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Sample records for bazro3 solid electrolyte

  1. Characterization and Development of BaZrO3 /NiO Composites for use as Anodes in Proton Conducting SOFCs

    NASA Astrophysics Data System (ADS)

    Khan, Islam; Dillon, Kelly; Camata, Renato; Genau, Amber

    2015-04-01

    Solid oxide fuel cells (SOFCs) are devices that convert chemical energy to electrical energy directly through oxidation of the fuel. The basic structure of SOFCs consists of three parts: an anode and a cathode that are separated by an electrolyte. The focus of this work is on developing and characterizing anode materials for proton-conducting SOFCs which use ceramic material BaZrO3 as the electrolyte. These anodes are made using a BaZrO3 -Ni composite, known as a cermet (ceramic and metal), which has shown potential as anode materials for these devices. The conventional method for making BaZrO3 -Ni cermets consist of an intermediate stage composite material BaZrO3 -NiO that have a strong influence on the final properties of the anode. Composites consisting of the two phases, BaZrO3 and NiO, with different weight ratios were made into pellets (0.5-inch diameter) using a mechanical mixing method followed by sintering at high temperatures. Optical microscopy image analysis showed grain growth in both phases as well as presence of porosity. The effect of sintering temperature on the densification of the composite powders was analyzed and the results showed that higher temperature enabled higher densification of the composites. Electrochemical impedance spectroscopy indicated there are two factors that contribute to the impedance in the structure of the composite materials, and possible sources for each factor are discussed. UAB College of Arts and Sciences.

  2. Solid electrolytes

    DOEpatents

    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).

  3. REACTIVE FORCE FIELDS FOR Y-DOPED BaZrO3 ELECTROLYTE AND NI-ANODE. POTENTIAL CATHODE MATERIALS FOR APPLICATION IN PROTON CERAMIC FUEL CELLS

    SciTech Connect

    Boris Merinov; Adri van Duin; Sossina Haile; William A. Goddard III

    2004-10-30

    Based on quantum mechanical data obtained for the Y-doped BaZrO{sub 3} electrolyte and Ni-anode Reactive Force Field parameters have been developed for further molecular dynamics simulations of the proton diffusion and electrode/electrolyte interfaces. Electronic and atomic structures of different terminations of the (001) BaZrO{sub 3} surface have been studied using first-principles calculations. Several potential cathode materials for the Y-doped BaZrO{sub 3} system were synthesized via glycine nitrate combustion method. Of the five potential cathode materials examined BaZr{sub 0.40}Pr{sub 0.40}Gd{sub 0.20}O{sub 3} and BaZr{sub 0.60}Y{sub 0.20}Co{sub 0.20}O{sub 3} appear to be the most promising for further applications in proton ceramic fuel cells. Fuel cell test of a Y-doped BaZrO{sub 3} thin film using platinum ink for both electrodes have been performed. The obtained results shows that a robust method for fabricating crack-free thin membranes, as well as methods for sealing anode and cathode chambers, have successfully been developed.

  4. Solid polymer electrolyte compositions

    DOEpatents

    Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

    2001-01-01

    An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

  5. Solid electrolyte cell

    NASA Technical Reports Server (NTRS)

    Richter, R. (Inventor)

    1982-01-01

    A solid electrolyte cell including a body of solid ionized gas-conductive electrolyte having mutually spaced surfaces and on which is deposited a multiplicity of mutually spaced electrodes is described. Strips and of bare substances are interposed between electrodes, so that currents of ionic gas may be established between the electrodes via the bare strips, whereby electrical resistance for the cells is lowered and the gas conductivity is enhanced.

  6. Solid polymer electrolytes

    DOEpatents

    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.

  7. Solid polymer electrolytes

    DOEpatents

    Abraham, K.M.; Alamgir, M.; Choe, H.S.

    1995-12-12

    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}. 2 figs.

  8. Solid electrolyte structure

    DOEpatents

    Fraioli, Anthony V.

    1984-01-01

    A solid electrolyte structure for fuel cells and other electrochemical devices providing oxygen ion transfer by a multiplicity of exposed internal surfaces made of a composition containing an oxide of a multivalent transition metal and forming small pore-like passages sized to permit oxygen ion transfer while limiting the transfer of oxygen gas.

  9. Polaronic contributions to oxidation and hole conductivity in acceptor-doped BaZrO3

    NASA Astrophysics Data System (ADS)

    Lindman, Anders; Erhart, Paul; Wahnström, Göran

    2016-08-01

    Acceptor-doped perovskite oxides like BaZrO3 are showing great potential as materials for renewable energy technologies where hydrogen acts an energy carrier, such as solid oxide fuel cells and hydrogen separation membranes. While ionic transport in these materials has been investigated intensively, the electronic counterpart has received much less attention and further exploration in this field is required. Here, we use density functional theory (DFT) to study hole polarons and their impact on hole conductivity in Y-doped BaZrO3. Three different approaches have been used to remedy the self-interaction error of local and semilocal exchange-correlation functionals: DFT +U , pSIC-DFT, and hybrid functionals. Self-trapped holes are found to be energetically favorable by about -0.1 eV and the presence of yttrium results in further stabilization. Polaron migration is predicted to occur through intraoctahedral transfer and polaron rotational processes, which are associated with adiabatic barriers of about 0.1 eV. However, the rather small energies associated with polaron formation and migration suggest that the hole becomes delocalized and bandlike at elevated temperatures. These results together with an endothermic oxidation reaction [A. Lindman, P. Erhart, and G. Wahnström, Phys. Rev. B 91, 245114 (2015), 10.1103/PhysRevB.91.245114] yield a picture that is consistent with experimental data for the hole conductivity. The results we present here provide new insight into hole transport in acceptor-doped BaZrO3 and similar materials, which will be of value in the future development of sustainable technologies.

  10. Solid state electrolyte systems

    SciTech Connect

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R.

    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.

  11. Synthesis and luminescence study of BaZrO3:Eu3+ phosphor

    NASA Astrophysics Data System (ADS)

    Parganiha, Yogita; Kaur, Jagjeet; Dubey, Vikas; Shrivastava, Ravi; Dhoble, S. J.

    2015-12-01

    The phosphor of BaZrO3 doped with different concentration of Eu3+ ions (0.1, 0.5, 1 mol%) was prepared by solid-state reaction method. The prepared samples were characterized by X-ray diffraction (XRD), photoluminescence (PL) and thermoluminescence (TL) techniques. Analysis of XRD data shows the formation of perovskite structure of prepared phosphor. The room temperature excitation spectra vary with the Eu3+ concentration and consist of an intense charge transfer band and weak f-f transitions. The PL emission spectra, excited at 254 nm, consist of 4f-4f emission transitions from the 5D0 excited level of the Eu3+ ions to the 7FJ (J = 0-3) levels. The dependence of luminescence intensity on the Eu3+ concentration in BaZrO3:Eu3+ was studied. The present phosphor can act as single host for intense red emission for display devices application. Commission internationale de I'Eclairage techniques gives information about correlated color temperature and prominent emissions in PL emission spectra. Detail process and possible mechanism for PL and TL are studied and discussed in this paper. For the variable concentration of Eu3+ ions on PL studies shows the PL intensity increase with increasing the concentration of dopant. In TL glow curve the optimized concentration in 1 mol% for UV irradiated sample. The kinetic parameters were calculated by computerized glow curve deconvolution (CGCD) technique.

  12. Application of Organic Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    Sekido, S.

    1982-01-01

    If ions are considered to be solid material which transport electric charges, polymer materials can then be considered as organic solid electrolytes. The role of these electrolytes is discussed for (1) ion concentration sensors; (2) batteries using lithium as the cathode and a charge complex of organic material and iodine in the anode; and (3) elements applying electrical double layer capability.

  13. Solid polymer electrolyte lithium batteries

    DOEpatents

    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).

  14. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, M.; Abraham, K.M.

    1993-10-12

    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). 3 figures.

  15. Electric dipole sheets in BaTiO3/BaZrO3 superlattices

    NASA Astrophysics Data System (ADS)

    Jiang, Zhijun; Xu, Bin; Li, Fei; Wang, Dawei; Jia, C.-L.

    2015-01-01

    We investigate two-dimensional electric dipole sheets in the superlattice made of BaTiO3 and BaZrO3 using first-principles-based Monte Carlo simulations and density functional calculations. Electric dipole domains and complex patterns are observed and complex dipole structures with various symmetries (e.g., P m a 2 ,C m c m , and P m c 21 ) are further confirmed by density functional calculations, which are found to be almost degenerate in energy with the ferroelectric ground state of the A m m 2 symmetry, therefore strongly resembling magnetic sheets. More complex dipole patterns, including vortices and antivortices, are also observed, which may constitute the intermediate states that overcome the high-energy barrier of different polarization orientations previously predicted by A. I. Lebedev [Phys. Solid State 55, 1198 (2013), 10.1134/S1063783413060218]. We also show that such system possesses large electrostrictive effects that may be technologically important.

