sensors on the base of solid electrolytes to control oxygen in lead and lead-bismuth coolants are considered. It is found out that ceramic detecting elements on the base of solid electrolytes from oxide ceramics are able to work a long time in conditions of high temperatures and thermal shocks in molten metals (in gases). They show stable conducting and mechanical properties, thermal resistance, low gas permeability. Using considered detecting elements different sensors, including ones for monoblock reactors and facilities, are developed and manufactured. The given sensors can be used for both continuous and periodical oxygen control in heavy liquid metal coolants [ru

  3. Solid Surfaces, Interfaces and Thin Films

    Lüth, Hans

    2010-01-01

    This book emphasises both experimental and theoretical aspects of surface, interface and thin film physics. As in previous editions the preparation of surfaces and thin films, their atomic and morphological, their vibronic and electronic properties as well as fundamentals of adsorption are treated. Because of their importance in modern information technology and nanostructure physics particular emphasis is paid to electronic surface and interface states, semiconductor space charge layers and heterostructures as well as to superconductor/semiconductor interfaces and magnetic thin films. The latter topic was significantly extended in this new edition by more details about the giant magnetoresistance and a section about the spin-transfer torque mechanism including one new problem as exercise. Two new panels about Kerr-effect and spin-polarized scanning tunnelling microscopy were added, too. Furthermore, the meanwhile important group III-nitride surfaces and high-k oxide/semiconductor interfaces are shortly discu...

  4. Scattering of light at the growing solid-melt interface

    Gontijo, I.

    1987-12-01

    The scattering of light at the growing solid-melt interface of biphenyl and naphthalene was studied using the Photon Correlation Spectroscopy technique. The origin of this light scattering remained without a satisfactory explanation since its discovery at the ice-water interface in 1978. Recently, a model based on the segregation of gaseous impurities at the interface and subsequent precipitation of microbubbles was proposed to explain this phenomenon. We report here the first experimental results that confirm the microbbubles hypothesis. (author)

  5. A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes.

    Li, Nian-Wu; Shi, Yang; Yin, Ya-Xia; Zeng, Xian-Xiang; Li, Jin-Yi; Li, Cong-Ju; Wan, Li-Jun; Wen, Rui; Guo, Yu-Guo

    2018-02-05

    Lithium (Li) metal is a promising anode material for high-energy density batteries. However, the unstable and static solid electrolyte interphase (SEI) can be destroyed by the dynamic Li plating/stripping behavior on the Li anode surface, leading to side reactions and Li dendrites growth. Herein, we design a smart Li polyacrylic acid (LiPAA) SEI layer high elasticity to address the dynamic Li plating/stripping processes by self-adapting interface regulation, which is demonstrated by in situ AFM. With the high binding ability and excellent stability of the LiPAA polymer, the smart SEI can significantly reduce the side reactions and improve battery safety markedly. Stable cycling of 700 h is achieved in the LiPAA-Li/LiPAA-Li symmetrical cell. The innovative strategy of self-adapting SEI design is broadly applicable, providing opportunities for use in Li metal anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Design of high quality doped CeO2 solid electrolytes with nanohetero structure

    Mori, T.; Ou, D.R.; Ye, F.; Drennan, J.

    2006-01-01

    Doped cerium (CeO 2 ) compounds are fluorite related oxides which show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, a considerable interest has been shown in application of these materials for low (400-650 o C) temperature operation of solid oxide fuel cells (SOFCs). In this paper, our experimental data about the influence of microstructure at the atomic level on electrochemical properties were reviewed in order to develop high quality doped CeO 2 electrolytes in fuel cell applications. Using this data in the present paper, our original idea for a design of nanodomain structure in doped CeO 2 electrolytes was suggested. The nanosized powders and dense sintered bodies of M doped CeO 2 (M:Sm,Gd,La,Y,Yb, and Dy) compounds were fabricated. Also nanostructural features in these specimens were introduced for conclusion of relationship between electrolytic properties and domain structure in doped CeO 2 . It is essential that the electrolytic properties in doped CeO 2 solid electrolytes reflect in changes of microstructure even down to the atomic scale. Accordingly, a combined approach of nanostructure fabrication, electrical measurement and structure characterization was required to develop superior quality doped CeO 2 electrolytes in the fuel cells. (author)

  7. Novel chemically cross-linked solid state electrolyte for dye-sensitized solar cells

    Yin Xiong; Tan Weiwei; Xiang Wangchun; Lin Yuan; Zhang Jingbo; Xiao Xurui; Li Xueping; Zhou Xiaowen; Fang Shibi

    2010-01-01

    Poly(vinylpyridine-co-ethylene glycol methyl ether methacrylate) (P(VP-co-MEOMA)) and α,ω-diiodo poly(ethylene oxide-co-propylene oxide) (I[(EO) 0.8 -co-(PO) 0.2 ] y I) were synthesized and used as chemically cross-linked precursors of the electrolyte for dye-sensitized solar cells. Meanwhile, α-iodo poly(ethylene oxide-co-propylene oxide) methyl ether (CH 3 O[(EO) 0.8 -co-(PO) 0.2 ] x I) was synthesized and added into the electrolyte as an internal plasticizer. Novel polymer electrolyte resulting from chemically cross-linked precursors was obtained by the quaterisation at 90 o C for 30 min. The characteristics for this kind of electrolyte were investigated by means of ionic conductivity, thermogravimetric and photocurrent-voltage. The ambient ionic conductivity was significantly enhanced to 2.3 x 10 -4 S cm -1 after introducing plasticizer, modified-ionic liquid. The weight loss of the solid state electrolyte at 200 o C was 1.8%, and its decomposition temperature was 287 o C. Solid state dye-sensitized solar cell based on chemically cross-linked electrolyte presented an overall conversion efficiency of 2.35% under AM1.5 irradiation (100 mW cm -2 ). The as-fabricated device maintained 88% of its initial performance at room temperature even without sealing for 30 days, showing a good stability.

  8. Development of oxygen sensors using zirconia solid electrolyte for fuel rods

    Hiura, Nobuo; Endou, Yasuichi; Yamaura, Takayuki; Matui, Yoshinori; Niimi, Motoji; Hoshiya, Taiji; Kobiyama, Mamoru; Motohashi, Yoshinobu

    1999-01-01

    The oxygen potential in oxide fuel pellet is an important parameter to understand behavior of high burn up fuel and its integrity. Zirconia solid electrolyte which is durable under irradiation and high temperature is considered as candidate material for the oxygen potential. Combined use of solid electrolyte and Ni/NiO as a solid standard electrode will realize small size oxygen sensor which can be easily loaded in the fuel rod. Prototypes of the oxygen sensor made of these materials were irradiated with neutrons the Japan Materials Testing Reactor (JMTR), and characteristics of electromotive force (EMF) by sensors were examined under irradiation. For a prototype using zirconia solid electrolyte stabilized by Y 2 O 3 (YSZ), measured EMF under irradiation was nearly equivalent to the value under unirradiated condition, and very stable within a range of neutron fluence (E>1 MeV) up to 1.52 x 10 23 m -2 and for the time of 600 h. However, the measured EMFs were slightly smaller than the theoretical values. The reason for this decrease of the EMF was thought as due to insufficient adhesion forces between solid electrolyte and standard electrode. After modification of the sensor to increase adhesion force, EMF was measured again under irradiation. The results showed improvement of the characteristics of the sensor in which measured EMFs were almost equivalent to the theoretical values. (author)

  9. Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

    Song, Jinsuk; Kim, Mahn Won

    2010-03-11

    Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

  10. In situ surface X-ray diffraction studies of the copper-electrolyte interface. Atomic structure and homoepitaxial grwoth

    Golks, Frederik

    2011-05-19

    electrolyte revealed a hexagonal, rotated adlayer structure, which was not reported before for this system. In comparison to other halide-metal(111) systems, the potential dependence of this structure suggests a strong adsorbate-adsorbate interaction. Operating under diffusion-limited conditions, i.e., at constant deposition rate, homoepitaxial growth of the Cu(001) single crystal electrode in chloride-containing solution has been investigated in situ for 1 and 5 mM Cu ion concentrations as a function of deposition overpotential. Detailed insight into the complex relationship between the atomic-scale structure of the solid-liquid interface, the growth behavior, and the resulting surface morphology was gained, revealing a pronounced mutual interaction of the Cu growth process and the Cl adlayer order. Depending on the latter, transitions from step-flow to layer-by-layer to 3D growth are observed, attributed to a reduction in the Cu surface mobility with increasing order. The kinetics of the c(2 x 2) adlayer ordering, in turn, are strongly affected during Cu deposition as compared to results obtained in Cu-free solution. Moreover, an oscillatory average strain in the surface layer is observed during layer-by-layer growth, indicating an expansion of the topmost layer occurring periodically for fractional coverages. Addition of polyethylene glycol (PEG), a commonly used inhibitor in the industrial damascene process, considerably changes the growth conditions. The chloride ordering kinetics are influenced such that the c(2 x 2) covered phase is stabilized in a widened potential regime. The onset of the transition to 3D growth is observed at more negative potentials, limiting the occurrence of layering oscillations to a narrower potential regime. Compared to the PEG-free electrolyte, the deposition rate is notably slowed down by a factor of approximately 3. The present study reports new direct experimental observations of the growth mechanisms at electrochemical interfaces on the

  11. In situ surface X-ray diffraction studies of the copper-electrolyte interface. Atomic structure and homoepitaxial grwoth

    Golks, Frederik

    2011-05-19

    hexagonal, rotated adlayer structure, which was not reported before for this system. In comparison to other halide-metal(111) systems, the potential dependence of this structure suggests a strong adsorbate-adsorbate interaction. Operating under diffusion-limited conditions, i.e., at constant deposition rate, homoepitaxial growth of the Cu(001) single crystal electrode in chloride-containing solution has been investigated in situ for 1 and 5 mM Cu ion concentrations as a function of deposition overpotential. Detailed insight into the complex relationship between the atomic-scale structure of the solid-liquid interface, the growth behavior, and the resulting surface morphology was gained, revealing a pronounced mutual interaction of the Cu growth process and the Cl adlayer order. Depending on the latter, transitions from step-flow to layer-by-layer to 3D growth are observed, attributed to a reduction in the Cu surface mobility with increasing order. The kinetics of the c(2 x 2) adlayer ordering, in turn, are strongly affected during Cu deposition as compared to results obtained in Cu-free solution. Moreover, an oscillatory average strain in the surface layer is observed during layer-by-layer growth, indicating an expansion of the topmost layer occurring periodically for fractional coverages. Addition of polyethylene glycol (PEG), a commonly used inhibitor in the industrial damascene process, considerably changes the growth conditions. The chloride ordering kinetics are influenced such that the c(2 x 2) covered phase is stabilized in a widened potential regime. The onset of the transition to 3D growth is observed at more negative potentials, limiting the occurrence of layering oscillations to a narrower potential regime. Compared to the PEG-free electrolyte, the deposition rate is notably slowed down by a factor of approximately 3. The present study reports new direct experimental observations of the growth mechanisms at electrochemical interfaces on the atomic-scale.

  12. Multi-layer thin-film electrolytes for metal supported solid oxide fuel cells

    Haydn, Markus; Ortner, Kai; Franco, Thomas; Uhlenbruck, Sven; Menzler, Norbert H.; Stöver, Detlev; Bräuer, Günter; Venskutonis, Andreas; Sigl, Lorenz S.; Buchkremer, Hans-Peter; Vaßen, Robert

    2014-06-01

    A key to the development of metal-supported solid oxide fuel cells (MSCs) is the manufacturing of gas-tight thin-film electrolytes, which separate the cathode from the anode. This paper focuses the electrolyte manufacturing on the basis of 8YSZ (8 mol.-% Y2O3 stabilized ZrO2). The electrolyte layers are applied by a physical vapor deposition (PVD) gas flow sputtering (GFS) process. The gas-tightness of the electrolyte is significantly improved when sequential oxidic and metallic thin-film multi-layers are deposited, which interrupt the columnar grain structure of single-layer electrolytes. Such electrolytes with two or eight oxide/metal layers and a total thickness of about 4 μm obtain leakage rates of less than 3 × 10-4 hPa dm3 s-1 cm-2 (Δp: 100 hPa) at room temperature and therefore fulfill the gas tightness requirements. They are also highly tolerant with respect to surface flaws and particulate impurities which can be present on the graded anode underground. MSC cell tests with double-layer and multilayer electrolytes feature high power densities more than 1.4 W cm-2 at 850 °C and underline the high potential of MSC cells.

  13. Performance of a novel type of electrolyte-supported solid oxide fuel cell with honeycomb structure

    Ruiz-Morales, Juan Carlos; Savvin, Stanislav N.; Nunez, Pedro [Departmento de Quimica Inorganica, Universidad de La Laguna, 38200 Tenerife (Spain); Marrero-Lopez, David [Departamento de Fisica Aplicada I, Universidad de Malaga, 29071 Malaga (Spain); Pena-Martinez, Juan; Canales-Vazquez, Jesus [Instituto de Energias Renovables-Universidad de Castilla la Mancha, 02006 Albacete (Spain); Roa, Joan Josep; Segarra, Merce [DIOPMA, Departamento de Ciencia de los Materiales e Ing. Metalurgica, 08028 Barcelona (Spain)

    2010-01-15

    A novel design, alternative to the conventional electrolyte-supported solid oxide fuel cell (SOFC) is presented. In this new design, a honeycomb-electrolyte is fabricated from hexagonal cells, providing high mechanical strength to the whole structure and supporting the thin layer used as electrolyte of a SOFC. This new design allows a reduction of {proportional_to}70% of the electrolyte material and it renders modest performances over 320 mW cm{sup -2} but high volumetric power densities, i.e. 1.22 W cm{sup -3} under pure CH{sub 4} at 900 C, with a high OCV of 1.13 V, using the standard Ni-YSZ cermet as anode, Pt as cathode material and air as the oxidant gas. (author)

  14. Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

    Schroeder, D.J. [Department of Engineering Technology, College of Engineering and Engineering Technology, Northern Illinois University, 301B Still Gym, DeKalb, IL 60115 (United States); Hubaud, A.A. [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439-4837 (United States); Vaughey, J.T., E-mail: vaughey@anl.gov [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439-4837 (United States)

    2014-01-01

    Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stability of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.

  15. Solid surfaces, interfaces and thin films

    Lüth, Hans

    2015-01-01

    This book emphasises both experimental and theoretical aspects of surface, interface and thin-film physics. As in previous editions the preparation of surfaces and thin films, their atomic and morphological structure, their vibronic and electronic properties as well as fundamentals of adsorption are treated. Because of their importance in modern information technology and nanostructure research, particular emphasis is paid to electronic surface and interface states, semiconductor space charge layers and heterostructures. A special chapter of the book is devoted to collective phenomena at interfaces and in thin films such as superconductivity and magnetism. The latter topic includes the meanwhile important issues giant magnetoresistance and spin-transfer torque mechanism, both effects being of high interest in information technology. In this new edition, for the first time, the effect of spin-orbit coupling on surface states is treated. In this context the class of the recently detected topological insulators,...

  16. Interaction between cobalt-containing materials and solid electrolyte on the basis of lanthanum gallate

    Bronin, D.I.; Kuzin, B.L.; Sokolova, Yu.V.; Polyakova, N.V.

    2000-01-01

    High-temperature interaction of solid electrolyte La 0.88 Sr 0.12 Mg 0.18 Ga 0.82 O 3-α with material of oxygen electrode La 0.7 Sr 0.3 CoO 3-δ (LSC) and with Co 3 O 4 and its influence on electrochemical activity of oxygen electrodes made of LSO and Pt were studied using the methods of X-ray microanalysis, conductometry and impedance-spectroscopy. It was ascertained that the surface of the solid electrolyte contacting LSC or Co 3 O 4 at a temperature of 1100 Deg C and higher is enriched by cobalt. Electric conductivity of the electrolyte layer modified by cobalt is noticeably higher than that of the initial one. Electrochemical activity of oxygen electrodes made of LSC is 1-2 ordered higher than the one characteristic of platinum electrode [ru

  17. Three-dimensional ionic conduction in the strained electrolytes of solid oxide fuel cells

    Han, Yupei; Zou, Minda; Lv, Weiqiang; He, Weidong; Mao, Yiwu; Wang, Wei

    2016-01-01

    Flexible power sources including fuel cells and batteries are the key to realizing flexible electronic devices with pronounced foldability. To understand the bending effects in these devices, theoretical analysis on three-dimensional (3-D) lattice bending is necessary. In this report, we derive a 3-D analytical model to analyze the effects of electrolyte crystal bending on ionic conductivity in flexible solid-state batteries/fuel cells. By employing solid oxide fuel cells as a materials' platform, the intrinsic parameters of bent electrolyte materials, including lattice constant, Young's modulus, and Poisson ratio, are evaluated. Our work facilitates the rational design of highly efficient flexible electrolytes for high-performance flexible device applications.

  18. 1-Dimensional Analysis of Ultrasound at Closed Interface of Solid

    Yamawaki, H

    2014-01-01

    As a first step to investigate mechanism of nonlinear ultrasonic generation at closed cracks, computer simulation for ultrasonic propagation in 1 -dimensional solid including closed interface was examined using Improved-FDM. Fundamental calculation model which described interaction between open / closure motion of the interface and ultrasonic stress was developed. In the model, compression stress is distributed over the entire solid, as motive force for closure of the interface. The interface is exhibited by the small region, and its open / closure are determined using calculated strain of the region. As a result, motion of the interface causing generation of saw-tooth like displacement waveform was observed. Amplitude modulation of displacement waveform was also observed, and it indicated possibility that small fluctuation of open / closure timing caused the modulation of the amplitude

  19. Electrocatalysis in Water Electrolysis with Solid Polymer Electrolyte

    Rasten, Egil

    2001-10-01

    Development and optimization of the electrodes in a water electrolysis system using a polymer membrane as electrolyte have been carried out in this work. A cell voltage of 1.59 V (energy consumption of about 3.8 kWh/Nm{sub 3} H{sub 2}) has been obtained at practical operation conditions of the electrolysis cell (10 kA . m2, 90{sup o}C) using a total noble metal loading of less than 2.4 mg.cm{sub 2} and a Nafion -115 membrane. It is further shown that a cell voltage of less than 1.5 V is possible at the same conditions by combination of the best electrodes obtained in this work. The most important limitation of the electrolysis system using polymer membrane as electrolyte has proven to be the electrical conductivity of the catalysts due to the porous backing/current collector system, which increases the length of the current path and decreases the cross section compared to the apparent one. A careful compromise must therefore be obtained between electrical conductivity and active surface area, which can be tailored by preparation and annealing conditions of the metal oxide catalysts. Anode catalysts of different properties have been developed. The mixed oxide of Ir-Ta (85 mole% Ir) was found to exhibit highest voltage efficiency at a current density of 10 kA.m{sub 2} or below, whereas the mixed oxide of Ir and Ru (60-80 mole% Ir) was found to give the highest voltage efficiency for current densities of above 10 kA.m{sub 2}. Pt on carbon particles, was found to be less suitable as cathode catalyst in water electrolysis. The large carbon particles introduced an unnecessary porosity into the catalytic layer, which resulted in a high ohmic drop. Much better voltage efficiency was obtained by using Pt-black as cathode catalyst, which showed a far better electrical conductivity. Ru-oxide as cathode catalyst in water electrolysis systems using a polymer electrolyte was not found to be of particular interest due to insufficient electrochemical activity and too low

  20. Thermal expansion of proton solid electrolytes on the basis of BaCeO3

    Gorelov, V.P.; Arestova, N.V.; Kurumchin, Eh.Kh.; Vdovin, G.K.

    1995-01-01

    Thermal expansion of BaCeO 3 base ceramics is under study. It is shown that within the range of 600-800 deg C solid electrolytes on barium cerate basis exhibity the anomaly of thermal expansion. This fact makes their application difficult. 9 refs., 3 figs

  1. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  2. Nitrogen dissociation during RF sputtering of Lipon electrolyte for all-solid-states batteries

    Stamate, Eugen; Christiansen, Ane Sælland; Holtappels, Peter

    2013-01-01

    Small size and high power density secondary batteries are desired for a large number of applications based on miniature wireless devices and sensors that need to be compatible with the microelectronic fabrication technology. This fact resulted in the development of solid electrolytes, like lithium...

  3. Proton-conducting solid acid electrolytes based upon MH(PO3H)

    Zhou, W.

    2011-01-01

    Solid acids, such as CsHSO4 and CsH2PO4, are a novel class of anhydrous proton-conducting compounds that can be used as electrolyte in H2/O2 and direct methanol fuel cells. The disordering of the hydrogen-bonded network above the so-called superprotonic phase transition results in an increase of the

  4. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  5. About Error in Measuring Oxygen Concentration by Solid-Electrolyte Sensors

    V. I. Nazarov

    2008-01-01

    Full Text Available The paper evaluates additional errors while measuring oxygen concentration in a gas mixture by a solid-electrolyte cell. Experimental dependences of additional errors caused by changes in temperature in a sensor zone, discharge of gas mixture supplied to a sensor zone, partial pressure in the gas mixture and fluctuations in oxygen concentrations in the air.

  6. Modeling of vapor-liquid-solid equilibrium in gas - aqueous electrolyte systems

    Thomsen, Kaj; Rasmussen, Peter

    1999-01-01

    A thermodynamic model for the description of vapor-liquid-solid equilibria is introduced. This model is a combination of the extended UNIQUAC model for electrolytes and the Soave-Redlich-Kwong cubic equation of state. The model has been applied to aqueous systems containing ammonia and/or carbon ...

  7. Determination of intrinsic equilibrium constants at an alumina/electrolyte interface

    SLOBODAN K. MILONJIC

    2004-12-01

    Full Text Available Intrinsic ionization and complexation constants at an alumina/electrolyte interface were studied by the site binding model, while the sorption of alkali cations from aqueous solutions was interpreted by the triple-layer model. The surface properties of alumina were investigated by the potentiometric acid-base titration method. The point of zero charge (pHpzc of alumina obtained by this method was found to be 7.2. The obtained mean values of the intrinsic protonation and ionization constants of the surface hydroxyl groups and the intrinsic surface complexation constant, in different electrolytes, are pKinta1 = 4.4, pKinta2 = 9.6 and pKintM+ = 9.5, respectively.

  8. Perovskite solid electrolytes: Structure, transport properties and fuel cell applications

    Bonanos, N.; Knight, K.S.; Ellis, B.

    1995-01-01

    Doped barium cerate perovskites, first investigated by Iwahara and co-workers, have ionic conductivities of the order of 20 mS/cm at 800 degrees C making them attractive as fuel cell electrolytes for this temperature region. They have been used to construct laboratory scale fuel cells, which...... vapour transfer in a cell in which the perovskite is exposed to wet hydrogen on both sides. The evolution of transport properties with temperature is discussed in relation to structure. Neutron diffraction studies of doped and undoped barium cerate are reported, revealing a series of phase transitions...... between ambient temperature and 1000 degrees C. The available literature on chemical stability of cerate perovskites to reduction and attack by carbon dioxide is reviewed in brief....

  9. Behavior of strontium- and magnesium-doped gallate electrolyte in direct carbon solid oxide fuel cells

    Zhang, Li; Xiao, Jie; Xie, Yongmin; Tang, Yubao; Liu, Jiang; Liu, Meilin

    2014-01-01

    Highlights: • La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ (LSGM) can be used as electrolyte of direct carbon SOFCs. • DC-SOFC with LSGM electrolyte gives higher performance than that with YSZ. • LSGM-electrolyte DC-SOFC gives maximum power density of 383 mW cm −2 at 850 °C. • Operation of LSGM-DC-SOFC at 210 mA cm −2 lasts 72 min, with fuel utilization of 60%. - Abstract: Perovskite-type La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ (LSGM) is synthesized by conventional solid state reaction. Its phase composition, microstructure, relative density, and oxygen-ionic conductivity are investigated. Tubular electrolyte-supported solid oxide fuel cells (SOFCs) are prepared with the LSGM as electrolyte and gadolinia doped ceria (GDC) mixed with silver as anode. The SOFCs are operated with Fe-loaded activated carbon as fuel and ambient air as oxidant. A typical single cell gives a maximum power density of 383 mW cm −2 at 850 °C, which is nearly 1.3 times higher than that of the similar cell with YSZ as electrolyte. A stability test of 72 min is carried out at a constant current density of 210 mA cm −2 , with a fuel utilization of 60%, indicating that LaGaO 3 -based electrolyte is promising to be applied in direct carbon SOFCs (DC-SOFCs)

  10. Behavior of strontium- and magnesium-doped gallate electrolyte in direct carbon solid oxide fuel cells

    Zhang, Li; Xiao, Jie; Xie, Yongmin [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Tang, Yubao [Key Laboratory of Sensor Analysis of Tumor Marker Ministry of Education, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao o 266042 (China); Liu, Jiang, E-mail: jiangliu@scut.edu.cn [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); New Energy Research Institute, College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); Liu, Meilin [New Energy Research Institute, College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); School of Materials Science and Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, GA 30332-0245 (United States)

    2014-09-01

    Highlights: • La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3−δ} (LSGM) can be used as electrolyte of direct carbon SOFCs. • DC-SOFC with LSGM electrolyte gives higher performance than that with YSZ. • LSGM-electrolyte DC-SOFC gives maximum power density of 383 mW cm{sup −2} at 850 °C. • Operation of LSGM-DC-SOFC at 210 mA cm{sup −2} lasts 72 min, with fuel utilization of 60%. - Abstract: Perovskite-type La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3−δ} (LSGM) is synthesized by conventional solid state reaction. Its phase composition, microstructure, relative density, and oxygen-ionic conductivity are investigated. Tubular electrolyte-supported solid oxide fuel cells (SOFCs) are prepared with the LSGM as electrolyte and gadolinia doped ceria (GDC) mixed with silver as anode. The SOFCs are operated with Fe-loaded activated carbon as fuel and ambient air as oxidant. A typical single cell gives a maximum power density of 383 mW cm{sup −2} at 850 °C, which is nearly 1.3 times higher than that of the similar cell with YSZ as electrolyte. A stability test of 72 min is carried out at a constant current density of 210 mA cm{sup −2}, with a fuel utilization of 60%, indicating that LaGaO{sub 3}-based electrolyte is promising to be applied in direct carbon SOFCs (DC-SOFCs)

  11. Non-Faradaic Li + Migration and Chemical Coordination across Solid-State Battery Interfaces

    Gittleson, Forrest S. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); El Gabaly, Farid [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2017-10-17

    Efficient and reversible charge transfer is essential to realizing high-performance solid-state batteries. Efforts to enhance charge transfer at critical electrode–electrolyte interfaces have proven successful, yet interfacial chemistry and its impact on cell function remains poorly understood. Using X-ray photoelectron spectroscopy combined with electrochemical techniques, we elucidate chemical coordination near the LiCoO2–LIPON interface, providing experimental validation of space-charge separation. Space-charge layers, defined by local enrichment and depletion of charges, have previously been theorized and modeled, but the unique chemistry of solid-state battery interfaces is now revealed. Here we highlight the non-Faradaic migration of Li+ ions from the electrode to the electrolyte, which reduces reversible cathodic capacity by ~15%. Inserting a thin, ion-conducting LiNbO3 interlayer between the electrode and electrolyte, however, can reduce space-charge separation, mitigate the loss of Li+ from LiCoO2, and return cathodic capacity to its theoretical value. This work illustrates the importance of interfacial chemistry in understanding and improving solid-state batteries.

  12. A solid-on-solid invasion percolation model for self-affine interfaces

    Arizmendi, C.M.; Martin, H.O.; Sanchez, J.R.

    1993-08-01

    The scaling properties of the interface of a new growth model are studied. The model is based on the standard invasion percolation without trapping in which the solid-on-solid condition is imposed. The local correlation between points of the interface can be controlled through a parameter. The self-affine properties of the interface show strong dependence on the existence of the local correlation. The dependence of the relevant exponents of the interface with the correlation is analysed. (author). 8 refs, 4 figs

  13. In situ electron holography of electric potentials inside a solid-state electrolyte: Effect of electric-field leakage

    Aizawa, Yuka; Yamamoto, Kazuo; Sato, Takeshi [Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya, Aichi 456-8587 (Japan); Murata, Hidekazu [Faculty of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku, Nagoya, Aichi 468-8502 (Japan); Yoshida, Ryuji; Fisher, Craig A.J. [Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya, Aichi 456-8587 (Japan); Kato, Takehisa; Iriyama, Yasutoshi [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8601 (Japan); Hirayama, Tsukasa, E-mail: t-hirayama@jfcc.or.jp [Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya, Aichi 456-8587 (Japan)

    2017-07-15

    In situ electron holography is used to observe changes of electric-potential distributions in an amorphous lithium phosphorus oxynitride (LiPON) solid-state electrolyte when different voltages are applied. 2D phase images are simulated by integrating the 3D potential distribution along the electron trajectory through a thin Cu/LiPON/Cu region. Good agreement between experimental and simulated phase distributions is obtained when the influence of the external electric field is taken into account using the 3D boundary-charge method. Based on the precise potential changes, the lithium-ion and lithium-vacancy distributions inside the LiPON layer and electric double layers (EDLs) are inferred. The gradients of the phase drops at the interfaces in relation to EDL widths are discussed. - Highlights: • Solid-state electrolyte LiPON has been observed by in situ electron holography. • Observed phase distributions are compared with those simulated numerically. • 3D electric fields around the specimen are taken into account in the simulation. • Electric-potential distributions inside LiPON have been obtained. • The lithium-ion and lithium-vacancy distributions inside the LiPON are inferred.

  14. Finite size melting of spherical solid-liquid aluminium interfaces

    Chang, J.; Johnson, Erik; Sakai, T.

    2009-01-01

    We have investigated the melting of nano-sized cone shaped aluminium needles coated with amorphous carbon using transmission electron microscopy. The interface between solid and liquid aluminium was found to have spherical topology. For needles with fixed apex angle, the depressed melting tempera...... to the conclusion that the depressed melting temperature is not controlled solely by the inverse radius 1/R. Instead, we found a direct relation between the depressed melting temperature and the ratio between the solid-liquid interface area and the molten volume.......We have investigated the melting of nano-sized cone shaped aluminium needles coated with amorphous carbon using transmission electron microscopy. The interface between solid and liquid aluminium was found to have spherical topology. For needles with fixed apex angle, the depressed melting...

  15. Heat transfer across the interface between nanoscale solids and gas.

    Cheng, Chun; Fan, Wen; Cao, Jinbo; Ryu, Sang-Gil; Ji, Jie; Grigoropoulos, Costas P; Wu, Junqiao

    2011-12-27

    When solid materials and devices scale down in size, heat transfer from the active region to the gas environment becomes increasingly significant. We show that the heat transfer coefficient across the solid-gas interface behaves very differently when the size of the solid is reduced to the nanoscale, such as that of a single nanowire. Unlike for macroscopic solids, the coefficient is strongly pressure dependent above ∼10 Torr, and at lower pressures it is much higher than predictions of the kinetic gas theory. The heat transfer coefficient was measured between a single, free-standing VO(2) nanowire and surrounding air using laser thermography, where the temperature distribution along the VO(2) nanowire was determined by imaging its domain structure of metal-insulator phase transition. The one-dimensional domain structure along the nanowire results from the balance between heat generation by the focused laser and heat dissipation to the substrate as well as to the surrounding gas, and thus serves as a nanoscale power-meter and thermometer. We quantified the heat loss rate across the nanowire-air interface, and found that it dominates over all other heat dissipation channels for small-diameter nanowires near ambient pressure. As the heat transfer across the solid-gas interface is nearly independent of the chemical identity of the solid, the results reveal a general scaling relationship for gaseous heat dissipation from nanostructures of all solid materials, which is applicable to nanoscale electronic and thermal devices exposed to gaseous environments.

  16. Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte

    Omed Gh. Abdullah

    Full Text Available Solid polymer electrolyte films of polyvinyl alcohol (PVA doped with a different weight percent of potassium permanganate (KMnO4 were prepared by standard solution cast method. XRD and FTIR techniques were performed for structural study. Complex formation between the PVA polymer and KMnO4 salt was confirmed by Fourier transform infrared (FTIR spectroscopy. The description of crystalline nature of the solid polymer electrolyte films has been confirmed by XRD analysis. The UV-Visible absorption spectra were analyzed in terms of absorption formula for non-crystalline materials. The fundamental optical parameters such as optical band gap energy, refractive index, optical conductivity, and dielectric constants have been investigated and showed a clear dependence on the KMnO4 concentration. The observed value of optical band gap energy for pure PVA is about 6.27 eV and decreases to a value 3.12 eV for the film sample formed with 4 wt% KMnO4 salt. The calculated values of refractive index and the dielectric constants of the polymer electrolyte films increase with increasing KMnO4 content. Keywords: Solid polymer electrolyte, XRD analysis, FTIR study, Optical band gap, Dielectric constant, Refractive index

  17. Ion transport property studies on PEO-PVP blended solid polymer electrolyte membranes

    Chandra, Angesh; Agrawal, R C; Mahipal, Y K

    2009-01-01

    The ion transport property studies on Ag + ion conducting PEO-PVP blended solid polymer electrolyte (SPE) membranes, (1 - x)[90PEO : 10AgNO 3 ] : xPVP, where x = 0, 1, 2, 3, 5, 7, 10 (wt%), are reported. SPE films were caste using a novel hot-press technique instead of the traditional solution cast method. The conventional solid polymeric electrolyte (SPE) film, (90PEO : 10AgNO 3 ), also prepared by the hot-press method and identified as the highest conducting composition at room temperature on the basis of PEO-AgNO 3 -salt concentration dependent conductivity studies, was used as the first-phase polymer electrolyte host into which PVP were dispersed as second-phase dispersoid. A two-fold conductivity enhancement from that of the PEO host could be achieved at room temperature for PVP blended SPE film composition: 98(90PEO : 10AgNO 3 ) : 2PVP. This has been referred to as optimum conducting composition (OCC). The formation of SPE membranes and material characterizations were done with the help of the XRD and DSC techniques. The ion transport mechanism in this SPE OCC has been characterized with the help of basic ionic parameters, namely ionic conductivity (σ), ionic mobility (μ), mobile ion concentration (n) and ionic transference number (t ion ). Solid-state polymeric batteries were fabricated using OCC as electrolyte and the cell-potential discharge characteristics were studied under different load conditions.

  18. Bioinspired Ultrastrong Solid Electrolytes with Fast Proton Conduction along 2D Channels.

    He, Guangwei; Xu, Mingzhao; Zhao, Jing; Jiang, Shengtao; Wang, Shaofei; Li, Zhen; He, Xueyi; Huang, Tong; Cao, Moyuan; Wu, Hong; Guiver, Michael D; Jiang, Zhongyi

    2017-07-01

    Solid electrolytes have attracted much attention due to their great prospects in a number of energy- and environment-related applications including fuel cells. Fast ion transport and superior mechanical properties of solid electrolytes are both of critical significance for these devices to operate with high efficiency and long-term stability. To address a common tradeoff relationship between ionic conductivity and mechanical properties, electrolyte membranes with proton-conducting 2D channels and nacre-inspired architecture are reported. An unprecedented combination of high proton conductivity (326 mS cm -1 at 80 °C) and superior mechanical properties (tensile strength of 250 MPa) are achieved due to the integration of exceptionally continuous 2D channels and nacre-inspired brick-and-mortar architecture into one materials system. Moreover, the membrane exhibits higher power density than Nafion 212 membrane, but with a comparative weight of only ≈0.1, indicating potential savings in system weight and cost. Considering the extraordinary properties and independent tunability of ion conduction and mechanical properties, this bioinspired approach may pave the way for the design of next-generation high-performance solid electrolytes with nacre-like architecture. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Solid polymer electrolyte on the basis of polyethylene carbonate-lithium perchlorate system

    Dukhanin, G.P.; Dumler, S.A.; Sablin, A.N.; Novakov, I.A.

    2009-01-01

    Reaction in the system polyethylene carbonate-lithium perchlorate was investigated by IR spectroscopy, differential thermal and X-ray structural analyses. Specific electric conductivity of the prepared composition has been measured. Solid polymer electrolytes on the basis of polyethylene carbonate have conducting properties as electrolytes on the basis of unmodified polyethylene oxide. Compositions of polyethylene carbonate : LiClO 4 =10 : 1Al 2 O 3 -ZrO 2 possess maximum value of electrical conductivity. Activation energies of the process is calculated for all investigated compositions, and dependence of these values from concentration of lithium perchlorate is established

  20. Further studies on the lithium phosphorus oxynitride solid electrolyte

    Pichonat, Tristan; Lethien, Christophe; Tiercelin, Nicolas; Godey, Sylvie; Pichonat, Emmanuelle; Roussel, Pascal; Colmont, Marie; Rolland, Paul Alain

    2010-01-01

    First step in the way to the fabrication of an all-solid microbattery for autonomous wireless sensor node, amorphous thin solid films of lithium phosphorus oxynitride (LiPON) were prepared by radio-frequency sputtering of a mixture target of P 2 O 5 /Li 2 O in ambient nitrogen atmosphere. The morphology, composition, and ionic conductivity were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and A.C. impedance spectroscopy. With a thickness of 1.4 μm, the obtained LiPON amorphous layer provided an ionic conductivity close to 6 x 10 -7 S cm -1 at room temperature. MicroRaman UV spectroscopy study was successfully carried out for the first time on LiPON thin films to complete the characterization and bring further information on LiPON structure.

  1. Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes

    Ahmad, Zeeshan; Viswanathan, Venkatasubramanian

    2017-08-01

    We generalize the conditions for stable electrodeposition at isotropic solid-solid interfaces using a kinetic model which incorporates the effects of stresses and surface tension at the interface. We develop a stability diagram that shows two regimes of stability: a previously known pressure-driven mechanism and a new density-driven stability mechanism that is governed by the relative density of metal in the two phases. We show that inorganic solids and solid polymers generally do not lead to stable electrodeposition, and provide design guidelines for achieving stable electrodeposition.

  2. Noncovalent Pi-Pi Stacking at the Carbon-Electrolyte Interface: Controlling the Voltage Window of Electrochemical Supercapacitors.

    Li, Mengya; Westover, Andrew S; Carter, Rachel; Oakes, Landon; Muralidharan, Nitin; Boire, Timothy C; Sung, Hak-Joon; Pint, Cary L

    2016-08-03

    A key parameter in the operation of an electrochemical double-layer capacitor is the voltage window, which dictates the device energy density and power density. Here we demonstrate experimental evidence that π-π stacking at a carbon-ionic liquid interface can modify the operation voltage of a supercapacitor device by up to 30%, and this can be recovered by steric hindrance at the electrode-electrolyte interface introduced by poly(ethylene oxide) polymer electrolyte additives. This observation is supported by Raman spectroscopy, electrochemical impedance spectroscopy, and differential scanning calorimetry that each independently elucidates the signature of π-π stacking between imidazole groups in the ionic liquid and the carbon surface and the role this plays to lower the energy barrier for charge transfer at the electrode-electrolyte interface. This effect is further observed universally across two separate ionic liquid electrolyte systems and is validated by control experiments showing an invariant electrochemical window in the absence of a carbon-ionic liquid electrode-electrolyte interface. As interfacial or noncovalent interactions are usually neglected in the mechanistic picture of double-layer capacitors, this work highlights the importance of understanding chemical properties at supercapacitor interfaces to engineer voltage and energy capability.