  16. Composite solid polymer electrolyte membranes

    SciTech Connect

    Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

    2006-05-30

    The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

  17. Composite solid polymer electrolyte membranes

    DOEpatents

    Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

    2001-06-19

    The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

  18. Pressure-induced improvement of grain boundary properties in yttrium-doped BaZrO3

    NASA Astrophysics Data System (ADS)

    Wu, Lei; Dai, LiDong; Li, HePing; Zhuang, YuKai; Liu, KaiXiang

    2016-09-01

    Yttrium-doped BaZrO3 (BZY) is a promising electrolyte for intermediate-temperature protonic ceramic fuel cells. However, BZY exhibits a high resistance because of the blocking effect of the grain boundaries. In this study, the effect of pressure on undoped and 5% yttrium-doped BaZrO3 (BZY0 and BZY5) were investigated at 0.45–24.01 GPa and 273–673 K with a diamond anvil cell. Their bulk, grain boundary, and total electrical conductivities were determined by impedance spectroscopy and direct-current resistance measurement. Both samples tended to show increasing electrical conductivity with increasing pressure, although each showed a discontinuous inflexion point (at ~14.54 GPa for BZY0 and at ~11.11 GPa for BZY5) indicating a phase transition from a cubic to a tetragonal structure. The samples showed a 3.43 GPa difference in the onset pressure of the structure change. Characteristic parameters, including space charge potential, relaxation frequency, and transport activation energy, were obtained before and after the phase transition. The results suggest that pressure significantly improves oxygen ion conduction in acceptor-doped perovskites oxides.

  19. Solid polymer electrolyte photovoltaic cell

    SciTech Connect

    Skotheim, T.; Lundstrom, I.

    1982-04-01

    Solid photoelectrochemical cells are described based on PEO-KI/I/sub 2/ electrolytes, n-Si/Pt/PPy photoanodes, and conductive tin-oxide glass counter electrodes. The performance of the present devices is limited by a high series resistance in the polymer film. 22 refs.

  20. Solid lithium-ion electrolyte

    DOEpatents

    Zhang, J.G.; Benson, D.K.; Tracy, C.E.

    1998-02-10

    The present invention relates to the composition of a solid lithium-ion electrolyte based on the Li{sub 2}O--CeO{sub 2}--SiO{sub 2} system having good transparent characteristics and high ion conductivity suitable for uses in lithium batteries, electrochromic devices and other electrochemical applications. 12 figs.

  1. Solid lithium-ion electrolyte

    DOEpatents

    Zhang, Ji-Guang; Benson, David K.; Tracy, C. Edwin

    1998-01-01

    The present invention relates to the composition of a solid lithium-ion electrolyte based on the Li.sub.2 O--CeO.sub.2 --SiO.sub.2 system having good transparent characteristics and high ion conductivity suitable for uses in lithium batteries, electrochromic devices and other electrochemical applications.

  2. Rechargeable solid polymer electrolyte battery cell

    DOEpatents

    Skotheim, Terji

    1985-01-01

    A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

  3. Solid electrolyte oxygen regeneration system

    NASA Technical Reports Server (NTRS)

    Shumar, J. W.; See, G. G.; Schubert, F. H.; Powell, J. D.

    1976-01-01

    A program to design, develop, fabricate and assemble a one-man, self-contained, solid electrolyte oxygen regeneration system (SX-1) incorporating solid electrolyte electrolyzer drums was completed. The SX-1 is a preprototype engineering model designed to produce 0.952 kg (2.1 lb)/day of breathable oxygen (O2) from the electrolysis of metabolic carbon dioxide (CO2) and water vapor. The CO2 supply rate was established based on the metabolic CO2 generation rate for one man of 0.998 kg (2.2 lb)/day. The water supply rate (0.254 kg (0.56 lb)/day) was designed to be sufficient to make up the difference between the 0.952 kg (2.1 lb)/day O2 generation specification and the O2 available through CO2 electrolysis, 0.726 kg (1.6 lb)/day. The SX-1 was successfully designed, fabricated and assembled. Design verification tests (DVT) or the CO Disproportionators, H2 separators, control instrumentation, monitor instrumentation, water feed mechanism were successfully completed. The erratic occurrence of electrolyzer drum leakage prevented the completion of the CO2 electrolyzer module and water electrolyzer module DVT's and also prevented the performance of SX-1 integrated testing. Further development work is required to improve the solid electrolyte cell high temperature seals.

  4. Preparation of BaZrO3 nanoparticles using a solvothermal reaction

    NASA Astrophysics Data System (ADS)

    Nakashima, Kouichi; Goto, Takayuki; Iwatsuki, Shougo; Kera, Masatoshi; Fujii, Ichiro; Wada, Satoshi

    2011-10-01

    Barium zirconate (BaZrO3) nanoparticles were successfully prepared by a solvothermal reaction. These were synthesized by a solvothermal method at 230°C -240°C for 18 h using a mixture solution of ethanol and 2-metoxy-thanol as the reaction medium. The prepared particles were collected using a centrifugal separator. The X-ray diffraction (XRD) measurement confirmed the presence of perovskite BaZrO3 particles. The scanning electron microscopy (SEM) observations revealed that the particles were composed of highly dispersed nanoparticles. The results of our study indicate that the addition of water to the reaction medium is an important for the preparation of a perovskite structure and control of the size of the BaZrO3.

  5. Dielectric response of BaZrO3/BaTiO3 superlattice

    NASA Astrophysics Data System (ADS)

    Wang, D.; Jiang, Z.

    2016-06-01

    We use the first-principles-based molecular dynamic approach to simulate dipolar dynamics of BaZrO3/BaTiO3 superlattice, and obtain its dielectric response. The dielectric response is decomposed into its compositional, as well as the in-plane and out-of-plane parts, which are then discussed in the context of chemical ordering of Zr/Ti ions. We reveal that, while the in-plane dielectric response of BaZrO3/BaTiO3 superlattice also shows dispersion over probing frequency, it shall not be categorized as relaxor.

  6. Solid-oxide fuel cell electrolyte

    DOEpatents

    Bloom, Ira D.; Hash, Mark C.; Krumpelt, Michael

    1993-01-01

    A solid-oxide electrolyte operable at between 600.degree. C. and 800.degree. C. and a method of producing the solid-oxide electrolyte are provided. The solid-oxide electrolyte comprises a combination of a compound having weak metal-oxygen interactions with a compound having stronger metal-oxygen interactions whereby the resulting combination has both strong and weak metal-oxygen interaction properties.

  7. Solid polymer electrolyte water electrolysis

    NASA Astrophysics Data System (ADS)

    Takenaka, H.; Torikai, E.; Kawami, Y.; Wakabayashi, N.

    Electrocatalyst performances and bonding to solid polymer electrolytes used for water electrolysis are investigated. Noble metal and metal alloy catalysts were plated to Nafion perfluorosulfonic acid polymer membranes without a binder by the use of a reducing agent solution held on the opposite side of the membrane from a metal salt solution. It was found that pretreatment of the membrane by hydrothermal treatment or gas plasma surface roughening improves metal adhesivity and thus reduces contact resistance between the membrane and the catalyst. Measurements of the constituents of cell voltage for platinum, rhodium and iridium anodes with platinum cathodes reveals that anodic overvoltage is a major component of voltage loss and depends on the type of electrocatalyst, being greatest for Pd and least for Ir. Ir and Ir-alloy electrodes, which were found to be the best catalysts for oxygen evolution, are found to have Tafel slopes of 0.04-0.06 V/decade. In a cell with a Pt cathode and Ir anode, cell voltage is observed to decrease with increasing temperature, reaching 1.56-1.59 V at a current density of 50 A/sq dm and 90 C, which corresponds to a thermal efficiency of 93-95%.

  8. Solid composite electrolytes for lithium batteries

    DOEpatents

    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.

  9. NIR to visible frequency upconversion in Er3+ and Yb3+ co-doped BaZrO3 phosphor

    NASA Astrophysics Data System (ADS)

    Singh, Vijay; Rai, Vineet Kumar; Al-Shamery, Katharina; Haase, Markus; Kim, Sang Hwan

    2013-05-01

    Phosphor powders of Yb3+ co-doped BaZrO3:Er3+ have been prepared by the urea combustion route. The formation of single-phase BaZrO3:Er3+ and BaZrO3:Er3+,Yb3+ was confirmed by X-ray powder diffraction (XRD). Green and red luminescence along with a weaker blue emission is observed upon excitation at ˜978 nm with a diode laser. These emissions are caused by frequency upconversion in the Er3+-doped BaZrO3 (BZO) phosphor. Both the green and red upconversion emissions of the Er3+ are enhanced by about ˜3 and ˜43 times respectively when triply ionized ytterbium is incorporated as a co-dopant. The frequency upconversion processes responsible for the blue, green and red emissions are discussed on the basis of the experimental data.

  10. Formation energies and electronic structure of intrinsic vacancy defects and oxygen vacancy clustering in BaZrO3.

    PubMed

    Muhammad Alay-E-Abbas, Syed; Nazir, Safdar; Shaukat, Ali

    2016-08-24

    Ab initio density functional theory calculations are employed for exploring the thermodynamic stability, vacancy defect formation energy and electronic structure of pristine and non-stoichiometric BaZrO3. The electronic properties of BaZrO3 show the hole-doped and insulating nature of cation and oxygen vacancies, respectively. The changes in the electronic properties of intrinsic vacancy containing BaZrO3 are analyzed in terms of electronic band structure, charge density and effective Bader charges. The relative stability of the formation of charge neutral and fully charged intrinsic vacancy defects in BaZrO3 is investigated in different chemical growth environments and the full and partial Schottky reactions are computed. Calculations are also performed to study the effects of oxygen vacancy clustering in different crystallographic planes. These calculations enable us to predict n-type conductivity in non-stoichiometric BaZrO3, which is useful for tailoring the electrical conduction of this material. Our results suggest that the semiconducting, p- and n-type character of BaZrO3 can be realized to enhance its device application by means of intentional incorporation of vacancy defects. PMID:27514742

  11. Vortex phases and dynamics in YBa2Cu3O7+BaZrO3 films as a function of angle and field up to 50 Tesla

    NASA Astrophysics Data System (ADS)

    Baily, S. A.; Maiorov, B.; Zhou, H.; Foltyn, S. R.; Holesinger, T. G.; Jia, Q. X.; Civale, Leonardo; Balakirev, F. F.; Jaime, M.

    2008-03-01

    Studying the vortex solid-liquid transition (resistivity=0) in high Tc superconductors is scientifically and technologically relevant. We have used low current transport measurements to study the melting line of YBa2Cu3O7 films with and without BaZrO3 additions in fields up to 50 T. Samples with mostly extended particle defects, mostly columnar defects, or a mixture of both will be compared. Plain YBa2Cu3O7 shows correlated pinning along the crystalline axes and the emergence of a smectic phase when field is aligned with the a-b plane. Inclusion of BaZrO3 not only alters the angular dependence of the irreversibility line indicating the stronger influence of c-axis correlated pinning, but also affects dissipation in the vortex-liquid state over the entire angular range. We will discuss the results in terms of vortex pinning, the corresponding types of phase transitions, micro-structural analysis, and information obtained from critical current measurements.

  12. Monolithic solid electrolyte oxygen pump

    DOEpatents

    Fee, Darrell C.; Poeppel, Roger B.; Easler, Timothy E.; Dees, Dennis W.

    1989-01-01

    A multi-layer oxygen pump having a one-piece, monolithic ceramic structure affords high oxygen production per unit weight and volume and is thus particularly adapted for use as a portable oxygen supply. The oxygen pump is comprised of a large number of small cells on the order of 1-2 millimeters in diameter which form the walls of the pump and which are comprised of thin, i.e., 25-50 micrometers, ceramic layers of cell components. The cell components include an air electrode, an oxygen electrode, an electrolyte and interconnection materials. The cell walls form the passages for input air and for exhausting the oxygen which is transferred from a relatively dilute gaseous mixture to a higher concentration by applying a DC voltage across the electrodes so as to ionize the oxygen at the air electrode, whereupon the ionized oxygen travels through the electrolyte and is converted to oxygen gas at the oxygen electrode.

  13. Solid polymer electrolyte from phosphorylated chitosan

    SciTech Connect

    Fauzi, Iqbal Arcana, I Made

    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.

  14. Density-functional calculations of prefactors and activation energies for H diffusion in BaZrO3

    NASA Astrophysics Data System (ADS)

    Sundell, Per G.; Björketun, Mårten E.; Wahnström, Göran

    2007-09-01

    Density-functional calculations are used to investigate hydrogen diffusion in the solid-state proton conductor BaZrO3 . Activation energies and prefactors for the rate of proton transfer and reorientation are evaluated for a defect-free region of this simple cubic perovskite-structured oxide. Both semiclassical over-barrier jumps and phonon-assisted tunneling transitions between sites are considered. It is found that the classical barriers for the elementary transfer and reorientation steps are both of the order of 0.2eV . The quantum-mechanical zero-point motion effects are found to be sizable, to effectively reduce the barrier heights, and to make the prefactors similar for the transfer and reorientation steps. The Flynn-Stoneham model [Phys. Rev. B 1, 3966 (1970)] of phonon-assisted tunneling yields an activation energy of around 0.2eV and a very small prefactor for proton transfer, whereas the corresponding adiabatic model gives a similar activation energy but a much larger prefactor. It is suggested that the effect of other defects such as dopants has to be included for a proper description of hydrogen diffusion in this material.

  15. Composite Solid Electrolyte Containing Li+- Conducting Fibers

    NASA Technical Reports Server (NTRS)

    Appleby, A. John; Wang, Chunsheng; Zhang, Xiangwu

    2006-01-01

    Improved composite solid polymer electrolytes (CSPEs) are being developed for use in lithium-ion power cells. The matrix components of these composites, like those of some prior CSPEs, are high-molecular-weight dielectric polymers [generally based on polyethylene oxide (PEO)]. The filler components of these composites are continuous, highly-Li(+)-conductive, inorganic fibers. PEO-based polymers alone would be suitable for use as solid electrolytes, were it not for the fact that their room-temperature Li(+)-ion conductivities lie in the range between 10(exp -6) and 10(exp -8) S/cm, too low for practical applications. In a prior approach to formulating a CSPE, one utilizes nonconductive nanoscale inorganic filler particles to increase the interfacial stability of the conductive phase. The filler particles also trap some electrolyte impurities. The achievable increase in conductivity is limited by the nonconductive nature of the filler particles.

  16. Lithium-ion batteries having conformal solid electrolyte layers

    SciTech Connect

    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.

  17. Performance comparison: Aluminum electrolytic and solid tantalum capacitor

    NASA Technical Reports Server (NTRS)

    Hawthornthwaite, B. G.; Piper, J.; Holland, H. W.

    1981-01-01

    Several key electrical and environmental parameters of latest technology aluminum electrolytic and solid tantalum capacitors were evaluated in terms of price fluctuations of tantalum metal. Performance differences between solid tantalums and aluminum electrolytics are examined.

  18. Morphology control in solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Li, Christopher

    2015-03-01

    Solid polymer electrolytes (SPEs) with high ionic conductivity are important for energy-related applications, such as solid state batteries and fuel cells. In this talk, I will discuss how nanoscale morphology affects the properties of SPEs. In the first part of the talk, I will show quantitatively that the effect of polymer crystallization on ion transport is twofold: structural (tortuosity) and dynamic (tethered chain confinement). We decouple these two effects by designing and fabricating a model polymer single crystal electrolyte system with controlled crystal structure, size, crystallinity, and orientation. Ion conduction is confined within the chain fold region and guided by the crystalline lamellae. We show that, at low ion content, due to the tortuosity effect, the in-plane conductivity is 2000 times greater than through-plane one. Contradictory to the general view, the dynamic effect is negligible at moderate ion contents. Our results suggest that semicrystalline polymer is a valid system for practical polymer electrolytes design. In the second part of the talk, I will discuss how to use holographic photopolymerization (HP) to fabricate long-range, defect-free, ordered SPEs with tunable ion conducting pathways. By incorporating polymer electrolytes into the carefully selected HP system, electrolyte layers/ion channels with length scales of a few tens of nanometers to micrometers can be formed. Confinement effects on ion transport will be reported.

  19. Hybrid improper ferroelectricity in SrZrO3/BaZrO3 superlattice.

    PubMed

    Zhang, Yajun; Wang, Jie; Sahoo, M P K; Wang, Xiaoyuan; Shimada, Takahiro; Kitamura, Takayuki

    2016-08-24

    Incipient ferroelectrics, which show a unique dielectric property, arouse tremendous interests due to their potential application in microwave dielectric devices. However, ferroelectric transition in incipient ferroelectrics is suppressed entirely by quantum fluctuation. Here, by means of first-principles calculations, we demonstrate that there exists hybrid improper ferroelectricity in a layered artificial superlattice composed of the incipient ferroelectrics of SrZrO3 and BaZrO3. The hybrid improper ferroelectric polarization stems from oxygen octahedral rotation and coexists with the strain-induced ferroelectric distortion. The coexistence of oxygen octahedral rotation and ferroelectric distortion results in an enhanced polarization in the superlattice. It is further found that the total polarization in the superlattice is mainly contributed by the oxygen octahedral rotation for zero or small strain, whereas the contribution from strain-induced ferroelectric distortion gradually becomes predominant as the strain increases. The phonon dispersion, energy surface and atomic displacements are calculated to shed light on the underlying mechanism of the hybrid improper ferroelectricity in the SrZrO3/BaZrO3 superlattice. PMID:27523881

  20. Electrolytic hydrogen fuel production with solid polymer electrolyte technology.

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Fickett, A. P.

    1973-01-01

    A water electrolysis technology based on a solid polymer electrolyte (SPE) concept is presented for applicability to large-scale hydrogen production in a future energy system. High cell current density operation is selected for the application, and supporting cell test performance data are presented. Demonstrated cell life data are included to support the adaptability of the SPE system to large-size hydrogen generation utility plants as needed for bulk energy storage or transmission. The inherent system advantages of the acid SPE electrolysis technology are explained. System performance predictions are made through the year 2000, along with plant capital and operating cost projections.