  3. Fracture mechanics of piezoelectric solids with interface cracks

    Govorukha, Volodymyr; Loboda, Volodymyr; Lapusta, Yuri

    2017-01-01

    This book provides a comprehensive study of cracks situated at the interface of two piezoelectric materials. It discusses different electric boundary conditions along the crack faces, in particular the cases of electrically permeable, impermeable, partially permeable, and conducting cracks. The book also elaborates on a new technique for the determination of electromechanical fields at the tips of interface cracks in finite sized piezoceramic bodies of arbitrary shape under different load types. It solves scientific problems of solid mechanics in connection with the investigation of electromechanical fields in piezoceramic bodies with interface cracks, and develops calculation models and solution methods for plane fracture mechanical problems for piecewise homogeneous piezoceramic bodies with cracks at the interfaces. It discusses the “open” crack model, which leads to a physically unrealistic oscillating singularity at the crack tips, and the contact zone model for in-plane straight interface cracks betw...

  4. Role of anisotropy in determining stability of electrodeposition at solid-solid interfaces

    Ahmad, Zeeshan; Viswanathan, Venkatasubramanian

    2017-10-01

    We investigate the stability of electrodeposition at solid-solid interfaces for materials exhibiting an anisotropic mechanical response. The stability of electrodeposition or resistance to the formation of dendrites is studied within a linear stability analysis. The deformation and stress equations are solved using the Stroh formalism and faithfully recover the boundary conditions at the interface. The stability parameter is used to quantify the stability of different solid-solid interfaces incorporating the full anisotropy of the elastic tensor of the two materials. Results show a high degree of variability in the stability parameter depending on the crystallographic orientation of the solids in contact, and point to opportunities for exploiting this effect in developing Li metal anodes.

  5. Dynamics of solid nanoparticles near a liquid-liquid interface

    Daher, Ali; Ammar, Amine; Hijazi, Abbas

    2018-05-01

    The liquid - liquid interface can be used as a suitable medium for generating some nanostructured films of metals, or inorganic materials such as semi conducting metals. This process can be controlled well if we study the dynamics of nanoparticles (NPs) at the liquid-liquid interface which is a new field of study, and is not understood well yet. The dynamics of NPs at liquid-liquid interfaces is investigated by solving the fluid-particle and particle-particle interactions. Our work is based on the Molecular Dynamics (MD) simulation in addition to Phase Field (PF) method. We modeled the liquid-liquid interface using the diffuse interface model, where the interface is considered to have a characteristic thickness. We have shown that the concentration gradient of one fluid in the other gives rise to a hydrodynamic force that drives the NPs to agglomerate at the interface. These obtained results may introduce new applications where certain interfaces can be considered to be suitable mediums for the synthesis of nanostructured materials. In addition, some liquid interfaces can play the role of effective filters for different species of biological NPs and solid state waste NPs, which will be very important in many industrial and biomedical domains.

  6. Effective improvement of interface modified strontium titanate based solid oxide fuel cell anodes by infiltration with nano-sized palladium and gadolinium-doped cerium oxide

    Abdul Jabbar, Mohammed Hussain; Høgh, Jens Valdemar Thorvald; Zhang, Wei

    2013-01-01

    The development of low temperature solid oxide fuel cell (SOFC) anodes by infiltration of Pd/Gd-doped cerium oxide (CGO) electrocatalysts in Nb-doped SrTiO3 (STN) backbones has been investigated. Modification of the electrode/electrolyte interface by thin layer of spin-coated CGO (400-500 nm) con...

  7. A novel temperature-gradient Na±β-alumina solid electrolyte based SOx gas sensor without gaseous reference electrode

    Rao, N.; Bleek, C.M. Van den; Schoonman, J.

    1992-01-01

    An electrochemical SOx ps sensor with a tubular Na+-beta"-alumina solid electrolyte has been fabricated and tested under non-isothermal conditions. The temperature difference between the reference and working electrode of the sensor cell is about 100-degrees-C, which causes a serious deviation...... of the experimental EMF response from the value as calculated using the Nernst equation for an isothermal system. The experimental results are Consistent with the theoretical prediction for a non-isothermal system. The response time is usually less then 10 min. SEM and EDX have been employed to investigate the sensor...... material before and after use, confirming the formation of a glassy phase of Na2SO4 by an electrochemical reaction at the interface of the platinum electrodes and Na+-beta"-alumina. According to this new theoretical derivation, the sensor design could be simplified by applying the same SO2 ps at the two...

  8. All-solid-state Al-air batteries with polymer alkaline gel electrolyte

    Zhang, Zhao; Zuo, Chuncheng; Liu, Zihui; Yu, Ying; Zuo, Yuxin; Song, Yu

    2014-04-01

    Aluminum-air (Al-air) battery is one of the most promising candidates for next-generation energy storage systems because of its high capacity and energy density, and abundance. The polyacrylic acid (PAA)-based alkaline gel electrolyte is used in all-solid-state Al-air batteries instead of aqueous electrolytes to prevent leakage. The optimal gel electrolyte exhibits an ionic conductivity of 460 mS cm-1, which is close to that of aqueous electrolytes. The Al-air battery peak capacity and energy density considering only Al can reach 1166 mAh g-1-Al and 1230 mWh g-1-Al, respectively, during constant current discharge. The battery prototype also exhibits a high power density of 91.13 mW cm-2. For the battery is a laminated structure, area densities of 29.2 mAh cm-2 and 30.8 mWh cm-2 are presented to appraise the performance of the whole cell. A novel design to inhibit anodic corrosion is proposed by separating the Al anode from the gel electrolyte when not in use, thereby effectively maintaining the available capacity of the battery.

  9. Preparation and Characterization of PVA Alkaline Solid Polymer Electrolyte with Addition of Bamboo Charcoal

    Lidan Fan

    2018-04-01

    Full Text Available Natural bamboo charcoal (BC powder has been developed as a novel filler in order to further improve performances of the polyvinyl alcohol (PVA-based alkaline solid polymer electrolyte (ASPE by solution casting method. X-ray diffraction patterns of composite polymer electrolyte with BC revealed the decrease in the degree of crystallinity with increasing content of BC. Scanning electron microscopy images showed pores on a micrometer scale (average diameter about 2 μm distributed inside and on the surface of the membranes, indicating a three-dimension network formed in the polymer framework. The ionic conductivity was measured by the alternating-current (AC impedance method, and the highest conductivity value of 6.63 × 10−2 S·cm−1 was obtained with 16 wt % of BC content and mKOH:mPVA = 2:1.5 at 30 °C. The contents of BC and KOH could significantly influence the conductivity. The temperature dependence of the bulk electrical conductivity displayed a combination of Arrhenius nature, and the activation energy for the ion in polymer electrolyte has been calculated. The electrochemical stability window of the electrolyte membrane was over 1.6 V. The thermogravimetric analysis curves showed that the degradation temperatures of PVA-BC-KOH ASPE membranes shifted toward higher with adding BC. A simple nickel-hydrogen battery containing PVA-BC-KOH electrolyte membrane was assembled with a maximum discharge capacity of 193 mAh·g−1.

  10. Preparation and Characterization of PVA Alkaline Solid Polymer Electrolyte with Addition of Bamboo Charcoal.

    Fan, Lidan; Wang, Mengyue; Zhang, Zhen; Qin, Gang; Hu, Xiaoyi; Chen, Qiang

    2018-04-26

    Natural bamboo charcoal (BC) powder has been developed as a novel filler in order to further improve performances of the polyvinyl alcohol (PVA)-based alkaline solid polymer electrolyte (ASPE) by solution casting method. X-ray diffraction patterns of composite polymer electrolyte with BC revealed the decrease in the degree of crystallinity with increasing content of BC. Scanning electron microscopy images showed pores on a micrometer scale (average diameter about 2 μm) distributed inside and on the surface of the membranes, indicating a three-dimension network formed in the polymer framework. The ionic conductivity was measured by the alternating-current (AC) impedance method, and the highest conductivity value of 6.63 × 10 −2 S·cm −1 was obtained with 16 wt % of BC content and m KOH : m PVA = 2:1.5 at 30 °C. The contents of BC and KOH could significantly influence the conductivity. The temperature dependence of the bulk electrical conductivity displayed a combination of Arrhenius nature, and the activation energy for the ion in polymer electrolyte has been calculated. The electrochemical stability window of the electrolyte membrane was over 1.6 V. The thermogravimetric analysis curves showed that the degradation temperatures of PVA-BC-KOH ASPE membranes shifted toward higher with adding BC. A simple nickel-hydrogen battery containing PVA-BC-KOH electrolyte membrane was assembled with a maximum discharge capacity of 193 mAh·g −1 .

  11. Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

    Soto, Fernando A. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Yan, Pengfei [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Engelhard, Mark H. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Marzouk, Asma [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Wang, Chongmin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Xu, Guiliang [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Liu, Jun [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Sprenkle, Vincent L. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; El-Mellouhi, Fedwa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Balbuena, Perla B. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Li, Xiaolin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA

    2017-03-07

    Solid-electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li- and Na-ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li- or Na-based electrolyte, and that ionic transport can be kinetically controlled. Selective Li- and Na-based SEI membranes are produced using Li- or Na-based electrolytes, respectively. The Na-based SEI allows easy transport of Li ions, while the Li-based SEI shuts off Na-ion transport. Na-ion storage can be manipulated by tuning the SEI layer with film-forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g(-1); approximate to 1/10 of the normal capacity (250 mAh g(-1)). Unusual selective/ preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion-selective conductors using electrochemical approaches.

  12. Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

    Soto, Fernando A. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Yan, Pengfei [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Engelhard, Mark H. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Marzouk, Asma [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Wang, Chongmin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Xu, Guiliang [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Argonne IL 60439 USA; Liu, Jun [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Sprenkle, Vincent L. [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; El-Mellouhi, Fedwa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha Qatar; Balbuena, Perla B. [Department of Chemical Engineering, Texas A& M University, College Station TX 77843-3122 USA; Li, Xiaolin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA

    2017-03-07

    Solid-electrolyte interphase (SEI) with controllable properties are highly desirable to improve battery performance. In this paper, we use a combined experimental and simulation approach to study the SEI formation on hard carbon in Li and Na-ion batteries. We show that with proper additives, stable SEI can be formed on hard carbon by pre-cycling the electrode materials in Li or Na-ion electrolyte. Detailed mechanistic studies suggest that the ion transport in the SEI layer is kinetically controlled and can be tuned by the applied voltage. Selective Na and Li-ion SEI membranes are produced using the Na or Li-ion based electrolytes respectively. The large Na ion SEI allows easy transport of Li ions, while the small Li ion SEI shuts off the Na-ion transport. Na-ion storage can be manipulated by tuning the SEI with film-forming electrolyte additives or preforming a SEI on the electrodes’ surface. The Na specific capacity can be controlled to <25 mAh/g, ~1/10 of the normal capacity (250 mAh/g). Unusual selective/preferential transport of Li-ion is demonstrated by preforming a SEI on the electrode’s surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion selective conductors using electrochemical approaches in the future.

  13. Lanthanum gallate and ceria composite as electrolyte for solid oxide fuel cells

    Li Shuai; Li Zhicheng; Bergman, Bill

    2010-01-01

    The composite of doped lanthanum gallate (La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 , LSGM) and doped ceria (Ce 0.8 Sm 0.2 O 1.9 , CSO) was investigated as an electrolyte for solid oxide fuel cell (SOFC). The LSGM-CSO composite was examined by X-ray diffraction (XRD) and impedance spectroscopy. It was found that the sintered LSGM-CSO composite contains mainly fluorite CeO 2 phase and a minority impurity phase, Sm 3 Ga 5 O 12 . The LSGM-CSO composite electrolyte shows a small grain boundary response in the impedance spectroscopy as compared to LSGM and CSO pellets. The composite electrolyte exhibits the highest conductivity in the temperature range of 250-600 o C, compared to LSGM and CSO. The LSGM-CSO composite can be expected to be an attractive intermediate temperature electrolyte material for solid oxide fuel cells.

  14. Lanthanum gallate and ceria composite as electrolyte for solid oxide fuel cells

    Li Shuai, E-mail: shuail@kth.s [Department of Materials Science and Engineering, School of Industrial Engineering and Management, Royal Institute of Technology, SE 10044 Stockholm (Sweden); Li Zhicheng [School of Materials Science and Engineering, Central South University, 410083 Changsha, Hunan (China); Bergman, Bill [Department of Materials Science and Engineering, School of Industrial Engineering and Management, Royal Institute of Technology, SE 10044 Stockholm (Sweden)

    2010-03-04

    The composite of doped lanthanum gallate (La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 2.85}, LSGM) and doped ceria (Ce{sub 0.8}Sm{sub 0.2}O{sub 1.9}, CSO) was investigated as an electrolyte for solid oxide fuel cell (SOFC). The LSGM-CSO composite was examined by X-ray diffraction (XRD) and impedance spectroscopy. It was found that the sintered LSGM-CSO composite contains mainly fluorite CeO{sub 2} phase and a minority impurity phase, Sm{sub 3}Ga{sub 5}O{sub 12}. The LSGM-CSO composite electrolyte shows a small grain boundary response in the impedance spectroscopy as compared to LSGM and CSO pellets. The composite electrolyte exhibits the highest conductivity in the temperature range of 250-600 {sup o}C, compared to LSGM and CSO. The LSGM-CSO composite can be expected to be an attractive intermediate temperature electrolyte material for solid oxide fuel cells.

  15. Composite electrolyte with proton conductivity for low-temperature solid oxide fuel cell

    Raza, Rizwan, E-mail: razahussaini786@gmail.com [Department of Physics, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Department of Energy Technology, Royal Institute of Technology, KTH, Stockholm 10044 (Sweden); Ahmed, Akhlaq; Akram, Nadeem; Saleem, Muhammad; Niaz Akhtar, Majid; Ajmal Khan, M.; Abbas, Ghazanfar; Alvi, Farah; Yasir Rafique, M. [Department of Physics, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Sherazi, Tauqir A. [Department of Chemistry, COMSATS Institute of Information Technology, Abbotabad 22060 (Pakistan); Shakir, Imran [Sustainable Energy Technologies (SET) center, College of Engineering, King Saud University, PO-BOX 800, Riyadh 11421 (Saudi Arabia); Mohsin, Munazza [Department of Physics, Lahore College for Women University, Lahore, 54000 (Pakistan); Javed, Muhammad Sufyan [Department of Physics, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Department of Applied Physics, Chongqing University, Chongqing 400044 (China); Zhu, Bin, E-mail: binzhu@kth.se, E-mail: zhubin@hubu.edu.cn [Department of Energy Technology, Royal Institute of Technology, KTH, Stockholm 10044 (Sweden); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Faculty of Physics and Electronic Science/Faculty of Computer and Information, Hubei University, Wuhan, Hubei 430062 (China)

    2015-11-02

    In the present work, cost-effective nanocomposite electrolyte (Ba-SDC) oxide is developed for efficient low-temperature solid oxide fuel cells (LTSOFCs). Analysis has shown that dual phase conduction of O{sup −2} (oxygen ions) and H{sup +} (protons) plays a significant role in the development of advanced LTSOFCs. Comparatively high proton ion conductivity (0.19 s/cm) for LTSOFCs was achieved at low temperature (460 °C). In this article, the ionic conduction behaviour of LTSOFCs is explained by carrying out electrochemical impedance spectroscopy measurements. Further, the phase and structure analysis are investigated by X-ray diffraction and scanning electron microscopy techniques. Finally, we achieved an ionic transport number of the composite electrolyte for LTSOFCs as high as 0.95 and energy and power density of 90% and 550 mW/cm{sup 2}, respectively, after sintering the composite electrolyte at 800 °C for 4 h, which is promising. Our current effort toward the development of an efficient, green, low-temperature solid oxide fuel cell with the incorporation of high proton conductivity composite electrolyte may open frontiers in the fields of energy and fuel cell technology.

  16. Fabrication of WO3-based electrochromic displays using solid or gel-like organic electrolytes

    Vasilopoulou, M; Aspiotis, G; Kostis, I; Argitis, P; Davazoglou, D

    2005-01-01

    New all solid-state electrochromic displays were fabricated by chemically vapor depositing and patterning a tungsten oxide film on SnO 2 :F covered glass substrates. Aluminum sheets were used as counter electrodes to form electrochromic displays using solid or gel-like organic electrolytes. These ionically conductive and electronically insulating electrolytes were based on poly(methyl methacrylate) (PMMA) and poly(2-hydrohyethyl methacrylate) (PHEMA) into which phospho-tungstic acid was added at various concentrations. In some devices the electrolyte was formed by addition of photoacid generator into the polymeric matrix and exposure at deep UV light. It was found that displays exhibit an intense, reversible electrochromic effect with reflectivity varying by a factor of five between the uncolored to the colored state. The coloring voltage depends strongly on the polymeric matrix, the thickness of the electrolyte and post-apply baking conditions and is of the order of 6-9 V. The response time was found to be of the order of 500 ms; coloration and bleaching times were comparable

  17. Composite electrolyte with proton conductivity for low-temperature solid oxide fuel cell

    Raza, Rizwan; Ahmed, Akhlaq; Akram, Nadeem; Saleem, Muhammad; Niaz Akhtar, Majid; Sherazi, Tauqir A.; Ajmal Khan, M.; Abbas, Ghazanfar; Shakir, Imran; Mohsin, Munazza; Alvi, Farah; Javed, Muhammad Sufyan; Yasir Rafique, M.; Zhu, Bin

    2015-11-01

    In the present work, cost-effective nanocomposite electrolyte (Ba-SDC) oxide is developed for efficient low-temperature solid oxide fuel cells (LTSOFCs). Analysis has shown that dual phase conduction of O-2 (oxygen ions) and H+ (protons) plays a significant role in the development of advanced LTSOFCs. Comparatively high proton ion conductivity (0.19 s/cm) for LTSOFCs was achieved at low temperature (460 °C). In this article, the ionic conduction behaviour of LTSOFCs is explained by carrying out electrochemical impedance spectroscopy measurements. Further, the phase and structure analysis are investigated by X-ray diffraction and scanning electron microscopy techniques. Finally, we achieved an ionic transport number of the composite electrolyte for LTSOFCs as high as 0.95 and energy and power density of 90% and 550 mW/cm2, respectively, after sintering the composite electrolyte at 800 °C for 4 h, which is promising. Our current effort toward the development of an efficient, green, low-temperature solid oxide fuel cell with the incorporation of high proton conductivity composite electrolyte may open frontiers in the fields of energy and fuel cell technology.

  18. Some regularities in aging of solid oxide electrolytes ZrO2+Y2O3

    Vlasov, A.N.

    1983-01-01

    A study was made on the temperature effect on the rate and depth of aging of solid oxide electrolytes ZrO 2 +Y 2 O 3 and ZrO 2 +Ho 2 O 3 , stabilized by 10-15 mol.% R 2 O 3 following isothermal hold-up during 2000-3000 h in the 725-1550 deg C range in oxidizing medium. It was shown that solid electrolyte aging proceeds only at temperatures below a certain boundary value. The depth of complete aging at that increases with the R 2 O 3 concentration and a temperature decrease. The aging rate depends substantially on both temperature and concentration of a stabilizing addition. A decrease in the electric conductivity with time is accompanied by an increase in the conductivity activation energy

  19. Synthesis of new solid polymer electrolyte and actuator based on PEDOT/NBR/ionic liquid

    Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

    2006-03-01

    The conducting polymer actuator was presented. The solid polymer electrolyte based on nitrile rubber (NBR) activated with different ionic liquids was prepared. The three different grades of NBR films were synthesized by emulsion polymerization with different amount of acrylonitrile, 23, 35, and 40 mol. %, respectively. The effect of acrylonitrile content on the ionic conductivity and dielectric constant of solid polymer electrolytes was characterized. A conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique, and room temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X [where X= BF 4 -, PF 6 -, (CF 3SO II) IIN -], were absorbed into the composite film. The effects of the anion size of the ionic liquids on the displacement of the actuator were examined. The displacement increased with increasing the anion-size of the ionic liquids.

  20. Synthesis, processing and characterization of the solid oxide half-cells cathode/electrolyte of strontium-doped lanthanum manganite/Yttria-stabilized zirconia

    Chiba, Rubens

    2010-01-01

    The ceramic films of strontium-doped lanthanum manganite (LSM) and strontium doped lanthanum manganite/Yttria-stabilized zirconia (LSM/YSZ) are used as cathodes of the high temperature solid oxide fuel cells (HTSOFC). These porous ceramic films had been deposited on the YSZ dense ceramic substrate, used as electrolyte, structural component of the module, thus conferring a configuration of half-cell called auto-support. The study of the half-cell it is basic, therefore in the interface cathode/electrolyte occurs the oxygen reduction reaction, consequently influencing in the performance of the HTSOFC. In this direction, the present work contributes for the processing of thin films, using the wet powder spraying technique, adopted for the conformation of the ceramic films for allowing the attainment of porous layers with thicknesses varied in the order of micrometers. The LSM powders were synthesized by the citrate technique and the LSM/YSZ powders synthesized by the solid mixture technique. In the stage of formation were prepared organic suspensions of LSM and LSM/YSZ fed by gravity in a manual aerograph. For the formation of the YSZ substrate was used a hydraulic uniaxial press. The attainment of solid oxide half-cells cathode/electrolyte was possible of crystalline structures hexagonal for phase LSM and cubic for phase YSZ. The half-cells micrographs show that the YSZ substrate is dense, enough to be used as solid electrolyte, and the LSM and LSM/YSZ films are presented porous with approximately 30 μm of thickness and good adherence between the cathodes and the electrolyte. The presence of composite cathode between the LSM cathode and YSZ substrate, presented an increase in the electrochemical performance in the oxygen reduction reaction. (author)

  1. Fabrication of thin yttria-stabilized-zirconia dense electrolyte layers by inkjet printing for high performing solid oxide fuel cells

    Esposito, Vincenzo; Gadea, Christophe; Hjelm, Johan

    2015-01-01

    In this work, we present how a low-cost HP Deskjet 1000 inkjet printer was used to fabricate a 1.2 mm thin, dense and gas tight 16 cm2 solid oxide fuel cells (SOFC) electrolyte. The electrolyte was printed using an ink made of highly diluted (

  2. Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes.

    Gu, Yu; Wang, Wei-Wei; Li, Yi-Juan; Wu, Qi-Hui; Tang, Shuai; Yan, Jia-Wei; Zheng, Ming-Sen; Wu, De-Yin; Fan, Chun-Hai; Hu, Wei-Qiang; Chen, Zhao-Bin; Fang, Yuan; Zhang, Qing-Hong; Dong, Quan-Feng; Mao, Bing-Wei

    2018-04-09

    Dendrite growth of alkali metal anodes limited their lifetime for charge/discharge cycling. Here, we report near-perfect anodes of lithium, sodium, and potassium metals achieved by electrochemical polishing, which removes microscopic defects and creates ultra-smooth ultra-thin solid-electrolyte interphase layers at metal surfaces for providing a homogeneous environment. Precise characterizations by AFM force probing with corroborative in-depth XPS profile analysis reveal that the ultra-smooth ultra-thin solid-electrolyte interphase can be designed to have alternating inorganic-rich and organic-rich/mixed multi-layered structure, which offers mechanical property of coupled rigidity and elasticity. The polished metal anodes exhibit significantly enhanced cycling stability, specifically the lithium anodes can cycle for over 200 times at a real current density of 2 mA cm -2 with 100% depth of discharge. Our work illustrates that an ultra-smooth ultra-thin solid-electrolyte interphase may be robust enough to suppress dendrite growth and thus serve as an initial layer for further improved protection of alkali metal anodes.

  3. The conductivity and stability of polymer composite solid electrolyte upon addition of graphene

    Hamid, Farzana Abd.; Salleh, Fauzani Md.; Mohamed, Nor Sabirin

    2017-12-01

    The effect of graphene composition on the conductivity and stability of polymer composite solid electrolyte was studied. These polymer composite solid electrolytes were synthesized by sol gel method and prepared via the solution-casting technique. The compositions of graphene were varied between 10 wt% to 70 wt%. The changes in the functional group of polymer composite after the addition of graphene were characterized by Fourier Transform InfraRed spectroscopy. Electrochemical impedance spectroscopy was conducted at ambient temperature in the frequency range of 10 Hz to 1 MHz to study the conductivity of the polymer composite. The highest conductivity was obtained at 60 wt% graphene with the value of 2.85×10-4 Scm-1. Sample without the addition of graphene showed the lowest conductivity value of 1.77×10-7 Scm-1 and acts as an insulator. The high conductivity at 60 wt% graphene loading is related to dehydration of cellulose. This is supported by the FTIR spectrum where the absorption peaks of C-O stretching vibrations of polymer composite is weakened and the hydroxyl group is slightly shifted compared to the FTIR spectrum without the addition of graphene. Linear sweep voltammetry results demonstrated that the polymer composite solid electrolyte exhibited electrochemical stability up to 3.2 V.

  4. Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

    Takeru Ito

    2017-07-01

    Full Text Available Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1, were successfully hybridized with heteropolyanions of [PW12O40]3− (PW12 to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10−4 S·cm−1 order under humidified conditions at 313 K.

  5. Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

    He, Weisheng; Cui, Zili; Liu, Xiaochen; Cui, Yanyan; Chai, Jingchao; Zhou, Xinhong; Liu, Zhihong; Cui, Guanglei

    2017-01-01

    The classic poly(ethylene oxide) (PEO) based solid polymer electrolyte suffers from poor ionic conductivity of ambient temperature, low lithium ion transference number and relatively narrow electrochemical window (<4.0 V vs. Li + /Li). Herein, the carbonate-linked PEO solid polymer such as poly(diethylene glycol carbonate) (PDEC) and poly(triethylene glycol carbonate) (PTEC) were explored to find out the feasibility of resolving above issues. It was proven that the optimized ionic conductivity of PTEC based electrolyte reached up to 1.12 × 10 −5 S cm −1 at 25 °C with a decent lithium ion transference number of 0.39 and a wide electrochemical window about 4.5 V vs. Li + /Li. In addition, the PTEC based Li/LiFePO 4 cell could be reversibly charged and discharged at 0.05 C-rates at ambient temperature. Moreover, the higher voltage Li/LiFe 0.2 Mn 0.8 PO 4 cell (cutoff voltage 4.35 V) possessed considerable rate capability and excellent cycling performance even at ambient temperature. Therefore, these carbonate-linked PEO electrolytes were demonstrated to be fascinating candidates for the next generation solid state lithium batteries simultaneously with high energy and high safety.

  6. Dextran based highly conductive hydrogel polysulfide electrolyte for efficient quasi-solid-state quantum dot-sensitized solar cells

    Chen, Hong-Yan; Lin, Ling; Yu, Xiao-Yun; Qiu, Kang-Qiang; Lü, Xian-Yong; Kuang, Dai-Bin; Su, Cheng-Yong

    2013-01-01

    Highlights: ► Dextran based hydrogel is first used to prepare quasi-solid-state polysulfide electrolyte for quantum dot-sensitized solar cells. ► The ion conductivity of hydrogel electrolyte shows almost the same value as the liquid electrolyte. ► The liquid state at elevated temperature of hydrogel electrolyte allows for a good contact between electrolyte and CdS/CdSe co-sensitized TiO 2 photoanode. ► The hydrogel electrolyte based cell exhibits slightly lower power conversion efficiency than that of liquid electrolyte based cell. ► The dynamic electron transfer mechanism in hydrogel electrolyte based cell is examined in detail by EIS and CIMPS/IMVS. -- Abstract: Highly conductive hydrogel polysulfide electrolyte is first fabricated using dextran as gelator and used as quasi-solid-state electrolyte for quantum dot-sensitized solar cells (QDSSCs). The hydrogel electrolyte with gelator concentration of 15 wt% shows almost the same conductivity as the liquid one. Moreover, its liquid state at elevated temperature allow for the well penetration into the pores in electrodeposited CdS/CdSe co-sensitized TiO 2 photoanode. This gel electrolyte based QDSSC exhibits power conversion efficiency (η) of 3.23% under AG 1.5 G one sun (100 mW cm −2 ) illumination, slightly lower than that of liquid electrolyte based cell (3.69%). The dynamic electron transfer mechanism of the gel and liquid electrolyte based QDSSC are examined by electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (CIMPS/IMVS). It is found that the electron transport in gel electrolyte based cell is much faster than the liquid electrolyte based cell but it tends to recombine more easily than the latter. However, these differences fade away with increasing the light intensity, showing declining electron collection efficiency at higher light intensity illumination. As a result, a conversion efficiency of 4.58% is obtained for the gel

  7. Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries

    Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sun, Xueliang; Sham, Tsun-Kong

    2014-01-01

    Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10 −8 S cm −1 at 323 K with ∼0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10 −8 S cm −1 at 26 °C (299 K). (paper)

  8. Impedance spectroscopy of ceramic solid electrolytes; Espectroscopia de impedancia de eletrolitos solidos ceramicos

    Muccillo, R.; Cosentino, I.C.; Florio, D.Z. de; Franca, Y.V. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil). Dept. de Engenharia de Materiais

    1996-12-31

    The Impedance Spectroscopy (IS) technique has been used to the study of Th O{sub 2}:Y{sub 2} O{sub 3}, Zr O{sub 2}:La{sub 2} O{sub 3} and Zr O{sub 2}:Y{sub 2} O{sub 3} solid electrolytes. The results show that solid solution has been attained, grain boundaries act as oxygen-ion blockers, and the importance of the IS technique to study phase transformation in ceramics. (author) 6 refs., 6 figs.

  9. A high pressure x-ray photoelectron spectroscopy experimental method for characterization of solid-liquid interfaces demonstrated with a Li-ion battery system

    Maibach, Julia; Xu, Chao; Gustafsson, Torbjörn; Edström, Kristina [Department of Chemistry–Ångström Laboratory, Uppsala University, Box 538, SE-751 21 Uppsala (Sweden); Eriksson, Susanna K. [Department of Chemistry–Ångström Laboratory, Uppsala University, Box 523, SE-751 20 Uppsala (Sweden); Åhlund, John [VG Scienta AB, Box 15120, SE-750 15 Uppsala (Sweden); Siegbahn, Hans; Rensmo, Håkan; Hahlin, Maria, E-mail: maria.hahlin@physics.uu.se [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden)

    2015-04-15

    We report a methodology for a direct investigation of the solid/liquid interface using high pressure x-ray photoelectron spectroscopy (HPXPS). The technique was demonstrated with an electrochemical system represented by a Li-ion battery using a silicon electrode and a liquid electrolyte of LiClO{sub 4} in propylene carbonate (PC) cycled versus metallic lithium. For the first time the presence of a liquid electrolyte was realized using a transfer procedure where the sample was introduced into a 2 mbar N{sub 2} environment in the analysis chamber without an intermediate ultrahigh vacuum (UHV) step in the load lock. The procedure was characterized in detail concerning lateral drop gradients as well as stability of measurement conditions over time. The X-ray photoelectron spectroscopy (XPS) measurements demonstrate that the solid substrate and the liquid electrolyte can be observed simultaneously. The results show that the solid electrolyte interphase (SEI) composition for the wet electrode is stable within the probing time and generally agrees well with traditional UHV studies. Since the methodology can easily be adjusted to various high pressure photoelectron spectroscopy systems, extending the approach towards operando solid/liquid interface studies using liquid electrolytes seems now feasible.

  10. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

    Chan, Candace K.; Ruffo, Riccardo; Hong, Seung Sae; Cui, Yi

    2009-01-01

    Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte

  11. Power and Thermal Technologies for Air and Space. Delivery Order 0001: Single Ionic Conducting Solid-State Electrolyte

    Turner, Allen

    2005-01-01

    This report focuses on the development of a lithium-ion conducting channel as a solid-state electrolyte for rechargeable lithium batteries through the use of thin films of dilithium phthalocyanine (Li2Pc...

  12. The LiBH4-LiI Solid Solution as an Electrolyte in an All-Solid-State Battery

    Sveinbjörnsson, Dadi Þorsteinn; Christiansen, Ane Sælland; Viskinde, Rasmus

    2014-01-01

    The charge and discharge performance of an all-solid-state lithium battery with the LiBH4-LiI solid solution as an electrolyte is reported. Lithium titanate (Li4Ti5O12) was used as the positive electrode and lithium metal as the negative electrode. The performance of the all-solid-state cell...

  13. Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

    Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

    2018-06-01

    Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

  14. Development of novel strategies for enhancing the cycle life of lithium solid polymer electrolyte batteries. Final report

    Macdonald, Digby D.; Urquidi-Macdonald, Mirna; Allcock, Harry; Engelhard, George; Bomberger, N.; Gao, L.; Olmeijer, D.

    2001-04-30

    Lithium/solid polymer electrolyte (Li/SPE) secondary batteries are under intense development as power sources for portable electronic devices as well as electric vehicles. These batteries offer high specific energy, high energy density, very low self-discharge rates, and flexibility in packaging; however, problems have inhibited their introduction into the marketplace. This report summarizes findings to examine processes that occur with Li/SPE secondary batteries upon cyclic charging/discharging. The report includes a detailed analysis of the impedance measured on the Li/SPE/IC and IC/SPE/IC systems. The SPE was a derivative of methoxyethoxyethoxyphosphazene (MEEP) with lithium triflate salt as the electrolyte, while the intercalated cathodes (IC) comprised mixtures of manganese dioxide, carbon powder, and MEEP as a binder. Studies on symmetrical Li/SPE/Li laminates show that cycling results in a significant expansion of the structure over the first few tens of cycles; however, no corresponding increase in the impedance was noted. The cycle life of the intercalation cathode was found to be very sensitive to the method of fabrication. Results indicate that the cycle life is due to the failure of the IC, not to the failure of the lithium/SPE interface. A pattern recognition neural network was developed to predict the cycle life of a battery from the charge/discharge characteristics.

  15. Application of sol gel spin coated yttria-stabilized zirconia layers for the improvement of solid oxide fuel cell electrolytes produced by atmospheric plasma spraying

    Rose, Lars [University of British Columbia, Department of Materials Engineering, 309-6350 Stores Road, Vancouver, British Columbia, V6T 1Z4 (Canada); National Research Council, Institute for Fuel Cell Innovation, 4250 Wesbrook Mall, Vancouver, British Columbia, V6T 1W5 (Canada); Kesler, Olivera [National Research Council, Institute for Fuel Cell Innovation, 4250 Wesbrook Mall, Vancouver, British Columbia, V6T 1W5 (Canada); University of British Columbia, Department of Mechanical Engineering, 2054-6250 Applied Science Lane, Vancouver, British Columbia, V6T 1Z4 (Canada); Tang, Zhaolin; Burgess, Alan [Northwest Mettech Corp., 467 Mountain Hwy, North Vancouver, British Columbia, V7J 2L3 (Canada)

    2007-05-15

    Due to its high thermal stability and purely oxide ionic conductivity, yttria-stabilized zirconia (YSZ) is the most commonly used electrolyte material for solid oxide fuel cells (SOFCs). Standard electrolyte fabrication techniques for planar SOFCs involve wet ceramic techniques such as tape-casting or screen printing, requiring sintering steps at temperatures above 1300 C. Plasma spraying (PS) may provide a more rapid and cost efficient method to produce SOFCs without sintering. High-temperature sintering requires long processing times and can lead to oxidation of metal alloys used as mechanical supports, or to detrimental interreactions between the electrolyte and adjacent electrode layers. This study investigates the use of spin coated sol gel derived YSZ precursor solutions to fill the pores present in plasma sprayed YSZ layers, and to enhance the surface area for reaction at the electrolyte-cathode interface, without the use of high-temperature firing steps. The effects of different plasma conditions and sol concentrations and solid loadings on the gas permeability and fuel cell performance have been investigated. (author)

  16. Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

    Guilherme, L.A.; Borges, R.S.; Moraes, E. Mara S.; Silva, G. Goulart; Pimenta, M.A.; Marletta, A.; Silva, R.A.

    2007-01-01

    The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO 4 have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10 -5 S/cm at room temperature and reached to 10 -3 S/cm at 100 deg. C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 deg. C to values close to 10 -4 S/cm and at room temperature values close to 3 x 10 -6 S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains

  17. Stable quasi-solid-state dye-sensitized solar cell using ionic gel electrolyte with low molecular mass organogelator

    Tao, Li; Huo, Zhipeng; Dai, Songyuan; Zhu, Jun; Zhang, Changneng; Pan, Xu; Huang, Yang; Yang, Shangfeng; Zhang, Bing; Yao, Jianxi

    2015-01-01

    Long-term stability is essential for the application and commercialization of dye-sensitized solar cells (DSCs). A quasi-solid-state DSC (QS-DSC) with excellent long-term stability is fabricated using ionic gel electrolyte (IGE) with N,N′-methylenebisdodecanamide as low molecular mass organogelator (LMOG). The gel to solution transition temperature (T gel ) of this IGE is 127 °C, well above the working temperature of the device, which contributes to the thermal properties of the IGE and the device. The electrochemical properties of the IGE and the kinetic processes of electron transport and recombination of the QS-DSC are investigated by means of electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). Due to the obstructed diffusion of redox species caused by the network of IGE, the electron recombination at the TiO 2 photoelectrode/electrolyte interface in the QS-DSC is accelerated. More importantly, compared with the ionic liquid electrolyte (ILE) based DSC, the QS-DSC based on the IGE exhibits excellent thermal and light-soaking stabilities during the accelerated aging tests for 1000 h. Especially, there is almost no degradation in the short-circuit current density (J sc ) in the IGE based QS-DSC, while the J sc of the ILE based DSC decreased to 85–94% of their initial values. - Highlights: • A novel IGE with high T gel is obtained by using a diamide derivative as LMOG. • The IGE based QS-DSC is very stable during the accelerated aging tests. • The influences of gelation on the electron kinetic processes are investigated

  18. Stable quasi-solid-state dye-sensitized solar cell using ionic gel electrolyte with low molecular mass organogelator

    Tao, Li [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Huo, Zhipeng, E-mail: zhipenghuo@163.com [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Dai, Songyuan, E-mail: sydai@ncepu.edu.cn [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Beijing Key Lab of Novel Thin Film Solar Cells, North China Electric Power University, Beijing 102206 (China); Zhu, Jun; Zhang, Changneng; Pan, Xu; Huang, Yang [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Yang, Shangfeng [Hefei National Laboratory for Physical Sciences at Microscale, Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei 230026 (China); Zhang, Bing; Yao, Jianxi [Beijing Key Lab of Novel Thin Film Solar Cells, North China Electric Power University, Beijing 102206 (China)

    2015-02-15

    Long-term stability is essential for the application and commercialization of dye-sensitized solar cells (DSCs). A quasi-solid-state DSC (QS-DSC) with excellent long-term stability is fabricated using ionic gel electrolyte (IGE) with N,N′-methylenebisdodecanamide as low molecular mass organogelator (LMOG). The gel to solution transition temperature (T{sub gel}) of this IGE is 127 °C, well above the working temperature of the device, which contributes to the thermal properties of the IGE and the device. The electrochemical properties of the IGE and the kinetic processes of electron transport and recombination of the QS-DSC are investigated by means of electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). Due to the obstructed diffusion of redox species caused by the network of IGE, the electron recombination at the TiO{sub 2} photoelectrode/electrolyte interface in the QS-DSC is accelerated. More importantly, compared with the ionic liquid electrolyte (ILE) based DSC, the QS-DSC based on the IGE exhibits excellent thermal and light-soaking stabilities during the accelerated aging tests for 1000 h. Especially, there is almost no degradation in the short-circuit current density (J{sub sc}) in the IGE based QS-DSC, while the J{sub sc} of the ILE based DSC decreased to 85–94% of their initial values. - Highlights: • A novel IGE with high T{sub gel} is obtained by using a diamide derivative as LMOG. • The IGE based QS-DSC is very stable during the accelerated aging tests. • The influences of gelation on the electron kinetic processes are investigated.