  1. Miniaturized Amperometric Solid Electrolyte Carbon Dioxide Sensors

    NASA Technical Reports Server (NTRS)

    Hunter, G. W.; Xu, J. C.; Liu, C. C.; Hammond, J. W.; Ward, B.; Lukco, D.; Lampard, P.; Artale, M.; Androjna, D.

    2006-01-01

    A miniaturized electrochemical carbon dioxide (CO2) sensor using Na3Z r2Si2PO12 (NASICON) as a solid electrolyte has been fabricated and de monstrated. Microfabrication techniques were used for sensor fabricat ion to yield a sensing area around 1.0 mm x 1.1 mm. The NASICON solid electrolyte and the Na2CO3/BaCO3 (1:1.7 molar ratio) auxiliary elect rolyte were deposited by sputtering in between and on top of the inte rdigitated finger-shaped platinum electrodes. This structure maximize s the length of the three-phase boundary (electrode, solid electrolyt e, and auxiliary electrolyte), which is critical for gas sensing. The robust CO2 sensor operated up to 600 C in an amperometric mode and a ttempts were made to optimize sensor operating parameters. Concentrat ions of CO2 between 0.02% and 4% were detected and the overall sensor performance was evaluated. Linear response of sensor current output to ln[CO2 concentration] ranging from 0.02% to 1% was achieved.

  2. Solid electrolytes strengthened by metal dispersions

    DOEpatents

    Lauf, R.J.; Morgan, C.S.

    1981-10-05

    An improvement in solid electrolytes of advanced secondary batteries of the sodium-sulfur, sodium-halogen, and like combinations is achieved by providing said battery with a cermet electrolyte containing a metal dispersion ranging from 0.1 to 10.0 vol. % of a substantially nonreactive metal selected from the group consisting essentially of Pt, Cr, Fe, Co, Ni, Nb, their alloys, and their physical mixtures in the elemental or uncombined state, the remainder of said cermet being an ion-conductive ceramic material.

  3. Solid electrolytes strengthened by metal dispersions

    DOEpatents

    Lauf, Robert J.; Morgan, Chester S.

    1983-01-01

    An improvement in solid electrolytes of advanced secondary batteries of the sodium-sulfur, sodium-halogen, and like combinations is achieved by providing said battery with a cermet electrolyte containing a metal dispersion ranging from 0.1 to 10.0 vol. % of a substantially nonreactive metal selected from the group consisting essentially of Pt, Cr, Fe, Co, Ni, Nb, their alloys, and their physical mixtures in the elemental or uncombined state, the remainder of said cermet being an ion-conductive ceramic material.

  4. Solid composite electrolytes for lithium batteries

    DOEpatents

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

    2001-01-01

    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 polymer-ceramic composite electrolyte containing poly(ethylene oxide), lithium tetrafluoroborate and titanium dioxide is provided in the form of an annealed film having a room temperature conductivity of from 10.sup.-5 S cm.sup.-1 to 10.sup.-3 S cm.sup.-1 and an activation energy of about 0.5 eV.

  5. Inorganic-organic composite solid polymer electrolytes

    SciTech Connect

    Abraham, K.M.; Koch, V.R.; Blakley, T.J.

    2000-04-01

    Inorganic-organic composite solid polymer electrolytes (CSPEs) have been prepared from the poly(ethylene oxide) (PEO)-like electrolytes of the general formula polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP)-PEO{sub n}-LiX and Li{sup +}-conducting ceramic powders. In the PEO-like electrolytes, PVdF-HFP is the copolymer of PVdF and HFP, PEO{sub n} is a nonvolatile oligomeric polyethylene oxide of {approximately}400 g/mol molecular weight, and LiX is lithium bis(trifluoroethylsulfonyl)imide. Two types of inorganic oxide ceramic powders were used: a highly Li{sup +}-conducting material of the composition 14 mol % Li{sub 2}O-9Al{sub 2}O{sub 3}-38TiO{sub 2}-39P{sub 2}O{sub 5}, and the poorly Li{sup +}-conducting Li-silicates Li{sub 4{minus}x}M{sub x}SiO{sub 4} where M is Ca or Mg and x is 0 or 0.05. The composite electrolytes can be prepared as thin membranes in which the Li{sup +} conductivity and good mechanical strength of the Li{sup +}-conducting inorganic ceramics are complemented by the structural flexibility and high conductivity of organic polymer electrolytes. Excellent electrochemical and thermal stabilities have been demonstrated for the electrolyte films. Li//composite electrolyte//LiCoO{sub 2} rechargeable cells have been fabricated and cycled at room temperature and 50 C.

  6. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Isenberg, Arnold O.; Ruka, Roswell J.; Zymboly, Gregory E.

    1985-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

  7. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Isenberg, Arnold O.; Ruka, Roswell J.

    1987-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

  8. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Isenberg, Arnold O.; Ruka, Roswell J.

    1986-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

  9. Improved Liquid-Electrode/Solid-Electrolyte Cell

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Distefano, Salvador; Williams, Roger M.; Bankston, Clyde P.

    1990-01-01

    Organic liquid in cathode extends working life. Rechargeable solid-electrolyte electrochemical cell includes novel mixture of organic and inorganic materials in liquid cathode. Operates at temperature about 120 to 170 degrees C lower than sodium/sulfur cells. Offers energy density comparable to that of sodium/sulfur cells - about 10 Wh/kg - and suited to such applications as military systems and electric vehicles.

  10. Anti-perovskite solid electrolyte compositions

    SciTech Connect

    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.

  11. Solid electrolyte-electrode system for an electrochemical cell

    DOEpatents

    Tuller, H.L.; Kramer, S.A.; Spears, M.A.

    1995-04-04

    An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is also provided. 17 figures.

  12. Solid electrolyte-electrode system for an electrochemical cell

    DOEpatents

    Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.

    1995-01-01

    An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is also provided.

  13. Proton conductivity of Y-doped BaZrO 3: Pellets and thin films

    NASA Astrophysics Data System (ADS)

    Pornprasertsuk, Rojana; Kosasang, Onthida; Somroop, Kittichai; Horprathum, Mati; Limnonthakul, Puenisara; Chindaudom, Pongpan; Jinawath, Supatra

    2011-07-01

    Y-doped BaZrO 3 (BYZ) pellets and thin films at various doping concentrations were fabricated by the cold isostatic press and 2-step sputtering techniques, respectively. By using BaCO 3, 3 mol% yttria stabilized zirconia (YSZ), nano-Y 2O 3 powders and 1 wt% ZnO as a sintering aid, 6-40 at% BYZ pellets with no second phase and relative bulk density higher than 97% can be achieved. The highest bulk and grain boundary proton conductivities of the BYZ pellets measured by the electrochemical impedance spectroscopy (EIS) technique were obtained at 10 and 20 at% BYZ, respectively. Due to the absence of the second phase and higher bulk density, our BYZ (1 wt% ZnO) pellets show higher bulk and grain boundary conductivity than several previously reported ZnO-BYZ results. The 2-step sputtering technique for BYZ film fabrication involved two sequential steps as followed: (i) DC sputtered Y onto BaZrO 3 target and (ii) RF sputtered Y-BaZrO 3 target onto SiO 2/Si substrate. EIS results of BYZ thin films also verify the dependence of conductivity on the Y doping concentration and reveal 10 2-10 3 times higher conductivities than those of BYZ pellets even with some YSZ phase present. The high conductivity may arise from several factors such as the surface conduction, low contamination and change of grain boundary structure. Two ionic conduction mechanisms were observed in the thin films (in air): (i) the proton conduction at T ≤ 450 °C and (ii) the oxide ion conduction at T > 450 °C. However, under humidified H 2 atmosphere, the proton conduction was dominant througout the temperature range of this study.

  14. Ceramic and polymeric solid electrolytes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Fergus, Jeffrey W.

    Lithium-ion batteries are important for energy storage in a wide variety of applications including consumer electronics, transportation and large-scale energy production. The performance of lithium-ion batteries depends on the materials used. One critical component is the electrolyte, which is the focus of this paper. In particular, inorganic ceramic and organic polymer solid-electrolyte materials are reviewed. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically have conductivities that are lower than those of organic liquid electrolytes. This paper provides a comparison of the conductivities of solid-electrolyte materials being used or developed for use in lithium-ion batteries.

  15. Interface Engineering of Garnet Solid Electrolytes

    NASA Astrophysics Data System (ADS)

    Cheng, Lei

    Solid lithium ion conductors represent a promising class of materials for next generation high energy density batteries, with the potential for enabling use of high capacity Li metal anodes and providing opportunities for novel lithium-free cathode materials. However, highly resistive interfaces stymie their practical use. This urgent scientific challenge requires mechanistic understanding of ion transport at interfaces, as well as development of novel processes to achieve low interfacial resistances. The goal of this PhD dissertation was to generate fundamental understandings of garnet-structured Al substituted Li7La3Zr2O 12 (LLZO) electrolyte surfaces and interfaces with lithium metal electrodes. Specifically in this research, the topmost surface microstructure, local chemical environment, and surface chemistry were carefully studied. The ceramic processing of garnet is discussed and ways to control the sintering behavior and microstructures were explored and successfully demonstrated. Factors contributing to high interfacial resistance were systematically studied. The source of the high interfacial impedance has been traced to the presence of Li2CO 3 on pellet surfaces resulting from air exposure after processing. In addition, it was discovered that surface grain boundaries are surprisingly fast ion transport pathways and surface microstructure is critically important to lithium ion transport at interfaces. Complex homo- and heterostructured LLZO solid electrolytes with controllable surface and bulk microstructures were successfully fabricated, which allowed the comparison and separation of the contribution from the surface and the bulk. Engineered pellet surfaces allowed us to achieve the lowest interfacial resistance ever reported for this composition, resulting in significantly improved cycling behavior. Lastly, it was found that LLZO surfaces can be effectively stabilized under air exposure conditions, preventing Li2CO3 formation and maintaining low

  16. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, T.A.

    1984-10-19

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  17. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, Terje A.

    1985-01-01

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  18. Annealing Would Improve beta" - Alumina Solid Electrolyte

    NASA Technical Reports Server (NTRS)

    Williams, Roger; Homer, Margie; Ryan, Margaret; Cortez, Roger; Shields, Virgil; Kisor, Adam

    2003-01-01

    A pre-operational annealing process is under investigation as a potential means of preventing a sudden reduction of ionic conductivity in a Beta"-alumina solid electrolyte (BASE) during use. On the basis of tests, the sudden reduction of ionic conductivity, followed by a slow recovery, has been found to occur during testing of the solid electrolyte and electrode components of an alkali metal thermal-to-electric converter (AMTEC) cell. At this time, high-temperature tests of limited duration have indicated the superiority of the treated BASE, but reproducible tests over thousands of hours are necessary to confirm that microcracking has been eliminated. The ionic conductivity of the treated BASE is also measured to be higher than untreated BASE at 1,073 K in low-pressure sodium vapor. Microcracking resulting in loss of conductivity was not observed with treated BASE in one high-temperature experiment, but this result must be duplicated over very long testing times to be sure of the effect. Shorter annealing times (10 to 20 hours) were found to result in significantly less loss of mass; it may be necessary for the packed powder mixture to evolve some Na2O before the Na2O can leave the ceramic.

  19. Lithium Polymer Electrolytes and Solid State NMR

    NASA Technical Reports Server (NTRS)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  20. Strong flux pinning enhancement in YBa2Cu3O7-x films by embedded BaZrO3 and BaTiO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Ding, Fa-Zhu; Gu, Hong-Wei; Zhang, Teng; Wang, Hong-Yan; Qu, Fei; Qiu, Qing-Quan; Dai, Shao-Tao; Peng, Xing-Yu

    2013-07-01

    YBa2Cu3O7-x (YBCO) films with embedded BaZrO3 and BaTiO3 nanoparticles were fabricated by metalorganic deposition using trifluoroacetates (TFA-MOD). Both X-ray diffraction and transmission electron microscopy revealed that these BaZrO3 and BaTiO3 nanoparticles had random orientations and were distributed stochastically in the YBCO matrix. The unique combined microstructure enhances the critical current density (Jc) of the BaZrO3/BaTiO3 doped-YBCO films, while keeping the critical transition temperature (Tc) close to that in the pure YBCO films. These results indicate that BaZrO3 and BaTiO3 nanoparticles provide strong flux pinning in YBCO films.

  1. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    DOEpatents

    Sharp, Donald J.; Armstrong, Pamela S.; Panitz, Janda Kirk G.

    1998-01-01

    A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

  2. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    DOEpatents

    Sharp, D.J.; Armstrong, P.S.; Panitz, J.K.G.

    1998-03-17

    A solid electrolytic capacitor is described having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects. 2 figs.

  3. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    SciTech Connect

    Sharp, D.J.; Armstrong, P.S.; Paintz, J.K.G.

    1998-04-01

    This report discusses the design of a solid electrolytic capacitor having a solid electrolyte comprised of manganese dioxide dispersed in an aromatic polyamide capable of to forming polyimide linkages. This solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

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

    NASA Technical Reports Server (NTRS)

    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.

  5. Electrical properties of BaZrO3 ceramic synthesized by flash pyrolysis process

    NASA Astrophysics Data System (ADS)

    Saini, Deepash S.; Bhattacharya, D.

    2016-04-01

    Barium Zirconate (BaZrO3) nanoparticles are synthesized by flash pyrolysis combustion process. Rietveld refinement of XRD pattern of calcined powder at 900 °C, 1100 °C and sintered at 1600 °C describes that a single-phase compound is formed of an Pm-3m cubic crystal structure with a lattice constant a = 4.19102, 4.192693, and 4.195276 Å respectively. Crystallize size of calcined powder at 900 °C, 1100 °C and sintered at 1600 °C is found 34.28, 37.7 and 47.14 nm respectively using Scherrer formula. The FESEM image of sintered pellet at 1600 °C for 4 h describes porous nature of the sample. The Nyquist plots indicate the dominant grain boundary effect in electrical processes in the sample. A decrease in the bulk resistance with increasing temperature demonstrates a semiconducting behavior. The temperature dependent relaxation and conduction mechanism brief involvements of different types of the charge species in the 250 to 500 °C temperature region as studied at different frequencies over 100 Hz to 1 MHz.

  6. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich's solution and analysis.

  7. Layered charge transfer complex cathodes or solid electrolyte cells

    SciTech Connect

    Louzos, D.V.

    1981-05-12

    Layered charge transfer complex cathodes for use in solid electrolyte cells are described wherein one layer of the cathode contains an electronic conductor which is isolated from the cell's solid electrolyte by a second layer of the cathode that does not contain an electronic conductor.

  8. Solid Polymer Electrolyte Fuel Cell Technology Program

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Work is reported on phase 5 of the Solid Polymer Electrolyte (SPE) Fuel Cell Technology Development program. The SPE fuel cell life and performance was established at temperatures, pressures, and current densities significantly higher than those previously demonstrated in sub-scale hardware. Operation of single-cell Buildup No. 1 to establish life capabilities of the full-scale hardware was continued. A multi-cell full-scale unit (Buildup No. 2) was designed, fabricated, and test evaluated laying the groundwork for the construction of a reactor stack. A reactor stack was then designed, fabricated, and successfully test-evaluated to demonstrate the readiness of SPE fuel cell technology for future space applications.

  9. Solid polymeric electrolytes for lithium batteries

    DOEpatents

    Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

    2006-03-14

    Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

  10. Solid electrolytes and impact-resistant ceramics

    SciTech Connect

    Angell, C.A.

    1991-08-01

    In this proposal, we describe a program to exploit recent achievements in two distinct areas of materials science, both of them dependent on the independent motion of singly charged ions through an immobile matrix. The first is the area of non-crystalline solid electrolytes in which this laboratory has gained prominence over the past decade. The second is an area proposed for study in our previous proposal and now verified as a principle worthy of considerable further investigation: it involves the use of mobile ions for fast absorption of mechanical energy from short time impacts hence inhibition of crack nucleation and failure in glassy substances. In the first area, we will study both glassy and polymeric systems. For glassy solid electrolytes, we will perform the first electrochemical measurements of cation and anion self-diffusion coefficients in glasses, to provide data to compare with neutron scattering results and thereby to resolve a theoretical dispute. We will look for an important but so-far-unstudied relationship between conductivity/viscosity decoupling in fast ion glasses, and fragility of the liquid above the glass transition temperature. In polymer-salt systems, we will perform both diagnostic and developmental studies. We will try to demonstrate a continuity of behavior, as function of solvent content, between highly decoupled glass and over-coupled salt/polymer solution behavior. This will incorporate a study of polymer-salt liquid immiscibility at high temperatures to seek the relationship between salts and molecular diluent as additives to the polymer solvent. We propose also to study the effects of perfluorination on both polymer fragility and glass transition, and also on carboxylate basicity for possible improvements in overall polymer-salt performance.

  11. Fabrication BaZrO3/PBI-based nanocomposite as a new proton conducting membrane for high temperature proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Hooshyari, Khadijeh; Javanbakht, Mehran; Shabanikia, Akbar; Enhessari, Morteza

    2015-02-01

    Novel PBI (polybenzimidazole)-BaZrO3 (PBZ) nanocomposite membranes have been prepared for the high temperature proton exchange membrane (HT-PEM) fuel cells. The results showed that the water uptake, acid doping level and proton conductivity of the PBZ nanocomposite membranes were higher than that of virgin PBI membrane due to the presence of perovskite structure BaZrO3 nanoparticles, which as protonic conductor can perform as a special pathway for hydrogen transport. The proton conductivity of the PBZ nanocomposite membranes with 13 mol phosphoric acid per PBI repeat unit was obtained 125 mS/cm at 180 °C and 5% relative humidity. It was found that the performance of the fuel cells increases by increasing temperature; this was explained by faster reaction kinetic and higher proton conductivity. The power density and current density at 0.5 V 180 °C with 5% relative humidity were observed 0.56 W/cm2 and 1.12 A/cm2, respectively for PBZ nanocomposite membranes containing 4 wt% of the nanofillers. The results suggested that PBZ nanocomposite membranes are promising electrolytes for HT-PEM fuel cells with improved proton conductivity.