  19. Photoelectrolysis at the oxide-electrolyte interface as interpreted through the 'transition' layer model

    Kalia, R. K.; Weber, Michael F.; Schumacher, L.; Dignam, M. J.

    1980-12-01

    A transition layer model of the oxide-electrolyte interface, proposed earlier by one of us, is outlined and then examined in the light of experimental data relating primarily to photoelectrolysis of water at semiconducting oxide electrodes. The model provides useful insight into the behaviour of the system and allows a calculation of thc minimum bias potential needed for photoelectrolysis, thus illuminating the origin of the requirement for such an external bias. In order to electrolyse water without a bias, the model requires an n-type oxide to be sufficiently reduced so that it is thermodynamically capable of chemically reducing water to produce hydrogen at 1 atm pressure. Similarly, for bias-free operation, a p-type metal oxide must be thermodynamically unstable with respect to the release of oxygen at 1 atm pressure. In the face of these requirements it is apparent that oxide stability is bound to be in general a serious problem for nonstoichiometric single metal oxides.

  20. Determination of the flat band potential for In sub 2 S sub 3 /electrolyte interfaces

    Herrasti, P; Fatas, E [Universidad Autonoma, Madrid (ES). Dept. de Quimica; Herrero, J; Ortega, J [CIEMAT, Madrid (ES). Inst. de Energias Renovables

    1990-02-01

    Flat band potentials V{sub fb} of In{sub 2}S{sub 3} polycrystalline thin films obtained by chalcogenization of electroplated metallic indium films on Ti substrates with a flowing stream of H{sub 2}S gas have been obtained. The variation of this potential with different redox couples, solution concentration and pH values has been studied. Photoelectrochemical characterization of the electrodes was accomplished in aqueous polysulphide solutions and the application of the Gartner-Butler model to the semiconductor/electrolyte interface makes it possible to obtain the semiconductor energy gap. The value obtained is 2.06 eV, corresponding to a direct allowed transition. (author).

  1. SFG study on potential-dependent structure of water at Pt electrode/electrolyte solution interface

    Noguchi, Hidenori; Okada, Tsubasa; Uosaki, Kohei [Physical Chemistry Laboratory, Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810 (Japan)

    2008-10-01

    Structure of water at Pt/electrolyte solution interface was investigated by sum frequency generation (SFG) spectroscopy. Two broad peaks were observed in OH stretching region at ca. 3200 cm{sup -1} and ca. 3400 cm{sup -1}, which are known to be due to the symmetric OH stretching (U{sub 1}) of tetrahedrally coordinated, i.e., strongly hydrogen bonded 'ice-like' water, and the asymmetric OH stretching (U{sub 3}) of water molecules in a more random arrangement, i.e., weakly hydrogen bonded 'liquid-like' water, respectively. The SFG intensity strongly depended on electrode potential. Several possibilities are suggested for the potential dependence of the SFG intensity. (author)

  2. Single- and double-ion type cross-linked polysiloxane solid electrolytes for lithium cells

    Tsutsumi, Hiromori; Yamamoto, Masahiro; Morita, Masayuki; Matsuda, Yoshiharu; Nakamura, Takashi; Asai, Hiroyuki

    Polymeric solid electrolytes, that have poly(dimethylsiloxane) (PMS) backbone and cross-linked network, were applied to a rechargeable lithium battery system. Single- (PMS-Li) and double-ion type (PMS-LiClO 4) electrolytes were prepared from the same prepolymers. Lithium electrode in the both electrolytes showed reversible stripping and deposition of lithium. Intercalation and deintercalation processes of lithium ion between lithium-manganese composite oxide (Li xMnO 2) electrode and the electrolytes were also confirmed by cyclic voltammetry, however, peak current decreased with several cycles in both cases. The model cell, Li/PMS-Li/Li xMnO 2 cell had 1.4 mA h g -1 (per 1 g of active material, current density: 3.77 μA cm -2), and the Li/PMS-LiClO 4/Li xMnO 2 cell had 1.6 mA h g -1 (current density: 75.3 μA cm -2).

  3. Materials system for intermediate temperature solid oxide fuel cells based on doped lanthanum-gallate electrolyte

    Gong, Wenquan

    2005-07-01

    The objective of this work was to identify a materials system for intermediate temperature solid oxide fuel cells (IT-SOFCs). Towards this goal, alternating current complex impedance spectroscopy was employed as a tool to study electrode polarization effects in symmetrical cells employing strontium and magnesium doped lanthanum gallate (LSGM) electrolyte. Several cathode materials were investigated including strontium doped lanthanum manganite (LSM), Strontium and iron doped lanthanum cobaltate (LSCF), LSM-LSGM, and LSCF-LSGM composites. Investigated Anode materials included nickel-gadolinium or lanthanum doped cerium oxide (Ni-GDC, or Ni-LDC) composites. The ohmic and the polarization resistances of the symmetrical cells were obtained as a function of temperature, time, thickness, and the composition of the electrodes. Based on these studies, the single phase LSM electrode had the highest polarization resistance among the cathode materials. The mixed-conducting LSCF electrode had polarization resistance orders of magnitude lower than that of the LSM-LSGM composite electrodes. Although incorporating LSGM in the LSCF electrode did not reduce the cell polarization resistance significantly, it could reduce the thermal expansion coefficient mismatch between the LSCF electrodes and LSGM electrolyte. Moreover, the polarization resistance of the LSCF electrode decreased asymptotically as the electrode thickness was increased thus suggesting that the electrode thickness needed not be thicker than this asymptotic limit. On the anode side of the IT-SOFC, Ni reacted with LSGM electrolyte, and lanthanum diffusion occurred from the LSGM electrolyte to the GDC barrier layer, which was between the LSGM electrolyte and the Ni-composite anode. However, LDC served as an effective barrier layer. Ni-LDC (70 v% Ni) anode had the largest polarization resistance, while all other anode materials, i.e. Ni-LDC (50 v% Ni), Ni-GDC (70 v% NO, and Ni-GDC (50 v% Ni), had similar polarization

  4. Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

    Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

    2018-05-02

    The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

  5. Amperometric detector for gas chromatography based on a silica sol-gel solid electrolyte.

    Steinecker, William H; Miecznikowski, Krzysztof; Kulesza, Pawel J; Sandlin, Zechariah D; Cox, James A

    2017-11-01

    An electrochemical cell comprising a silica sol-gel solid electrolyte, a working electrode that protrudes into a gas phase, and reference and counter electrodes that contact the solid electrolyte comprises an amperometric detector for gas chromatography. Under potentiostatic conditions, a current related to the concentration of an analyte in the gas phase is produced by its oxidation at the three-phase boundary among the sol-gel, working electrode, and the gas phase. The sol-gel is processed to contain an electrolyte that also serves as a humidistat to maintain a constant water activity even in the presence the gas chromatographic mobile phase. Response was demonstrated toward a diverse set of analytes, namely hydrogen, 1,2-ethandithiol, phenol, p-cresol, and thioanisole. Using flow injection amperometry of hydrogen with He as the carrier gas, 90% of the steady-state current was achieved in < 1s at a flow rate of 20mLmin -1 . A separation of 1,2-ethandithiol, phenol, p-cresol, and thioanisole at a 2.2mLmin -1 flow rate was achieved with respective detection limits (k = 3 criterion) of 4, 1, 3, and 70 ppmv when the working electrode potential was 800mV. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Impedance and dielectric characterizations of ionic partitioning in interfaces that membranous, biomimetic and gold surfaces form with electrolytes

    Chilcott, Terry C.; Guo, Chuan

    2013-01-01

    Silicon dioxide, organic monolayers covalently attached to silicon and gold are used as biosensor substrates and anchoring platforms for hybrid, tethered and supported lipid membranes used in membrane-protein studies. Electrical impedance spectroscopy (EIS) studies of gold in contact with potassium chloride electrolytes of concentrations ranging from 1 mM to 300 mM, characterized the gold–electrolyte interface as principally a Stern layer 20–30 Å thick and conductivity many orders of magnitude less than that of the bulk electrolyte. EIS studies of SiO 2 –electrolyte system that were similar to studies of a tetradecane–electrolyte system are presented herein that reveal an interface comprised of at least two interfacial layers and extending some 10 5 Å into the electrolyte. The average conductivity and thickness values for the layer in contact with the SiO 2 surface (∼10 −6 S m −1 and ∼28 Å, respectively) were of the order of magnitude expected for the Gouy–Chapman layer but the dependency of the thickness on concentration did not reflect the expected dependency of the Debye length over the full range of concentrations. The average values for the next layer (∼10 −3 S m −1 and ∼10 5 Å) exhibited a dependency on concentration similar to that expected for the bulk electrolyte. The theoretical derivations of ionic partitioning arising from the Born (dielectric) energy distributions in both the SiO 2 and gold interfaces were generally consistent with the respective EIS studies and revealed that partitioning in the SiO 2 interface mimicked that in bio-membranous interfaces. The dielectric characterizations suggest that; ionic partitioning in biomimetic interfaces play a role in long-ranging sequestration of organic molecules, the extensiveness of these interfaces contributes to differences in the lipid densities of bilayers formed on biomimetic substrates, and chloride ions have a greater affinity than the smaller potassium ions for gold

  7. A continuum treatment of sliding in Eulerian simulations of solid-solid and solid-fluid interfaces

    Subramaniam, Akshay; Ghaisas, Niranjan; Lele, Sanjiva

    2017-11-01

    A novel treatment of sliding is developed for use in an Eulerian framework for simulating elastic-plastic deformations of solids coupled with fluids. In this method, embedded interfacial boundary conditions for perfect sliding are imposed by enforcing the interface normal to be a principal direction of the Cauchy stress and appropriate consistency conditions ensure correct transmission and reflection of waves at the interface. This sliding treatment may be used either to simulate a solid-solid sliding interface or to incorporate an internal slip boundary condition at a solid-fluid interface. Sliding laws like the Coulomb friction law can also be incorporated with relative ease into this framework. Simulations of sliding interfaces are conducted using a 10th order compact finite difference scheme and a Localized Artificial Diffusivity (LAD) scheme for shock and interface capturing. 1D and 2D simulations are used to assess the accuracy of the sliding treatment. The Richmyer-Meshkov instability between copper and aluminum is simulated with this sliding treatment as a demonstration test case. Support for this work was provided through Grant B612155 from the Lawrence Livermore National Laboratory, US Department of Energy.

  8. Spectroscopic Analysis of Ion Concentration Profile at Electrode/Electrolyte Interface by Interferometry

    Moore, David; Saraf, Ravi

    2014-03-01

    Owing to the difference in Fermi levels at an electrode/electrolyte interface, ions form an electrical double layer (EDL) with ion concentrations well over 10-fold compared to bulk. The concentration profile of the EDL intrinsically affects the electrochemical reaction rates at the electrode, which is of great significance in many applications, such as batteries and biosensors. Conventionally, using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the electrical properties of the EDL are represented as ``equivalent circuits'' consisting of the resistance to charge transfer (Rct), the double layer capacitance (Cdl) and a ``Warburg (constant phase) diffusion element'' that represents the long range diffusion of ions to the electrode. The translation to the well-understood physical structure can be lost as complicated effects are often lumped together. For example, the effect of subtle modification of the electrode surface by say, redox compounds, enzymes, or polymers is not directly measured, and must be inferred by capacitance changes. An interferometer method will be described to directly measure changes in concentration at the interface during redox process. This method in concert with CV or EIS performed concomitantly will lead to more information to model the diffuse layer for improved understanding of the kinetics of the reaction at different distances from the electrode. Applications to DNA and polymer adsorption binding will be discussed.

  9. Synthesis and characterization of novel electrolyte materials for intermediate temperature solid oxide fuel cells

    Chaubey, Nityanand; Chattopadhyaya, M.C.; Wani, B.N.; Bharadwaj, S.R.

    2008-01-01

    The high operating temperature of SOFCs using zirconia based electrolyte have several restrictions on materials used as interconnect and sealing and also requires use of expensive ceramics. Lowering the operating temperature of SOFCs to 600-800 deg C will enable to use cheaper materials and reduce the cost of fabrication while keeping the high power density. Lanthanide gallates are considered to be very promising solid electrolytes for intermediate temperature (600-800 deg C) solid oxide fuel cells (IT-SOFCs) due to their high ionic conductivity at lower temperatures. Phase purity of this material is a concern for the researchers for a long time. These materials are prepared at very high temperature (∼1400 deg C), since it is known that at around 1100 deg C, solubilities of Sr and Mg in LaGaO 3 were close to zero. Hence in the present work perovskite oxides of Ln 1-x Sr x Ga 1-y Mg y O 3-δ (Ln= Sm, Gd and x = 0.10, y=0.20) have been prepared by different methods i.e. solid state reaction, gel combustion and co-precipitation methods

  10. Characterisation of the Ni/ScYSZ interface in a model solid oxide fuel cell anode

    Schmidt, Michael Stenbæk; Hansen, Karin Vels; Norrman, Kion

    2008-01-01

    A nickel point electrode setup was used as a model of an SOFC anode on three slightly different electrolytes of zirconia stabilised by co-doping with scandia and yttria. The effect of electrolyte impurities on the electrode polarisation resistance was investigated by correlating electrochemical...... impedance spectroscopy data with time-of-flight secondary ion mass spectrometry, scanning electron microscopy and atomic force microscopy data. A semi-quantitative analysis of the electrolyte surfaces showed that the levels of surface impurities inside the electrode/electrolyte interface in close proximity...

  11. A modified anode/electrolyte structure for a solid oxide electrochemical cell and a method for making said structure

    2013-01-01

    -stabilised zirconium oxide electrolyte and (c) a metallic and/or a ceramic electrocatalyst in the shape of interlayers incorporated in the interface between the anode and the electrolyte. This assembly is first sintered at a given temperature and then at a lower temperature in reducing gas mixtures. These heat...... treatments resulted in a distribution of the metallic and/or ceramic interlayers in the electrolyte/anode backbone junction taking place. The structure is prepared by (a) depositing a ceramic interlayer onto one side of the electrolyte, (b) optionally applying a metallic interlayer thereon, (c) repeating...... steps (a) and (b), (d) applying a layer of the selected anode backbone onto the electrolyte with applied interlayers, (e) sintering the raw assembly and (f) infiltrating the electrocatalyst precursor into the sintered assembly and heat treating the assembly to incorporate additional electrocatalyst...

  12. All-Solid-State Lithium-Sulfur Battery based on a nanoconfined LiBH 4 Electrolyte

    Das, Supti; Ngene, Peter; Norby, Poul; Vegge, Tejs; de Jongh, P.E.; Blanchard, Didier

    2016-01-01

    In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4in mesoporous silica as solid electrolytes. The nano-confined LiBH4has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport

  13. Molecular motion in polymer electrolytes. An investigation of methods for improving the conductivity of solid polymer electrolytes

    Webster, Mark Ian

    2002-01-01

    Three methods were explored with a view to enhancing the ionic conductivity of polymer electrolytes; namely the addition of an inert, inorganic filler, the addition of a plasticizer and the incorporation of the electrolyte in the pores of silica matrices. There have been a number of reports, which suggest the addition of nanocrystalline oxides to polymer electrolytes increases the ionic conductivities by about a factor of two. In this thesis studies of the polymer electrolyte NaSCN.P(EO) 8 with added nanocrystalline alumina powder are reported which show no evidence of enhanced conductivity. The addition of a plasticizer to polymer electrolytes will increase the ionic conductivity. A detailed study was made of the polymer electrolytes LiT.P(EO) 10 and LiClO 4 .P(EO) 10 with added ethylene carbonate plasticizer. The conductivities showed an enhancement, however this disappeared on heating under vacuum. The present work suggests that the plasticised system is not thermodynamically stable and will limit the applications of the material. A series of samples were prepared from the polymer electrolyte LiT.P(EO) 8 and a range of porous silicas. The silicas were selected to give a wide range of pore size and included Zeolite Y, ZSM5, mesoporous silica and a range of porous glasses. This gave pore sizes from less than one nm to 50 nm. A variety of experiments, including X-ray diffraction, DSC and NMR, showed that the polymer electrolyte entered to pores of the silica. As a result the polymer was amorphous and the room temperature conductivity was enhanced. The high temperature conductivity was not increased above that for the pure electrolyte. The results suggest that this could be employed in applications, however would require higher conducting electrolytes to be of practical benefit. (author)

  14. Yttria-doped zirconia as solid electrolyte for fuel-cell applications

    Butz, Benjamin

    2009-11-27

    7.3-10 mol% yttria-doped zirconia (YDZ) was studied with emphasis on its long-term stability as solid electrolyte. The decomposition of common 8.5YDZ (950 C) was detected by analytical TEM. As second issue, the microstructural and chemical properties of nanocrystalline 7.3YDZ thin films were investigated. Metastable t''-YDZ was found to precipitate in nanoscaled regions in YDZ up to 10 mol% yttria. Furthermore, a revised boundary of the c+t phase field, in which YDZ decomposes, is presented. (orig.)

  15. Yttria-doped zirconia as solid electrolyte for fuel-cell applications

    Butz, Benjamin

    2009-11-27

    7.3-10 mol% yttria-doped zirconia (YDZ) was studied with emphasis on its long-term stability as solid electrolyte. The decomposition of common 8.5YDZ (950 C) was detected by analytical TEM. As second issue, the microstructural and chemical properties of nanocrystalline 7.3YDZ thin films were investigated. Metastable t''-YDZ was found to precipitate in nanoscaled regions in YDZ up to 10 mol% yttria. Furthermore, a revised boundary of the c+t phase field, in which YDZ decomposes, is presented. (orig.)

  16. TAMOAS: In Situ Gasometry in the Atmosphere with Solid Electrolyte Sensors on BEXUS-19

    Bronowski, A.; Clemens, R.; Jaster, T.; Kosel, F.; Matyash, I.; Westphal, A.

    2015-09-01

    A student experiment developed for testing gas sensors in the stratosphere is described. The setup consists of a measurement electronic running miniaturized in situ amperiometric gas sensors based on different solid state electrolytes dedicated for oxygen, ozone and atomic oxygen. The experiment took place at Esrange Space Center in October 2014. The setup was attached to the high-altitude balloon BEXUS-19 and reached an altitude of 27 km at night. The primary objective was to test the prototype sensors and to gain data during flight.

  17. Effects of Sublattice Symmetry and Frustration on Ionic Transport in Garnet Solid Electrolytes

    Kozinsky, Boris; Akhade, Sneha A.; Hirel, Pierre; Hashibon, Adham; Elsässer, Christian; Mehta, Prateek; Logeat, Alan; Eisele, Ulrich

    2016-02-01

    We use rigorous group-theoretic techniques and molecular dynamics to investigate the connection between structural symmetry and ionic conductivity in the garnet family of solid Li-ion electrolytes. We identify new ordered phases and order-disorder phase transitions that are relevant for conductivity optimization. Ionic transport in this materials family is controlled by the frustration of the Li sublattice caused by incommensurability with the host structure at noninteger Li concentrations, while ordered phases explain regions of sharply lower conductivity. Disorder is therefore predicted to be optimal for ionic transport in this and other conductor families with strong Li interaction.

  18. Status of solid polymer electrolyte fuel cell technology and potential for transportation applications

    McElroy, J. F.; Nuttall, L. J.

    The solid polymer electrolyte (SPE) fuel cell represents the first fuel cell technology known to be used operationally. Current activities are mainly related to the development of a space regenerative fuel cell system for energy storage on board space stations, or other large orbiting vehicles and platforms. During 1981, a study was performed to determine the feasibility of using SPE fuel cells for automotive or other vehicular applications, using methanol as the fuel. The results of this study were very encouraging. Details concerning a conceptual automotive fuel cell power plant study are discussed, taking into account also a layout of major components for compact passenger car installation.

  19. Sensing sulfur oxides and other sulfur bearing pollutants with solid electrolyte pellets. I. Gas concentration cells

    Chamberland, A M; Gauthier, J M

    1977-01-01

    A new sensing technique using a solid electrolyte has been demonstrated for sulfur-bearing pollutants. Based on potentiometric measurements across a pellet of potassium sulfate, this sensor allows concentrations of sulfur dioxides, sulfur trioxide, hydrogen sulfide, methyl mercaptan and carbonyl sulfide in air to be measured with accuracy. Its operational concentration range at the present time is 0.1 ppM up to at least 10,000 ppM. The presence of other common pollutants such as carbon dioxide, methane, nitric oxide and nitrogen dioxide does not interfere with the measurement of air samples containing sulfur-bearing pollutants.

  20. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

    Savinell, R. F.; Fritts, S. D.

    1988-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  1. Properties of solid polymer electrolyte fluorocarbon film. [used in hydrogen/oxygen fuel cells

    Alston, W. B.

    1973-01-01

    The ionic fluorocarbon film used as the solid polymer electrolyte in hydrogen/oxygen fuel cells was found to exhibit delamination failures. Polarized light microscopy of as-received film showed a lined region at the center of the film thickness. It is shown that these lines were not caused by incomplete saponification but probably resulted from the film extrusion process. The film lines could be removed by an annealing process. Chemical, physical, and tensile tests showed that annealing improved or sustained the water contents, spectral properties, thermo-oxidative stability, and tensile properties of the film. The resistivity of the film was significantly decreased by the annealing process.

  2. Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

    Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

    2018-05-01

    Ionic liquids (ILs) are considered as attractive electrolyte solvents in modern battery concepts such as Li-ion batteries. Here we present a comprehensive review of the results of previous model studies on the interaction of the battery relevant IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]+[TFSI]-) with a series of structurally and chemically well-defined model electrode surfaces, which are increasingly complex and relevant for battery applications [Ag(111), Au(111), Cu(111), pristine and lithiated highly oriented pyrolytic graphite (HOPG), and rutile TiO2(110)]. Combining surface science techniques such as high resolution scanning tunneling microscopy and X-ray photoelectron spectroscopy for characterizing surface structure and chemical composition in deposited (sub-)monolayer adlayers with dispersion corrected density functional theory based calculations, this work aims at a molecular scale understanding of the fundamental processes at the electrode | electrolyte interface, which are crucial for the development of the so-called solid electrolyte interphase (SEI) layer in batteries. Performed under idealized conditions, in an ultrahigh vacuum environment, these model studies provide detailed insights on the structure formation in the adlayer, the substrate-adsorbate and adsorbate-adsorbate interactions responsible for this, and the tendency for chemically induced decomposition of the IL. To mimic the situation in an electrolyte, we also investigated the interaction of adsorbed IL (sub-)monolayers with coadsorbed lithium. Even at 80 K, postdeposited Li is found to react with the IL, leading to decomposition products such as LiF, Li3N, Li2S, LixSOy, and Li2O. In the absence of a [BMP]+[TFSI]- adlayer, it tends to adsorb, dissolve, or intercalate into the substrate (metals, HOPG) or to react with the substrate (TiO2) above a critical temperature, forming LiOx and Ti3+ species in the latter case. Finally, the formation of stable

  3. Nanostructured TiO2 microspheres for dye-sensitized solar cells employing a solid state polymer electrolyte

    Jung, Hun-Gi; Nagarajan, Srinivasan; Kang, Yong Soo; Sun, Yang-Kook

    2013-01-01

    Bimodal mesoporous, anatase TiO 2 microspheres with particle sizes ranging from 0.3 to 2 μm were synthesized using a facile solvothermal method. The photovoltaic performance of TiO 2 microspheres in dye-sensitized solar cells (DSSCs) using a solid state electrolyte was investigated. The solid state electrolyte DSSC device based on the TiO 2 microspheres exhibits an energy conversion efficiency of 4.2%, which is greater than that of commercial P25 TiO 2 (3.6%). The higher photocurrent density was primarily achieved as a result of the greater specific surface area and pore size, which resulted in an increase in the dye uptake of the TiO 2 microspheres and easy transport of solid electrolyte through mesopores. In addition, the greater electron lifetime and superior light scattering ability also enhanced the photovoltaic performance of the TiO 2 microsphere-based, solid state DSSCs

  4. Radial restricted solid-on-solid and etching interface-growth models

    Alves, Sidiney G.

    2018-03-01

    An approach to generate radial interfaces is presented. A radial network recursively obtained is used to implement discrete model rules designed originally for the investigation in flat substrates. I used the restricted solid-on-solid and etching models as to test the proposed scheme. The results indicate the Kardar, Parisi, and Zhang conjecture is completely verified leading to a good agreement between the interface radius fluctuation distribution and the Gaussian unitary ensemble. The evolution of the radius agrees well with the generalized conjecture, and the two-point correlation function exhibits also a good agreement with the covariance of the Airy2 process. The approach can be used to investigate radial interfaces evolution for many other classes of universality.

  5. Stability study of cermet-supported solid oxide fuel cells with bi-layered electrolyte

    Zhang, Xinge; Gazzarri, Javier; Robertson, Mark; Deces-Petit, Cyrille [National Research Council, Institute for Fuel Cell Innovation, 4250 Wesbrook Mall, Vancouver, BC (Canada); Kesler, Olivera [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, ON (Canada)

    2008-12-01

    Performance and stability of five cermet-supported button-type solid oxide fuel cells featuring a bi-layered electrolyte (SSZ/SDC), an SSC cathode, and a Ni-SSZ anode, were analyzed using polarization curves, impedance spectroscopy, and post-mortem SEM observation. The cell performance degradation at 650 C in H{sub 2}/air both with and without DC bias conditions was manifested primarily as an increase in polarization resistance, approximately at a rate of 2.3 m{omega} cm{sup 2} h{sup -1} at OCV, suggesting a decrease in electrochemical kinetics as the main phenomenon responsible for the performance decay. In addition, the initial series resistance was about ten times higher than the calculated resistance corresponding to the electrolyte, reflecting a possible inter-reaction between the electrolyte layers that occurred during the sintering stage. In situ and ex situ sintered cathodes showed no obvious difference in cell performance or decay rate. The stability of the cells with and without electrical load was also investigated and no significant influence of DC bias was recorded. Based on the experimental results presented, we preliminarily attribute the performance degradation to electrochemical and microstructural degradation of the cathode. (author)

  6. Stability study of cermet-supported solid oxide fuel cells with bi-layered electrolyte

    Zhang, Xinge; Gazzarri, Javier; Robertson, Mark; Decès-Petit, Cyrille; Kesler, Olivera

    Performance and stability of five cermet-supported button-type solid oxide fuel cells featuring a bi-layered electrolyte (SSZ/SDC), an SSC cathode, and a Ni-SSZ anode, were analyzed using polarization curves, impedance spectroscopy, and post-mortem SEM observation. The cell performance degradation at 650 °C in H 2/air both with and without DC bias conditions was manifested primarily as an increase in polarization resistance, approximately at a rate of 2.3 mΩ cm 2 h -1 at OCV, suggesting a decrease in electrochemical kinetics as the main phenomenon responsible for the performance decay. In addition, the initial series resistance was about ten times higher than the calculated resistance corresponding to the electrolyte, reflecting a possible inter-reaction between the electrolyte layers that occurred during the sintering stage. In situ and ex situ sintered cathodes showed no obvious difference in cell performance or decay rate. The stability of the cells with and without electrical load was also investigated and no significant influence of DC bias was recorded. Based on the experimental results presented, we preliminarily attribute the performance degradation to electrochemical and microstructural degradation of the cathode.

  7. An all-solid-state electrochemical double-layer capacitor based on a plastic crystal electrolyte

    Ali eaabouimrane

    2015-08-01

    Full Text Available A plastic crystal, solid electrolyte was prepared by mixing tetrabutylammonium hexafluorophosphate salt, (C4H94NPF6, (10 molar % with succinonitrile, SCN, (N C−CH2−CH2−C N, [SCN-10%TBA-PF6]. The resultant waxy material shows a plastic crystalline phase that extend from -36 °C up to its melting at 23 °C. It shows a high ionic conductivity reaching 4 × 10−5 S/cm in the plastic crystal phase (15 °C and ~ 3 × 10−3 S/cm in the molten state (25 °C. These properties along with the high electrochemical stability rendered the use of this material as an electrolyte in an electrochemical double-layer capacitor (EDLC. The EDLC was assembled and its performance was tested by cyclic voltammetry, AC impedance spectroscopy and galvanostatic charge-discharge methods. Specific capacitance values in the range of 4-7 F/g. (of electrode active material were obtained in the plastic crystal phase at 15 °C, that although compare well with those reported for some polymer electrolytes, can be still enhanced with further development of the device and its components, and only demonstrate their great potential use for capacitors as a new application.

  8. An All-Solid-State Electrochemical Double-Layer Capacitor Based on a Plastic Crystal Electrolyte

    Abouimrane, Ali; Belharouak, Ilias [Qatar Environment and Energy Research Institute, Qatar Foundation, Doha (Qatar); Abu-Lebdeh, Yaser A., E-mail: yaser.abu-lebdeh@nrc.gc.ca [Energy, Mining and Environment Portfolio and Automotive and Surface Transportation Portfolio, National Research Council of Canada, Ottawa, ON (Canada)

    2015-08-18

    A plastic crystal, solid electrolyte was prepared by mixing tetrabutylammonium hexafluorophosphate salt, (C{sub 4}H{sub 9}){sub 4}-NPF{sub 6}, (10 molar %) with succinonitrile, SCN, (N≡C−CH{sub 2}−CH{sub 2}−C≡N), [SCN-10%TBA-PF{sub 6}]. The resultant waxy material shows a plastic crystalline phase that extends from −36°C up to its melting at 23°C. It shows a high ionic conductivity reaching 4 × 10{sup -5} S/cm in the plastic crystal phase (15°C) and ~ 3 × 10{sup -3} S/cm in the molten state (25°C). These properties along with the high electrochemical stability rendered the use of this material as an electrolyte in an electrochemical double-layer capacitor (EDLC). The EDLC was assembled, and its performance was tested by cyclic voltammetry, AC impedance spectroscopy, and galvanostatic charge–discharge methods. Specific capacitance values in the range of 4–7 F/g (of electrode active material) were obtained in the plastic crystal phase at 15°C, that although compare well with those reported for some polymer electrolytes, can be still enhanced with further development of the device and its components, and only demonstrate their great potential use for capacitors as a new application.

  9. An All-Solid-State Electrochemical Double-Layer Capacitor Based on a Plastic Crystal Electrolyte

    Abouimrane, Ali; Belharouak, Ilias; Abu-Lebdeh, Yaser A.

    2015-01-01

    A plastic crystal, solid electrolyte was prepared by mixing tetrabutylammonium hexafluorophosphate salt, (C 4 H 9 ) 4 -NPF 6 , (10 molar %) with succinonitrile, SCN, (N≡C−CH 2 −CH 2 −C≡N), [SCN-10%TBA-PF 6 ]. The resultant waxy material shows a plastic crystalline phase that extends from −36°C up to its melting at 23°C. It shows a high ionic conductivity reaching 4 × 10 -5 S/cm in the plastic crystal phase (15°C) and ~ 3 × 10 -3 S/cm in the molten state (25°C). These properties along with the high electrochemical stability rendered the use of this material as an electrolyte in an electrochemical double-layer capacitor (EDLC). The EDLC was assembled, and its performance was tested by cyclic voltammetry, AC impedance spectroscopy, and galvanostatic charge–discharge methods. Specific capacitance values in the range of 4–7 F/g (of electrode active material) were obtained in the plastic crystal phase at 15°C, that although compare well with those reported for some polymer electrolytes, can be still enhanced with further development of the device and its components, and only demonstrate their great potential use for capacitors as a new application.

  10. High-performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. Pt. 2. La(Sr)CoO{sub 3} cathode

    Inagaki, Toru; Yoshida, Hiroyuki [The Kansai Electric Power, Hyogo (Japan); Miura, Kazuhiro [Kanden Kakou, Hyogo (Japan); Maric, Radenka; Ohara, Satoshi; Zhang, Xinge; Mukai, Kazuo; Fukui, Takehisa [Japan Fine Ceramics Center, Nagoya (Japan)

    2000-03-01

    The reduced temperature solid oxide fuel cell (SOFC) with 0.5 mm thick La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{alpha}} (LSGM) electrolyte, La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} (LSCo) cathode, and Ni-(CeO{sub 2}){sub 0.8}(SmO{sub 1.5}){sub 0.2} (SDC) cermet anode showed an excellent initial performance, and high maximum power density, 0.47 W/cm{sup 2}, at 800 C. The results were comparable to those for the conventional SOFC with yttria-stabilized zirconia (YSZ) electrolyte, La(Sr)MnO{sub 3}-YSZ cathode and Ni-YSZ cermet anode at 1000 C. Using an LSCo powder prepared by spray pyrolysis, and selecting appropriate sintering temperatures, the lowest cathodic polarization of about 25 mV at 300 mA/cm{sup 2} was measured for a cathode prepared by sintering at 1000 C. Life time cell test results, however, showed that the polarization of the LSCo cathode increased with operating time. From EPMA results, this behavior was considered to be related to the interdiffusion of the elements at the cathode/electrolyte interface. Calcination of LSCo powder could be a possible way to suppress this interdiffusion at the interface. (orig.)

  11. High-performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. II. La(Sr)CoO 3 cathode

    Inagaki, Toru; Miura, Kazuhiro; Yoshida, Hiroyuki; Maric, Radenka; Ohara, Satoshi; Zhang, Xinge; Mukai, Kazuo; Fukui, Takehisa

    The reduced temperature solid oxide fuel cell (SOFC) with 0.5 mm thick La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- α (LSGM) electrolyte, La 0.6Sr 0.4CoO 3- δ (LSCo) cathode, and Ni-(CeO 2) 0.8(SmO 1.5) 0.2 (SDC) cermet anode showed an excellent initial performance, and high maximum power density, 0.47 W/cm 2, at 800°C. The results were comparable to those for the conventional SOFC with yttria-stabilized zirconia (YSZ) electrolyte, La(Sr)MnO 3-YSZ cathode and Ni-YSZ cermet anode at 1000°C. Using an LSCo powder prepared by spray pyrolysis, and selecting appropriate sintering temperatures, the lowest cathodic polarization of about 25 mV at 300 mA/cm 2 was measured for a cathode prepared by sintering at 1000°C. Life time cell test results, however, showed that the polarization of the LSCo cathode increased with operating time. From EPMA results, this behavior was considered to be related to the interdiffusion of the elements at the cathode/electrolyte interface. Calcination of LSCo powder could be a possible way to suppress this interdiffusion at the interface.

  12. Na3Si2Y0.16Zr1.84PO12-ionic liquid hybrid electrolytes: An approach for realizing solid-state sodium-ion batteries?

    de la Torre-Gamarra, Carmen; Appetecchi, Giovanni Battista; Ulissi, Ulderico; Varzi, Alberto; Varez, Alejandro; Passerini, Stefano

    2018-04-01

    Ceramic electrolytes are prepared through sintering processes which are carried out at high temperatures and require prolonged operating times, resulting unwelcome in industrial applications. We report a physicochemical characterization on hybrid, sodium conducting, electrolyte systems obtained by coating NASICON ceramic powders with the N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid. The goal is to realize a ceramic-IL interface with improved sodium mobility, aiming to obtain a solid electrolyte with high ion transport properties but avoiding sintering thermal treatment. The purpose of the present work, however, is showing how simply combining NASICON powder and Py14TFSI does not lead to any synergic effect on the resulting hybrid electrolyte, evidencing that an average functionalization of the ceramic powder surface and/or ionic liquid is needed. Also, the processing conditions for preparing the hybrid samples are found to affect their ion transport properties.

  13. Internal shorting and fuel loss of a low temperature solid oxide fuel cell with SDC electrolyte

    Zhang, Xinge; Robertson, Mark; Deces-Petit, Cyrille; Qu, Wei; Kesler, Olivera; Maric, Radenka; Ghosh, Dave [Institute for Fuel Cell Innovation, National Research Council Canada, 4250 Wesbrook Mall, Vancouver, BC V6T 1W5 (Canada)

    2007-02-10

    A solid oxide fuel cell with Sm{sub 0.2}Ce{sub 0.8}O{sub 1.9} (SDC) electrolyte of 10 {mu}m in thickness and Ni-SDC anode of 15 {mu}m in thickness on a 0.8 mm thick Ni-YSZ cermet substrate was fabricated by tape casting, screen printing and co-firing. A composite cathode, 75 wt.% Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3} (SSCo) + 25 wt.% SDC, approximately 50 {mu}m in thickness, was printed on the co-fired half-cell, and sintered at 950 C. The cell showed a high electrochemical performance at temperatures ranging from 500 to 650 C. Peak power density of 545 mW cm{sup -2} at 600 C was obtained. However, the cell exhibited severe internal shorting due to the mixed conductivity of the SDC electrolyte. Both the amount of water collected from the anode outlet and the open circuit voltage (OCV) indicated that the internal shorting current could reach 0.85 A cm{sup -2} or more at 600 C. Zr content inclusions were found at the surface and in the cross-section of the SDC electrolyte, which could be one of the reasons for reduced OCV and oxygen ionic conductivity. Fuel loss due to internal shorting of the thin SDC electrolyte cell becomes a significant concern when it is used in applications requiring high fuel utilization and electrical efficiency. (author)

  14. Properties of nanostructured undoped ZrO{sub 2} thin film electrolytes by plasma enhanced atomic layer deposition for thin film solid oxide fuel cells

    Cho, Gu Young; Noh, Seungtak; Lee, Yoon Ho; Cha, Suk Won, E-mail: ybkim@hanyang.ac.kr, E-mail: swcha@snu.ac.kr [Department of Mechanical and Aerospace Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-744 (Korea, Republic of); Ji, Sanghoon [Graduate School of Convergence Science and Technology, Seoul National University, Iui-dong, Yeongtong-gu, Suwon 443-270 (Korea, Republic of); Hong, Soon Wook; Koo, Bongjun; Kim, Young-Beom, E-mail: ybkim@hanyang.ac.kr, E-mail: swcha@snu.ac.kr [Department of Mechanical Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 133-791 (Korea, Republic of); An, Jihwan [Manufacturing Systems and Design Engineering Programme, Seoul National University of Science and Technology, 232 Gongneung-ro, Nowon-gu, Seoul 139-743 (Korea, Republic of)

    2016-01-15

    Nanostructured ZrO{sub 2} thin films were prepared by thermal atomic layer deposition (ALD) and by plasma-enhanced atomic layer deposition (PEALD). The effects of the deposition conditions of temperature, reactant, plasma power, and duration upon the physical and chemical properties of ZrO{sub 2} films were investigated. The ZrO{sub 2} films by PEALD were polycrystalline and had low contamination, rough surfaces, and relatively large grains. Increasing the plasma power and duration led to a clear polycrystalline structure with relatively large grains due to the additional energy imparted by the plasma. After characterization, the films were incorporated as electrolytes in thin film solid oxide fuel cells, and the performance was measured at 500 °C. Despite similar structure and cathode morphology of the cells studied, the thin film solid oxide fuel cell with the ZrO{sub 2} thin film electrolyte by the thermal ALD at 250 °C exhibited the highest power density (38 mW/cm{sup 2}) because of the lowest average grain size at cathode/electrolyte interface.

  15. Study of gadolinia-doped ceria solid electrolyte surface by XPS

    Datta, Pradyot; Majewski, Peter; Aldinger, Fritz

    2009-01-01

    Gadolinia-doped ceria (CGO) is an important material to be used as electrolyte for solid oxide fuel cell for intermediate temperature operation. Ceria doped with 10 mol% gadolinia (Ce 0.9 Gd 0.1 O 1.95 ) was prepared by conventional solid state synthesis and found to be single phase by room temperature X-ray diffraction (XRD). The chemical states of the surface of the prepared sample were analyzed by X-ray photoelectron spectroscopy (XPS). Though Gd was present in its characteristic chemical state, Ce was found in both Ce 4+ and Ce 3+ states. Presence of Ce 3+ state was ascribed to the differential yield of oxygen atoms in the sputtering process

  16. A mathematical model of the solid-polymer-electrolyte fuel cell

    Bernardi, D.M.; Verbrugge, M.W.

    1992-01-01

    This paper presents a mathematical model of the solid-polymer-electrolyte fuel cell and apply it to (i) investigate factors that limit cell performance and (ii) elucidate the mechanism of species transport in the complex network of gas, liquid, and solid phases of the cell. Calculations of cell polarization behavior compare favorably with existing experimental data. For most practical electrode thicknesses, model results indicate that the volume fraction of the cathode available for gas transport must exceed 20% in order to avoid unacceptably low cell-limiting current densities. It is shown that membrane dehydration can also pose limitations on operating current density; circumvention of this problem by appropriate membrane and electrode design and efficient water-management schemes is discussed. The authors' model results indicate that for a broad range of practical current densities there are no external water requirements because the water produced at the cathode is enough to satisfy the water requirement of the membrane

  17. Evaluation of solid polymer electrolytes for use in conducting polymer/nanotube actuators

    Lewis, Trevor W.; Kim, B. C.; Spinks, Geoffrey M.; Wallace, Gordon G.

    2000-06-01

    The stringent requirements for a solid polymer electrolyte (SPE) in solid state devices such as batteries or supercapacitors are even more demanding when used in electromechanical actuators. Not only is the SPE expected to exhibit good conductivity, mechanical properties, adhesion and mechanical/electrical stability, but it must also be flexible, maintained good adhesion while flexing, be easily processible and be able to function in air. In this work polyacrylonitrile and Kynar based non-aqueous SPEs and water based polyacrylamide hydrogel ion source/sinks containing various perchlorate salts were tested for their applicability to polypyrrole and carbon nanotube actuators and supercapacitors. The results indicate that the optimum SPE for both polypyrrole and carbon nanotube actuators would be a polyacrylonitrile plasticized with propylene carbonate and ethylene carbonate containing 1.0M NaClO4. It is also apparent that the same SPE would be the most suitable for supercapacitor applications with these materials.

  18. Friction mechanisms and interfacial slip at fluid-solid interfaces

    Leger, L

    2003-01-01

    We present series of experiments based on near field laser velocimetry, developed to characterize the friction mechanisms at fluid-solid interfaces. For polymers, entangled polymer melts are sheared against smooth solid surfaces, covered by surface attached polymer chains of the same chemical species, having a controlled surface density. Direct measurements of the interfacial velocity and of the shear force allow identification of the molecular mechanisms of friction. Depending on the value of the inverse of the shear rate experienced by the polymer compared to the reptation time, the transition between a regime of high and a regime of low friction observed when increasing the shear rate can be related to disentanglement or to the extraction of the surface chains from the bulk polymer. Surfaces with adjusted friction properties can thus be designed by choosing chain anchored length and surface density. For simple fluids, the direct measurements of the interfacial velocity show that, contrary to the usual hypo...

  19. The Effect of 1-Pentylamine as Solid Electrolyte Interphase Precursor on Lithium Metal Anodes

    Ding, Markus S.; Koch, Stephan L.; Passerini, Stefano

    2017-01-01

    Highlights: • Manufacturing of a well-controlled artificial SEI on lithium metal electrodes. • Native SEI-free lithium electrodes. • Lithium electrodes with decreased impedance and overpotential due to artificial SEI. • Process development to remove influence of native SEI. • 1-pentylamine in n-pentane as artificial SEI precursor for lithium metal. - Abstract: In this study, the formation of an artificial primary solid electrolyte interphase on a fresh Li surface, via reaction with 1-pentylamine (PA), is reported, allowing removing the influence of the metal electrode’s prior history. Electrochemical impedance spectroscopy, galvanostatic cycling, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) are used in order to investigate the effect of PA as solid electrolyte interphase precursor on Li metal. It is shown that pretreating native SEI-free Li metal surfaces with 1 M PA in n-pentane sharply decreases the electrode impedance and overpotential with respect to the treatment with only n-pentane. The treatment with 1 M PA in n-pentane results in surface roughening, but no increase of dendrite formation upon cycling. However, the use of higher PA concentration (5 M) increases impedance and overpotential and leads to dendrite growth.

  20. Atomic scale imaging of structural changes in solid electrolyte lanthanum lithium niobate upon annealing

    Hu, Xiaobing; Fisher, Craig A.J.; Kobayashi, Shunsuke; Ikuhara, Yumi H.; Fujiwara, Yasuyuki; Hoshikawa, Keigo; Moriwake, Hiroki; Kohama, Keiichi; Iba, Hideki; Ikuhara, Yuichi

    2017-01-01

    La (1-x)/3 Li x NbO 3 (LLNbO) is a promising electrolyte material for solid-state lithium-ion batteries because it is stable in contact with Li metal and contains a high concentration of intrinsic Li-ion vacancies. One strategy for improving its ionic conductivity and making it more competitive with other solid-state Li-ion electrolytes is to disorder the Li-ion vacancies by appropriate post-synthesis heat treatment, e.g., annealing. In this study, we examine the effects of annealing on single crystals of LLNbO with Li contents x = 0.07 and 0.13 based on simultaneous atomic resolution high angle annular dark field and annular bright field imaging methods using state-of-the-art aberration corrected scanning transmission electron microscopes. It is found that La modulation within A1 layers of the cation-deficient layered perovskite structure becomes more diffuse after annealing. In addition, some La atoms move to A-site positions and O4 window positions in the nominally vacant A2 layer, while O atom columns in this layer become rumpled in the [001] p direction, indicating that the NbO 6 octahedra are more heavily distorted after annealing. The observed crystal structure differences between as-prepared and annealed single crystals explain the drop in Li-ion conductivities of LLNbO single crystals after heat treatment.

  1. Development of layered anode structures supported over Apatite-type Solid Electrolytes

    Pandis P.

    2016-01-01

    Full Text Available Apatite-type lanthanum silicates (ATLS materials have attracted interest in recent literature as solid electrolytes for SOFCs. The fabrication of an ATLS based fuel cell with the state-of-art electrodes (NiO/YSZ as anode and LSCF or LSM as cathode can show degradation after long operation hours due to Si diffusion mainly towards the anode. In this work, we report a “layer-by-layer anodic electrodes” fabrication by means of spin coating and physical spraying. The overall aim of this work is the successful fabrication of such a layered structure including suitable blocking layers towards the inhibition of Si interdiffusion from the apatite electrolyte to the anode. The results showed that the deposition of 3 layers of LFSO/GDC (3μm, NiO/GDC (4μm and the final NiO/YSZ anode layer provided a stable half-cell, with no solid state reaction occurring among the electrodes and no Si diffusion observed towards the anode after thermal treatment at 800°C for 120h.

  2. [A toxicologic hygiene evaluation of electrolytic oxygen obtained from the water in a system with a solid polymeric electrolyte].

    Bardov, V G; Koziarin, I P; Suk, V G; Maslenko, A A; Shmuter, G M

    1990-01-01

    The authors evaluated the problems of hygienic aspects of oxygen obtained by the method of electrolytic decomposition of water with a different content of chemical substances in the system with a hard polymere electrolyte. On the basis of sanitary-chemical qualities and toxicological properties electrolysis gaseous oxygen may be recommended for use in creating an artificial gaseous atmosphere in hermetically sealed compartments in mixture with gaseous nitrogen (ratio 1:4).

  3. Amplifier spurious input current components in electrode-electrolyte interface impedance measurements

    Madrid Rossana E

    2005-03-01

    Full Text Available Abstract Background In Impedance Microbiology, the time during which the measuring equipment is connected to the bipolar cells is rather long, usually between 6 to 24 hrs for microorganisms with duplication times in the order of less than one hour and concentrations ranging from 101 to 107 [CFU/ml]. Under these conditions, the electrode-electrolyte interface impedance may show a slow drift of about 2%/hr. By and large, growth curves superimposed on such drift do not stabilize, are less reproducible, and keep on distorting all over the measurement of the temporal reactive or resistive records due to interface changes, in turn originated in bacterial activity. This problem has been found when growth curves were obtained by means of impedance analyzers or with impedance bridges using different types of operational amplifiers. Methods Suspecting that the input circuitry was the culprit of the deleterious effect, we used for that matter (a ultra-low bias current amplifiers, (b isolating relays for the selection of cells, and (c a shorter connection time, so that the relays were maintained opened after the readings, to bring down such spurious drift to a negligible value. Bacterial growth curves were obtained in order to test their quality. Results It was demonstrated that the drift decreases ten fold when the circuit remained connected to the cell for a short time between measurements, so that the distortion became truly negligible. Improvement due to better-input amplifiers was not as good as by reducing the connection time. Moreover, temperature effects were insignificant with a regulation of ± 0.2 [°C]. Frequency did not influence either. Conclusion The drift originated either at the dc input bias offset current (Ios of the integrated circuits, or in discrete transistors connected directly to the electrodes immersed in the cells, depending on the particular circuit arrangement. Reduction of the connection time was the best countermeasure.

  4. PREFACE: Liquid-solid interfaces: structure and dynamics from spectroscopy and simulations Liquid-solid interfaces: structure and dynamics from spectroscopy and simulations

    Gaigeot, Marie-Pierre; Sulpizi, Marialore

    2012-03-01

    Liquid-solid interfaces play an important role in a number of phenomena encountered in biological, chemical and physical processes. Surface-induced changes of the material properties are not only important for the solid support but also for the liquid itself. In particular, it is now well established that water at the interface is substantially different from bulk water, even in the proximity of apparently inert surfaces such as a simple metal. The complex chemistry at liquid-solid interfaces is typically fundamental to heterogeneous catalysis and electrochemistry, and has become especially topical in connection with the search for new materials for energy production. A quite remarkable example is the development of cheap yet efficient solar cells, whose basic components are dye molecules grafted to the surface of an oxide material and in contact with an electrolytic solution. In life science, the most important liquid-solid interfaces are the water-cell-membrane interfaces. Phenomena occurring at the surface of phospholipid bilayers control the docking of proteins, the transmission of signals as well as transport of molecules in and out of the cell. Recently the development of bio-compatible materials has lead to research on the interface between bio-compatible material and lipid/proteins in aqueous solution. Gaining a microscopic insight into the processes occurring at liquid-solid interfaces is therefore fundamental to a wide range of disciplines. This special section collects some contributions to the CECAM Workshop 'Liquid/Solid interfaces: Structure and Dynamics from Spectroscopy and Simulations' which took place in Lausanne, Switzerland in June 2011. Our main aim was to bring together knowledge and expertise from different communities in order to advance our microscopic understanding of the structure and dynamics of liquids at interfaces. In particular, one of our ambitions was to foster discussion between the experimental and theoretical

  5. Solid state electrolytes for all-solid-state 3D lithium-ion batteries

    Kokal, I.

    2012-01-01

    The focus of this Ph.D. thesis is to understand the lithium ion motion and to enhance the Li-ionic conductivities in commonly known solid state lithium ion conductors by changing the structural properties and preparation methods. In addition, the feasibility for practical utilization of several

  6. Solid oxide fuel cell electrolytes produced via very low pressure suspension plasma spray and electrophoretic deposition

    Fleetwood, James D.

    Solid oxide fuel cells (SOFCs) are a promising element of comprehensive energy policies due to their direct mechanism for converting the oxidization of fuel, such as hydrogen, into electrical energy. Both very low pressure plasma spray and electrophoretic deposition allow working with high melting temperature SOFC suspension based feedstock on complex surfaces, such as in non-planar SOFC designs. Dense, thin electrolytes of ideal composition for SOFCs can be fabricated with each of these processes, while compositional control is achieved with dissolved dopant compounds that are incorporated into the coating during deposition. In the work reported, sub-micron 8 mole % Y2O3-ZrO2 (YSZ) and gadolinia-doped ceria (GDC), powders, including those in suspension with scandium-nitrate dopants, were deposited on NiO-YSZ anodes, via very low pressure suspension plasma spray (VLPSPS) at Sandia National Laboratories' Thermal Spray Research Laboratory and electrophoretic deposition (EPD) at Purdue University. Plasma spray was carried out in a chamber held at 320 - 1300 Pa, with the plasma composed of argon, hydrogen, and helium. EPD was characterized utilizing constant current deposition at 10 mm electrode separation, with deposits sintered from 1300 -- 1500 °C for 2 hours. The role of suspension constituents in EPD was analyzed based on a parametric study of powder loading, powder specific surface area, polyvinyl butyral (PVB) content, polyethyleneimine (PEI) content, and acetic acid content. Increasing PVB content and reduction of particle specific surface area were found to eliminate the formation of cracks when drying. PEI and acetic acid content were used to control suspension stability and the adhesion of deposits. Additionally, EPD was used to fabricate YSZ/GDC bilayer electrolyte systems. The resultant YSZ electrolytes were 2-27 microns thick and up to 97% dense. Electrolyte performance as part of a SOFC system with screen printed LSCF cathodes was evaluated with peak

  7. Subsonic leaky Rayleigh waves at liquid-solid interfaces.

    Mozhaev, V G; Weihnacht, M

    2002-05-01

    The paper is devoted to the study of leaky Rayleigh waves at liquid-solid interfaces close to the border of the existence domain of these modes. The real and complex roots of the secular equation are computed for interface waves at the boundary between water and a binary isotropic alloy of gold and silver with continuously variable composition. The change of composition of the alloy allows one to cross a critical velocity for the existence of leaky waves. It is shown that, contrary to popular opinion, the critical velocity does not coincide with the phase velocity of bulk waves in liquid. The true threshold velocity is found to be smaller, the correction being of about 1.45%. Attention is also drawn to the fact that using the real part of the complex phase velocity as a velocity of leaky waves gives only approximate value. The most interesting feature of the waves under consideration is the presence of energy leakage in the subsonic range of the phase velocities where, at first glance, any radiation by harmonic waves is not permitted. A simple physical explanation of this radiation with due regard for inhomogeneity of radiated and radiating waves is given. The controversial question of the existence of leaky Rayleigh waves at a water/ice interface is reexamined. It is shown that the solution considered previously as a leaky wave is in fact the solution of the bulk-wave-reflection problem for inhomogeneous waves.

  8. Study of strontium- and magnesium-doped lanthanum gallate solid electrolyte surface by X-ray photoelectron spectroscopy

    Datta, Pradyot; Majewski, Peter; Aldinger, Fritz

    2008-01-01

    The chemical states of the surface of the oxygen ion conducting solid electrolyte La 0.9 Sr 0.1 Ga 0.85 Mg 0.15 O 3-δ (LSGM 1015) as prepared by solid-state synthesis was analyzed by X-ray photoelectron spectroscopy. It was found that adventitious carbon did not interact with any of the constituent elements of LSGM 1015. Ga and La were found to exist in trivalent states. But, due to ionic bombardment presence of Mg could not be detected in the electrolyte surface

  9. All-solid-state lithium-sulfur battery based on a nanoconfined LiBH4 electrolyte

    Das, Supti; Ngene, Peter; Norby, Poul

    2016-01-01

    In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4 in mesoporous silica as solid electrolytes. The nano-confined LiBH4 has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport...... number (t+ = 0.96), close to unity, demonstrates a purely cationic conductor. The electrolyte has an excellent stability against lithium metal. The behavior of the batteries is studied by cyclic voltammetry and repeated charge/discharge cycles in galvanostatic conditions. The batteries show very good...

  10. Study on component interface evolution of a solid oxide fuel cell stack after long term operation

    Yang, Jiajun; Huang, Wei; Wang, Xiaochun; Li, Jun; Yan, Dong; Pu, Jian; Chi, Bo; Li, Jian

    2018-05-01

    A 5-cell solid oxide fuel cell (SOFC) stack with external manifold structure is assembled and underwent a durability test with an output of 250 W for nearly 4400 h when current density and operating temperature are 355 mA/cm2 and 750 °C. Cells used in the stack are anode-supported cells (ASC) with yttria-stabilized zirconia (YSZ) electrolytes, Ni/YSZ hydrogen electrodes, and YSZ based composite cathode. The dimension of the cell is 150 × 150 mm (active area: 130 × 130 mm). Ceramic-glass sealant is used in the stack to keep the gas tightness between cells, interconnects and manifolds. Pure hydrogen and dry air are used as fuel and oxidant respectively. The stack has a maximum output of 340 W at 562 mA/cm2 current density at 750 °C. The stack shows a degradation of 1.5% per 1000 h during the test with 2 thermal cycles to room temperature. After the test, the stack was dissembled and examined. The relationship between microstructure changes of interfaces and degradation in the stack are discussed. The microstructure evolution of interfaces between electrode, contact material and current collector are unveiled and their relationship with the degradation is discussed.

  11. Influence of Li10GeP2S12-type solid electrolyte on cell thermodynamics

    Jishnu Bhattacharya

    2016-06-01

    Full Text Available We elucidate few critical facts about the lithium superionic conductor (Li10GeP2S12 and few other compounds of the same family as the electrolyte in Li-ion cells. The dimensionality of diffusion process and existence of ‘structural’ lithiums are not well understood in this material. From the ab-initio MD simulations, we find that the material transport Li-ions predominantly in the crystallographic c-direction. Nevertheless, the cross-channel diffusion is significant as well. We explored the mobility of individual Li-ions and do not find evidence that supports the proposition of structural Li-ions in LGPS. We find nominal effect of local Ge-P ordering and of Li-concentration change on diffusivity, which not only provides information about the invariance of diffusivity at different conditions of operation, but also ensures that identification of the ground state structure in LGPS having partially occupied Li and Ge/P sublattices should have minimal effect on the diffusion analysis. We computed the dilute Li insertion and extraction voltages for LGPS from ab-initio total energy calculation. The dilute voltages indicate that the material is prone to react by exchanging Li-ions with the electrodes at typical operating range of voltages indicating formation of some interphase at the electrode-electrolyte interface, which necessitates further experimental investigation

  12. Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

    Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan; Li, Qiuyan; Lv, Dongping; Xiao, Jie; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

    2015-11-10

    Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupled with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.

  13. Present status of solid state photoelectrochemical solar cells and dye sensitized solar cells using PEO-based polymer electrolytes

    Singh, Pramod Kumar; Bhattacharya, Bhaskar; Nagarale, R K; Pandey, S P; Rhee, H W

    2011-01-01

    Due to energy crises in the future, much effort is being directed towards alternate sources. Solar energy is accepted as a novel substitute for conventional sources of energy. Out of the long list of various types of solar cells available on the market, solid state photoelectrochemical solar cells (SSPECs) and dye sensitized solar cells (DSSCs) are proposed as an alternative to costly crystalline solar cell. This review provides a common platform for SSPECs and DSSCs using polymer electrolyte, particularly on polyethylene oxide (PEO)-based polymer electrolytes. Due to numerous advantageous properties of PEO, it is frequently used as an electrolyte in both SSPECs as well as DSSCs. In DSSCs, so far high efficiency (more than 11%) has been obtained only by using volatile liquid electrolyte, which suffers many disadvantages, such as corrosion, leakage and evaporation. The PEO-based solid polymer proves its importance and could be used to solve the problems stated above. The recent developments in SSPECs and DSSCs using modified PEO electrolytes by adding nano size inorganic fillers, blending with low molecular weight polymers and ionic liquid (IL) are discussed in detail. The role of ionic liquid in modifying the electrical, structural and photoelectrochemical properties of PEO polymer electrolytes is also described. (review)

  14. Present status of solid state photoelectrochemical solar cells and dye sensitized solar cells using PEO-based polymer electrolytes

    Singh, Pramod Kumar; Nagarale, R. K.; Pandey, S. P.; Rhee, H. W.; Bhattacharya, Bhaskar

    2011-06-01

    Due to energy crises in the future, much effort is being directed towards alternate sources. Solar energy is accepted as a novel substitute for conventional sources of energy. Out of the long list of various types of solar cells available on the market, solid state photoelectrochemical solar cells (SSPECs) and dye sensitized solar cells (DSSCs) are proposed as an alternative to costly crystalline solar cell. This review provides a common platform for SSPECs and DSSCs using polymer electrolyte, particularly on polyethylene oxide (PEO)-based polymer electrolytes. Due to numerous advantageous properties of PEO, it is frequently used as an electrolyte in both SSPECs as well as DSSCs. In DSSCs, so far high efficiency (more than 11%) has been obtained only by using volatile liquid electrolyte, which suffers many disadvantages, such as corrosion, leakage and evaporation. The PEO-based solid polymer proves its importance and could be used to solve the problems stated above. The recent developments in SSPECs and DSSCs using modified PEO electrolytes by adding nano size inorganic fillers, blending with low molecular weight polymers and ionic liquid (IL) are discussed in detail. The role of ionic liquid in modifying the electrical, structural and photoelectrochemical properties of PEO polymer electrolytes is also described.

  15. Investigation of the Reversible Lithiation of an Oxide Free Aluminum Anode by a LiBH4 Solid State Electrolyte

    Jason A. Weeks

    2017-11-01

    Full Text Available In this study, we analyze and compare the physical and electrochemical properties of an all solid-state cell utilizing LiBH4 as the electrolyte and aluminum as the active anode material. The system was characterized by galvanostatic lithiation/delithiation, cyclic voltammetry (CV, X-ray diffraction (XRD, energy dispersive X-ray spectroscopy (EDS, Raman spectroscopy, electrochemical impedance spectroscopy (EIS, and scanning electron microscopy (SEM. Constant current cycling demonstrated that the aluminum anode can be reversibly lithiated over multiple cycles utilizing a solid-state electrolyte. An initial capacity of 895 mAh/g was observed and is close to the theoretical capacity of aluminum. Cyclic voltammetry of the cell was consistent with the constant current cycling data and showed that the reversible lithiation/delithiation of aluminum occurs at 0.32 V and 0.38 V (vs. Li+/Li respectively. XRD of the aluminum anode in the initial and lithiated state clearly showed the formation of a LiAl (1:1 alloy. SEM-EDS was utilized to examine the morphological changes that occur within the electrode during cycling. This work is the first example of reversible lithiation of aluminum in a solid-state cell and further emphasizes the robust nature of the LiBH4 electrolyte. This demonstrates the possibility of utilizing other high capacity anode materials with a LiBH4 based solid electrolyte in all-solid-state batteries.

  16. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes.

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-24

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 , LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li 2 CO 3 . Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g -1 carbon at 20 μA cm -2 . Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g -1 carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g -1 carbon at 20 μA cm -2 and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage.

  17. Critical role of the semiconductor-electrolyte interface in photocatalytic performance for water-splitting reactions using Ta3N5 particles

    Nurlaela, Ela; Ould-Chikh, Samy; Harb, Moussab; Del Gobbo, Silvano; Aouine, Mimoun; Puzenat, Eric; Sautet, Philippe; Domen, Kazunari; Basset, Jean-Marie; Takanabe, Kazuhiro

    2014-01-01

    the experiments. Electrochemical and Mott-Schottky analyses demonstrated that the surface layer drastically affects the energetic picture at the semiconductor-electrolyte interface, which can consequently affect the photocatalytic performance. Chemical etching

  18. A New All-Solid-State Hyperbranched Star Polymer Electrolyte for Lithium Ion Batteries: Synthesis and Electrochemical Properties

    Wang, Ailian; Xu, Hao; Zhou, Qian; Liu, Xu; Li, Zhengyao; Gao, Rui; Wu, Na; Guo, Yuguo; Li, Huayi; Zhang, Liaoyun

    2016-01-01

    Highlights: • A new hyperbranched multi-arm star polymer was successfully synthesized. • The star polymer electrolyte has good thermal stability and forming-film property. • The ion conductivity electrolyte can reach 8.3 × 10"−"5 S cm"−"1 at room temperature. • The star polymer electrolyte has wide electrochemical windows of 4.7 V. - Abstract: A new hyperbranched multi-arm star polymer with hyperbranched polystyrene (HBPS) as core and polymethyl methacrylate-block-poly(ethylene glycol) methyl ether methacrylate(PMMA-b-PPEGMA) as arms was firstly synthesized by atom transfer radical polymerization. The obtained hyperbranched multi-arm star polymer (HBPS-(PMMA-b-PPEGMA)_x) exhibited good thermal stability with a thermal decomposition temperature of 372 °C. The transparent, free-standing, flexible polymer electrolyte film of the blending of HBPS-(PMMA-b-PPEGMA)_x and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was successfully fabricated by a solution casting method. The ionic conductivity of the hyperbranched star polymer electrolyte with a molar ratio of [EO]/[Li] of 30 could reach 8.3 × 10"−"5 S cm"−"1 at 30 °C (with the content of PPEGMA of 83.7%), and 2.0 × 10"−"4 S cm"−"1 at 80 °C (with the content of PPEGMA of 51.6%). The effect of the concentration of lithium salts on ionic conductivity was also investigated. The obtained all-solid-state polymer electrolyte possessed a wide electrochemical stability window of 4.7 V (vs. Li"+/Li), and a lithium-ion transference number (t_L_i"+) up to 0.31. The interfacial impedance of the fabricated LiÔöépolymer electrolyteÔöéLi symmetric cell based on hyperbranched star multi-arm polymer electrolyte exhibited good interfacial compatibility between all-solid-state polymer electrolyte and electrodes. The excellent properties of the hyperbranched star polymer electrolyte made it attractive as solid-state polymer electrolyte for lithium-ion batteries.

  19. High temperature mechanical properties of zirconia tapes used for electrolyte supported solid oxide fuel cells

    Fleischhauer, Felix; Bermejo, Raul; Danzer, Robert; Mai, Andreas; Graule, Thomas; Kuebler, Jakob

    2015-01-01

    Solid-Oxide-Fuel-Cell systems are efficient devices to convert the chemical energy stored in fuels into electricity. The functionality of the cell is related to the structural integrity of the ceramic electrolyte, since its failure can lead to drastic performance losses. The mechanical property which is of most interest is the strength distribution at all relevant temperatures and how it is affected with time due to the environment. This study investigates the impact of the temperature on the strength and the fracture toughness of different zirconia electrolytes as well as the change of the elastic constants. 3YSZ and 6ScSZ materials are characterised regarding the influence of sub critical crack growth (SCCG) as one of the main lifetime limiting effects for ceramics at elevated temperatures. In addition, the reliability of different zirconia tapes is assessed with respect to temperature and SCCG. It was found that the strength is only influenced by temperature through the change in fracture toughness. SCCG has a large influence on the strength and the lifetime for intermediate temperature, while its impact becomes limited at temperatures higher than 650 °C. In this context the tetragonal 3YSZ and 6ScSZ behave quite different than the cubic 10Sc1CeSZ, so that at 850 °C it can be regarded as competitive compared to the tetragonal compounds.

  20. Electrical and morphological analysis of chitosan:AgTf solid electrolyte

    Aziz, Shujahadeen B., E-mail: shujaadeen78@yahoo.com [School of Physics, Faculty of Science and Science Education, University of Sulaimani, Kurdistan Regional Government, Sulaimani (Iraq); Abidin, Zul Hazrin Z. [Centre for Ionics University of Malaya (CIUM), Department of Physics, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2014-04-01

    Solution cast technique is employed to prepare solid polymer electrolyte films based on chitosan (host polymer) and silver triflate (AgCF{sub 3}SO{sub 3}, doping salt) using (1%) acetic acid as a common solvent. The effect of salt concentration on both EP and bulk materials dielectric properties has been analyzed. Physically the original relationship between the bulk dielectric constant and DC conductivity has been interpreted. It is demonstrated that the dielectric constant and dielectric loss values decrease at higher temperatures due to the reduction of silver ions. Scanning electron microscopy (SEM) and energy dispersive analysis of X-ray (EDAX) indicate the presence of metallic silver particles. The ac conductivity spectra shows three distinct regions and obeys the Jonscher's power law at high frequency regions. The temperature dependence of frequency exponent (s) shows the crossover from CBH model to SP model. - Highlights: • A strong relationship exists between DC conductivity and dielectric constant. • The decrease of ε′ and ε″ is due to the reduction of silver ions (Ag{sup +} → Ag{sup o}). • The morphological results reveal the formation of silver particles. • The AC conduction models can be applicable for ion conducting polymer electrolytes.

  1. Some laws governing the electrosynthesis of organic compounds with a solid polymetric electrolyte

    Rodionova, N.A.; Avrutskaya, I.A.; Fioshin, M. Ya.; Khrizolitova, M.A.

    1986-01-01

    The electrosynthesis of organic compounds with a solid polymetric electrolyte (SPE) makes it possible to carry out the process in the absence of a supporting electrolyte. This facilitates the recovery of the desired product, eliminates the inorganic waste products, and allows a small interelectrode distance, and the absence of the accumulation of gases lowers the voltage in the cell. Some laws governing syntheses of SPE were studied in the example cases of the electrochemical reduction of 2,2,6,6-tetramethyl-4-oxopiperidine to 2,2,6,6-tetramethyl-4-hydroxy-piperidine, the reduction of triacetonamine oxime and triacetonamine azine to 2,2,6,6-tetramethyl-4- aminopiperidine and the oxidation of isobutanol to isobutyric acid. The electrolysis with an SPE was carried out under galvanostatic conditions in an electrolyzer of the filter-press type with forced circulation of the catholyte and anolyte. Low reaction rates are found to be characteristic of all the compounds investigated when the electrolysis is carried out with an SPE.

  2. Hydrogen production by electrochemical decomposition of formic acid via solid polymer electrolyte

    Kilic, Ebru Oender [KOSGEB Bursa Business Development Center, Besevler Kucuk Sanayi Sitesi 16149 Nilufer/Bursa (Turkey); Koparal, Ali Savas; Oeguetveren, Uelker Bakir [Anadolu University, Iki Eylul Campus, Applied Research Center for Environmental Problems 26555 Eskisehir (Turkey); Anadolu University, Iki Eylul Campus, Department of Environmental Engineering, 26555 Eskisehir (Turkey)

    2009-01-15

    The aim of this work is to investigate the feasibility of simultaneous hydrogen production by electrochemical decomposition of formic acid via solid polymer electrolyte (SPE) in an electrochemical reactor. Titanium oxide coated with iridium oxide as anode and carbon fibre with Pt catalyst as cathode were used in the experiments. Effects of applied current density, flow rates and temperature of formic acid solution, concentration of supporting electrolyte and pH of the solution on performance of the process have been investigated. The effect of membrane thickness has also been examined. The results suggest that electrolysis using SPE is a promising method for the treatment of organic pollutants. Hydrogen with purity of 99.999% at ambient temperature by using carbon fibre cathode with Pt catalyst can be produced simultaneously and COD removal efficiency of 95% has been achieved not requiring any chemical addition and temperature increase. Also complete electrochemical oxidation of formic acid at the original pH to CO{sub 2} and H{sub 2}O without production of intermediate has been proved by HPLC analysis. (author)

  3. Demonstration of high efficiency intermediate-temperature solid oxide fuel cell based on lanthanum gallate electrolyte

    Inagaki, Toru; Nishiwaki, Futoshi; Kanou, Jirou; Yamasaki, Satoru; Hosoi, Kei; Miyazawa, Takashi; Yamada, Masaharu; Komada, Norikazu

    2006-01-01

    The Kansai Electric Power Co., Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been jointly developing intermediate-temperature solid oxide fuel cells (SOFCs). The operation temperatures between 600 and 800 o C were set as the target, which enable SOFC to use less expensive metallic separators for cell-stacking and to carry out internal reforming of hydrocarbon fuels. The electrolyte-supported planar-type cells were fabricated using highly conductive lanthanum gallate-based electrolyte, La(Sr)Ga(Mg,Co)O 3-δ , Ni-(CeO 2 ) 1-x (SmO 1.5 ) x cermet anode, and Sm(Sr)CoO 3-δ cathode. The 1 kW-class power generation modules were fabricated using a seal-less stack of the cells and metallic separators. The 1 kW-class prototype power generation system with the module was developed with the high performance cell, which showed the thermally self-sustainability. The system included an SOFC module, a dc-ac inverter, a desulfurizer, and a heat recovery unit. It provided stable ac power output of 1 kW with the electrical efficiency of 45% LHV based on ac output by using city gas as a fuel, which was considered to be excellent for such a small power generation system. And the hot water of 90 o C was obtained using high temperature off-gas from SOFC

  4. Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

    Inagaki, Toru; Nishiwaki, Futoshi; Yamasaki, Satoru [The Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-choume, Amagasaki, Hyogo 661-0974 (Japan); Akbay, Taner; Hosoi, Kei [Mitsubishi Materials Corporation, Corporate Technology and Development Division, 1002-14 Mukohyama, Naka, Ibaraki 311-0102 (Japan)

    2008-07-01

    The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 C. There are some significant features in IT-SOFC of KEPCO-MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system. (author)

  5. Demonstration of high efficiency intermediate-temperature solid oxide fuel cell based on lanthanum gallate electrolyte

    Inagaki, Toru [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan)]. E-mail: inagaki@rdd.kepco.co.jp; Nishiwaki, Futoshi [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Kanou, Jirou [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Yamasaki, Satoru [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Hosoi, Kei [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Miyazawa, Takashi [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Yamada, Masaharu [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Komada, Norikazu [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan)

    2006-02-09

    The Kansai Electric Power Co., Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been jointly developing intermediate-temperature solid oxide fuel cells (SOFCs). The operation temperatures between 600 and 800 {sup o}C were set as the target, which enable SOFC to use less expensive metallic separators for cell-stacking and to carry out internal reforming of hydrocarbon fuels. The electrolyte-supported planar-type cells were fabricated using highly conductive lanthanum gallate-based electrolyte, La(Sr)Ga(Mg,Co)O{sub 3-{delta}}, Ni-(CeO{sub 2}){sub 1-x}(SmO{sub 1.5}) {sub x} cermet anode, and Sm(Sr)CoO{sub 3-{delta}} cathode. The 1 kW-class power generation modules were fabricated using a seal-less stack of the cells and metallic separators. The 1 kW-class prototype power generation system with the module was developed with the high performance cell, which showed the thermally self-sustainability. The system included an SOFC module, a dc-ac inverter, a desulfurizer, and a heat recovery unit. It provided stable ac power output of 1 kW with the electrical efficiency of 45% LHV based on ac output by using city gas as a fuel, which was considered to be excellent for such a small power generation system. And the hot water of 90 {sup o}C was obtained using high temperature off-gas from SOFC.

  6. Long-term Steam Electrolysis with Electrolyte-Supported Solid Oxide Cells

    Schefold, Josef; Brisse, Annabelle; Poepke, Hendrik

    2015-01-01

    Steam electrolysis over 11000 h with an electrolyte-supported solid oxide cell is discussed. The cell of 45 cm"2 area consists of a scandia/ceria doped zirconia electrolyte (6Sc1CeSZ), CGO diffusion-barrier/adhesion layers, a lanthanum strontium cobaltite ferrite (LSCF) oxygen electrode, and a nickel steam/hydrogen electrode. After initial 2500 h operation with lower current-density magnitude, the current density was set to j = -0.9 A cm"−"2 and the steam conversion rate to 51%. This led to a cell voltage of 1.185 V at 847 °C cell temperature. Average voltage degradation was 7.3 mV/1000 h ( 100% throughout the test (with an external heat source for evaporation). Impedance spectroscopic measurements revealed a degradation almost entirely due to increasing ohmic resistance. The rate of resistance increase was initially faster (up to 40 mΩ cm"2/1000 h) and stabilised after several 1000 h operation. After 9000 h a small (non-ohmic) electrode degradation became detectable (<2 mV/1000 h), superimposed to ohmic degradation. The small electrode degradation is understood as indication for largely reversible (electrolysis cell/fuel cell) behaviour.

  7. Lithium dendrite and solid electrolyte interphase investigation using OsO4

    Zier, Martin; Scheiba, Frieder; Oswald, Steffen; Thomas, Jürgen; Goers, Dietrich; Scherer, Torsten; Klose, Markus; Ehrenberg, Helmut; Eckert, Jürgen

    2014-11-01

    Osmium tetroxide (OsO4) staining, commonly used to enhance scattering contrast in electron microscopy of biologic tissue and polymer blends, has been adopted for studies of graphite anodes in lithium-ion batteries. OsO4 shows a coordinated reaction with components of the solid electrolyte interphase (SEI) and lithium dendrites, thereby increasing material contrast for scanning electron microscopy investigations. Utilizing the high affinity of lithium metal to react with osmium tetroxide it was possible to localize even small lithium deposits on graphite electrodes. In spite of their reaction with the OsO4 fume, the lithium dendrite morphology remains almost untouched by the staining procedure, offering information on the dendrite growth process. Correlating the quantity of osmium detected with the amount of residual ("dead") lithium of a discharged electrode, it was possible to obtain a practical measure for lithium plating and stripping efficiencies. EDX mappings allowed for a localization of electrochemically stripped lithium dendrites by their residual stained SEI shells. Cross sections, prepared by focused ion beam (FIB) of cycled graphite electrodes treated with OsO4, revealed important information about deposition and distribution of metallic lithium and the electrolyte reduction layer across the electrode.