  12. MultiLayer solid electrolyte for lithium thin film batteries

    SciTech Connect

    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.

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

    DOEpatents

    Liu, Han; LaConti, Anthony B.; Mittelsteadt, Cortney K.; McCallum, Thomas J.

    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.

  14. Lithium-ion transport in inorganic solid state electrolyte

    NASA Astrophysics Data System (ADS)

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

    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. Project supported by the National Natural Science Foundation of China (Grant No. 51372228), the Shanghai Pujiang Program, China (Grant No. 14PJ1403900), and the Shanghai Institute of Materials Genome from the Shanghai Municipal Science and Technology Commission, China (Grant No. 14DZ2261200).

  15. Solid biopolymer electrolytes came from renewable biopolymer

    NASA Astrophysics Data System (ADS)

    Wang, Ning; Zhang, Xingxiang; Qiao, Zhijun; Liu, Haihui

    2009-07-01

    Solid polymer electrolytes (SPEs) have attracted many attentions as solid state ionic conductors, because of their advantages such as high energy density, electrochemical stability, and easy processing. SPEs obtained from starch have attracted many attentions in recent years because of its abundant, renewable, low price, biodegradable and biocompatible. In addition, the efficient utilization of biodegradable polymers came from renewable sources is becoming increasingly important due to diminishing resources of fossil fuels as well as white pollution caused by undegradable plastics based on petroleum. So N, N-dimethylacetamide (DMAc) with certain concentration ranges of lithium chloride (LiCl) is used as plasticizers of cornstarch. Li+ can complexes with the carbonyl atoms of DMAc molecules to produce a macro-cation and leave the Cl- free to hydrogen bond with the hydroxyl or carbonyl of starch. This competitive hydrogen bond formation serves to disrupt the intra- and intermolecular hydrogen bonding existed in starch. Therefore, melt extrusion process conditions are used to prepare conductive thermoplastic starch (TPS). The improvements of LiCl concentration increase the water absorption and conductance of TPS. The conductance of TPS containing 0.14 mol LiCl achieve to 10-0.5 S cm-1 with 18 wt% water content.

  16. New Solid Polymer Electrolytes for Improved Lithium Batteries

    NASA Technical Reports Server (NTRS)

    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.

  17. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich`s solution and analysis.

  18. Growth process of BaZrO3 doped YBCO films by TFA-MOD method

    NASA Astrophysics Data System (ADS)

    Konya, K.; Masuda, Y.; Teranishi, R.; Kiss, T.; Munetoh, S.; Yamada, K.; Yoshizumi, M.; Izumi, T.

    Crystal growth process of YBa2Cu3O7-X (YBCO) films with BaZrO3 (BZO) pinning centers were investigated to enhance JC property by controlling microstructure of the films. The YBCO films were fabricated by a metal organic deposition (MOD) method using solutions with trifluoroacetates (TFA) and Zr-salts. Quenched films were prepared by cooling them rapidly during crystallization process and crystallized phases were identified by an X-ray diffraction (XRD) measurement. It is indicating that BZO forms at lower temperature than that of YBCO formation and that BZO and BaF2 are crystallized at the similar temperature range around 700°C. Then, we kept the heating temperature which is under 600°C before crystallization temperature of YBCO and investigated the effect of temperature keeping on film growth. In the film kept for more than 3 hours, BZO peak was detected by XRD measurement. However, BZO particles were not observed in the film even kept for 9 hours by transmission electron microscopy (TEM) and energy dispersive X-ray (EDS) analyses. It is indicated that growth rate of BZO is slow at 600°C. On the other hand, smaller YBCO particles and decreasing of surface roughness (Ra) were observed for the film which were kept at 600°C for 3 hours and then crystallized. This result suggests the density of YBCO film is higher than that for YBCO without that process. In summary, it can be considered that YBCO film density become high by temperature keeping process below 600°C before YBCO crystallization and that size of BZO particles are determined by heat treatment at the temperature of above 600°C

  19. An advanced model framework for solid electrolyte intercalation batteries.

    PubMed

    Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

    2011-07-28

    Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. PMID:21681301

  20. Electrochemical processes at solid electrode-electrolyte-gas interfaces

    SciTech Connect

    Youngblood, G.E.; Weber, W.J; Bates, J.L.

    1991-05-01

    Electrochemical reactions at solid electrolyte-electrode-gas interfaces are being investigated with ac impedance and dc polarization techniques using an unbonded interface cell (UIC). The UIC approach eliminates influence of sample size and interface morphology resulting from electrode-electrolyte fabrication. The electrochemical reactions of oxygen with solid electrode (La{sub 1-x}Sr{sub x}MnO{sub 3} or Pt) and solid electrolyte (0.08Y{sub 2}O{sub 3} - 0.92ZrO{sub 2}) interfaces are described. 6 refs., 4 figs., 2 tabs.

  1. Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes

    SciTech Connect

    Tenhaeff, Wyatt E; Yu, Xiang; Hong, Kunlun; Perry, Kelly A; Dudney, Nancy J

    2011-01-01

    A study of lithium cation transport across solid-solid electrolyte interfaces to identify critical resistances in nanostructured solid electrolytes is reported. Bilayers of glass and polymer thin film electrolytes were fabricated and characterized for this study. The glass electrolyte was lithium phosphorous oxynitride (Lipon), and two polymer electrolytes were studied: poly(methyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) and poly(styrene-co-poly(ethylene glycol) methyl ether methacrylate). Both copolymers contained LiClO{sub 4} salt. In bilayers where polymer electrolyte layers are fabricated on top of Lipon, the interfacial resistance dominates transport. At 25 C, the interfacial resistance is at least three times greater than the sum of the Lipon and polymer electrolyte resistances. By reversing the structure and fabricating Lipon on top of the polymer electrolytes, the interfacial resistance is eliminated. Experiments to elucidate the origin of the interfacial resistance in the polymer-on-Lipon bilayers reveal that the solvent mixtures used to fabricate the polymer layers do not degrade the Lipon layer. The importance of the polymer electrolytes' mechanical properties is also discussed.

  2. Self-Passivating Lithium/Solid Electrolyte/Iodine Cells

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar; Whitcare, Jay; Narayanan, Sekharipuram; West, William

    2006-01-01

    Robust lithium/solid electrolyte/iodine electrochemical cells that offer significant advantages over commercial lithium/ iodine cells have been developed. At room temperature, these cells can be discharged at current densities 10 to 30 times those of commercial lithium/iodine cells. Moreover, from room temperature up to 80 C, the maximum discharge-current densities of these cells exceed those of all other solid-electrolyte-based cells. A cell of this type includes a metallic lithium anode in contact with a commercial flexible solid electrolyte film that, in turn, is in contact with an iodine/ graphite cathode. The solid electrolyte (the chemical composition of which has not been reported) offers the high ionic conductivity needed for high cell performance. However, the solid electrolyte exhibits an undesirable chemical reactivity to lithium that, if not mitigated, would render the solid electrolyte unsuitable for use in a lithium cell. In this cell, such mitigation is affected by the formation of a thin passivating layer of lithium iodide at the anode/electrolyte interface. Test cells of this type were fabricated from iodine/graphite cathode pellets, free-standing solid-electrolyte films, and lithium-foil anodes. The cathode mixtures were made by grinding together blends of nominally 10 weight percent graphite and 90 weight percent iodine. The cathode mixtures were then pressed into pellets at 36 kpsi (248 MPa) and inserted into coin-shaped stainless-steel cell cases that were coated with graphite paste to minimize corrosion. The solid-electrolyte film material was stamped to form circular pieces to fit in the coin cell cases, inserted in the cases, and pressed against the cathode pellets with polyethylene gaskets. Lithium-foil anodes were placed directly onto the electrolyte films. The layers described thus far were pressed and held together by stainless- steel shims, wave springs, and coin cell caps. The assembled cells were then crimped to form hermetic seals

  3. Basic investigation into the electrical performance of solid electrolyte membranes

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1982-01-01

    The electrical performance of solid electrolyte membranes was investigated analytically and the results were compared with experimental data. It is concluded that in devices that are used for pumping oxygen the major power losses have to be attributed to the thin film electrodes. Relations were developed by which the effectiveness of tubular solid electrolyte membranes can be determined and the optimum length evaluated. The observed failure of solid electrolyte tube membranes in very localized areas is explained by the highly non-uniform current distribution in the membranes. The analysis points to a possible contact resistance between the electrodes and the solid electrolyte material. This possible contact resistance remains to be investigated experimentally. It is concluded that film electrodes are not appropriate for devices which operate with current flow, i.e., pumps though they can be employed without reservation in devices that measure oxygen pressures if a limited increase in the response time can be tolerated.

  4. High temperature solid electrolyte fuel cell configurations and interconnections

    DOEpatents

    Isenberg, Arnold O.

    1984-01-01

    High temperature fuel cell configurations and interconnections are made including annular cells having a solid electrolyte sandwiched between thin film electrodes. The cells are electrically interconnected along an elongated axial outer surface.