  8. Low temperature electrochemical cells with sodium β″-alumina solid electrolyte (BASE)

    Girija, T. C.; Virkar, Anil V.

    Cells of Daniell-type with copper-zinc electrochemical couples and sodium β″-alumina solid electrolyte (BASE) were constructed. The cathode consisted of copper in contact with its ions (Cu/Cu 2+) while zinc in contact with its ions (Zn/Zn 2+) constituted the anode. Dimethyl sulfoxide (DMSO) containing 1 M NaBF 4 was used as the liquid electrolyte. The configuration of the cell constructed can be written as follows: Zn(s)/ZnCl 2(DMSO)(0.1 M), NaBF 4(1 M)/BASE/NaBF 4(1 M), CuCl 2(DMSO)(0.1 M)/Cu(s). The cell was subjected to charge-discharge cycles at 100 °C. The BASE discs were found to be stable even after the cell was subjected to several electrochemical charge-discharge cycles. Cells were also constructed using BASE discs with porous BASE surface layers introduced to lower the interfacial resistance. Cells with surface modified BASE exhibited a lower resistance in comparison to those using unmodified BASE. XRD and SEM analyses indicated that no detectable degradation of BASE discs occurred after cell testing. Preliminary cell tests were also conducted with NaCF 3SO 3 in place of NaBF 4.

  9. Low temperature electrochemical cells with sodium {beta}''-alumina solid electrolyte (BASE)

    Girija, T.C.; Virkar, Anil V. [Department of Materials Science and Engineering, 122 S. Central Campus Drive, University of Utah, Salt Lake City, UT 84112 (United States)

    2008-05-15

    Cells of Daniell-type with copper-zinc electrochemical couples and sodium {beta}''-alumina solid electrolyte (BASE) were constructed. The cathode consisted of copper in contact with its ions (Cu/Cu{sup 2+}) while zinc in contact with its ions (Zn/Zn{sup 2+}) constituted the anode. Dimethyl sulfoxide (DMSO) containing 1 M NaBF{sub 4} was used as the liquid electrolyte. The configuration of the cell constructed can be written as follows: Zn(s)/ZnCl{sub 2}(DMSO)(0.1 M), NaBF{sub 4}(1 M)/BASE/NaBF{sub 4}(1 M), CuCl{sub 2}(DMSO)(0.1 M)/Cu(s) The cell was subjected to charge-discharge cycles at 100 C. The BASE discs were found to be stable even after the cell was subjected to several electrochemical charge-discharge cycles. Cells were also constructed using BASE discs with porous BASE surface layers introduced to lower the interfacial resistance. Cells with surface modified BASE exhibited a lower resistance in comparison to those using unmodified BASE. XRD and SEM analyses indicated that no detectable degradation of BASE discs occurred after cell testing. Preliminary cell tests were also conducted with NaCF{sub 3}SO{sub 3} in place of NaBF{sub 4}. (author)

  10. Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

    Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com [Dielectric Research Laboratory, Department of Physics, Jai Narain Vyas University, Jodhpur – 342 005 (India)

    2016-05-06

    Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.

  11. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    Manjunatha, H., E-mail: h-manjunath@blr.amrita.edu; Kumaraswamy, G. N. [Department of Physics, Amrita Vishwa Vidyapeetham, Bengaluru-560 035 (India); Damle, R. [Department of Physics, Bangalore University, Bengaluru-560 056 (India)

    2016-05-06

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10{sup −1} – 10{sup −3} Scm{sup −1}, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEO{sub x}NaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O{sup +1} ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  12. Morphology and conductivity study of solid electrolyte Li{sub 3}PO{sub 4}

    Prayogi, Lugas Dwi, E-mail: ldprayodi@gmail.com; Faisal, Muhamad [Engineering Physics, Sepuluh Nopember Institute of Technology ITS Campus, Sukolilo, Surabaya 6011 (Indonesia); Kartini, Evvy, E-mail: kartini@batan.go.id; Honggowiranto, Wagiyo; Supardi [Center for Science and Technology of Advanced Materials, National Nuclear Energy Agency Kawasan Puspiptek Serpong, Tangerang Selatan15314, Banten (Indonesia)

    2016-02-08

    The comparison between two different methods of synthesize of solid electrolyte Li{sub 3}PO{sub 4} as precursor material for developing lithium ion battery, has been performed. The first method is to synthesize Li{sub 3}PO{sub 4} prepared by wet chemical reaction from LiOH and H{sub 3}PO{sub 4} which provide facile, abundant available resource, low cost, and low toxicity. The second method is solid state reaction prepared by Li{sub 2}CO{sub 3} and NH{sub 4}H{sub 2}PO{sub 4.} In addition, the possible morphology identification of comparison between two different methods will also be discussed. The composition, morphology, and additional identification phase and another compound of Li{sub 3}PO{sub 4} powder products from two different reaction are characterized by SEM, EDS, and EIS. The Li{sub 3}PO{sub 4} powder produced from wet reaction and solid state reaction have an average diameter of 0.834 – 7.81 µm and 2.15 – 17.3 µm, respectively. The density of Li{sub 3}PO{sub 4} prepared by wet chemical reaction is 2.238 gr/cm{sup 3}, little bit lower than the sample prepared by solid state reaction which density is 2.3560 gr/cm{sup 3}. The EIS measurement result shows that the conductivity of Li{sub 3}PO{sub 4} is 1.7 x 10{sup −9} S.cm{sup −1} for wet chemical reaction and 1.8 x 10{sup −10} S.cm{sup −1} for solid state reaction. The conductivity of Li{sub 3}PO{sub 4} is not quite different between those two samples even though they were prepared by different method of synthesize.

  13. Solid-state electric double layer capacitors fabricated with plastic crystal based flexible gel polymer electrolytes: Effective role of electrolyte anions

    Suleman, Mohd; Kumar, Yogesh; Hashmi, S.A.

    2015-01-01

    Flexible gel polymer electrolyte (GPE) thick films incorporated with solutions of lithium trifluoromethanesulfonate (Li-triflate or LiTf) and lithium bis trifluoromethane-sulfonimide (LiTFSI) in a plastic crystal succinonitrile (SN), entrapped in poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) have been prepared and characterized. The films have been used as electrolytes in the electrical double layer capacitors (EDLCs). Coconut-shell derived activated carbon with high specific surface area (∼2100 m 2 g −1 ) and mixed (micro- and meso-) porosity has been used as EDLC electrodes. The structural, thermal, and electrochemical characterization of the GPEs have been performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impedance measurements and cyclic voltammetry. The high ionic conductivity (∼10 −3 S cm −1 at 25 °C), good electrochemical stability window (>4.0 V) and flexible nature of the free-standing films of GPEs show their competence in the fabrication of EDLCs. The EDLCs have been tested using electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge studies. The EDLCs using LiTf based electrolyte have been found to give higher values of specific capacitance, specific energy, power density (240–280 F g −1 , ∼39 Wh kg −1 and ∼19 kW kg −1 , respectively) than the EDLC cell with LiTFSI based gel electrolyte. EDLCs have been found to show stable performance for ∼10 4 charge–discharge cycles. The comparative studies indicate the effective role of electrolyte anions on the capacitive performance of the solid-state EDLCs. - Graphical abstract: Display Omitted - Highlights: • Flexible EDLCs with succinonitrile based gel electrolyte membranes are reported. • Anionic size of salts in gel electrolytes plays important role on capacitive performance. • Li-triflate incorporated gel electrolyte shows better performance over LiTFSI-based gel.

  14. Solid-state electric double layer capacitors fabricated with plastic crystal based flexible gel polymer electrolytes: Effective role of electrolyte anions

    Suleman, Mohd; Kumar, Yogesh; Hashmi, S.A., E-mail: sahashmi@physics.du.ac.in

    2015-08-01

    Flexible gel polymer electrolyte (GPE) thick films incorporated with solutions of lithium trifluoromethanesulfonate (Li-triflate or LiTf) and lithium bis trifluoromethane-sulfonimide (LiTFSI) in a plastic crystal succinonitrile (SN), entrapped in poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) have been prepared and characterized. The films have been used as electrolytes in the electrical double layer capacitors (EDLCs). Coconut-shell derived activated carbon with high specific surface area (∼2100 m{sup 2} g{sup −1}) and mixed (micro- and meso-) porosity has been used as EDLC electrodes. The structural, thermal, and electrochemical characterization of the GPEs have been performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impedance measurements and cyclic voltammetry. The high ionic conductivity (∼10{sup −3} S cm{sup −1} at 25 °C), good electrochemical stability window (>4.0 V) and flexible nature of the free-standing films of GPEs show their competence in the fabrication of EDLCs. The EDLCs have been tested using electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge studies. The EDLCs using LiTf based electrolyte have been found to give higher values of specific capacitance, specific energy, power density (240–280 F g{sup −1}, ∼39 Wh kg{sup −1} and ∼19 kW kg{sup −1}, respectively) than the EDLC cell with LiTFSI based gel electrolyte. EDLCs have been found to show stable performance for ∼10{sup 4} charge–discharge cycles. The comparative studies indicate the effective role of electrolyte anions on the capacitive performance of the solid-state EDLCs. - Graphical abstract: Display Omitted - Highlights: • Flexible EDLCs with succinonitrile based gel electrolyte membranes are reported. • Anionic size of salts in gel electrolytes plays important role on capacitive performance. • Li-triflate incorporated gel electrolyte shows better

  15. Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-01-01

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

  16. Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-07-30

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.

  17. Solid polymer electrolyte water electrolysis system development. [to generate oxygen for manned space station applications

    1975-01-01

    Solid polymer electrolyte technology used in a water electrolysis system (WES) to generate oxygen and hydrogen for manned space station applications was investigated. A four-man rated, low pressure breadboard water electrolysis system with the necessary instrumentation and controls was fabricated and tested. A six man rated, high pressure, high temperature, advanced preprototype WES was developed. This configuration included the design and development of an advanced water electrolysis module, capable of operation at 400 psig and 200 F, and a dynamic phase separator/pump in place of a passive phase separator design. Evaluation of this system demonstrated the goal of safe, unattended automated operation at high pressure and high temperature with an accumulated gas generation time of over 1000 hours.

  18. Development status of solid polymer electrolyte water electrolysis for manned spacecraft life support systems

    Nuttall, L. J.; Titterington, W. A.

    1974-01-01

    Details of the design and system verification test results are presented for a six-man-rated oxygen generation system. The system configuration incorporates components and instrumentation for computer-controlled operation with automatic start-up/shutdown sequencing, fault detection and isolation, and with self-contained sensors and controls for automatic safe emergency shutdown. All fluid and electrical components, sensors, and electronic controls are designed to be easily maintainable under zero-gravity conditions. On-board component spares are utilized in the system concept to sustain long-term operation (six months minimum) in a manned spacecraft application. The system is centered on a 27-cell solid polymer electrolyte water electrolysis module which, combined with the associated system components and controls, forms a total system envelope 40 in. high, 40 in. wide, and 30 in. deep.

  19. Investigations of a zirconia solid electrolyte oxygen sensor in liquid lead

    Rivai, Abu Khalid, E-mail: rivai.abukhalid@jaea.go.j [Department of Nuclear Engineering, Graduate School of Science and Engineering, Tokyo Institute of Technology, N1-18, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8550 (Japan); Takahashi, Minoru, E-mail: mtakahas@nr.titech.ac.j [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, N1-18, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8550 (Japan)

    2010-03-15

    Investigations of a magnesia-stabilized zirconia solid electrolyte oxygen sensor for oxygen control measurement in liquid lead were carried out. The fluid of Bi/Bi{sub 2}O{sub 3} as a reference electrode and a molybdenum wire as a working electrode to detect the output signal of the sensor were used. The Nernst equation was used to estimate the electromotive force (EMF) values theoretically. The temperatures of liquid lead were 500, 550 and 600 deg. C. The results showed that the injection gas temperatures did not affect the detected EMF, the sensor responded well to quick changes of oxygen activity in liquid lead, and the discrepancy between the measured and theoretical EMF of the oxygen sensor output signal was higher at 500 deg. C than at 550 and 600 deg. C.

  20. Optimization of spin-coated electrodes for electrolyte-supported solid oxide fuel cells

    Nobrega, Shayenne Diniz da; Monteiro, Natalia Kondo; Tabuti, Francisco; Fonseca, Fabio Coral; Florio, Daniel Zanetti de

    2017-01-01

    Electrodes for electrolyte-supported solid oxide fuel cells (SOFC’s) were fabricated by spin coating. Strontium-doped lanthanum manganite (LSM) cathode and nickel yttria-stabilized zirconia cermet anodes were synthesized and processed for enhanced deposition conditions. The influence of electrode microstructural parameters was investigated by a systematic experimental procedure aiming at optimized electrochemical performance of single cells. Polarization curves showed a strong dependence on both electrode thickness and sintering temperature. By a systematic control of such parameters, the performance of single cells was significantly enhanced due to decreasing of polarization resistance from 26 Ω cm² to 0.6 Ω cm² at 800°C. The results showed that spin-coated electrodes can be optimized for fast and cost effective fabrication of SOFCs. (author)

  1. Toward fast and cost-effective ink-jet printing of solid electrolyte for lithium microbatteries

    Delannoy, P.-E.; Riou, B.; Lestriez, B.; Guyomard, D.; Brousse, T.; Le Bideau, J.

    2015-01-01

    Ink-jet printing of ionogel for low-cost microbattery is presented. Such an approach allows to provide liquid-like electrolyte performances for all-solid microdevices. Ink-jet printing process is possible thanks to sol precursor of the ionogel. This full silica based ionogels confining ionic liquid are known to be thermal resistant, serving safety and technologies requiring solder reflow. High ionic conductivity and compatibility with porous composite electrodes allow reaching good electrochemical cycling performance: full Li-ion cell with LiFePO4 and Li4Ti5O12 porous composite electrodes shows a surface capacity of 300 μAh cm-2 for more than 100 cycles. Such surface capacities are very competitive as compared to those obtained for microdevices based on expensive PVD processes.

  2. An electroactive conducting polymer actuator based on NBR/RTIL solid polymer electrolyte

    Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

    2007-04-01

    This paper reports the fabrication of a dry-type conducting polymer actuator using nitrile rubber (NBR) as the base material in a solid polymer electrolyte. The conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique. Room-temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X (where X = BF4-, PF6-, (CF3SO2)2N-), were absorbed into the composite film. The compatibility between the ionic liquids and the NBR polymer was confirmed by DMA. The effect of the anion size of the ionic liquids on the displacement of the actuator was examined. The displacement increased with increasing anion size of the ionic liquids. The cyclic voltammetry responses and the redox switching dynamics of the actuators were examined in different ionic liquids.

  3. Development of solid electrolytes for water electrolysis at intermediate temperatures. Task 3 report; Annual report

    Linkous, C.A.; Anderson, R.; Kopitzke, R.W.

    1995-12-01

    This project is an attempt to synthesize and fabricate proton exchange membranes for hydrogen production via water electrolysis that can take advantage of the better kinetic and thermodynamic conditions that exist at higher temperatures. Current PEM technology is limited to the 125--150 C range. Based on previous work evaluating thermohydrolytic stability, some 5 families of polymers were chosen as viable candidates: polyether ketones, polyether sulfones, fluorinated polyimides, polybenzimidazoles, and polyphenyl quinoxalines. Several of these have been converted into ionomers via sulfonation and fashioned into membranes for evaluation. In particular, the sulfonated polyetheretherketone, or SPEEK, was tested for water uptake, thermo-conductimetric analysis, and performance as the solid electrolyte material in an electrolysis cell. Results comparable to commercial perfluorocarbon sulfonates were obtained.

  4. Slip casting of thoria-10 mole per cent yttria solid electrolyte

    Ramanathan, S.; Rao, S.V.K.

    1990-01-01

    One end closed thoria-yttria solid electrolyte have been fabricated by the slip casting technique. A systematic study of the influence of the process parameters on the characteristics of the final bodies has been carried out. Slips of ThO 2 -10 mole % Y 2 O 3 were prepared; their fluidity and castability were studied as a function of concentration, pH and particle size. The bodies were sintered at 2000degC and the physical properties like density and microstructure were evaluated. Slip cast bodies of bulk densities around 95% T.D. with relatively inhomogenous but predominantly fine grained structure could be obtained by optimizing the process variables. (author). 5 figs., 10 refs

  5. A new percolation model for composite solid electrolytes and dispersed ionic conductors

    Risyad Hasyim, Muhammad; Lanagan, Michael T.

    2018-02-01

    Composite solid electrolytes (CSEs) including conductor/insulator composites known as dispersed ionic conductors (DICs) have motivated the development of novel percolation models that describe their conductivity. Despite the long history, existing models lack in one or more key areas: (1) rigorous foundation for their physical theory, (2) explanation for non-universal conductor-insulator transition, (3) classification of DICs, and (4) extension to frequency-domain. This work describes a frequency-domain effective medium approximation (EMA) of a bond percolation model for CSEs. The EMA is derived entirely from Maxwell’s equations and contains basic microstructure parameters. The model was applied successfully to several composite systems from literature. Simulations and fitting of literature data address these key areas and illustrate the interplay between space charge layer properties and bulk microstructure.

  6. Nanostructured Gd-CeO2 electrolyte for solid oxide fuel cell by aqueous tape casting

    Akbari-Fakhrabadi, A.; Mangalaraja, R. V.; Sanhueza, Felipe A.; Avila, Ricardo E.; Ananthakumar, S.; Chan, S. H.

    2012-11-01

    Gadolinia-doped ceria (Ce0.9Gd0.1O1.95, GDC) electrolyte was fabricated by aqueous-based tape casting method for solid oxide fuel cells (SOFCs). The ceramic powder prepared by combustion synthesis was used with poly acrylic acid (PAA), poly vinyl alcohol (PVA), poly ethylene glycol (PEG), Octanol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate and double distilled water as dispersant, binder, plasticizer, defoamer, surfactant and solvent respectively, to prepare stable GDC slurry. The conditions for preparing stable GDC slurries were studied and optimized by sedimentation, zeta potential and viscosity measurements. Green tapes with smooth surface, flexibility, thickness in the range of 0.35-0.4 mm and 45% relative green density were prepared. Conventional and flash sintering techniques were used and compared for densification which demonstrated the possibility of surpassing sintering at high temperatures and retarding related grain growth.

  7. Optimization of spin-coated electrodes for electrolyte-supported solid oxide fuel cells

    Nobrega, Shayenne Diniz da; Monteiro, Natalia Kondo; Tabuti, Francisco; Fonseca, Fabio Coral, E-mail: shaynnedn@hotmail.com, E-mail: nataliakm@usp.br, E-mail: fntabuti@ipen.br, E-mail: fabiocf@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN-CNEN/SP), Sao Paulo, SP (Brazil); Florio, Daniel Zanetti de, E-mail: daniel.florio@ufabc.edu.br [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil)

    2017-01-15

    Electrodes for electrolyte-supported solid oxide fuel cells (SOFC’s) were fabricated by spin coating. Strontium-doped lanthanum manganite (LSM) cathode and nickel yttria-stabilized zirconia cermet anodes were synthesized and processed for enhanced deposition conditions. The influence of electrode microstructural parameters was investigated by a systematic experimental procedure aiming at optimized electrochemical performance of single cells. Polarization curves showed a strong dependence on both electrode thickness and sintering temperature. By a systematic control of such parameters, the performance of single cells was significantly enhanced due to decreasing of polarization resistance from 26 Ω cm² to 0.6 Ω cm² at 800°C. The results showed that spin-coated electrodes can be optimized for fast and cost effective fabrication of SOFCs. (author)

  8. Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

    Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

    2017-11-27

    Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Study of the distribution of magnesium in zirconia-magnesia ceramic solid electrolytes

    Muccillo, R.; Nogueira, R.A.

    1988-01-01

    ZrO 2 : 3%MgO ceramic samples have been prepared according to three different experimental procedures in order to find out the best method for processing powders for the conformation of solid electrolytes for disposable oxygen sensors. These procedures were I) simple mechanical mixing, II) homogeneization in liquid medium, and III) homogeneization of the ceramic pellet by grinding, pressing and sintering. All samples have been analysed by electron microprobe and electrical resistivity measurements. The main results show the same degree of homogeneity and electrical resistivity are obtained for the specimens of the 2nd and 3rd group, whereas the specimens of the 1st group have non-homogeneous distribution of magnesium and scattered values of electrical resistivity. (author) [pt

  10. Magnetorheological technology for fabricating tunable solid electrolyte with enhanced conductivity and mechanical property

    Peng, Gangrou; Ge, Yu; Ding, Jie; Wang, Caiyun; Wallace, Gordon G.; Li, Weihua

    2018-03-01

    Ionogels are a new class of hybrid materials where ionic liquids are immobilized by macromolecular support. The excessive amount of crosslinking polymer enhances the mechanical strength but compromises the conductivity. Here, we report an elastomeric magnetorheological (MR) ionogel with an enhanced conductivity and mechanical strength as well. Following the application of magnetic nanoparticles into an ionic liquid containing minimum cross-linking agent, the formation, thus physical properties, of MR ionogels are co-controlled by simultaneously applied UV light and external magnetic field. The application of MR ionogels as solid electrolytes in supercapacitors is also demonstrated to study electrochemical performance. This work opens a new avenue to synthesize robust ionogels with the desired conductivity and controllable mechanical properties for soft flexible electronic devices. Besides, as a new class of conductive MR elastomers, the proposed MR ionogel also possesses the potential for engineering applications, such as sensors and actuators.

  11. Alkali Influence on Synthesis of Solid Electrolyte Based on Alkali Nitrate-Alumina

    Yustinus Purwamargapratala; Purnama, S.; Purwanto, P.

    2008-01-01

    Research of solid electrolyte based on alumina with addition of alkali materials of barium nitrate, calcium nitrate, sodium nitrate and lithium nitrate has been done. Aluminium hydroxide and alkali nitrate were mixed in mole ratio of 1 : 1 in water media and pyrolyzed at 300 o C for 1 hour Pyrolysis result were then mixed with alumina in mole ratio of 1 : 1, compacted and heated at 600 o C for 3 hours. To characterize the sample, XRD (X-Ray Diffractometers) and LCR meter (impedance, capacitance, and resistance) were used for analysis the phase and conductivity properties. The result showed formation of alkali-aluminate in which Li-base have the highest room temperature conductivity of 3.1290 x 10 -5 S.cm -1 , while Ba-base have the lowest conductivity of 5.7266 x 10 -8 S.cm -1 . (author)

  12. The thermal stability of sodium beta'-Alumina solid electrolyte ceramic in AMTEC cells

    Williams, Roger M.; Ryan, Margaret A.; Homer, Margie L.; Lara, Liana; Manatt, Ken; Shields, Virgil; Cortez, Roger H.; Kulleck, James

    1999-01-01

    A critical component of alkali metal thermal-to electric converter (AMTEC) devices for long duration space missions is the beta'-alumina solid electrolyte ceramic (BASE), for which there exists no substitute. The temperature and environmental conditions under which BASE remains stable control operational parameters of AMTEC devices. We have used mass loss experiments in vacuum to 1573K to characterize the kinetics of BASE decomposition, and conductivity and exchange current measurements in sodium vapor filled exposure cells to 1223K to investigate changes in the BASE which affect its ionic conductivity. There is no clear evidence of direct thermal decomposition of BASE below 1273K, although limited soda loss may occur. Reactive metals such as Mn or Cr can react with BASE at temperatures at least as low as 1223K

  13. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina

    2016-01-01

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical bar...

  14. Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries.

    Liu, Boyang; Fu, Kun; Gong, Yunhui; Yang, Chunpeng; Yao, Yonggang; Wang, Yanbin; Wang, Chengwei; Kuang, Yudi; Pastel, Glenn; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

    2017-08-09

    High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V 2 O 5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V 2 O 5 cathode was significantly decreased from 2.5 × 10 4 to 71 Ω·cm 2 at room temperature and from 170 to 31 Ω·cm 2 at 100 °C. Additionally, the diffusion resistance in the V 2 O 5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm 2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V 2 O 5 cathode and garnet solid electrolyte without compromising battery safety or performance.

  15. A Li-Garnet composite ceramic electrolyte and its solid-state Li-S battery

    Huang, Xiao; Liu, Cai; Lu, Yang; Xiu, Tongping; Jin, Jun; Badding, Michael E.; Wen, Zhaoyin

    2018-04-01

    A high strength Li-Garnet solid electrolyte composite ceramic is successfully prepared via conventional solid state method with Li6.4La3Zr1.4Ta0.6O12 and nano MgO powders. Well sintered ceramic pellets and bars are obtained with 0-9 wt.% MgO. Fracture strength is approximately 135 MPa for composite ceramics with 5-9 wt.% MgO, which is ∼50% higher than that of pure Li6.4La3Zr1.4Ta0.6O12 (90 MPa). Lithium-ion conductivity of the composite is above 5 × 10-4 S cm-1 at room temperature; comparable to the pure Li6.4La3Zr1.4Ta0.6O12 material. SEM cross-sections of the composite ceramic shows a much more uniform microstructure comparing with pure ones, owing to the grain growth inhibition effect of the MgO second phase. A battery cell consisting of Li/composite ceramics/Sulfur-Carbon at 25 °C exhibits a capacity of 685 mAh g-1 at 0.2 C at the 200th cycle, while maintaining a coulombic efficiency of 100%. These results indicate that the composite ceramic Li6.4La3Zr1.4Ta0.6O12-MgO is promising for the production of electrolyte membrane and fabrication of Li-Sulfur batteries.

  16. Resolving amorphous solid-liquid interfaces by atomic force microscopy

    Burson, Kristen M.; Gura, Leonard; Kell, Burkhard; Büchner, Christin; Lewandowski, Adrian L.; Heyde, Markus; Freund, Hans-Joachim

    2016-01-01

    Recent advancements in liquid atomic force microscopy make it an ideal technique for probing the structure of solid-liquid interfaces. Here, we present a structural study of a two-dimensional amorphous silica bilayer immersed in an aqueous solution utilizing liquid atomic force microscopy with sub-nanometer resolution. Structures show good agreement with atomically resolved ultra-high vacuum scanning tunneling microscopy images obtained on the same sample system, owing to the structural stability of the silica bilayer and the imaging clarity from the two-dimensional sample system. Pair distance histograms of ring center positions are utilized to develop quantitative metrics for structural comparison, and the physical origin of pair distance histogram peaks is addressed by direct assessment of real space structures.

  17. A planar, solid-state amperometric sensor for nitrogen dioxide, employing an ionic liquid electrolyte contained in a polymeric matrix

    Nádherná, M.; Opekar, F.; Reiter, Jakub; Stulík, K.

    2012-01-01

    Roč. 161, č. 1 (2012), s. 811-817 ISSN 0925-4005 R&D Projects: GA MŠk LC523; GA AV ČR KJB200320901 Institutional research plan: CEZ:AV0Z40320502 Keywords : Amperometry * Gas sensor * Solid-state sensor * Planar sensor * Ionic liquid * Solid polymer electrolyte * Gold minigrid electrode * Nitrogen dioxide Subject RIV: CG - Electrochemistry Impact factor: 3.535, year: 2012

  18. Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

    Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

    2013-07-16

    Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

  19. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

    2016-01-12

    Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  20. Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

    Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

    2018-04-07

    A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

  1. Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

    Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

    2018-01-01

    A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

  2. Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

    Po-Hsin Wang

    2018-04-01

    Full Text Available A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL and ionic liquid (IL. This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br and TFSI− in PIL-M-(TFSI, respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br and (PIL-M-(TFSI solid electrolytes, respectively.

  3. Using Dark Field X-Ray Microscopy To Study In-Operando Yttria Stabilized Zirconia Electrolyte Supported Solid Oxide Cell

    Sierra, J. X.; Poulsen, H. F.; Jørgensen, P. S.

    Dark Field X-Ray Microscopy is a promising technique to study the structure of materials in nanometer length scale. In combination with x-ray diffraction technique, the microstructure evolution of Yttria Stabilized Zirconia electrolyte based solid oxide cell was studied running at extreme operating...

  4. Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

    Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

    2016-10-01

    A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

  5. Nanoarchitectonics for Controlling the Number of Dopant Atoms in Solid Electrolyte Nanodots.

    Nayak, Alpana; Unayama, Satomi; Tai, Seishiro; Tsuruoka, Tohru; Waser, Rainer; Aono, Masakazu; Valov, Ilia; Hasegawa, Tsuyoshi

    2018-02-01

    Controlling movements of electrons and holes is the key task in developing today's highly sophisticated information society. As transistors reach their physical limits, the semiconductor industry is seeking the next alternative to sustain its economy and to unfold a new era of human civilization. In this context, a completely new information token, i.e., ions instead of electrons, is promising. The current trend in solid-state nanoionics for applications in energy storage, sensing, and brain-type information processing, requires the ability to control the properties of matter at the ultimate atomic scale. Here, a conceptually novel nanoarchitectonic strategy is proposed for controlling the number of dopant atoms in a solid electrolyte to obtain discrete electrical properties. Using α-Ag 2+ δ S nanodots with a finite number of nonstoichiometry excess dopants as a model system, a theory matched with experiments is presented that reveals the role of physical parameters, namely, the separation between electrochemical energy levels and the cohesive energy, underlying atomic-scale manipulation of dopants in nanodots. This strategy can be applied to different nanoscale materials as their properties strongly depend on the number of doping atoms/ions, and has the potential to create a new paradigm based on controlled single atom/ion transfer. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Subcontract Report: Diffusion Mechanisms and Bond Dynamics in Solid Electrolyte Ion-Conductors

    Zevgolis, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Hall, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Alvez, T. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehmedovic, Z. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Shea, P. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Varley, J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Wood, B. C. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Adelstein, N. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-10-03

    We employ first-principles molecular dynamics simulations and Maximally Localized Wannier Function (MLWF) analysis to explore how halide substitution and nano-phase microstructures affect diffusivity, through the activation energy barrier - Ea and D0, in the solid electrolyte Li3InBr6-xClx. We find that nano-phase microstructures with x=3 (50-50 Br-Cl) mixed composition have a higher diffusivity compared to x=2 and x=3 solid solutions. There is a positive linear relationship between ln(D0.) and Ea, which suggests that for superionic conductivity optimizing both the activation energy and the D0 is important. Bond frustration due to mismatch in crystal geometry and ideal coordination number leads to especially high diffusivity through a high D0 in the x=3 composition.

  7. Quasi-solid-state dye-sensitized solar cells from hydrophobic poly(hydroxyethyl methacrylate/glycerin)/polyaniline gel electrolyte

    Li, Qinghua [National Defence Key Discipline Laboratory of Light Alloy Processing Science and Technology, Nanchang Hangkong University, Nanchang 330063 (China); Tang, Qunwei, E-mail: tangqunwei@hotmail.com [Institute of Materials Science and Engineering, Ocean University of China, Shandong Province, Qingdao 266100 (China); Chen, Haiyan [Institute of Materials Science and Engineering, Ocean University of China, Shandong Province, Qingdao 266100 (China); Xu, Haitao; Qin, Yuancheng [National Defence Key Discipline Laboratory of Light Alloy Processing Science and Technology, Nanchang Hangkong University, Nanchang 330063 (China); He, Benlin, E-mail: blhe@ouc.edu.cn [Institute of Materials Science and Engineering, Ocean University of China, Shandong Province, Qingdao 266100 (China); Liu, Zhichao; Jin, Suyue; Chu, Lei [Institute of Materials Science and Engineering, Ocean University of China, Shandong Province, Qingdao 266100 (China)

    2014-04-01

    Hydrophobic poly(hydroxyethyl methacrylate/glycerin) [poly(HEMA/GR)] gel with a three-dimensional (3D) framework was successfully fabricated and employed to integrate with polyaniline (PANi). The resultant poly(HEMA/GR)/PANi gel electrolyte exhibited interconnective porous structure for holding I{sup −}/I{sub 3}{sup −}, giving a similar conduction mechanism and ionic conductivity to that of liquid system but a much enhanced retention of I{sup −}/I{sub 3}{sup −} redox couple. Fourier transform infrared spectroscopy, X-ray diffraction patterns, cyclic voltammograms as well as electrochemical impedance spectroscopy were employed to evaluate the molecular structure, crystallinity, and the electrochemical behaviors, showing that the combination of PANi with poly(HEMA/GR) caused a lower charge-transfer resistance and higher electrocatalytic activity for the I{sub 3}{sup −}/I{sup −} redox reaction in the gel electrolyte. An efficiency of 6.63% was recorded from the quasi-solid-state DSSC assembled with the poly(HEMA/GR)/PANi gel electrolyte at 100 mW cm{sup −2}. - Graphical abstract: A poly(HEMA/GR)/PANi gel electrolyte is synthesized through in situ polymerization of PANi in 3D framework of poly(HEMA/GR) hydrophobic hydrogel. The recorded ionic conductivity and electrochemical performances are significantly enhanced by integrating with PANi The resultant overall photo-to-electric conversion efficiency is 6.63%. The high ionic conductivity, along with good electrolyte retention ability, reasonable DSSC performance, low cost, simple and scalable synthesis procedure, and competitive cost, promises the electrolyte to find applications in quasi-solid-state DSSCs. - Highlights: • Poly(HEMA/GR) was employed to combine with PANi in the 3D framework. • The conductivity and electrochemical performances were enhanced. • The conversion efficiency of the quasi-solid-state DSSC was 6.63%.

  8. All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

    Kang, Yu Jin; Kim, Woong; Chung, Haegeun; Han, Chi-Hwan

    2012-01-01

    All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf 2 ]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g −1 at a current density of 2 A g −1 , when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg −1 and 41 Wh kg −1 , respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications. (paper)

  9. Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

    Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2016-09-01

    Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

  10. Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

    Inagaki, Toru; Nishiwaki, Futoshi; Yamasaki, Satoru; Akbay, Taner; Hosoi, Kei

    The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 °C. There are some significant features in IT-SOFC of KEPCO-MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 °C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system.

  11. Synthesis, characterization and electrical properties of solid electrolyte for solid oxide fuel cell; Preparacao, caracterizacao e propriedades eletricas de eletrolito solido para celula a combustivel de oxido solido

    Berton, Marco Antonio Coelho; Garcia, Carlos Mario; Matos, Jeferson Hrenechen [Instituto de Tecnologia para o Desenvolvimento (LACTEC), Curitiba, PR (Brazil)], Emails: felsky@latec.org.br, garcia@latec.org.br, jeferson.h@latec.org.br

    2010-04-15

    Solid electrolytes of BaCe{sub 08}Gd{sub O29} were prepared by the polymeric precursor method. X-ray diffraction data shows a single phase with orthorhombic crystalline structure. The densification process was followed by scanning electronic microscopy and apparent density measurements. The apparent density was developed for different temperatures of sintering, reaching > 96% for sintered temperature of 1550 {sup 0}C deg . The electrochemical impedance analysis was development in the temperature of 400-700 deg C, in air atmosphere at 700 deg C a value of 30,6 mS.cm{sup -1} was obtained. The results of conductivity have confirmed the gadolinium doped barium cerate has a great potential for use as solid electrolyte for intermediate temperature solid oxide fuel cell, at experimental controlled conditions. (author)

  12. Synthesis and ceramic processing of zirconia alumina composites for application as solid oxide fuel cell electrolytes

    Garcia, Rafael Henrique Lazzari

    2007-01-01

    The global warmness and the necessity to obtain clean energy from alternative methods than petroleum raises the importance of developing cleaner and more efficient systems of energy generation, among then, the solid oxide fuel cell (SOFC). Cubic stabilized zirconia (CSZ) has been the most studied material as electrolyte in SOFC, due to its ionic conductivity and great stability at operation conditions. However, its low fracture toughness difficulties its application as a thin layer, what could lead to an improvement of cell efficiency. In this sense, the alumina addition in CSZ forms a composite, which can shift its mechanical properties, without compromising its electrical properties. In this work, coprecipitation synthesis route and ceramic processing of zirconia-alumina composites were studied, in order to establish optimum conditions to attain high density, homogeneous microstructure, and better mechanical properties than CSZ, without compromising ionic conductivity. For this purpose, composites containing up to 40 wt % of alumina, in a 9 mol % yttria-stabilized zirconia (9Y-CSZ) matrix were evaluated. In order to optimize the synthesis of the composites, a preliminary study of powder obtaining and processing were carried out, at compositions containing 20 wt % of alumina, in 9Y-CSZ. The ceramic powders were characterized by helium picnometry, X-ray diffraction, scanning electronic microscopy, transmission electronic microscopy, thermogravimetry, differential scanning calorimetry, granulometry by laser diffraction and gas adsorption (BET). The characterization of sinterized compacts were performed by X-ray diffraction, scanning electron microscopy, optical microscopy, density measurements, Vickers indentation and impedance spectroscopy. The obtained results show that the alumina addition, in the 9Y-CSZ matrix powders, raises the specific surface area, promotes deagglomeration of powders and elevates the oxides crystallization temperature, requiring higher

  13. The use of poly(vinylpyridine-co-acrylonitrile) in polymer electrolytes for quasi-solid dye-sensitized solar cells

    Li, Minyu; Feng, Shujing; Fang, Shibi; Xiao, Xurui; Li, Xueping; Zhou, Xiaowen; Lin, Yuan

    2007-01-01

    Poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) was used to form polymer electrolytes for dye-sensitized solar cells (DSSCs). The effects of P(VP-co-AN) on the photovoltaic performances of DSSCs have been investigated with nonaqueous electrolytes containing alkali-iodide and iodine. It was found that the effect of P(VP-co-AN) on V oc closely related to its amount in the electrolyte. Lower amount of P(VP-co-AN) was benefit for the construction of a solar cell containing P(VP-co-AN) with higher energy conversion efficiency. Chemically crosslinking solidification with backbone polymer P(VP-co-AN) amount of 3% fabricated quasi-solid DSSCs with 10% increased conversion efficiencies with relative to that of the initial liquid DSSCs

  14. Electrolyte bi-layering strategy to improve the performance of an intermediate temperature solid oxide fuel cell: A review

    Shri Prakash, B.; Pavitra, R.; Senthil Kumar, S.; Aruna, S. T.

    2018-03-01

    Lowering of operation temperature has become one of the primary goals of solid oxide fuel (SOFC) research as reduced temperature improves the prospects for widespread commercialization of this energy system. Reduced operational temperature also mitigates the issues associated with high temperature SOFCs and paves way not only for the large scale stationary power generation but also makes SOFCs viable for portable and transport applications. However, there are issues with electrolyte and cathode materials at low temperatures, individually as well as in association with other components, which makes the performance of the SOFCs less satisfactory than expected at lowered temperatures. Bi-layering of electrolytes and impregnation of cathodes have emerged as two important strategies to overcome these issues and achieve higher performance at low temperatures. This review article provides the perspective on the strategy of bi-layering of electrolyte to achieve the desired high performance from SOFC at low to intermediate temperatures.

  15. Theory of electroreduction of solid oxide electrolytes. Kinetics and mechanism of the galvanostatic process with blocking cathodes

    Chebotin, V.N.; Brainin, M.I.; Lukach, Yu. S.; Pakhnutov, I.A.; Solov'eva, L.M.

    1986-01-01

    This paper discusses dc flow through cells with MO 2 + MeOΓ solid electrolyte (M = Zr, Hf, Ce, or Th; Me = Ca, Sr, Sc, Y, or lanthanides), a blocking cathode, and a reversible anode which leads to departures of the electrolytes from stoichiometry in the direction of oxygen deficiency. A nonlinear differential equation of the diffusion type describes the degree of this departure and the n-type electronic conductivity which is proportional to it, as functions of the coordinate and time. The electrolyte's electronic conductivity increases with time near the cathode, and approaches a limiting value that is proportional to the current being passed. The electronic conductivity falls off exponentially with increasing distance from the cathode; this changes to a linear fall as a function of time

  16. Fabrication of hydrogenase-cationic electrolyte biohybrids at interfaces and their electrochemical properties in Langmuir-Blodgett films

    Liu An; Zorin, Nikolay A.; Nakamura, Chikashi; Miyake, Jun; Qian Dongjin

    2010-01-01

    Hydrogenase (H 2 ase)-cationic electrolyte biohybrids were assembled at the air-water interface via intermolecular electrostatic interaction. The H 2 ase used was purified from the phototropic bacterium of Thiocapsa roseopersicina. Two kinds of cationic electrolyte compounds (CECs) were used, the difference of which was whether they contained viologen substituent or not. Surface pressure-area isotherms indicated that these CECs were co-existed with the H 2 ase in the monolayers, which were then transferred to substrate surfaces to form H 2 ase-CECs hybrid films by the Langmuir-Blodgett (LB) method. Uniform film was formed when polyelectrolyte was used as the subphase. Cyclic voltammograms (CVs) of the LB films showed a couple of redox waves in the potential range of -0.4 to -0.65 V vs. Ag/AgCl, which was ascribed to one electron process of either [4Fe-4S] clusters of H 2 ase or viologens of the CECs. A direct electron transfer between the H 2 ase and electrode surface was achieved in the LB films. Stronger current intensity was recorded when the CV measurements were done in H 2 saturated electrolyte solution than that in Ar. It was confirmed that the H 2 ase biocatalytic activity remained in the LB films. Thus, we suggest that the present H 2 ase-CECs biohybrids could act as potential materials for the studies of interconversion reaction of H 2 and protons.

  17. Transport Properties Of PbI2 Doped Silver Oxysalt Based Amorphous Solid Electrolytes

    Shrisanjaykumar Jayswal, Manishkumar

    Solid electrolytes are a class of materials that conduct electricity by means of motion of ions like Ag+, Na+, Li +, Cu+, H+, F-, O -2 etc. in solid phase. The host materials include crystalline, polycrystalline, glasses, polymers and composites. Ion conducting glasses are one of the most sought after solid electrolytes that are useful in various electrochemical applications like solid state batteries, gas sensors, supercapacitors, electrochromic devices, to name a few. Since the discovery of fast silver ion transport in silver oxyhalide glasses at the end of the 1960s, many glasses showing large ionic conductivity up to 10-4 10-2 S/cm at room temperature have been developed, chiefly silver and copper ion conductors. The silver ion conducting glasses owe their high ionic conductivity mainly to stabilized alpha-AgI. AgI, as we know, undergoes a structural phase transition from wurtzite (beta phase) at room temperature to body centered cubic (alpha phase) structure at temperatures higher than 146 °C. The alpha-AgI possesses approximately six order of higher ionic conductivity than beta-AgI. The high ionic conductivity of alpha-AgI is attributed to its molten sublattice type of structure, which facilitates easy Ag+ ion migration, like a liquid. And hence, several attempts have been made to stabilize it at room temperature in crystalline as well as non-crystalline hosts like oxide and non-oxide glasses. Recently, in order to stabilize AgI in glasses, instead of directly doping it, indirect routes have also been explored. Where, a metal iodide salt along with silver oxide or silver phosphate is taken and an exchange reaction permitted by Hard and Soft, Acid and Base (HSAB) principle occurs between the two and AgI and metal oxide form in the glass forming melt. Work done in the present thesis has been organized in seven chapters as follows: Chapter 1: A review and background information of different solid electrolyte materials and their development is presented. Along

  18. Effect of substrate and cathode parameters on the properties of suspension plasma sprayed solid oxide fuel cell electrolytes

    Waldbillig, D.; Tang, Z.; Burgess, A. [British Columbia Univ., Vancouver, BC (Canada); Kesler, O. [Toronto Univ., ON (Canada)

    2008-07-01

    An axial injection suspension plasma spray system has been used to produce layers of fully stabilized yttriastabilized zirconia (YSZ) that could be used as solid oxide fuel cell (SOFC) electrolytes. Suspension plasma spraying is a promising technique for the rapid production of coatings with fine microstructures and controlled porosity without requiring a post-deposition heat treatment. This new manufacturing technique to produce SOFC active layers requires the build up of a number of different plasma sprayed SOFC functional layers (cathode, electrolyte and anode) sequentially on top of each other. To understand the influence of the substrate and previouslydeposited coating layers on subsequent coating layer properties, YSZ layers were deposited on top of plasma sprayed composite lanthanum strontium manganite (LSM)/YSZ cathode layers that were first deposited on porous ferritic stainless steel substrates. Three layer half cells consisting of the porous steel substrate, composite cathode, and suspension plasma sprayed electrolyte layer were then characterized. A systematic study was performed in order to investigate the effect of parameters such as substrate and cathode layer roughness, substrate surface pore size, and cathode microstructure and thickness on electrolyte deposition efficiency, cathode and electrolyte permeability, and layer microstructure. (orig.)

  19. In situ electrochemical-mass spectroscopic investigation of solid electrolyte interphase formation on the surface of a carbon electrode

    Gourdin, Gerald; Zheng, Dong; Smith, Patricia H.; Qu, Deyang

    2013-01-01

    The energy density of an electrochemical capacitor can be significantly improved by utilizing a lithiated negative electrode and a high surface area positive electrode. During lithiation of the negative carbon electrode, the electrolyte reacts with the electrode surface and undergoes decomposition to form a solid electrolyte interphase (SEI) layer that passivates the surface of the carbon electrode from further reactions between Li and the electrolyte. The reduction reactions that the solvent undergoes also form insoluble and gaseous by-products. In this work, those gaseous by-products generated by reductive decomposition of a carbonate-based electrolyte, 1.2 M LiPF 6 in EC/PC/DEC (3:1:4), were analyzed at different stages during the lithiation process of an amorphous carbon electrode. The stages in the generation of gaseous by-products were determined to come as a result of two, 1-electron reduction steps of the cyclic carbonate components of the electrolyte. Electrochemical impedance spectroscopy was also used to investigate the two distinct electrochemical processes and the development of the two phases of the SEI structure. This is the first time that the state of an electrochemical cell during the formation of the SEI layer has been systematically correlated with theoretical reaction mechanisms through the use of in situ electrochemical-MS and impedance spectroscopy analyses

  20. Alkaline direct ethanol fuel cell performance using alkali-impregnated polyvinyl alcohol/functionalized carbon nano-tube solid electrolytes

    Huang, Chien-Yi; Lin, Jia-Shiun; Pan, Wen-Han; Shih, Chao-Ming; Liu, Ying-Ling; Lue, Shingjiang Jessie

    2016-01-01

    This study investigates the application of a polyvinyl alcohol (PVA)/functionalized carbon nano-tubes (m-CNTs) composite in alkaline direct ethanol fuel cells (ADEFC). The m-CNTs are functionalized with PVA using the ozone mediation method, and the PVA composite containing the modified CNTs is prepared. Adding m-CNT into the PVA matrix enhances the alkaline uptake and the ionic conductivity of the KOH-doped electrolyte. Meanwhile, the m-CNT-containing membrane exhibited a lower swelling ratio and suppressed ethanol permeability compared to the pristine PVA film. The optimal condition for the ADEFC is determined to be under operation at an anode feed of 3 M ethanol in a 5 M KOH solution (at a flow rate of 5 cm3 min-1) with a cathode feed of moisturized oxygen (with a flow rate of 100 cm3 min-1) and the KOH-doped PVA/m-CNT electrolyte. We achieved a peak power density value of 65 mW cm-2 at 60 °C, which is the highest among the ADEFC literature data and several times higher than the proton-exchange direct ethanol fuel cells using sulfonated membrane electrolytes. Therefore, the KOH-doped PVA/m-CNT electrolyte is a suitable solid electrolyte for ADEFCs and has potential for commercialization in alkaline fuel cell applications.

  1. Fast ion transport at solid-solid interfaces in hybrid battery anodes

    Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J.; Wei, Shuya; Zhang, Kaihang; Kourkoutis, Lena F.; Archer, Lynden A.

    2018-04-01

    Carefully designed solid-electrolyte interphases are required for stable, reversible and efficient electrochemical energy storage in batteries. We report that hybrid battery anodes created by depositing an electrochemically active metal (for example, Sn, In or Si) on a reactive alkali metal electrode by a facile ion-exchange chemistry lead to very high exchange currents and stable long-term performance of electrochemical cells based on Li and Na electrodes. By means of direct visualization and ex situ electrodeposition studies, Sn-Li anodes are shown to be stable at 3 mA cm-2 and 3 mAh cm-2. Prototype full cells in which the hybrid anodes are paired with high-loading LiNi0.8Co0.15Al0.05O2(NCA) cathodes are also reported. As a second demonstration, we create and study Sn-Na hybrid anodes and show that they can be cycled stably for more than 1,700 hours with minimal voltage divergence. Charge storage at the hybrid anodes is reported to involve a combination of alloying and electrodeposition reactions.

  2. Modification of a solid polymer electrolyte (SPE) electrolyser to ensure tritium compatibility

    Eichelhardt, F.; Cristescu, I.; Michling, R.; Welte, S.

    2010-01-01

    A Water Detritiation System (WDS) is required for the ITER Tritium Plant in order to process tritiated water which is accumulated in various subsystems (e.g. the hall ventilation systems). For the ITER-WDS, the Combined Electrolysis Catalytic Exchange (CECE) process with an electrolyser unit as one of the major components is envisaged. An experimental WDS was built and commissioned at the Tritium Laboratory Karlsruhe (TLK) for the investigation of various subsystems of the CECE process in tritium environment. The TLK-WDS consists of an 8 m Liquid Phase Catalytic Exchange column and two Solid Polymer Electrolyte electrolysers, each with a maximum hydrogen output of 1 m 3 /h. The commercially available Hogen40 electrolyser units from Proton Energy Systems are not tritium compatible concerning materials, joints and quality documentation (e.g. necessary certificates). In order to process tritiated water with tritium concentrations up to 370 GBq/kg, tritium compatibility had to be ensured by appropriate modifications. Up to now, the modified system has been operated with tritiated water for 3500 h, the maximum tritium concentration in the electrolysers being 190 GBq/kg. This contribution reports on the necessary modifications of the electrolyser units and the experiences gained thereby. The results are equally important for the ITER-WDS, where the maximum tritium concentration in the feed water of the electrolyser units will be even higher with 11 TBq/kg.

  3. Chemically durable polymer electrolytes for solid-state alkaline water electrolysis

    Park, Eun Joo; Capuano, Christopher B.; Ayers, Katherine E.; Bae, Chulsung

    2018-01-01

    Generation of high purity hydrogen using electrochemical splitting of water is one of the most promising methods for sustainable fuel production. The materials to be used as solid-state electrolytes for alkaline water electrolyzer require high thermochemical stability against hydroxide ion attack in alkaline environment during the operation of electrolysis. In this study, two quaternary ammonium-tethered aromatic polymers were synthesized and investigated for anion exchange membrane (AEM)-based alkaline water electrolyzer. The membranes properties including ion exchange capacity (IEC), water uptake, swelling degree, and anion conductivity were studied. The membranes composed of all C-C bond polymer backbones and flexible side chain terminated by cation head groups exhibited remarkably good chemical stability by maintaining structural integrity in 1 M NaOH solution at 95 °C for 60 days. Initial electrochemical performance and steady-state operation performance were evaluated, and both membranes showed a good stabilization of the cell voltage during the steady-state operation at the constant current density at 200 mA/cm2. Although both membranes in current form require improvement in mechanical stability to afford better durability in electrolysis operation, the next generation AEMs based on this report could lead to potentially viable AEM candidates which can provide high electrolysis performance under alkaline operating condition.

  4. Performance of solid electrolyte type oxygen sensor in flowing lead bismuth

    Kondo, Masatoshi; Takahashi, Minoru

    2005-01-01

    A solid electrolyte type oxygen sensor for liquid 45%lead-55%bismuth (Pb-Bi) was developed. The performance of the oxygen sensor in the flowing lead-bismuth (Pb-Bi) was investigated. The initial performance of the sensor was not reliable, since the reference fluid of the oxygen saturated bismuth in the sensor cell was not compact initially. The electromotive force (EMF) obtained from the yttria stabilized zirconia (YSZ) cell was the same as that from the magnesia stabilized zirconia (MSZ) cell in the flowing Pb-Bi. The EMF of the sensor in the flowing Pb-Bi was lower than that in the stagnant Pb-Bi. However, the difference was small. The sensor showed repeatability after the long term interruption and the Pb-Bi drain/charge operation. After the performance tests, the corrosion of the sensor cells were investigated metallurgically. The YSZ cell was eroded around the free surface of the flowing Pb-Bi after 3500 hour-exposure in the flowing Pb-Bi. The MSZ cell showed smooth surface without the erosion. Although the YSZ cell worked more stably than the MSZ cell, the mechanical strength of the YSZ cell is weaker than that of the MSZ cell. (author)

  5. Prediction of battery storage ageing and solid electrolyte interphase property estimation using an electrochemical model

    Ashwin, T. R.; Barai, A.; Uddin, K.; Somerville, L.; McGordon, A.; Marco, J.

    2018-05-01

    Ageing prediction is often complicated due to the interdependency of ageing mechanisms. Research has highlighted that storage ageing is not linear with time. Capacity loss due to storing the battery at constant temperature can shed more light on parametrising the properties of the Solid Electrolyte Interphase (SEI); the identification of which, using an electrochemical model, is systematically addressed in this work. A new methodology is proposed where any one of the available storage ageing datasets can be used to find the property of the SEI layer. A sensitivity study is performed with different molecular mass and densities which are key parameters in modelling the thickness of the SEI deposit. The conductivity is adjusted to fine tune the rate of capacity fade to match experimental results. A correlation is fitted for the side reaction variation to capture the storage ageing in the 0%-100% SoC range. The methodology presented in this paper can be used to predict the unknown properties of the SEI layer which is difficult to measure experimentally. The simulation and experimental results show that the storage ageing model shows good accuracy for the cases at 50% and 90% and an acceptable agreement at 20% SoC.

  6. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

    2013-01-01

    Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF 3 SO 3 ) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10 −6 S cm −1 when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm −1 , carbonyl (-C=O) at 1750–1650 cm −1 and ether (-C-O-C-) at 1150–1000 cm −1 of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF 3 SO 3 salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF 3 SO 3

  7. Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

    Praveen, D. [Department of Physics, Amrita Viswha Vidyapeetham, Bangalore, India, E-mail: d-praveen@blr.amrita.edu (India); Damle, Ramakrishna [Department of Physics, Bangalore University, Bangalore, India. E-mail: ramkrishnadamle@bub.ernet.in (India)

    2016-05-23

    Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO{sub 4}){sub 2}, NH{sub 4}I etc., have already been tried in the past with some success. Also various nanoparticles like Al{sub 2}O{sub 3}, TiO{sub 2} etc., have been tried in the past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.

  8. Electrolytic Production of Ti5Si3/TiC Composites by Solid Oxide Membrane Technology

    Zheng, Kai; Zou, Xingli; Xie, Xueliang; Lu, Changyuan; Chen, Chaoyi; Xu, Qian; Lu, Xionggang

    2018-02-01

    This paper investigated the electrolytic production of Ti5Si3/TiC composites from TiO2/SiO2/C in molten CaCl2. The solid-oxide oxygen-ion-conducting membrane tube filled with carbon-saturated liquid tin was served as the anode, and the pressed spherical TiO2/SiO2/C pellet was used as the cathode. The electrochemical reduction process was carried out at 1273 K and 3.8 V. The characteristics of the obtained cathode products and the reaction mechanism of the electroreduction process were studied by a series of time-dependent electroreduction experiments. It was found that the electroreduction process generally proceeds through the following steps: TiO2/SiO2/C → Ti2O3, CaTiO3, Ca2SiO4, SiC → Ti5Si3, TiC. The morphology observation and the elemental distribution analysis indicate that the reaction routes for Ti5Si3 and TiC products are independent during the electroreduction process.

  9. Neutron irradiation characteristic tests of oxygen sensors using zirconia solid electrolyte

    Hiura, Nobuo; Endou, Yasuichi; Yamaura, Takayuki; Niimi, Motoji; Hoshiya, Taiji; Saito, Junichi; Souzawa, Shizuo; Ooka, Norikazu; Kobiyama, Mamoru.

    1997-03-01

    In the Department of JMTR of Japan Atomic Energy Research Institute (JAERI), the in-situ measuring technique of oxygen potential has been being developed to study the chemical behavior of high burn-up fuel base-irradiated in the Light Water Reactor. In this test for development of the technique, oxygen sensors using zirconia solid electrolyte stabilized by MgO, CaO and Y 2 O 3 , named MSZ, CSZ and YSZ, respectively, were irradiated by neutrons in the Japan Materials Testing Reactor (JMTR) of JAERI and the characteristics of electromotive force of these sensors under and after irradiation were discussed. From the experimental results, the electromotive force of YSZ sample under irradiation decreased with an increase in irradiation fluence within a range of neutron fluence (E>1 MeV) up to 1 x 10 23 m -2 . The electromotive force of MSZ sensor irradiated with neutron fluences (E>1 MeV) up to 9 x 10 21 m -2 was almost equal to the theoretical value of the electromotive force. It was shown that after irradiation, a decrease in the electromotive force of CSZ sensor was smaller than those of MSZ and YSZ sensors, although the electromotive forces of MSZ, CSZ and YSZ sensors were smaller than the theoretical value. (author)

  10. Studies on the Properties of Plasticizer and Lithium Salt on PMMA-based Solid Polymer Electrolytes

    Chew, K. W.; Tan, C. G.; Osman, Z.

    2010-01-01

    The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF 3 SO 3 salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF 3 SO 3 ) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10 -10 Scm -1 is obtained. This may be due to the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF 3 SO 3 ) system is 1.36x10 -5 Scm -1 . Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.

  11. Conductivity and optical studies of plasticized solid polymer electrolytes doped with carbon nanotube

    Ibrahim, Suriani, E-mail: sue_83@um.edu.my [Advanced Materials Research Laboratory, Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur (Malaysia); Ahmad, Roslina; Johan, Mohd Rafie [Advanced Materials Research Laboratory, Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2012-01-15

    Solid polymer electrolyte films based on Poly(ethylene oxide) (PEO) complexed with lithium hexafluorophosphate (LiPF{sub 6}), ethylene carbonate (EC) and amorphous carbon nanotube ({alpha}CNTs) were prepared by the solution cast technique. The conductivity increases from 10{sup -10} to 10{sup -5} Scm{sup -1} upon the addition of salt. The incorporation of EC and {alpha}CNTs to the salted polymer enhances the conductivity significantly to 10{sup -4} and 10{sup -3} Scm{sup -1}. The complexation of doping materials with polymer were confirmed by X-ray diffraction and infrared studies. Optical properties like direct band gap and indirect band gap were investigated for pure and doped polymer films in the wavelength range 200-400 nm. It was found that the energy gaps and band edge values shifted to lower energies on doping. - Highlights: > Optical band gap values show the decreasing trend with an increasing dopant concentration. > It is also observed that the absorption edge shifted to longer wavelength on doping. > Results of the optical measurements indicate the presence of a well-defined {pi}{yields}{pi}* transition associated with the formation of a conjugated C=O and/or C=O electronic structure.

  12. Configuring PSx tetrahedral clusters in Li-excess Li7P3S11 solid electrolyte

    Wo Dum Jung

    2018-04-01

    Full Text Available We demonstrate that the Li-ion conductivity can be improved by adding a certain amount of Li (x = 0.25–0.5 as a charge carrier to the composition of glass-ceramic Li7+xP3S11. Structural analysis clarified that the structural changes caused by the ratio of ortho-thiophosphate tetrahedra PS43− and pyro-thiophosphate ditetrahedra P2S74− affect the Li-ion conductivity. The ratio of PS43− and P2S74− varies depending on x and the highest Li-ion conductivity (2.5 × 10−3 S cm−1 at x = 0.25. All-solid-state LiNi0.8Co0.15Al0.05O2/Li7.25P3S11/In-metal cell exhibits the discharge capacity of 106.2 mAh g−1. This ion conduction enhancement from excess Li is expected to contribute to the future design of sulfide-type electrolytes.

  13. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji [School of Chemical Science and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia)

    2013-11-27

    Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF{sub 3}SO{sub 3}) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10{sup −6} S cm{sup −1} when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm{sup −1}, carbonyl (-C=O) at 1750–1650 cm{sup −1} and ether (-C-O-C-) at 1150–1000 cm{sup −1} of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF{sub 3}SO{sub 3} salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF{sub 3}SO{sub 3}.

  14. Electrical, thermal and structural properties of plasticized waste cooking oil-based polyurethane solid polymer electrolyte

    Huzaizi, Rahmatina Mohd; Tahir, Syuhada Mohd; Mahbor, Kamisah Mohamad

    2017-12-01

    Waste cooking oil-based polyol was synthesized using epoxidation and hydroxylation methods. The polyol was combined with 4,4-diphenylmethane diisocyanate to produce polyurethane (PU) to be used as polymer host in solid polymer electrolyte. 30 wt% LiClO4 was added as doping salt and two types of plasticizers were used; ethylene carbonate (PU-EC) and polyethylene glycol (PU-PEG). The SPE films were characterized using Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The highest conductivity achieved was 8.4 x 10-8 S cm-1 upon addition of 10 wt% EC. The XRD results showed a decrease of crystalline peaks in PU-EC and the increase in PU-PEG. DSC results revealed that the films; PU, PU-EC and PU-PEG had glass transition temperatures of 159.7, 106.0 and 179.7 °C, respectively. The results showed that the addition of EC increased the amorphous region and the free volume in the SPE structure, thus resulted in higher ionic conductivity.

  15. Conductivity and optical studies of plasticized solid polymer electrolytes doped with carbon nanotube

    Ibrahim, Suriani; Ahmad, Roslina; Johan, Mohd Rafie

    2012-01-01

    Solid polymer electrolyte films based on Poly(ethylene oxide) (PEO) complexed with lithium hexafluorophosphate (LiPF 6 ), ethylene carbonate (EC) and amorphous carbon nanotube (αCNTs) were prepared by the solution cast technique. The conductivity increases from 10 -10 to 10 -5 Scm -1 upon the addition of salt. The incorporation of EC and αCNTs to the salted polymer enhances the conductivity significantly to 10 -4 and 10 -3 Scm -1 . The complexation of doping materials with polymer were confirmed by X-ray diffraction and infrared studies. Optical properties like direct band gap and indirect band gap were investigated for pure and doped polymer films in the wavelength range 200-400 nm. It was found that the energy gaps and band edge values shifted to lower energies on doping. - Highlights: → Optical band gap values show the decreasing trend with an increasing dopant concentration. → It is also observed that the absorption edge shifted to longer wavelength on doping. → Results of the optical measurements indicate the presence of a well-defined π→π* transition associated with the formation of a conjugated C=O and/or C=O electronic structure.

  16. Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

    Praveen, D.; Damle, Ramakrishna

    2016-01-01

    Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO_4)_2, NH_4I etc., have already been tried in the past with some success. Also various nanoparticles like Al_2O_3, TiO_2 etc., have been tried in the past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.

  17. Optical and Electrical Characteristics of Silver Ion Conducting Nanocomposite Solid Polymer Electrolytes Based on Chitosan

    Aziz, Shujahadeen B.; Rasheed, Mariwan A.; Abidin, Zul H. Z.

    2017-10-01

    Optical and electrical properties of nanocomposite solid polymer electrolytes based on chitosan have been investigated. Incorporation of alumina nanoparticles into the chitosan:silver triflate (AgTf) system broadened the surface plasmon resonance peaks of the silver nanoparticles and shifted the absorption edge to lower photon energy. A clear decrease of the optical bandgap in nanocomposite samples containing alumina nanoparticles was observed. The variation of the direct-current (DC) conductivity and dielectric constant followed the same trend with alumina concentration. The DC conductivity increased by two orders of magnitude, which can be attributed to hindrance of silver ion reduction. Transmission electron microscopy was used to interpret the space-charge and blocking effects of alumina nanoparticles on the DC conductivity and dielectric constant. The ion conduction mechanism was interpreted based on the dependences of the electrical and dielectric parameters. The dependence of the DC conductivity on the dielectric constant is explained empirically. Relaxation processes associated with conductivity and viscoelasticity were distinguished based on the incomplete semicircular arcs in plots of the real and imaginary parts of the electric modulus.

  18. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  19. Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

    Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

    2017-10-04

    We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

  20. Nuclear magnetic resonance studies in solid polymeric electrolyte. Estudos por ressonancia magnetica nuclear em eletrolitos polimericos solidos

    Donoso, J P; Mattoso, L H.C.; Cavalcante, M G [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Fisica e Quimica; Gorecki, W; Berthier, C; Armand, M [Universite J. Fourier, Grenoble (France)

    1990-01-01

    Solid complexes formed between Poly (ethylene oxide) and various alkali metal salts, are generally referred to as polymer electrolytes conductivity and NMR properties were investigated in POE - Li Cl sub(7)O sub(4) and POE - Li BF sub(4) complexes. Our sup(1)H, Li and sup(19)F relaxation study suggest that cation motion is controlled by segmental motions of the polymer chain while the anion have additional mobility associated with BG sub(4) rotation. (author).

  1. Solid state double layer capacitor based on a polyether polymer electrolyte blend and nanostructured carbon black electrode composites

    Lavall, Rodrigo L.; Borges, Raquel S.; Calado, Hallen D.R.; Welter, Cezar; Trigueiro, Joao P.C.; Silva, Glaura G. [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal de Minas Gerais, CEP 31270-901, Belo Horizonte (Brazil); Rieumont, Jacques [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal de Minas Gerais, CEP 31270-901, Belo Horizonte (Brazil); Facultad de Quimica, Universidad de La Habana, Habana 10400 (Cuba); Neves, Bernardo R.A. [Departamento de Fisica, Instituto de Ciencias Exatas, Universidade Federal de Minas Gerais, CEP 31270-901, Belo Horizonte (Brazil)

    2008-03-01

    An all solid double layer capacitor was assembled by using poly(ethylene oxide)/poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)-bis(2-aminopropyl ether) blend (PEO-NPPP) and LiClO{sub 4} as polymer electrolyte layer and PEO-NPPP-carbon black (CB) as electrode film. High molecular weight PEO and the block copolymer NPPP with molecular mass of 2000 Da were employed, which means that the design is safe from the point of view of solvent or plasticizer leakage and thus, a separator is not necessary. Highly conductive with large surface area nanostructured carbon black was dispersed in the polymer blend to produce the electrode composite. The electrolyte and electrode multilayers prepared by spray were studied by differential scanning calorimetry, atomic force microscopy (AFM) and impedance spectroscopy. The ionic conductivity as a function of temperature was fitted with the Williams-Landel-Ferry equation, which indicates a conductivity mechanism typical of solid polymer electrolyte. AFM images of the nanocomposite electrode showed carbon black particles of approximately 60 nm in size well distributed in a semicrystalline and porous polymer blend coating. The solid double layer capacitor with 10 wt.% CB was designed with final thickness of approximately 130 {mu}m and delivered a capacitance of 17 F g{sup -1} with a cyclability of more than 1000 cycles. These characteristics make possible the construction of a miniature device in complete solid state which will avoid electrolyte leakage and present a performance superior to other similar electric double layer capacitors (EDLCs) presented in literature, as assessed in specific capacitance by total carbon mass. (author)

  2. Detection and classification of gaseous sulfur compounds by solid electrolyte cyclic voltammetry of cermet sensor array.

    Kramer, Kirsten E; Rose-Pehrsson, Susan L; Hammond, Mark H; Tillett, Duane; Streckert, Holger H

    2007-02-12

    Electrochemical sensors composed of a ceramic-metallic (cermet) solid electrolyte are used for the detection of gaseous sulfur compounds SO(2), H(2)S, and CS(2) in a study involving 11 toxic industrial chemical (TIC) compounds. The study examines a sensor array containing four cermet sensors varying in electrode-electrolyte composition, designed to offer selectivity for multiple compounds. The sensors are driven by cyclic voltammetry to produce a current-voltage profile for each analyte. Raw voltammograms are processed by background subtraction of clean air, and the four sensor signals are concatenated to form one vector of points. The high-resolution signal is compressed by wavelet transformation and a probabilistic neural network is used for classification. In this study, training data from one sensor array was used to formulate models which were validated with data from a second sensor array. Of the 11 gases studied, 3 that contained sulfur produced the strongest responses and were successfully analyzed when the remaining compounds were treated as interferents. Analytes were measured from 10 to 200% of their threshold-limited value (TLV) according to the 8-h time weighted average (TWA) exposure limits defined by the National Institute of Occupational Safety and Health (NIOSH). True positive classification rates of 93.3, 96.7, and 76.7% for SO(2), H(2)S, and CS(2), respectively, were achieved for prediction of one sensor unit when a second sensor was used for modeling. True positive rates of 83.3, 90.0, and 90.0% for SO(2), H(2)S, and CS(2), respectively, were achieved for the second sensor unit when the first sensor unit was used for modeling. Most of the misclassifications were for low concentration levels (such 10-25% TLV) in which case the compound was classified as clean air. Between the two sensors, the false positive rates were 2.2% or lower for the three sulfur compounds, 0.9% or lower for the interferents (eight remaining analytes), and 5.8% or lower for

  3. Detection and classification of gaseous sulfur compounds by solid electrolyte cyclic voltammetry of cermet sensor array

    Kramer, Kirsten E.; Rose-Pehrsson, Susan L.; Hammond, Mark H.; Tillett, Duane; Streckert, Holger H.

    2007-01-01

    Electrochemical sensors composed of a ceramic-metallic (cermet) solid electrolyte are used for the detection of gaseous sulfur compounds SO 2 , H 2 S, and CS 2 in a study involving 11 toxic industrial chemical (TIC) compounds. The study examines a sensor array containing four cermet sensors varying in electrode-electrolyte composition, designed to offer selectivity for multiple compounds. The sensors are driven by cyclic voltammetry to produce a current-voltage profile for each analyte. Raw voltammograms are processed by background subtraction of clean air, and the four sensor signals are concatenated to form one vector of points. The high-resolution signal is compressed by wavelet transformation and a probabilistic neural network is used for classification. In this study, training data from one sensor array was used to formulate models which were validated with data from a second sensor array. Of the 11 gases studied, 3 that contained sulfur produced the strongest responses and were successfully analyzed when the remaining compounds were treated as interferents. Analytes were measured from 10 to 200% of their threshold-limited value (TLV) according to the 8-h time weighted average (TWA) exposure limits defined by the National Institute of Occupational Safety and Health (NIOSH). True positive classification rates of 93.3, 96.7, and 76.7% for SO 2 , H 2 S, and CS 2 , respectively, were achieved for prediction of one sensor unit when a second sensor was used for modeling. True positive rates of 83.3, 90.0, and 90.0% for SO 2 , H 2 S, and CS 2 , respectively, were achieved for the second sensor unit when the first sensor unit was used for modeling. Most of the misclassifications were for low concentration levels (such 10-25% TLV) in which case the compound was classified as clean air. Between the two sensors, the false positive rates were 2.2% or lower for the three sulfur compounds, 0.9% or lower for the interferents (eight remaining analytes), and 5.8% or lower for

  4. Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

    Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

    2017-11-30

    Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

  5. Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

    Kumar, Nitin; Siegel, Donald J.

    2016-01-01

    A promising strategy for increasing the energy density of Li-ion batteries is to substitute a multivalent (MV) metal for the commonly used lithiated carbon anode. Magnesium is a prime candidate for such a MV battery due to its high volumetric capacity, abundance, and limited tendency to form...... dendrites. One challenge that is slowing the implementation of Mg-based batteries, however, is the development of efficient and stable electrolytes. Computational screening for molecular species having sufficiently wide electrochemical windows is a starting point for the identification of optimal...... of several common electrolyte solvents on model electrodes of relevance for Mg batteries. Many-body perturbation theory calculations based on the G0W0 method were used to predict shifts in a solvent's electronic levels arising from interfacial interactions. In molecules exhibiting large dipole moments, our...

  6. Bulk solid state rechargeable lithium ion battery fabrication with Al-doped Li7La3Zr2O12 electrolyte and Cu0.1V2O5 cathode

    Jin, Ying; McGinn, Paul J.

    2013-01-01

    A simple, low-temperature route was developed to process bulk solid-state Li-ion batteries employing Al-doped Li 7 La 3 Zr 2 O 12 solid electrolyte (thickness: ∼ 0.5 mm; 25 °C conductivity: ∼ 2 × 10 −4 S cm −1 ). A composite Cu 0.1 V 2 O 5 –based slurry was directly painted on Li 7 La 3 Zr 2 O 12 and dried at 120 °C to prepare the cathode film. The opposite side of the electrolyte was subsequently exposed to molten Li to form the anode. The discharge capacity of the solid state battery was 53 mAh g −1 (calculated based on the weight of active cathode material) at room temperature with 5 μA cm −2 discharging current. Severe capacity decay occurred after the initial discharging. A comparable liquid electrolyte battery was tested at room temperature for comparison and had a much slower decay rate. However, when the operating temperature of the solid state battery was increased to 50 °C, the cell performance significantly improved. At 50 °C, the battery exhibited 176 mAh g −1 initial discharging capacity at 5 μA cm −2 current density and 93 mAh g −1 initial capacity under a 10 μA cm −2 discharging current density. After 20 cycles, the capacity decayed to 68.6 mAh g −1 when cycled at a 10 μA cm −2 current density. Impedance spectroscopy was used to investigate the interface resistance of the battery at different temperatures. The results indicated that both the cathode and anode interface resistance were dramatically reduced at 50 °C. The decrease in interface resistances at elevated temperature is proposed as the main reason for the observed battery performance enhancement

  7. Cross-linking of polymer and ionic liquid as high-performance gel electrolyte for flexible solid-state supercapacitors

    Zhong, Xiongwei; Tang, Jun; Cao, Lujie; Kong, Weiguang; Sun, Zheng; Cheng, Hua; Lu, Zhouguang; Pan, Hui; Xu, Baomin

    2017-01-01

    Highlights: •A facile method to prepare gel polymer electrolyte with high conductivity is proposed. •A flexible symmetric capacitor based on the prepared GPE shows ultra-flexibility. •The capacitor with high voltage can power up a 3.0 V LED even bended to a angle of 180°. -- Abstract: It is highly desirable to develop flexible solid-state electrochemical double-layer capacitors (EDLCs) with non-liquid electrolyte. However, it is still a great challenge to prepare gel polymer electrolyte (GPE) possessing high ionic conductivity and good mechanical property. In this work, a simple and novel method to improve the conductivity and mechanical properties of GPE film for their applications as electrolyte and separator in EDLC is presented. The GPE film is prepared by cross-linking ionic liquid (IL) with poly (ethylene oxide) (PEO) and benzophenone (Bp) followed by ultraviolet (UV) irradiation. Then, a non-woven cellulose separator (FPC) is used to absorb the GPE. By tuning the mass ratio (n) between IL and PEO, the flexible EDLC cooperated with low-cost active carbon and the electrolyte film with n = 10 has a high capacitance of 70.84 F∙g −1 , a wide and stable electrochemical window of 3.5 V, an energy density of 30.13 Wh∙kg −1 and a power density of 874.8 W∙kg −1 at a current density of 1 A∙g −1 , which can drive a 3.0 V light-emitting diode (LED). Importantly, the excellent performance of the flexible and low-cost EDLC can be maintained at a bending angle up to 180°, indicating the ultra-flexibility. It is expected that the IL-PEO-FPC electrolyte film is a promising candidate of GPE for flexible devices and energy storage systems.

  8. Rational coating of Li7P3S11 solid electrolyte on MoS2 electrode for all-solid-state lithium ion batteries

    Xu, R. C.; Wang, X. L.; Zhang, S. Z.; Xia, Y.; Xia, X. H.; Wu, J. B.; Tu, J. P.

    2018-01-01

    Large interfacial resistance between electrode and electrolyte limits the development of high-performance all-solid-state batteries. Herein we report a uniform coating of Li7P3S11 solid electrolyte on MoS2 to form a MoS2/Li7P3S11 composite electrode for all-solid-state lithium ion batteries. The as-synthesized Li7P3S11 processes a high ionic of 2.0 mS cm-1 at room temperature. Due to homogeneous union and reduced interfacial resistance, the assembled all-solid-state batteries with the MoS2/Li7P3S11 composite electrode exhibit higher reversible capacity of 547.1 mAh g-1 at 0.1 C and better cycling stability than the counterpart based on untreated MoS2. Our study provides a new reference for design/fabrication of advanced electrode materials for high-performance all-solid-state batteries.