  5. Optimization of BaZrO3 concentration as secondary phase in superconducting YBa2Cu3O7 for high current applications

    NASA Astrophysics Data System (ADS)

    Malik, Bilal A.; Malik, Manzoor A.; Asokan, K.

    2016-04-01

    We report the superconducting state properties of YBa2Cu3O7 (YBCO) on introduction of BaZrO3 (BZO) as a secondary phase. YBCO+xBZO (x= 0, 2, 4, 6, and 10 wt%) composite samples were prepared by solid state reaction method and characterized for structural, morphological and superconducting properties. X-ray diffraction confirms the increased crystallinity and images of scanning electron microscopy measurement show an increase in both grain size and grain connectivity on addition of BZO in YBCO. These effects are well pronounced in an applied magnetic field. Critical current density, JC, as well as the pinning force peaks at 4% of BZO concentration showed significant difference. A three-fold enhancement in JC and a six-fold enhancement in pinning force were observed at this optimum BZO concentration. This has been attributed to the pinning of flux lines in YBCO due to introduction of BZO as a secondary phase. These results show that this composite has potential application in high current applications.

  6. Modeling for CVD of Solid Oxide Electrolyte

    SciTech Connect

    Starr, T.L.

    2002-09-18

    Because of its low thermal conductivity, high thermal expansion and high oxygen ion conductivity yttria-stabilized zirconia (YSZ) is the material of choice for high temperature electrolyte applications. Current coating fabrication methods have their drawbacks, however. Air plasma spray (APS) is a relatively low-cost process and is suitable for large and relatively complex shapes. it is difficult to produce uniform, relatively thin coatings with this process, however, and the coatings do not exhibit the columnar microstructure that is needed for reliable, long-term performance. The electron-beam physical vapor deposition (EB-PVD) process does produce the desirable microstructure, however, the capital cost of these systems is very high and the line-of-sight nature of the process limits coating uniformity and the ability to coat large and complex shapes. The chemical vapor deposition (CVD) process also produces the desirable columnar microstructure and--under proper conditions--can produce uniform coatings over complex shapes. CVD has been used for many materials but is relatively undeveloped for oxides, in general, and for zirconia, in particular. The overall goal of this project--a joint effort of the University of Louisville and Oak Ridge National Laboratory (ORNL)--is to develop the YSZ CVD process for high temperature electrolyte applications. This report describes the modeling effort at the University of Louisville, which supports the experimental work at ORNL. Early work on CVD of zirconia and yttria used metal chlorides, which react with water vapor to form solid oxide. Because of this rapid gas-phase reaction the water generally is formed in-situ using the reverse water-gas-shift reaction or a microwave plasma. Even with these arrangements gas-phase nucleation and powder formation are problems when using these precursors. Recent efforts on CVD of zirconia and YSZ have focused on use of metal-organic precursors (MOCVD). These are more stable in the gas

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

    PubMed Central

    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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

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

    PubMed

    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

  10. Size-controlled growth of spherical nanoparticles of Y-doped BaZrO3 perovskite

    NASA Astrophysics Data System (ADS)

    Srinivas Reddy, G.; Bauri, Ranjit

    2016-04-01

    Yttrium-doped BaZrO3 (BZY) was processed by a simple yet effective chemical synthesis route that yielded perfectly spherical particles. The particle size was found to decrease with increasing molar concentration of cations in the solution. Thus, the process offered a great ease of controlling the particle size as well. The close control over morphology and size can provide an opportunity of tuning the properties of such particles. The average particle size as obtained from high-resolution scanning electron microscopy (HR-SEM) was 243, 206, 149, and 79 nm at 0.2, 0.5, 0.8, and 1 M concentration, respectively. At a processing temperature of 60 °C, the undesirable phases, BaCO3 and Zr1-xYxO2, were present along with BZY even after calcination at 600 °C, and it took a very long processing time (160 min) for complete phase formation. The BZY phase formed within 45 min at a reaction temperature of 90 °C and yielded phase pure powders on calcination at the same temperature (600 °C). The d-spacing (2.98 Å) obtained from the lattice fringes in high-resolution transmission electron microscopy (HR-TEM) confirmed the cubic perovskite phase of BaZrO3. The average crystallite size calculated from XRD analysis coupled with the TEM observations revealed that each spherical particle consists of only few crystallites.

  11. Structure and thermodynamic stability of hydrogen interstitials in BaZrO3 perovskite oxide from density functional calculations.

    PubMed

    Björketun, Mårten E; Sundell, Per G; Wahnström, Göran

    2007-01-01

    Density functional calculations have been used to study the electronic structure, preferred sites in the lattice, formation energies and vibrational frequencies for hydrogen interstitials in different charge states in the cubic phase of perovskite-structured BaZrO3. By combining ab initio results with thermodynamic modeling, defect formation at finite temperature and pressure has been investigated. We demonstrate how the site selectivity and spatial distribution of dopant atoms in the lattice can be affected by changes in the environmental conditions (atomic chemical potentials, oxygen partial pressure and temperature) used during processing of the material. In addition, we have calculated the thermodynamic parameters of the water uptake reaction for an acceptor-doped BaZrO3 crystal in equilibrium with a humid atmosphere. The interaction energies between a protonic defect and the investigated Ga, Gd, In, Nd, Sc, and Y dopants were found to be attractive, and we show that a simple model of defect association may reproduce an experimentally observed trend in the hydration enthalpy. PMID:17326572

  12. Theoretical analysis of solid oxide fuel cells with two-layer, composite electrolytes - Electrolyte stability

    NASA Astrophysics Data System (ADS)

    Virkar, Anil V.

    1991-05-01

    Theoretical analysis of solid oxide fuel cells (SOFCs) using two-layer, composite electrolytes consisting of a solid electrolyte of a significantly higher conductivity compared to zirconia (such as ceria or bismuth oxide) with a thin layer of zirconia or thoria on the fuel side is presented. Electrochemical transport in the two-layer composite electrolytes is examined by taking both ionic and electronic fluxes into account. Similar to most electrochemical transport phenomena, it is assumed that local equilibrium prevails. An equivalent circuit approach is used to estimate the partial pressure of oxygen at the interface. It is shown that thermodynamic stability of the electrolyte (ceria or bismuth oxide) depends upon the transport characteristics of the composite electrolyte, in particular the electronic conductivity of the air-side part of the electrolyte. The analysis shows that it would be advantageous to use composite electrolytes instead of all-zirconia electrolytes, thus making low-temperature (about 600-800 C) SOFCs feasible. Implications of the analysis from the standpoint of the desired characteristics of SOFC components are discussed.

  13. Solid lithium ion conducting electrolytes and methods of preparation

    SciTech Connect

    Narula, Chaitanya K.; Daniel, Claus

    2015-11-19

    A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

  14. Solid lithium ion conducting electrolytes and methods of preparation

    DOEpatents

    Narula, Chaitanya K; Daniel, Claus

    2013-05-28

    A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

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

    SciTech Connect

    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.

  16. Solid electrolyte: The key for high-voltage lithium batteries

    SciTech Connect

    Li, Juchuan; Ma, Cheng; Chi, Miaofang; Liang, Chengdu; Dudney, Nancy J.

    2014-10-14

    A solid-state high-voltage (5 V) lithium battery is demonstrated to deliver a cycle life of 10 000 with 90% capacity retention. Furthermore, the solid electrolyte enables the use of high-voltage cathodes and Li anodes with minimum side reactions, leading to a high Coulombic efficiency of 99.98+%.

  17. First-Principles Study of LiPON Solid Electrolyte

    NASA Astrophysics Data System (ADS)

    Santosh, K. C.; Xiong, Ka; Cho, Kyeongjae

    2011-03-01

    There has been much interest in the thin-film solid electrolyte for solid state battery and ionics applications. LiPON is a representative material developed by Oak Ridge National Laboratory. In this work, we use first principles calculations based on the density functional theory to investigate the Li- ion migration mechanisms of LiPON family materials. We investigate atomic structures, electronic structures and defect formation energies of these materials. To determine the migration path of Li diffusion, the activation energies are calculated. This study helps us to understand fundamental mechanisms of Li-ion migration and to improve Li ion conductivity in the solid electrolytes.

  18. Solid electrolyte material manufacturable by polymer processing methods

    DOEpatents

    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

    DOEpatents

    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. Making Three-Layer Solid Electrolyte/Electrode Sandwiches

    NASA Technical Reports Server (NTRS)

    Schroeder, James E.

    1991-01-01

    Tape-casting-and-sintering process joins two ceramic materials having widely different sintering temperatures into integral sandwich structure. Layers retain their identities, without migration of constituents. Used to make three-layer structure composed of outer porous layers of strontium-doped lanthanum manganite and inner dense layer of yttria-stabilized zirconia. Structures used to make electrolytic and fuels cells with solid electrolytes for use at high temperatures. Other potential applications include oxygen pumps and oxygen sensors.