  9. A New Miniaturized Inkjet Printed Solid State Electrolyte Sensor for Applications in Life Support Systems - First Results

    Hill, Christine; Stefanos Fasoulas, -; Eberhart, Martin; Berndt, Felix

    New generations of integrated closed loop systems will combine life support systems (incl. biological components) and energy systems such as fuel cell and electrolysis systems. Those systems and their test beds also contain complex safety sensor monitoring systems. Especially in fuel cells and electrolysis systems, the hydrogen and oxygen flows and exchange into other areas due to diffusion processes or leaks need to be monitored. Knowledge of predominant gas concentrations at all times is essential to avoid explosive gas mixtures. Solid state electrolyte sensors are promising for use as safety sensors. They have already been developed and produced at various institutes, but the power consumption for heating an existing solid state electrolyte sensor element still lies between 1 to 1.5 W and the operational readiness still takes about 20 to 30 s. This is partially due to the current manufacturing process for the solid state electrolyte sensor elements that is based on screen printing technology. However this technology has strong limitations in flexibility of the layout and re-designs. It is therefore suitable for mass production, but not for a flexible development and the production of specific individual sensors, e.g. for space applications. Moreover a disadvantage is the relatively high material consumption, especially in combination with the sensors need of expensive noble metal and ceramic pastes, which leads to a high sensor unit price. The Inkjet technology however opens up completely new possibilities in terms of dimensions, geometries, structures, morphologies and materials of sensors. This new approach is capable of printing finer high-resolution layers without the necessity of meshes or masks for patterning. Using the Inkjet technology a design change is possible at any time on the CAD screen. Moreover the ink is only deposited where it is needed. Custom made sensors, as they are currently demanded in space sensor applications, are thus realized simply

  10. Coupled Fluid-Solid Interaction Under Shock Wave Loading: Part II - Dynamic Interfaces

    Tipton, David Gregory [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Christon, Mark Allen [CTO Offce, Dassault Systµemes SIMULIA, Providence, RI (United States); Ingber, Marc Stuart [Univ. of New Mexico, Albuquerque, NM (United States). Department of Mechanical Engineering

    2009-07-01

    This article is the second of two that consider the treatment of fluid-solid interaction problems where the solid experiences wave loading and large bulk Lagrangian displacements. In part-I, we presented the formulation for the edge-based unstructured-grid Euler solver in the context of a discontinuous- Galerkin framework with the extensions used to treat internal fluid-solid interfaces. A super-sampled L2 projection was used to construct level-set data from the Lagrangian interface, and a narrow-band approach was used to identify and construct appropriate ghost data and boundary conditions at the fluid-solid interface. A series of benchmark problems were used to verify the treatment of the fluid-solid interface conditions with a static interface position. In this paper, we consider the treatment of dynamic interfaces and the associated large bulk Lagrangian displacements of the solid.We present the coupled dynamic fluid-solid system, and develop an explicit, monolithic treatment of the fully-coupled system. The conditions associated with moving interfaces and their implementation are discussed. A comparison of moving vs. fixed reference frames is used to verify the dynamic interface treatment. Lastly, a series of two and and three-dimensional projectile and shock-body interaction calculations are presented. Ultimately, the use of the Lagrangian interface position and a super-sampled projection for fast level-set construction, the narrow-band extraction of ghost data, and monolithic explicit solution algorithm has proved to be a computationally efficient means for treating shock induced fluid-solid interaction problems.

  11. The influence of Ferric ion contamination on the solid polymer electrolyte water electrolysis performance

    Wang, Xunying; Zhang, Linsong; Li, Guangfu; Zhang, Geng; Shao, Zhi-Gang; Yi, Baolian

    2015-01-01

    Highlights: • The cathode possesses higher tolerance for the Fe 3+ contamination than the anode. • Fe 3+ are mostly reduced to Fe 2+ rather than occur underpotential deposition. • Increased electrolysis voltage was mainly attributed to ohmic overpotential. • Voltage lags behind current for minutes in the multi-current-step test. • Poisoned electrolyser is mostly recovered by 0.5 M H 2 SO 4 solution treatment for 13 h. - Abstract: Fe 3+ is a sort of common metal ion contaminant for the solid polymer electrolyte (SPE) water electrolyser. In this paper, the effect of Fe 3+ on the performance of SPE water electrolyser has been investigated by both in-situ and ex-situ characterizations. The electron probe microanalysis and ultraviolet test results showed that Fe 3+ could migrate from the anode to the cathode and mostly be reduced to Fe 2+ in the cathode rather than occurred underpotential deposition as described in the previous report. The in-situ dynamic contamination test showed that the anode voltage increased sharply as soon as the Fe 3+ was fed into the anode, while the cathode voltage kept constant until the contamination time was over 30 minutes, indicating the higher tolerance of the cathode than the anode for the Fe 3+ contamination. The calculation results based on the electrochemistry impedance spectroscopy test results revealed that the striking increase of the electrolysis voltage was mainly attributed to the ohmic overpotential, which was due to the replacement of H + by Fe 3+ in the Nafion resin. Interestingly, the voltage lagged behind the current for several minutes in the multi-current-step test for the contaminated electrolyser, which phenomenon may be used for judging whether the SPE water electrolyser performance degradation is due to the metal ions contamination. Furthermore, recovery strategy has been developed, and it was found that the contaminated electrolyser could be mostly recovered by 0.5 M H 2 SO 4 solution treatment for 13 h

  12. Obtaining of ceria - samaria - gadolinia ceramics for application as solid oxide fuel cell (SOFC) electrolyte

    Arakaki, Alexander Rodrigo

    2010-01-01

    Cerium oxide (CeO 2 ) when doped with rare earth oxides has its ionic conductivity enhanced, enabling its use as electrolyte for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC), which is operated in temperatures between 500 e 700 degree C. The most effective additives or dopants for ionic conductivity improvement are (samarium oxide - Sm 2 O 3 ) and gadolinia (gadolinium oxide - Gd 2 O 3 ), fixing the concentration between 10 and 20 molar%. In this work, Ce 0,8 (SmGd) 0,2 O 1,9 powders have been synthesized by hydroxide, carbonate and oxalate coprecipitation routes. The hydrothermal treatment has been studied for powders precipitated with ammonium hydroxide. A concentrate of rare earths containing 90wt% of CeO 2 and other containing 51% of Sm 2 O 3 and 30% of Gd 2 O 3 , both prepared from monazite processing, were used as starting materials. These concentrates were used due the lower cost compared to pure commercial materials and the chemical similarity of others rare earth elements. Initially, the coprecipitation and calcination conditions were defined. The process efficiency was verified by ceramic sinterability evaluation. The results showed that powders calcined in the range of 450 and 800 degree C presented high specific surface area (90 - 150 m 2 .g -1 ) and fluorite cubic structure, indicating the solid solution formation. It was observed, by scanning electron microscopy, that morphology of particles and agglomerates is a function of precipitant agent. The dilatometric analysis indicated the higher rate of shrinkage at temperatures around 1300-1350 degree C. High densification values (>95% TD) was obtained at temperatures above 1400 degree C. Synthesis by hydroxides coprecipitation followed by hydrothermal treatment demonstrated to be a promising route for crystallization of ceria nano powders at low temperatures (200 degree C). High values of specific surface area were reached with the employment of hydrothermal treatment (about 100 m 2 .g -1

  13. Formation of nanotubes in poly (vinylidene fluoride): Application as solid polymer electrolyte in DSC fabricated using carbon counter electrode

    Muthuraaman, B. [Department of Energy, University of Madras, Guindy campus, Chennai 600025 (India); Maruthamuthu, P., E-mail: pmaruthu@yahoo.com [Department of Energy, University of Madras, Guindy campus, Chennai 600025 (India)

    2011-09-01

    Highlights: > Incorporation of a {pi}-electron donor compound as dopant in poly(vinylidene fluoride) along with redox couple (I{sup -}/I{sub 3}{sup -}) which forms brush like nanotubes. > Investigations about the use of conducting carbon coated FTO as a durable counter electrode and its effects in DSC. > High charge separation and the channelized flow of electrons in the nanotubes in electrolyte favors stable performance. - Abstract: In the present work, we report the incorporation of 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) in poly(vinylidene fluoride) (PVDF) along with the redox couple (I{sup -}/I{sub 3}{sup -}). When ABTS, a {pi}-electron donor, is used to dope PVDF, the polymer composite forms brush-like nanotubes and has been successfully used as a solid polymer electrolyte in dye-sensitized solar cells. Under the given conditions, the electrolyte composition forms nanotubes while it is doped with ABTS, a {pi}-electron donor. With this new electrolyte, a dye-sensitized solar cell was fabricated using N3 dye adsorbed over TiO{sub 2} nanoparticles as the photoanode and conducting carbon cement coated FTO as counter electrode.

  14. Dense garnet-like Li5La3Nb2O12 solid electrolyte prepared by self-consolidation method

    Zhao, Pengcheng; Xiang, Yu; Xu, Yan; Wen, Yuehua; Zhang, Wenfeng; Zhu, Xiayu; Li, Meng; Zhang, Sontong; Ming, Hai; Jin, Zhaoqing; Cao, Gaoping

    2018-06-01

    Li5La3Nb2O12 (LLNO) is a typical garnet-like solid electrolyte with solitary cubic structure. However, its ionic conductivity is relatively low due to the low relative density when prepared by cold isostatic pressing method, which usually involves high-pressure machines, poor productivity, tedious pressing operations, and low density. In this paper, self-consolidation method is developed to sinter dense LLNO electrolyte. Although not any pressing operations are employed in the entire process, the relative density of LLNO is promoted up to 95%, which is much higher than the reported values of 45-80%. SEM images reveal that the sample is built by huge particles in size of 80 μm indicating that there are few boundaries in the sample. Moreover, a rich content of Li-Al-O compounds is detected out in the boundary areas, which may act as sintering aids for the sample to consolidate automatically. According to the highest density, the bulk ionic conductivity of LLNO sample reaches up to 1.61 × 10-4 S cm-1 at 30 °C, which is in the same order of magnitude as the value of cubic Li7La3Zr2O12 electrolyte. This work verifies the self-consolidation mechanism for the sintering of ceramic electrolytes and could significantly facilitate the development of LLNO membrane technology.

  15. Influence of solvent on the poly (acrylic acid)-oligo-(ethylene glycol) polymer gel electrolyte and the performance of quasi-solid-state dye-sensitized solar cells

    Wu, Jihuai; Lan, Zhang; Lin, Jianming; Huang, Miaoliang; Hao, Shancun; Fang, Leqing

    2007-01-01

    The influence of solvents on the property of poly (acrylic acid)-oligo-(ethylene glycol) polymer gel electrolyte and photovoltaic performance of quasi-solid-state dye-sensitized solar cells (DSSCs) were investigated. Solvents or mixed solvents with large donor number enhance the liquid electrolyte absorbency, which further influences the ionic conductivity of polymer gel electrolyte. A polymer gel electrolyte with ionic conductivity of 4.45 mS cm -1 was obtained by using poly (acrylic acid)-oligo-(ethylene glycol) as polymer matrix, and absorbing 30 vol.% N-methyl pyrrolidone and 70 vol.% γ-butyrolactone with 0.5 M NaI and 0.05 M I 2 . By using this polymer gel electrolyte coupling with 0.4 M pyridine additive, a quasi-solid-state dye-sensitized solar cell with conversion efficiency of 4.74% was obtained under irradiation of 100 mW cm -2 (AM 1.5)

  16. New field of actinides solution chemistry; electrochemical study on actinide ion transfer at the interface of two immiscible electrolyte solutions

    Kitatsuji, Yoshihiro; Yoshida, Zenko [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kudo, Hiroshi [Tohoku Univ., Graduate School of Science, Sendai, Miyagi (Japan); Kihara, Sorin [Kyoto Inst. of Technolgy, Dept. of Chemistry, Kyoto (Japan)

    2002-04-01

    A novel electrochemical method on the basis of a controlled electrolysis has been developed for the study of the ion transfer at the interface of two immiscible electrolyte solutions (ITIES). The controlled-potential electrolysis for ITIES (CPEITIES) was applied to the transfer of actinide ions, and Gibbs energies for the transfer of UO{sub 2}{sup 2+} and Am{sup 3+} from aqueous solution (w) to nitrobenzene solution (nb) were determined to be 71.7 and 113 kJ mol{sup -1}, respectively. The ion transfer potentials for the facilitated transfer of UO{sub 2{sup +}} and Am{sup 3+} from w to nb in the presence of bis(diphenylphosphoryl)methane were determined, from which the stability constants of UO{sub 2}(BDPPM){sub 3}{sup 2+} and Am(BDPPM){sub 3}{sup 3+} complexes involved in the facilitated ion transfer reaction, were calculated to be 10{sup 23.9} and 10{sup 27.5}, respectively. On the basis of the results of CPEITIES, a feasibility of a new separation method, i.e., an electrolytic ion transfer separation, of actinide ions is evaluated. (author)

  17. Electrochemical noise and impedance of Au electrode/electrolyte interfaces enabling extracellular detection of glioma cell populations.

    Rocha, Paulo R F; Schlett, Paul; Kintzel, Ulrike; Mailänder, Volker; Vandamme, Lode K J; Zeck, Gunther; Gomes, Henrique L; Biscarini, Fabio; de Leeuw, Dago M

    2016-10-06

    Microelectrode arrays (MEA) record extracellular local field potentials of cells adhered to the electrodes. A disadvantage is the limited signal-to-noise ratio. The state-of-the-art background noise level is about 10 μVpp. Furthermore, in MEAs low frequency events are filtered out. Here, we quantitatively analyze Au electrode/electrolyte interfaces with impedance spectroscopy and noise measurements. The equivalent circuit is the charge transfer resistance in parallel with a constant phase element that describes the double layer capacitance, in series with a spreading resistance. This equivalent circuit leads to a Maxwell-Wagner relaxation frequency, the value of which is determined as a function of electrode area and molarity of an aqueous KCl electrolyte solution. The electrochemical voltage and current noise is measured as a function of electrode area and frequency and follow unambiguously from the measured impedance. By using large area electrodes the noise floor can be as low as 0.3 μVpp. The resulting high sensitivity is demonstrated by the extracellular detection of C6 glioma cell populations. Their minute electrical activity can be clearly detected at a frequency below about 10 Hz, which shows that the methodology can be used to monitor slow cooperative biological signals in cell populations.

  18. Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries

    He, Zijian; Chen, Long; Zhang, Bochen; Liu, Yongchang; Fan, Li-Zhen

    2018-07-01

    Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li6.25Al0.25La3Zr2O12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number (tLi+). PEC, as a fast ion-conducting polymer, possesses high tLi+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high tLi+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO4|Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g-1 and good cycling stability at 55 °C.

  19. Determination of the Solid Electrolyte Interphase Structure Grown on a Silicon Electrode Using a Fluoroethylene Carbonate Additive

    Veith, Gabriel M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Doucet, Mathieu [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Data Analysis and Visualization Division; Sacci, Robert L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Vacaliuc, Bogdan [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Research Accelerator Division; Baldwin, J. Kevin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Browning, James F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division

    2017-07-24

    In this work we explore how an electrolyte additive (fluorinated ethylene carbonate – FEC) mediates the thickness and composition of the solid electrolyte interphase formed over a silicon anode in situ as a function of state-of-charge and cycle. We show the FEC condenses on the surface at open circuit voltage then is reduced to C-O containing polymeric species around 0.9 V (vs. Li/Li+). The resulting film is about 50 Å thick. Upon lithiation the SEI thickens to 70 Å and becomes more organic-like. With delithiation the SEI thins by 13 Å and becomes more inorganic in nature, consistent with the formation of LiF. This thickening/thinning is reversible with cycling and shows the SEI is a dynamic structure. We compare the SEI chemistry and thickness to 280 Å thick SEI layers produced without FEC and provide a mechanism for SEI formation using FEC additives.

  20. Nanoporous palladium anode for direct ethanol solid oxide fuel cells with nanoscale proton-conducting ceramic electrolyte

    Li, Yong; Wong, Lai Mun; Xie, Hanlin; Wang, Shijie; Su, Pei-Chen

    2017-02-01

    In this work, we demonstrate the operation of micro-solid oxide fuel cells (μ-SOFCs) with nanoscale proton-conducting Y-BaZrO3 (BZY) electrolyte to avoid the fuel crossover problem for direct ethanol fuel cells (DEFCs). The μ-SOFCs are operated with the direct utilisation of ethanol vapour as a fuel and Pd as anode at the temperature range of 300-400 °C. The nanoporous Pd anode is achieved by DC sputtering at high Ar pressure of 80 mTorr. The Pd-anode/BYZ-electrolyte/Pt-cathode cell show peak power densities of 72.4 mW/cm2 using hydrogen and 15.3 mW/cm2 using ethanol at 400 °C. No obvious carbon deposition is seen from XPS analysis after fuel cell test with ethanol fuel.

  1. Structural and electrical properties of NASICON type solid electrolyte nanoscaled glass-ceramic powder by mechanical milling for thin film batteries.

    Patil, Vaishali; Patil, Arun; Yoon, Seok-Jin; Choi, Ji-Won

    2013-05-01

    During last two decades, lithium-based glasses have been studied extensively as electrolytes for solid-state secondary batteries. For practical use, solid electrolyte must have high ionic conductivity as well as chemical, thermal and electrochemical stability. Recent progresses have focused on glass electrolytes due to advantages over crystalline solid. Glass electrolytes are generally classified into two types oxide glass and sulfide glass. Oxide glasses do not react with electrode materials and this chemical inertness is advantageous for cycle performances of battery. In this study, major effort has been focused on the improvement of the ion conductivity of nanosized LiAlTi(PO4)3 oxide electrolyte prepared by mechanical milling (MM) method. After heating at 1000 degrees C the material shows good crystallinity and ionic conductivity with low electronic conductivity. In LiTi2(PO4)3, Ti4+ ions are partially substituted by Al3+ ions by heat-treatment of Li20-Al2O3-TiO2-P2O5 glasses at 1000 degrees C for 10 h. The conductivity of this material is 1.09 x 10(-3) S/cm at room temp. The glass-ceramics show fast ion conduction and low E(a) value. It is suggested that high conductivity, easy fabrication and low cost make this glass-ceramics promising to be used as inorganic solid electrolyte for all-solid-state Li rechargeable batteries.

  2. On the sliding friction at the interface between a fluid and a solid

    Minetti-Mezzetti, E.

    1976-01-01

    A method is reported to investigate the possible existence and the numerical value of the sliding friction coefficient β at the contact interface between a fluid and a solid. Some preliminary experimental results at the interface glycerol-aluminium give 1/β -4 . (author)

  3. Ni-SDC cermet anode for medium-temperature solid oxide fuel cell with lanthanum gallate electrolyte

    Zhang, Xinge; Ohara, Satoshi; Maric, R.; Mukai, Kazuo; Fukui, Takehisa [Japan Fine Ceramics Center, Nagoya (Japan); Yoshida, Hiroyuki; Nishimura, Masayoshi; Inagaki, Toru [Kansai Electr. Power Co. Inc., Hyogo (Japan); Miura, Kazuhiro [Kanden Kakou, Amagasaki (Japan)

    1999-10-01

    The polarization properties and microstructure of Ni-SDC (samaria-doped ceria) cermet anodes prepared from spray pyrolysis (SP) composite powder, and element interface diffusion between the anode and a La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{delta}} (LSGM) electrolyte are investigated as a function of anode sintering temperature. The anode sintered at 1250 C displays minimum anode polarization (with anode ohmic loss), while the anode prepared at 1300 C has the best electrochemical overpotential, viz., 27 mV at 300 mA cm{sup -2} operating at 800 C. The anode ohmic loss gradually increases with increase in the sintering temperature at levels below 1300 C, and sharply increases at 1350 C. Electron micrographs show a clear grain growth at sintering temperatures higher than 1300 C. The anode microstructure appears to be optimized at 1300 C, in which nickel particles form a network with well-connected SDC particles finely distributed over the surfaces of the nickel particles. The anode sintered at 1350 C has severe grain growth and an apparent interface diffusion of nickel from the anode to the electrolyte. The nickel interface diffusion is assumed to be the main reason for the increment in ohmic loss, and the resulting loss in anode performance. The findings suggest that sintering Ni-SDC composite powder near 1250 C is the best method to prepare the anode on a LSGM electrolyte. (orig.)

  4. Ni-SDC cermet anode for medium-temperature solid oxide fuel cell with lanthanum gallate electrolyte

    Zhang, Xinge; Ohara, Satoshi; Maric, Radenka; Mukai, Kazuo; Fukui, Takehisa; Yoshida, Hiroyuki; Nishimura, Masayoshi; Inagaki, Toru; Miura, Kazuhiro

    The polarization properties and microstructure of Ni-SDC (samaria-doped ceria) cermet anodes prepared from spray pyrolysis (SP) composite powder, and element interface diffusion between the anode and a La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- δ (LSGM) electrolyte are investigated as a function of anode sintering temperature. The anode sintered at 1250°C displays minimum anode polarization (with anode ohmic loss), while the anode prepared at 1300°C has the best electrochemical overpotential, viz., 27 mV at 300 mA cm -2 operating at 800°C. The anode ohmic loss gradually increases with increase in the sintering temperature at levels below 1300°C, and sharply increases at 1350°C. Electron micrographs show a clear grain growth at sintering temperatures higher than 1300°C. The anode microstructure appears to be optimized at 1300°C, in which nickel particles form a network with well-connected SDC particles finely distributed over the surfaces of the nickel particles. The anode sintered at 1350°C has severe grain growth and an apparent interface diffusion of nickel from the anode to the electrolyte. The nickel interface diffusion is assumed to be the main reason for the increment in ohmic loss, and the resulting loss in anode performance. The findings suggest that sintering Ni-SDC composite powder near 1250°C is the best method to prepare the anode on a LSGM electrolyte.

  5. About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

    Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

    2016-10-12

    The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

  6. Solid state electrolyte composites based on complex hydrides and metal doped fullerenes/fulleranes for batteries and electrochemical applications

    Zidan, Ragaiy; Teprovich, Jr., Joseph A.; Colon-Mercado, Hector R.; Greenway, Scott D.

    2018-05-01

    A LiBH4--C60 nanocomposite that displays fast lithium ionic conduction in the solid state is provided. The material is a homogenous nanocomposite that contains both LiBH4 and a hydrogenated fullerene species. In the presence of C60, the lithium ion mobility of LiBH4 is significantly enhanced in the as prepared state when compared to pure LiBH4. After the material is annealed the lithium ion mobility is further enhanced. Constant current cycling demonstrated that the material is stable in the presence of metallic lithium electrodes. The material can serve as a solid state electrolyte in a solid-state lithium ion battery.

  7. Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

    Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

    2018-04-01

    Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

  8. Effect of T-stress on crack growth along an interface between ductile and elastic solids

    Tvergaard, Viggo

    2003-01-01

    For crack growth along an interface joining an elastic-plastic solid to an elastic substrate the effect of a non-singular stress component in the crack growth direction in the elastic-plastic solid is investigated. Conditions of small scale yielding are assumed, and due to the mismatch of elastic...

  9. The electrochemical transfer reactions and the structure of the iron|oxide layer|electrolyte interface

    Petrović, Željka; Metikoš-Huković, Mirjana; Babić, Ranko

    2012-01-01

    The thickness, barrier (protecting) and semiconducting properties of the potentiostatically formed oxide films on the pure iron electrode in an aqueous borate buffer solution were investigated by electrochemical quartz crystal nanobalance (EQCN), electrochemical impedance spectroscopy (EIS), and Mott–Schottky (MS) analysis. The thicknesses of the prepassive Fe(II)hydroxide layer (up to monolayer) nucleated on the bare iron surface and the passive Fe(II)/Fe(III) layer (up to 2 nm), deposited on the top of the first one, were determined using in situ gravimetry. Electronic properties of iron prepassive and passive films as well as ionic and electronic transfer reactions at the film|solution interface were discussed on the basis of a band structure model of the surface oxide film and the potential distribution at the interface. The anodic oxide film formation and cathodic decomposition are coupled processes and their reversible inter-conversion is mediated by the availability of free charge carriers on the electrode|solution interface. The structure of the reversible double layer at the iron oxide|solution interface was discussed based on the concept of the specific adsorption of the imidazolium cation on the negatively charged electrode surface at pH > pH pzc .

  10. Boron cross-linked graphene oxide/polyvinyl alcohol nanocomposite gel electrolyte for flexible solid-state electric double layer capacitor with high performance

    Huang, Yi-Fu; Wu, Peng-Fei; Zhang, Ming-Qiu; Ruan, Wen-Hong; Giannelis, Emmanuel P.

    2014-01-01

    Highlights: • Gel electrolyte is prepared and used in electric double layer capacitor. • Insertion of boron crosslinks into GO agglomerates opens channels for ion migration. • Solid supercapacitors show excellent specific capacitance and cycle stability. • Nanocomposite electrolyte shows better thermal stability and mechanical properties. - Abstract: A new family of boron cross-linked graphene oxide/polyvinyl alcohol (GO-B-PVA) nanocomposite gels is prepared by freeze-thaw/boron cross-linking method. Then the gel electrolytes saturated with KOH solution are assembled into electric double layer capacitors (EDLCs). Structure, thermal and mechanical properties of GO-B-PVA are explored. The electrochemical properties of EDLCs using GO-B-PVA/KOH are investigated, and compared with those using GO-PVA/KOH gel or KOH solution electrolyte. FTIR shows that boron cross-links are introduced into GO-PVA, while the boronic structure inserted into agglomerated GO sheets is demonstrated by DMA analysis. The synergy effect of the GO and the boron crosslinking benefits for ionic conductivity due to unblocking ion channels, and for improvement of thermal stability and mechanical properties of the electrolytes. Higher specific capacitance and better cycle stability of EDLCs are obtained by using the GO-B-PVA/KOH electrolyte, especially the one at higher GO content. The nanocomposite gel electrolytes with excellent electrochemical properties and solid-like character are candidates for the industrial application in high-performance flexible solid-state EDLCs

  11. Electrochemical performance of all-solid-state lithium batteries using inorganic lithium garnets particulate reinforced PEO/LiClO4 electrolyte

    Cheng, Samson Ho-Sum; He, Kang-Qiang; Liu, Ying; Zha, Jun-Wei; Kamruzzaman, Md; Ma, Robin Lok-Wang; Dang, Zhi-Min; Li, Robert K.Y.; Chung, C.Y.

    2017-01-01

    All-solid-state batteries are proposed to have ultimate safety and higher power and energy densities over conventional lithium ion batteries with liquid electrolytes. The Li ion conductivity and interfacial resistance between electrolyte and electrodes are the major bottleneck of the development of all-solid-state batteries for practical uses. Here, we reported a novel composite electrolyte which is composed of uniform distributed Li ion conducting Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) fillers in PEO/LiClO 4 matrix. The EO:Li + ratio of 15:1 is being used to achieve lower interfacial resistance between electrolyte and electrodes through the melting process. The composite electrolyte is fabricated by simple solution casting method, which is more advantageous comparing with high temperature sintering or sol-gel method used in the fabrication of ceramic electrolytes. The composite electrolyte exhibits good Li ion conductivity of 4.8 × 10 −4 Scm −1 at 60 °C and excellent interfacial stability against Li metal. The all-solid-state lithium battery using this composite electrolyte shows a specific capacity of 140mAhg −1 and an unprecedentedly high capacity retention of 83% after 500 cycles at 60 °C and the rate of 1C. It is concluded that good electrode/electrolyte interfacial stability and contact as well as fast Li ion conductivity obtained by the addition of active garnet particulates to PEO/LiClO 4 matrix are essential criteria for good charge/discharge performance of all-solid-state lithium batteries.

  12. Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells

    Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

    2015-07-01

    Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC).

  13. Stabilizing the Electrode/Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 through Tailoring Aluminum Distribution in Microspheres as Long-Life, High-Rate, and Safe Cathode for Lithium-Ion Batteries.

    Hou, Peiyu; Zhang, Hongzhou; Deng, Xiaolong; Xu, Xijin; Zhang, Lianqi

    2017-09-06

    The unstable electrode/electrolyte interface of high-capacity LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) cathodes, especially at a highly delithiated state, usually leads to the transformation of layered to spinel and/or rock-salt phases, resulting in drastic capacity fade and poor thermal stability. Herein, the Al-increased and Ni-,Co-decreased electrode surface is fabricated through tailoring element distribution in micrometer-sized spherical NCA secondary particles via coprecipitation and solid-state reactions, aimed at stabilizing the electrode/electrolyte interface during continuous cycles. As expected, it shows much extended cycle life, 93.6% capacity retention within 100 cycles, compared with that of 78.5% for the normal NCA. It also delivers large reversible capacity of about 140 mAh g -1 even at 20 C, corresponding to energy density of around 480 Wh kg -1 , which is enhanced by 45% compared to that of the normal NCA (about 330 Wh kg -1 ). Besides, the delayed heat emission temperature and reduced heat generation mean remarkably improved thermal stability. These foregoing improvements are ascribed to the Al-increased spherical secondary particle surface that stabilizes the electrode/electrolyte interface by protecting inner components from directly contacting with electrolyte and suppressing the side reaction on electrode surface between high oxidizing Ni 4+ and electrolyte.

  14. Influence of interface scattering on shock waves in heterogeneous solids

    Zhuang Shiming; Ravichandran, Guruswami; Grady, Dennis E.

    2002-01-01

    In heterogeneous media, the scattering due to interfaces between dissimilar materials play an important role in shock wave dissipation and dispersion. In this work the influence of interface scattering effect on shock waves was studied by impacting flyer plates onto periodically layered polycarbonate/6061 aluminum, polycarbonate/304 stainless steel and polycarbonate/glass composites. The experimental results (using VISAR and stress gauges) indicate that the rise time of the shock front decreases with increasing shock strength, and increases with increasing mechanical impedance mismatch between layers; the strain rate at the shock front increases by about the square of the shock stress. Experimental and numerical results also show that due to interface scattering effect the shock wave velocity in periodically layered composites decreases. In some cases the shock velocity of a layered heterogeneous composite can be lower than that of either of its components

  15. Electrophoretic deposition of 9-YSZ solid electrolyte on Ni- YSZ composite; Estudos de deposicao eletroforetica de ceramicas de 9-YSZ sobre Ni-YSZ

    Santos, F.S.; Yoshito, W.K.; Lazar, D.R.R.; Ussui, V., E-mail: vussui@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (CCTM/IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencia e Tecnologia de Materiais

    2010-07-01

    9-YSZ ceramic and Ni-YSZ metal/ceramic composite are the more commonly used materials for the fabrication of solid oxide fuel cell electrolyte and anode, respectively. The main challenges for these applications are the forming of both materials as superposed double thin layers. In the present work ceramic powder of 9- YSZ was synthesized by a coprecipitation technique and the Ni O-YSZ composite by a combustion technique. The later was formed by uniaxial pressing as cylindrical pellets of 15 mm diameter. Thin ceramic layers of 9-YSZ were deposited on composite pellets from a suspension with 10% solid content by an Electrophoretic Deposition technique. Applied voltage varied in the range of 30 to 200 V and deposition time from 15 to 90 seconds, evaluating the deposited mass, porosity on the interface and adhesion of layers. Resulted ceramics were characterized by X-ray diffraction and were observed in a scanning electron microscope. Results showed that deposited layers are thin ({approx}20{mu}m), dense and have good adhesion on the surface of composite substrate. (author)

  16. Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

    Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

    2017-02-01

    A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

  17. Determination of diffusion coefficients for sulfide ions in solid electrolytes on the basis of BaSm2S4 and CaGd2S4

    Yurlov, I.S.; Ushakova, Yu.N.; Medvedeva, O.V.; Kalinina, L.A.; Shirokova, G.I.; Ananchenko, B.A.

    2007-01-01

    Coefficients of self-diffusion and coefficients of diffusion of the sulfur ion in solid electrolytes BaSm 2 S 4 and CaGd 2 S 4 are determined with recourse to methods of conductometry and potentiostatic chronoamperometry. A vacancy mechanism for the defect formation in solid solutions on the basis of barium thiosamarate and calcium thiogadolynate is proposed [ru

  18. Mechanisms of Degradation and Strategies for the Stabilization of Cathode-Electrolyte Interfaces in Li-Ion Batteries.

    Cabana, Jordi; Kwon, Bob Jin; Hu, Linhua

    2018-02-20

    Undesired reactions at the interface between a transition metal oxide cathode and a nonaqueous electrolyte bring about challenges to the performance of Li-ion batteries in the form of compromised durability. These challenges are especially severe in extreme conditions, such as above room temperature or at high potentials. The ongoing push to increase the energy density of Li-ion batteries to break through the existing barriers of application in electric vehicles creates a compelling need to address these inefficiencies. This goal requires a combination of deep knowledge of the mechanisms underpinning reactivity, and the ability to assemble multifunctional electrode systems where different components synergistically extend cycle life by imparting interfacial stability, while maintaining, or even increasing, capacity and potential of operation. The barriers toward energy storage at high density apply equally in Li-ion, the leading technology in the battery market, and in related, emerging concepts for high energy density, such as Na-ion and Mg-ion, because they also conceptually rely on electroactive transition metal oxides. Therefore, their relevance is broad and the quest for solutions inevitable. In this Account, we describe mechanisms of reaction that can degrade the interface between a Li-ion battery electrolyte and the cathode, based on an oxide with transition metals that can reach high formal oxidation states. The focus is placed on cathodes that deliver high capacity and operate at high potential because their development would enable Li-ion battery technologies with high capacity for energy storage. Electrode-electrolyte instabilities will be identified beyond the intrinsic potential windows of stability, by linking them to the electroactive transition metals present at the surface of the electrode. These instabilities result in irreversible transformations at these interfaces, with formation of insulating layers that impede transport or material loss due

  19. Effect of Al2O3 nanoparticles in plasticized PMMA-LiClO4 based solid polymer electrolyte

    Pal, P.; Ghosh, A.

    2017-05-01

    We have studied the broadband complex conductivity spectra covering a 0.01 Hz-3 GHz frequency range for plasticized PMMA-LiClO4 based solid polymer electrolyte embedded with Al2O3 nanoparticle. We have analyzed the conductivity spectra using the random free-energy barrier model (RBM) coupled with electrode polarization contribution in the low frequency region and at high temperatures. The temperature dependence of the ionic conductivity obtained from the analysis has been analyzed using Vogel-Tammann-Fulcher equation. The maximum ionic conductivity ˜ 1.93×10-4 S/cm has been obtained for 1 wt% Al2O3 nanoparticle.

  20. Effects of chemical synthesis parameters on the Zr O2: 8% mol Mg O solid electrolytes electric conductivity and microstructure

    Avila, D.M.; Muccillo, E.N.S.

    1996-01-01

    Electrical conductivity measurements and scanning electron microscope observations have been done in Zr O 2 - 8 mol % Mg O solid electrolytes. The main purpose was to investigate to what extent some processing variables can influence the electrical behaviour and microstructural characteristics of the sintered ceramic. Zirconia powders have been prepared under different pH and temperature of precipitation, and washing media conditions. The results show that many structural characteristics of the calcined powders are 'lost' during sintering, giving rise to ceramics with similar electrical properties, besides minor differences in the final microstructure. The washing media play the major role on both microstructural development and electrical conductivity. (author)

  1. Ultrahigh-vacuum in situ electrochemistry with solid polymer electrolyte and x-ray photoelectron spectroscopy studies of polypyrrole

    Skotheim, T.A.; Florit, M.I.; Melo, A.; O'Grady, W.E.

    1984-01-01

    A new in situ combined electrochemistry and x-ray-photoelectron-spectroscopy (XPS) technique using solid polymer electrolytes has been used to characterize electrically conducting films of polypyrrole perchlorate. The technique allows in situ electrochemical oxidation and reduction (doping and undoping) in ultrahigh vacuum and the simultaneous study of the polymer with XPS as a function of its electrochemical potential. We demonstrate that some anion species interact strongly electrostatically with the nitrogen heteroatoms. We also show conclusively that the electrochemistry of polypyrrole is highly irreversible

  2. The effect of heat currents on the stability of the liquid solid interface

    Bowley, R.M.; Nozieres, P.

    1992-01-01

    Rapid changing of the temperature of a liquid in equilibrium with its solid can lead to instabilities of the interface in two ways : the change in pressure, induced by a temperature change at the interface, leads to a uniaxial stress which can cause a Grinfeld instability at the capillary wavelength; a temperature gradient is set up which modifies the effective gravity at the interface. When the effective gravity becomes negative, the interface is unstable at very long wavelengths. For a superfluid, such as 4 He, the situation is more complex. If we ignore surface dissipation, there is still a small critical temperature gradient across the solid above which the interface is unstable. However surface dissipation -in particular the growth resistance- pushes the instability to huge temperature gradients, ones which cannot be realised experimentally. The only instability that can be seen is caused by uniaxial stress

  3. Microstructure degradation of an anode/electrolyte interface in SOFC studied by transmission electron microscopy

    Liu, Y.L.; Jiao, C.G.

    2005-01-01

    accumulated at the interface seen earlier by SEM have been characterized. It is a silicate glass with an amorphous structure and a composition of similar to90 mol% SiO2 as well as a few percent of Na2O,CaO, ZrO2, V2O3 etc. The silicate glass phase is distributed as films of nanoscale along the anode...

  4. Degradation of some ceria electrolytes under hydrogen contact nearby anode in solid oxide fuel cells (SOFCs

    Malta Luiz Fernando Brum

    2004-01-01

    Full Text Available This work is concerned with thermodynamic analysis of the stability of some ceria electrolytes under contact with hydrogen gas nearby anode in fuel cells. It was considered the following types of ceria-electrolytes: pure ceria, strontium-doped ceria, calcium-doped ceria and calcium-bismuth-doped ceria. The equilibrium Log (pH2O/pH2 vs. T diagrams were constructed for x = 0.1 and 0.01, where x is the fraction of initial ceria converted to Ce2O3 (proportional to the ratio between activities of Ce3+ and Ce4+ in the ceria electrolyte, which is proportional to the fraction of electronic conduction in the electrolyte at a given temperature. The predictions of the diagrams are as follows: (a Ce1.9Ca0.1Bi0.8O5.1 and Ce0.9Sr0.1O1.9 are less stable than pure ceria for the whole temperature range (from 0 to 1000 °C; (b Ce0.9Ca0.1O1.9 is more stable than pure ceria below about 650 °C for x = 0.1 and below about 400 °C for x = 0.01; (c at each temperature in the considered range the pressure ratio pH2O(g/pH2(g has to be higher than thermodynamically predicted in order to keep CeO2 stable in the electrolyte contacting hydrogen gas. Thermodynamic predictions are entirely capable of explaining experimental data published on the subject (irreversible cell degradation in the case of SrO-doped ceria; weight loss from doped-ceria electrolyte above 700 °C; oxygen gas release during sintering of ceria.

  5. Ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with propylene carbonate

    S. Das

    2015-02-01

    Full Text Available We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of free ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.

  6. Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

    Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in [Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2015-02-15

    We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of free ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.

  7. Application of atmospheric-pressure plasma jet processed carbon nanotubes to liquid and quasi-solid-state gel electrolyte supercapacitors

    Kuok, Fei-Hong; Kan, Ken-Yuan; Yu, Ing-Song; Chen, Chieh-Wen; Hsu, Cheng-Che; Cheng, I.-Chun; Chen, Jian-Zhang

    2017-12-01

    We use a dc-pulse nitrogen atmospheric-pressure plasma jet (APPJ) to calcine carbon nanotubes (CNTs) pastes that are screen-printed on carbon cloth. 30-s APPJ treatment can efficiently oxidize and vaporize the organic binders, thereby forming porous structures. As indicated by X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA), the oxygen content decreases after APPJ treatment owing to the oxidation and vaporization of ethyl cellulose, terpineol, and ethanol. Nitrogen doping was introduced to the materials by the nitrogen APPJ. APPJ-calcination improves the wettability of the CNTs printed on carbon cloth, as evidenced by water contact angle measurement. Raman spectroscopy indicates that reactive species of nitrogen APPJ react violently with CNTs in only 30-s APPJ processing time and introduce defects and/or surface functional groups on CNTs. Carbon cloths with calcined CNT layers are used as electrodes for liquid and quasi-solid-state electrolyte supercapacitors. Under a cyclic voltammetry test with a 2 mV/s potential scan rate, the specific capacitance is 73.84 F/g (areal capacitance = 5.89 mF/cm2) with a 2 M KCl electrolyte and 66.47 F/g (areal capacitance = 6.10 mF/cm2) with a H2SO4/polyvinyl alcohol (PVA) gel electrolyte.

  8. New Insights of Graphite Anode Stability in Rechargeable Batteries: Li-Ion Coordination Structures Prevail over Solid Electrolyte Interphases

    Ming, Jun

    2018-01-04

    Graphite anodes are not stable in most noncarbonate solvents (e.g., ether, sulfoxide, sulfone) upon Li ion intercalation, known as an urgent issue in present Li ions and next-generation Li–S and Li–O2 batteries for storage of Li ions within the anode for safety features. The solid electrolyte interphase (SEI) is commonly believed to be decisive for stabilizing the graphite anode. However, here we find that the solvation structure of the Li ions, determined by the electrolyte composition including lithium salts, solvents, and additives, plays a more dominant role than SEI in graphite anode stability. The Li ion intercalation desired for battery operation competes with the undesired Li+–solvent co-insertion, leading to graphite exfoliation. The increase in organic lithium salt LiN(SO2CF3)2 concentration or, more effectively, the addition of LiNO3 lowers the interaction strength between Li+ and solvents, suppressing the graphite exfoliation caused by Li+–solvent co-insertion. Our findings refresh the knowledge of the well-known SEI for graphite stability in metal ion batteries and also provide new guidelines for electrolyte systems to achieve reliable and safe Li–S full batteries.

  9. New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

    Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith; Wang, Shen; Sina, Mahsa; Lu, Bingyu; Bouwer, James; Xu, Wu [Energy; Xiao, Jie [Energy; Zhang, Ji-Guang [Energy; Liu, Jun [Energy; Meng, Ying Shirley

    2017-11-02

    Lithium metal has been considered as the “holy grail” anode material for rechargeable batteries though the dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanied solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and meso- structures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)- electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nano scale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation dominated EDLi (five minutes at 0.5 mA cm-2) is amorphous while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials, but it yields crucial structural information of the EDLi evolution with and without electrolyte additives.

  10. Application of silver vanadate solid electrolyte mixed with Al2O3 in Ag/I2 batteries

    Abdul Karim bin Arof.

    1993-01-01

    The glassy silver vanadate electrolyte of the composition 70AgI-20Ag20-10V205 was added with Al2O3 in varying percentages to form several physical mixtures that will be used to fabricate several solid stare electrochemical cells in order to study the influence of the dispersoid on the silver vanadate cells internal resistance and lifetime of the silver vanadate cells. The internal resistance of the cells increased on addition of Al2O3 but the cell with the mixture of Al2O3 and electrolyte in the weight ratio 2:3 has the lowest internal resistance. The increase in the internal resistance of the cell is attributed to the insulating nature of Al2O3. Although the internal resistance of the cell increased, it was observed that the time needed for the cell potential to drop to 400 mV at a constant discharge current of 30 uA increase in discharge lifetime was also observed when a second cell of the same mixed electrolyte constituents was discharged at 40 uA current drain. We have attempted to explain the increase in discharge lifetime in terms of the space charge layer developed between the insulator and the ionic conductor which results in a dipole region across which a potential difference is developed. This potential difference is responsible in prolonging the discharge lifetime of the cells

  11. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

    Chan, Candace K.

    2009-04-01

    Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte interphase (SEI) formed on silicon due to the reduction of the electrolyte. Given that a good, passivating SEI layer plays such a crucial role in graphite anodes, we have characterized the surface composition and morphology of the SEI formed on the SiNWs using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). We have found that the SEI is composed of reduction products similar to that found on graphite electrodes, with Li2CO3 as an important component. Combined with electrochemical impedance spectroscopy, the results were used to determine the optimal cycling parameters for good cycling. The role of the native SiO2 as well as the effect of the surface area of the SiNWs on reactivity with the electrolyte were also addressed. © 2009 Elsevier B.V. All rights reserved.

  12. Electron transfer through solid-electrolyte-interphase layers formed on Si anodes of Li-ion batteries

    Benitez, L.; Cristancho, D.; Seminario, J.M.; Martinez de la Hoz, J.M.; Balbuena, P.B.

    2014-01-01

    Solid-electrolyte interphase (SEI) films are formed on the electrode surfaces due to aggregation of products of reduction or oxidation of the electrolyte. These films may grow to thicknesses in the order of 50-100 nm and contain a variety of organic and inorganic products but their structure is not well defined. Although in some cases the films exert a passivating role, this is not always the case, and these phenomena are particularly more complex on Silicon anodes due to swelling and cracking of the electrode during lithiation and delithiation. Since the driving force for SEI growth is electron transfer, it is important to understand how electron transfer may keep occurring through the heterogeneous film once the bare electron surface is covered. Here we introduce a novel approach for studying electron transfer through model films and show preliminary results for the analysis of electron transfer through model composite interfacial systems integrated by electrode/SEI layer/electrolyte. Ab initio molecular dynamics simulations are used to identify deposition of SEI components, and a density functional theory/Green's function approach is utilized for characterizing electron transfer. Three degrees of lithiation are modeled for the electrodes, the SEI film is composed by LiF or Li 2 O, and the ethylene carbonate reduction is studied. An applied potential is used as driving force for the leakage current, which is evaluated as a function of the applied potential. Comparative analyses are done for LiF and Li 2 O model SEI layers

  13. In-situ Multimodal Imaging and Spectroscopy of Mg Electrodeposition at Electrode-Electrolyte Interfaces

    Wu, Yimin A.; Yin, Zuwei; Farmand, Maryam; Yu, Young-Sang; Shapiro, David A.; Liao, Hong-Gang; Liang, Wen-I.; Chu, Ying-Hao; Zheng, Haimei

    2017-02-01

    We report the study of Mg cathodic electrochemical deposition on Ti and Au electrode using a multimodal approach by examining the sample area in-situ using liquid cell transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy (XAS). Magnesium Aluminum Chloride Complex was synthesized and utilized as electrolyte, where non-reversible features during in situ charging-discharging cycles were observed. During charging, a uniform Mg film was deposited on the electrode, which is consistent with the intrinsic non-dendritic nature of Mg deposition in Mg ion batteries. The Mg thin film was not dissolvable during the following discharge process. We found that such Mg thin film is hexacoordinated Mg compounds by in-situ STXM and XAS. This study provides insights on the non-reversibility issue and failure mechanism of Mg ion batteries. Also, our method provides a novel generic method to understand the in situ battery chemistry without any further sample processing, which can preserve the original nature of battery materials or electrodeposited materials. This multimodal in situ imaging and spectroscopy provides many opportunities to attack complex problems that span orders of magnitude in length and time scale, which can be applied to a broad range of the energy storage systems.

  14. Point of zero potential of single-crystal electrode/inert electrolyte interface.

    Zarzycki, Piotr; Preočanin, Tajana

    2012-03-15

    Most of the environmentally important processes occur at the specific hydrated mineral faces. Their rates and mechanisms are in part controlled by the interfacial electrostatics, which can be quantitatively described by the point of zero potential (PZP). Unfortunately, the PZP value of specific crystal face is very difficult to be experimentally determined. Here we show that PZP can be extracted from a single-crystal electrode potentiometric titration, assuming the stable electrochemical cell resistivity and lack of specific electrolyte ions sorption. Our method is based on determining a common intersection point of the electrochemical cell electromotive force at various ionic strengths, and it is illustrated for a few selected surfaces of rutile, hematite, silver chloride, and bromide monocrystals. In the case of metal oxides, we have observed the higher PZP values than those theoretically predicted using the MultiSite Complexation Model (MUSIC), that is, 8.4 for (001) hematite (MUSIC-predicted ~6), 8.7 for (110) rutile (MUSIC-predicted ~6), and about 7 for (001) rutile (MUSIC-predicted 6.6). In the case of silver halides, the order of estimated PZP values (6.4 for AgClsoils and groundwaters. Copyright © 2012 Elsevier Inc. All rights reserved.

  15. Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

    Kim, Jun Young [Department of Polymer Science and Engineering, SungKyunKwan University, Suwon, Kyunggi-do 440-746 (Korea); Functional Polymer Lab., Korea Institute of Science and Technology, Seoul 136-791 (Korea); Kim, Tae Ho [Department of Polymer Science and Engineering, SungKyunKwan University, Suwon, Kyunggi-do 440-746 (Korea); Kim, Dong Young; Park, Nam-Gyu [Energy Materials Research Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea); Ahn, Kwang-Duk [Functional Polymer Lab., Korea Institute of Science and Technology, Seoul 136-791 (Korea)

    2008-01-03

    Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4-tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm{sup -2}). (author)

  16. Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

    Kim, Jun Young; Kim, Tae Ho; Kim, Dong Young; Park, Nam-Gyu; Ahn, Kwang-Duk

    Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4- tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm -2).

  17. Charge Control And Wettability Alteration At Solid-liquid Interfaces

    Mugele, Friedrich Gunther; Sîretanu, Igor; Kumar, Naveen; Bera, B.; Wang, Lei; Maestro, Armando; Duits, Michael H.G.; van den Ende, Henricus T.M.; Collins, I

    2014-01-01

    Most solid surfaces acquire a finite surface charge upon exposure to aqueous environments due to desorption and/or adsorption of ionic species. The resulting electrostatic forces play a crucial role in many fields of science, including colloidal stability, self-assembly, wetting, and biophysics as

  18. Preparation and characterization of novel solid polymer blend electrolytes based on poly (vinyl pyrrolidone) with various concentrations of lithium perchlorate

    Kesavan, K., E-mail: kesavanphysics@gmail.com [School of Physics, Alagappa University, Karaikudi 630003, Tamilnadu (India); Mathew, Chithra M. [School of Physics, Alagappa University, Karaikudi 630003, Tamilnadu (India); Rajendran, S., E-mail: sraj54@yahoo.com [School of Physics, Alagappa University, Karaikudi 630003, Tamilnadu (India); Ulaganathan, M. [Energy Research Institute @ NTU, Nanyang Technological University, Singapore 637 553 (Singapore)

    2014-05-01

    Graphical abstract: - Highlights: • The maximum ionic conductivity value was found to be 0.2307 × 10{sup −5} S cm{sup −1} for PEO(90 wt%)/PVP(10 wt%)/LiClO{sub 4}(8 wt%) based electrolyte at room temperature. • The structural and functional groups were studied by XRD and FTIR. • Both direct and indirect optical band gap values were evaluated from UV–vis analysis. • The change in viscosity of the polymer electrolytes was studied by photoluminescence spectra. - Abstract: A series of conducting novel solid polymer blend electrolytes (SPE) based on the fixed ratio of poly (ethylene oxide)/poly (vinyl pyrrolidone) (PEO/PVP) and various concentrations of salt lithium perchlorate (LiClO{sub 4}) were prepared by solvent casting technique. Structural and complex formation of the prepared electrolytes was confirmed by X-ray diffraction and FTIR analyses. The maximum ionic conductivity value was found to be 0.2307 × 10{sup −5} S cm{sup −1} for 8 wt% of LiClO{sub 4} based system at ambient temperature. Thermal stability of the present system was studied by thermo gravimetric/differential thermal analysis (TG/DTA). Surface morphology of the sample having maximum ionic conductivity was studied by atomic force microscope (AFM). Optical properties like direct and indirect band gaps were investigated by UV–vis analysis. The change in viscosity of the polymer complexes were also identified using photoluminescence emission spectra. PEO(90)/PVP(10)/LiClO{sub 4}(8) has the highest conductivity which is supported by the lowest optical band gap and lowest intensity in photoluminescence spectroscopy near 400–450 nm.

  19. Alkali-Resistant Quasi-Solid-State Electrolyte for Stretchable Supercapacitors.

    Tang, Qianqiu; Wang, Wenqiang; Wang, Gengchao

    2016-10-05

    Research on stretchable energy-storage devices has been motivated by elastic electronics, and considerable research efforts have been devoted to the development of stretchable electrodes. However, stretchable electrolytes, another critical component in stretchable devices, have earned quite little attention, especially the alkali-resistant ones. Here, we reported a novel stretchable alkali-resistant electrolyte made of a polyolefin elastomer porous membrane supported potassium hydroxide-potassium polyacrylate (POE@KOH-PAAK). The as-prepared electrolyte shows a negligible plastic deformation even after 1000 stretching cycles at a strain of 150% as well as a high conductivity of 0.14 S cm -1 . It also exhibits excellent alkali resistance, which shows no obvious degradation of the mechanical performance after immersion in 2 M KOH for up to 2 weeks. To demonstrate its good properties, a high-performance stretchable supercapacitor is assembled using a carbon-nanotube-film-supported NiCo 2 O 4 (CNT@NiCo 2 O 4 ) as the cathode and Fe 2 O 3 (CNT@Fe 2 O 3 ) as the anode, proving great application promise of the stretchable alkali-resistant electrolyte in stretchable energy-storage devices.

  20. Estimation of energy density of Li-S batteries with liquid and solid electrolytes

    Li, Chunmei; Zhang, Heng; Otaegui, Laida; Singh, Gurpreet; Armand, Michel; Rodriguez-Martinez, Lide M.

    2016-09-01

    With the exponential growth of technology in mobile devices and the rapid expansion of electric vehicles into the market, it appears that the energy density of the state-of-the-art Li-ion batteries (LIBs) cannot satisfy the practical requirements. Sulfur has been one of the best cathode material choices due to its high charge storage (1675 mAh g-1), natural abundance and easy accessibility. In this paper, calculations are performed for different cell design parameters such as the active material loading, the amount/thickness of electrolyte, the sulfur utilization, etc. to predict the energy density of Li-S cells based on liquid, polymeric and ceramic electrolytes. It demonstrates that Li-S battery is most likely to be competitive in gravimetric energy density, but not volumetric energy density, with current technology, when comparing with LIBs. Furthermore, the cells with polymer and thin ceramic electrolytes show promising potential in terms of high gravimetric energy density, especially the cells with the polymer electrolyte. This estimation study of Li-S energy density can be used as a good guidance for controlling the key design parameters in order to get desirable energy density at cell-level.

  1. Applications of Computed Tomography to Evaluate Cellular Solid Interfaces

    Maisano, Josephine; Marse, Daryl J.; Schilling, Paul J.

    2008-01-01

    The major morphological features - foam cells, voids, knit lines, and the bondline interface were evaluated. The features identified by micro-CT correlate well to those observed by SEM. 3D reconstructions yielded volumetric dimensions for large voids (max 30 mm). Internal voids and groupings of smaller cells at the bondline are concluded to be the cause of the indications noted during the NDE prescreening process.

  2. A multiphase electrokinetic flow model for electrolytes with liquid/liquid interfaces

    Berry, J.D., E-mail: joe.d.berry@gmail.com; Davidson, M.R., E-mail: m.davidson@unimelb.edu.au; Harvie, D.J.E., E-mail: daltonh@unimelb.edu.au

    2013-10-15

    A numerical model for electrokinetic flow of multiphase systems with deformable interfaces is presented, based on a combined level set-volume of fluid technique. A new feature is a multiphase formulation of the Nernst–Planck transport equation for advection, diffusion and conduction of individual charge carrier species that ensures their conservation in each fluid phase. The numerical model is validated against the analytical results of Zholkovskij et al. (2002) [1], and results for the problem of two drops coalescing in the presence of mobile charge carriers are presented. The time taken for two drops containing ions to coalesce decreases with increasing ion concentration.

  3. Graphene/activated carbon supercapacitors with sulfonated-polyetheretherketone as solid-state electrolyte and multifunctional binder

    Chen, Y.-R.; Chiu, K.-F.; Lin, H. C.; Chen, C.-L.; Hsieh, C. Y.; Tsai, C. B.; Chu, B. T. T.

    2014-11-01

    Sulfonated polyetheretherketone (SPEEK) has been synthesised by sulphonation process and used as the solid-state electrolyte, binder and surfactant for supercapacitors. Reduced graphene dispersed by SPEEK is used as a high-efficiency conducting additive in solid-state supercapacitors. It is found that SPEEK can improve the stability of the reduced graphene dispersion significantly, and therefore, the solid-state supercapacitors show a large decrease in IR drop and charge-transfer resistance (Rct), resulting in a higher rate capability. The solid-state supercapacitors with the activated carbon/reduced graphene/SPEEK/electrode can be operated from 1 to 8 A/g and exhibit capacity retention of 93%. The noteworthy is more than twice higher value for capacity retention by comparison with the solid-state supercapacitors using activated carbon/reduced graphene/PVDF electrode (capacity retention is 36%). The cell of reduced graphene with SPEEK can be cycled over 5000 times at 5 A/g with no capacitance fading.

  4. Influence of process parameters to composite interface organization and performance of liquid/solid bimetal

    Rong, S F; Zhu, Y C; Wu, Y H; Yang, P H; Duan, X L; Zhou, H T

    2015-01-01

    The liquid-solid composite technique was used to prepare the high carbon high chromium steel (HCHCS) and low alloy steel (LCS) bimetal composite materials by means of insert casting method. The influence of some process parameters such as liquid-solid ratio, preheat temperature, pouring temperature on the interface microstructure and mechanical properties were studied. Interface microstructure and element distribution were analyzed. The results show that the interface microstructure becomes better, and bonding area becomes thicker with the increase of the volume of liquid to solid ratio, preheating temperature and pouring temperature. When the liquid-solid ratio is 8:1, the preheating temperature is 300 °C and the pouring temperature is 1565 °C, a good metallurgical bonding area without any hole can be obtained with the interface combination of diffusion and fusion. The composite interface structure was composed of a core material diffusion layer, a cooling solidification layer, a direction growth layer and some cell particles. The elements of C, Cr and Mn diffuse from the HCHCS side to the alloy steel side. The microhardness increased in the gradient from the LCS side to the HCHCS. The microhardness of the interface is significantly higher than that of LCS. (paper)

  5. Voltammetry for the charge transfer at two immiscible electrolyte solutions interface

    Kihara, S.; Suzuki, M.; Maeda, K.; Ogura, K.; Matsui, M.; Yoshida, Z.

    1989-01-01

    The voltammetry for the charge transfer (VCT) at the interface of immicible solutions is a very powerful method for understanding the dynamic features of the charge transfer because of its unmatched advantage that the transfer energy and the number of charges transferred can be measured simultaneously and in situ. In the present paper, several novel systems for electron transfer are outlined, and the following topics are discussed based on results obtained by the current scan polarography at the solution dropping electrode developed as a technique for VCT: the relation between the half-wave potential in VCT for ion transfer and the characteristics of the ion transferred; the relation between the half-wave potential in VCT for electron transfer and the electrochemical nature of a redox couple added in water and that added in organic solution; and the ion transfer through a liquid membrane promoted by electron transfer. Observations are presented and discussion is made on the characteristics of ion transfer polarograms, those of electron transfer polarograms, and ion transfer promoted by electron transfer at a liquid/membrane interface. (N.K.)

  6. Oxides with polyatomic anions considered as new electrolyte materials for solid oxide fuel cells (SOFCs)

    Bin Hassan, Oskar Hasdinor

    2010-10-21

    Materials with Polyatomic anions of [Al{sub 2}O{sub 7}]{sup -8}, [Ti{sub 2}O{sub 8}]{sup -8} and [P{sub 2}O{sub 7}]{sup -4} were investigated with respect to their ionic conductivity properties as well as its thermal expansion properties with the aim to use them as SOFCs electrolytes. The polyatomic anion groups selected from the oxy-cuspidine family of Gd{sub 4}Al{sub 2}O{sub 9} and Gd{sub 4}Ti{sub 2}O{sub 10} as well as from pyrophosphate SnP{sub 2}O{sub 7}. The pure oxy-cuspidine Gd{sub 4}Al{sub 2}O{sub 9}, the series of Gd{sub 4}Al{sub 2-x}Mg{sub x}O{sub 9-x/2} with x=0.10-1.0 and Gd{sub 4-x}M{sub x}Al{sub 2}O{sub 9-x/2} (M=Ca, Sr) with x = 0.05-0.5 were prepared successfully by the citrate complexation method. All samples showed the crystal structure of monoclinic oxycuspidine structure with space group of P2{sub 1/c} and Z=4. No solid solution was observed for Gd{sub 4}Al{sub 2-x}Mg{sub x}O{sub 9-x/2} where additional phases of Gd{sub 2}O{sub 3} and MgO were presence. XRD semiquantitative analysis together with SEM-EDX analysis revealed that Mg{sup 2+} was not able to substitute the Al{sup 3+} ions even at low Mg{sup 2+} concentration. The solid solution limit of Gd{sub 4-x}Ca{sub x}Al{sub 2}O{sub 9-x/2} and Gd{sub 4-x}Sr{sub x}Al{sub 2}O{sub 9-x/2} was determined between 0.05-0.10 and 0.01-0.05 mol for Ca and Sr, respectively. Beyond the substitution limit Gd{sub 4}Al{sub 2}O{sub 9}, GdAlO{sub 3} and SrGd{sub 2}Al{sub 2}O{sub 7} appeared as additional phases. The highest electrical conductivity obtained at 900 C yielded {sigma}= 1.49 x 10{sup -4}Scm{sup -1} for Gd{sub 3.95}Ca{sub 0.05}Al{sub 2}O{sub 8.98}. In comparison, the conductivity of pure Gd{sub 4}Al{sub 2}O{sub 9} was {sigma}= 1.73 x 10{sup -5} Scm{sup -1}. The conductivities determined were in a similar range as those of other cuspidine materials investigated previously. The thermal expansion coefficient of Gd{sub 4}Al{sub 2}O{sub 9} at 1000 C was 7.4 x 10{sup -6}K{sup -1}. The earlier reported

  7. Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

    Harun, Fatin; Chan, Chin Han; Winie, Tan [Faculty of Applied Sciences, UniversitiTeknologi MARA (UiTM), Shah Alam, 40450 Selangor Darul Ehsan (Malaysia); Sim, Lai Har; Zainal, Nurul Fatahah Asyqin [Center of Foundation Studies, PuncakAlam Campus, UniversitiTeknologi MARA, 40430 Selangor Darul Ehsan (Malaysia)

    2015-08-28

    Effect of epoxide content on the thermal and conductivity properties of epoxidized natural rubber (ENR) solid polymer nanocomposite electrolytes was investigated. Commercial available epoxidized natural rubber having 25 (ENR25) and 50 mole% (ENR50) epoxide, respectively were incorporated with lithium perchlorate (LiClO{sub 4}) salt and titanium dioxide (TiO{sub 2}) nanofiller via solution casting method. The solid polymer nanocomposite electrolytes were characterized by differential scanning calorimetry (DSC) and impedance spectroscopy (IS) for their thermal properties and conductivity, respectively. It was evident that introduction of LiClO{sub 4} causes a greater increase in glass transition temperature (T{sub g}) and ionic conductivity of ENR50 as compared to ENR25. Upon addition of TiO{sub 2} in ENR/LiClO{sub 4} system, a remarkable T{sub g} elevation was observed for both ENRs where ENR50 reveals a more pronounced changes. It is interesting to note that they exhibit different phenomenon in ionic conductivity with TiO{sub 2} loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.

  8. All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

    Higa, Mitsuru; Fujino, Yukiko; Koumoto, Taihei; Kitani, Ryousuke; Egashira, Satsuki

    2005-01-01

    We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM 9 whose POEM content = 51 wt% shows 2 x 10 -5 S/cm at 30 deg. C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte

  9. Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

    Black, Hayden T; Harrison, Katharine Lee

    2016-10-01

    The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Li+ ions, and that the mobility of polymer associated Li+ was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li+ within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.

  10. Development of Lithium Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries

    Ryoji Inada

    2016-07-01

    Full Text Available All-solid-state lithium-ion battery (LiB is expected as one of the next generation energy storage devices because of their high energy density, high safety and excellent cycle stability. Although oxide-based solid electrolyte materials have rather lower conductivity and poor deformability than sulfide-based one, they have other advantages such as their chemical stability and easiness for handling. Among the various oxide-based SEs, lithium stuffed garnet-type oxide with the formula of Li7La3Zr2O12 (LLZ have been widely studied because of their high conductivity above 10-4 Scm-1 at room temperature, excellent thermal performance and stability against Li metal anode.Here, we present our recent progress for the development of garnet-type solid electrolytes with high conductivity by simultaneous substitution of Ta5+ into Zr4+ site and Ba2+ into La3+ site in LLZ. Li+ concentration was fixed to 6.5 per chemical formulae, so that the formulae of our Li garnet-type oxide is expressed as Li6.5La3-xBaxZr1.5-xTa0.5+xO12 (LLBZT and Ba contents x are changed from 0 to 0.3. As results, all LLBZT samples have cubic garnet structure without containing any secondary phases. The lattice parameters of LLBZT decrease with increasing Ba2+ contents x < 0.10 while increase with x from 0.10 to 0.30, possibly due to the simultaneous change of Ba2+ and Ta5+ substitution levels. Relative densities of LLBZT are in the range between 89% and 93% and not influenced so much by the compositions. From AC impedance spectroscopy measurements, the total (bulk + grain conductivity at 27ºC of LLBZT shows its maximum value of 8.34 x 10-4 S cm-1 at x = 0.10, which is slightly higher than the conductivity (= 7.94 x 10-4 S cm-1 of LLZT without substituting Ba (x = 0. Activation energy of the conductivity tends to become lower by Ba substation, while excess Ba substitution degrades the conductivity in LLBZT. LLBZT has wide electrochemical potential window of 0-6 V vs. Li+/Li and

  11. Role of perfluoropolyether-based electrolytes in lithium metal batteries: Implication for suppressed Al current collector corrosion and the stability of Li metal/electrolytes interfaces

    Cong, Lina; Liu, Jia; Armand, Michel; Mauger, Alain; Julien, Christian M.; Xie, Haiming; Sun, Liqun

    2018-03-01

    The development of safe and high performance lithium metal batteries represents a major technological challenge for this new century. Historically, intrinsic instabilities of conventional liquid organic electrolytes induced battery failures and safety issues that hinder the practical utilization of advanced rechargeable lithium metal batteries. Herein, we report a multifunctional perfluoropolyether-based liquid polymer electrolyte (PFPE-MC/LiTFSI), presenting a unique "anion-solvent" interaction. This interaction optimizes the interfacial chemistry of lithium metal batteries, which effectively inhibits the corrosion of aluminum current collectors, suppresses lithium dendrite growth, and also facilitates the formation of a thin and stable SEI layer on Li anode. Even at a high current density of 0.7 mA cm-2, the lithium dendrites do not form after 1360 h of continuous operation. The LiFePO4|PFPE-MC/LiTFSI|Li cell delivers a stable cycling performance with over 99.9% columbic efficiency either at ambient temperature or high temperature, which is significantly superior to those using traditional carbonate electrolytes. In addition, PFPE-MC/LiTFSI electrolyte also possesses eye-catching properties, such as being non-flammable, non-volatile, non-hygroscopic, and existing in the liquid state between -90 °C and 200 °C, which further ensures the high safety of the lithium metal batteries, making this electrolyte promising for the development of high energy lithium metal batteries.

  12. A study of ion exchange at the poly(butyl viologen)-electrolyte interface by SECM

    Hsu, Chih-Yu.; Vasantha, V.S. [Department of Chemical Engineering, National Taiwan University, Taipei 10617 (China); Ho, Kuo-Chuan [Department of Chemical Engineering, National Taiwan University, Taipei 10617 (China); Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617 (China)

    2008-09-01

    In this work, the ion exchange characteristics of poly(butyl viologen) (PBV) thin films on a platinum electrode has been investigated by cyclic voltammetric (CV) scans. Since ferrocyanide anions (Fe(CN){sub 6}{sup 4-}) were added during the polymerization of the PBV thin-film for its stability, Fe(CN){sub 6}{sup 4-} could form charge transfer complex with monomer and co-deposited with polymer. Scanning electrochemical microscopy (SECM) was used to probe the released Fe(CN){sub 6}{sup 4-} ions from PBV film with Os(bpy){sub 3}Cl{sub 2} as a mediator for the approaching process in 0.5 M KCl medium. Mass changes during the redox process of the film were also monitored in-situ by electrochemical quartz crystal microbalance (EQCM). The ion exchange and transport behavior was observed during CV cycling of the film of the SECM and EQCM. The insertion and extraction of anions were found to be potential-dependence. Moreover, the decrease in tip current of released Fe(CN){sub 6}{sup 4-} with increasing cycle number accounted for the ion exchange between Fe(CN){sub 6}{sup 4-} and Cl{sup -} in the KCl electrolyte. However, the Fe(CN){sub 6}{sup 4-}/Fe(CN){sub 6}{sup 3-} redox couple was found to be highly stable between 0.0 and 0.5 V (vs. Ag/AgCl/saturated KCl) in the phosphate buffer solution. Therefore, the electrochemical property of Fe(CN){sub 6}{sup 4-}/Fe(CN){sub 6}{sup 3-} redox couple was studied at different scan rates using CV technique. The peak currents were directly proportional to the scan rate as predicted for a surface confined diffusionless system. The surface coverage ({gamma}) and the concentration of Fe(CN){sub 6}{sup 4-} were determined to be 1.88 x 10{sup -8} mol/cm{sup 2} and 0.641 mol/dm{sup 3}, respectively. By neglecting cations incorporation during redox reaction of the PBV film and also based on the results obtained from energy-dispersive X-ray spectroscopy for the films of as-deposited, reduced and oxidized states, an ion exchange mechanism was

  13. Chemical compatibility of alternative perovskite oxide SOFC cathodes with doped lanthanum gallate solid electrolyte

    Kostogloudis, G.C.; Ftikos, C. [Laboratory of Inorganic Materials Technology, Department of Chemical Engineering, National Technical University of Athens, 9 Heroon Polytechniou Str., Zografou Campus, GR-15780 Athens (Greece); Ahmad-Khanlou, A.; Naoumidis, A.; Stoever, D. [Research Centre Juelich, Institute for Materials and Processes in Energy Systems IWV1, D-52425 Juelich (Germany)

    2000-10-01

    This paper reports on the investigations of the chemical compatibility between SOFC cathode materials with compositions Pr{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Mn{sub 0.8}O{sub 3-{delta}}, Pr{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3-{delta}}, Pr{sub 0.8}Sr{sub 0.2}Co{sub 0.3}Mn{sub 0.7}O{sub 3-{delta}} and Pr{sub 0.75}Sr{sub 0.2}Co{sub 0.2}Mn{sub 0.8}O{sub 3-{delta}} and the electrolyte materials with compositions La{sub 0.8}Sr{sub 0.2}Ga{sub 0.9}Mg{sub 0.1}O{sub 3-{delta}}, and La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{delta}}. The lanthanum gallate electrolyte with 20 mol.% Sr contained two additional phases, namely, LaSrGa{sub 3}O{sub 7} and LaSrGaO{sub 4}, while that with 10 mol.% Sr was formed in nearly single phase. Two types of experiments were performed: (a) reactivity experiments of powder mixtures and (b) diffusion experiments in cathode/electrolyte double-layer pellets. No reaction products were detected by XRD. High Co diffusion into the electrolyte was identified with SEM/EDX in all diffusion experiments examined. The transition metals diffuse in the order Mnelectrolyte La{sub 0.8}Sr{sub 0.2}Ga{sub 0.9}Mg{sub 0.1}O{sub 3-{delta}} caused the destabilisation and disappearance of the second phases in the interdiffusion zone. In the case of the A-site deficient cathode, the formation of LaSrGa{sub 3}O{sub 7} second phase was identified on the electrolyte side, near the interdiffusion zone.

  14. Cellular interface morphologies in directional solidification. III - The effects of heat transfer and solid diffusivity

    Ungar, Lyle H.; Bennett, Mark J.; Brown, Robert A.

    1985-01-01

    The shape and stability of two-dimensional finite-amplitude cellular interfaces arising during directional solidification are compared for several solidification models that account differently for latent heat released at the interface, unequal thermal conductivities of melt and solid, and solute diffusivity in the solid. Finite-element analysis and computer-implemented perturbation methods are used to analyze the families of steadily growing cellular forms that evolve from the planar state. In all models a secondary bifurcation between different families of finite-amplitude cells exists that halves the spatial wavelength of the stable interface. The quantitative location of this transition is very dependent on the details of the model. Large amounts of solute diffusion in the solid retard the growth of large-amplitude cells.

  15. The structure of the solid-liquid interface: atomic size effect; La structure de l'interface solide-liquide: effet de taille atomique

    Geysermans, P.; Pontikis, V. [Centre National de la Recherche Scientifique (CNRS), 94 - Vitry-sur-Seine (France). Centre d' Etudes de Chimie Metallurgique

    2002-09-01

    The atomic structure of the solid-liquid heterophase interface was investigated by using molecular dynamics. Two kinds of systems were studied; the first one was crystalline copper with (100) and (111) surface terminations in contact with liquid aluminium, while in the second one the interface was modelled by two systems in contact made of Lennard-Jones particles with different size ({sigma}) and energy ({epsilon}) parameters. We found that at the interface the liquid was layered whatever the crystallographic orientation of the surface. The layering of the liquid is still preserved when the ratio of particles sites ({chi}={sigma}{sub 1}/{sigma}{sub 2}) changes while an epitaxial relationship is always found between the crystal and the first liquid layer. The average density of the latter is closely related to the {chi} value. (authors)

  16. All-solid-state lithium batteries – The Mg2FeH6-electrode LiBH4-electrolyte system

    Huen, Priscilla; Ravnsbæk, Dorthe B.

    2018-01-01

    The complex hydride Mg2FeH6 is investigated as conversion type anode in a solid-state all-hydride Li-battery employing LiBH4 as solid-state electrolyte. In the solid-state battery, Mg2FeH6 exhibits improvements in the capacity retention and initial Coulombic efficiency of > 3 and > 2.5 times......, respectively, compared to the conventional liquid-electrolyte battery. Through investigations of the conversion reactions of Mg2FeH6, formation of MgH2 as intermediate in the conversion to Mg is discovered the first time. In addition, the effect of mixing procedure for the electrode-electrolyte composite...... on the battery performance is discussed....

  17. Ab initio investigation of ground-states and ionic motion in particular in zirconia-based solid-oxide electrolytes

    Hirschfeld, Julian Arndt

    2012-01-01

    Electrolytes with high ionic conductivity at lower temperatures are the prerequisite for the success of Solid Oxide Fuel Cells (SOFC). One candidate is doped zirconia. In the past, the electrical resistance of zirconia based SOFC electrolytes has mainly been decreased by reducing its thickness. But there are limits to reducing the thickness and one can say that nowadays the normal ways are basically exhausted to further enhance the conductivity of well-known electrolyte materials. Hence, new approaches need to be found to discover windows of enhanced ionic conductivity. This can be achieved by understanding the quantum-mechanical oxygen transport in unconventional configurations of doped zirconia. Therefore, such an understanding is of fundamental importance. In this thesis two approaches are pursued, the investigation of the strain dependent ionic migration in zirconia based electrolytes and the designing of an electrolyte material structure with enhanced and strongly anisotropic ionic conductivity. The first approach expands the elementary understanding of oxygen migration in oxide lattices. The migration barrier of the oxygen ion jumps in zirconia is determined by applying the Density Functional Theory (DFT) calculations in connection with the Nudged Elastic Band (NEB) method. These computations show an unexpected window of decreased migration barriers at high compressive strains. Similar to other publications a decrease in the migration barrier for expansive strain is observed. But, in addition, a migration barrier decrease under high compressive strains is found beyond a maximal height of the migration barrier. A simple analytic model offers an explanation. The drop of the migration barrier at high compressions originates from the elevation of the ground-state energy. This means: Increasing ground state energies becomes an interesting alternative to facilitate ionic mobility. The second approach is based on the idea, that actually, only in the direction of ion

  18. Ab initio investigation of ground-states and ionic motion in particular in zirconia-based solid-oxide electrolytes

    Hirschfeld, Julian Arndt

    2012-12-11

    Electrolytes with high ionic conductivity at lower temperatures are the prerequisite for the success of Solid Oxide Fuel Cells (SOFC). One candidate is doped zirconia. In the past, the electrical resistance of zirconia based SOFC electrolytes has mainly been decreased by reducing its thickness. But there are limits to reducing the thickness and one can say that nowadays the normal ways are basically exhausted to further enhance the conductivity of well-known electrolyte materials. Hence, new approaches need to be found to discover windows of enhanced ionic conductivity. This can be achieved by understanding the quantum-mechanical oxygen transport in unconventional configurations of doped zirconia. Therefore, such an understanding is of fundamental importance. In this thesis two approaches are pursued, the investigation of the strain dependent ionic migration in zirconia based electrolytes and the designing of an electrolyte material structure with enhanced and strongly anisotropic ionic conductivity. The first approach expands the elementary understanding of oxygen migration in oxide lattices. The migration barrier of the oxygen ion jumps in zirconia is determined by applying the Density Functional Theory (DFT) calculations in connection with the Nudged Elastic Band (NEB) method. These computations show an unexpected window of decreased migration barriers at high compressive strains. Similar to other publications a decrease in the migration barrier for expansive strain is observed. But, in addition, a migration barrier decrease under high compressive strains is found beyond a maximal height of the migration barrier. A simple analytic model offers an explanation. The drop of the migration barrier at high compressions originates from the elevation of the ground-state energy. This means: Increasing ground state energies becomes an interesting alternative to facilitate ionic mobility. The second approach is based on the idea, that actually, only in the direction of ion

  19. Measuring oxygen activity in liquid sodium with the use of solid electrolytes

    Jakes, D.; Skvor, F.

    1976-01-01

    Doped Y 2 O 3 (CaO or MgO up to 20 mol.%) was studied as a possible electrolyte. La 2 O 3 did not prove advantageous. The proposed version of an analyzer is described and the problems of calibration discussed. The reduction of the chemical gradient and the increase in material purity of the electrolytical tube significantly reduced the difference between the theoretical and experimentally obtained emf value, so that measurements may be carried out under these conditions even without calibration. The dependence of log σsub(T) on partial O 2 pressure is given for doped La and Y oxides at a temperature of 700 degC. (M.K.)

  20. Performance of Electrolyte Supported Solid Oxide Fuel Cells with STN Anodes

    Veltzé, Sune; Reddy Sudireddy, Bhaskar; Jørgensen, Peter Stanley

    2013-01-01

    In order to replace the state of the art Ni-cermet as SOFC anode, electrolyte supported cells comprising CGO/Ni infiltrated Nbdoped SrTiO3 anodes, and LSM/YSZ cathodes have been developed and tested as single 5 x 5 cm2 cells. The initial performance reached 0.4 W/cm2 at 850 C. Further tests under...