  1. High temperature solid electrolyte fuel cell with ceramic electrodes

    DOEpatents

    Marchant, David D.; Bates, J. Lambert

    1984-01-01

    A solid oxide electrolyte fuel cell is described having a central electrolyte comprised of a HfO.sub.2 or ZrO.sub.2 ceramic stabilized and rendered ionically conductive by the addition of Ca, Mg, Y, La, Nd, Sm, Gd, Dy Er, or Yb. The electrolyte is sandwiched between porous electrodes of a HfO.sub.2 or ZrO.sub.2 ceramic stabilized by the addition of a rare earth and rendered electronically conductive by the addition of In.sub.2 O.sub.3. Alternatively, the anode electrode may be made of a metal such as Co, Ni, Ir Pt, or Pd.

  2. High temperature solid electrolyte fuel cell with ceramic electrodes

    DOEpatents

    Bates, J.L.; Marchant, D.D.

    A solid oxide electrolyte fuel cell is described having a central electrolyte comprised of a HfO/sub 2/ or ZrO/sub 2/ ceramic stabilized and rendered ionically conductive by the addition of Ca, Mg, Y, La, Nd, Sm, Gd, Dy Er, or Yb. The electrolyte is sandwiched between porous electrodes of a HfO/sub 2/ or ZrO/sub 2/ ceramic stabilized by the addition of a rare earth and rendered electronically conductive by the addition of In/sub 2/O/sub 3/. Alternatively, the anode electrode may be made of a metal such as Co, Ni, Ir Pt, or Pd.

  3. Development of high performance proton-conducting solid electrolytes

    SciTech Connect

    Linkous, C.A.; Kopitzke, R.W.

    1998-08-01

    This work seeks to improve the efficiency of fuel cell and electrolyzer operation by developing solid electrolytes that will function at higher temperatures. Two objectives were pursued: (1) determine the mechanism of hydrolytic decomposition of aromatic sulfonic acid ionomers, with the intent of identifying structural weaknesses that can be avoided in future materials; and (2) identify new directions in solid electrolyte development. After evaluating a number of aromatic sulfonates, it became apparent that no common mechanism was going to be found; instead, each polymer had its own sequence of degradation steps, involving some combination of desulfonation and/or chain scission. For electrochemical cell operation at temperatures > 200 C, it will be necessary to develop solid electrolytes that do not require sulfonic acids and do not require water to maintain its conductivity mechanism.

  4. Quasi Solid Polymer Electrolytes for Dye Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Dissanayake, M. A. K. Lakshman

    2013-07-01

    Dye-sensitized solar cell (DSSC) has been considered as an alternative to the conventional silicon solar cell because of low cost, easy fabrication and relatively high conversion efficiency. A DSSC consists of a dye-sensitized nanoparticulated TiO2 electrode, an electrolyte containing redox couple and a Pt coated counter electrode. Such solar cells based on an I-/I3- redox couple in an organic solvent usually have conversion efficiencies reaching around 11%. However, a major drawback of these solution based solar cells, originally developed by Gratzel and coworkers is the lack of long-term stability due to liquid leakage, usage of volatile liquids such as acetonitrile, electrode corrosion, and photodecomposition of the dye in the solvent medium. Therefore considerable research efforts have been made in recent years to replace the liquid electrolytes with solid polymer or quasi-solid polymer (gel) electrolytes. Among these approaches, the use of gel polymer electrolytes appears to give rise to successful results in terms of conversion efficiency. Conventional poly (ethylene oxide)(PEO)-based solid polymer electrolytes exhibit poor ionic conductivities at room temperature, which is not sufficient for practical applications. Therefore, most of the recent studies have been directed to the preparation and characterization of gel polymer electrolytes which exhibit higher ionic conductivity at ambient temperature while maintain quai-solid structure. These gel polymer electrolytes prepared by incorporating a liquid electrolyte into a matrix polymer such as polyacrylonitrile(PAN), poly(vinylidene fluoride)(PVdF), poly (methyl methacrylate) (PMMA) and PEO have been employed in quasi-solid-state DSSCs to achieve power conversion efficiencies of more than 5%. Significant improvements have been achieved in recent years by modifications of the electrolytes by optimizing the ionic salt, introducing additives such as inorganic nanofillers, organic molecules and ionic liquids in

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

    SciTech Connect

    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 Polymer Electrolyte (SPE) fuel cell technology program

    NASA Technical Reports Server (NTRS)

    1979-01-01

    The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

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

    PubMed Central

    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

  8. Solid polymer electrolytes for rechargeable batteries. Final report

    SciTech Connect

    Narang, S.C.; Ventura, S.C.

    1992-02-01

    SRI International has synthesized and tested new, dimensionally stable polymer electrolytes for high energy density rechargeable lithium batteries. We have prepared semi-interpenetrating networks of sulfur-substituted polyethyleneoxide with tetmethylorthosilicate (TEOS). The in situ hydrolysis of TEOS produces a mechanically stable three-dimensional network that entangles the polymer electrolytes and makes the film dimensionally flexible and stable. With this approach, the best dimensionally stable polymer electrolyte of this type produced so far, has a room temperature lithium ion conductivity of 7.5 {times} 10{sup {minus}4} S cm{sup {minus}1}. Another type of solid polymer electrolytes, polydiacetylene-based single-ion conductors with high room temperature proton conductivity were also developed. The best conductivity of these polymers is two orders of magnitude higher than that of Nafion under comparable experimental conditions. With further appropriate chemical modification, the new polymers could be used in fuel cells.

  9. All-solid-state lithium batteries with inorganic solid electrolytes: Review of fundamental science

    NASA Astrophysics Data System (ADS)

    Xiayin, Yao; Bingxin, Huang; Jingyun, Yin; Gang, Peng; Zhen, Huang; Chao, Gao; Deng, Liu; Xiaoxiong, Xu

    2016-01-01

    The scientific basis of all-solid-state lithium batteries with inorganic solid electrolytes is reviewed briefly, touching upon solid electrolytes, electrode materials, electrolyte/electrode interface phenomena, fabrication, and evaluation. The challenges and prospects are outlined as well. Project supported by the National High Technology Research and Development Program of China (Grant No. 2013AA050906), the National Natural Science Foundation of China (Grant Nos. 51172250 and 51202265), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDA09010201), and Zhejiang Province Key Science and Technology Innovation Team, China (Grant No. 2013PT16).

  10. Quasi-Solid Electrolytes for High Temperature Lithium Ion Batteries.

    PubMed

    Kalaga, Kaushik; Rodrigues, Marco-Tulio F; Gullapalli, Hemtej; Babu, Ganguli; Arava, Leela Mohana Reddy; Ajayan, Pulickel M

    2015-11-25

    Rechargeable batteries capable of operating at high temperatures have significant use in various targeted applications. Expanding the thermal stability of current lithium ion batteries requires replacing the electrolyte and separators with stable alternatives. Since solid-state electrolytes do not have a good electrode interface, we report here the development of a new class of quasi-solid-state electrolytes, which have the structural stability of a solid and the wettability of a liquid. Microflakes of clay particles drenched in a solution of lithiated room temperature ionic liquid forming a quasi-solid system has been demonstrated to have structural stability until 355 °C. With an ionic conductivity of ∼3.35 mS cm(-1), the composite electrolyte has been shown to deliver stable electrochemical performance at 120 °C, and a rechargeable lithium battery with Li4Ti5O12 electrode has been tested to deliver reliable capacity for over several cycles of charge-discharge. PMID:26535786

  11. Oxygen separation from air using zirconia solid electrolyte membranes

    NASA Technical Reports Server (NTRS)

    Suitor, J. W.; Marner, W. J.; Schroeder, J. E.; Losey, R. W.; Ferrall, J. F.

    1988-01-01

    Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.

  12. Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

    NASA Technical Reports Server (NTRS)

    Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

    2003-01-01

    This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

  13. High throughput ab-intio modeling of proton transport in solid electrolytes

    NASA Astrophysics Data System (ADS)

    Balachandran, Janakiraman; Lin, Lianshan; Ganesh, Panchapakesan

    Solid oxide materials that can selectively transport protons have great potential for fuel cell applications. However several fundamental questions remain unanswered such as (a) How do the dopants organize at various dopant concentrations, (b) How spatial organization of dopants influence proton migration energy, (c) How disorder and strain in a material influence its ionic transport. In this work have developed an integrated high throughput framework to calculate proton transport properties by integrating open source packages (such as pymatgen, fireworks) The high throughput framework scales well on supercomputing clusters. We have used this framework to analyze over 100 perovskites compounds with over 12 different dopant atoms. These computational models enable us to obtain insights how the proton transport properties depend on host and dopant atoms. Further, we also perform ab-initio modeling to understand how dopants spatially organize at different dopant concentrations, and how this spatial organization affects proton conductivity. This analysis enabled us to obtain fundamental insights on why proton conductivity decreases in Y doped BaZrO3 at high dopant concentrations.

  14. Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

    PubMed Central

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

    2013-01-01

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (<80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase 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. PMID:23963203

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

    PubMed

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

    2013-01-01

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (< 80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase 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. PMID:23963203

  16. Recent advances in solid polymer electrolyte fuel cell technology

    SciTech Connect

    Ticianelli, E.A.; Srinivasan, S.; Gonzalez, E.R.

    1988-01-01

    With methods used to advance solid polymer electrolyte fuel cell technology, we are close to obtaining the goal of 1 A/cm/sup 2/ at 0.7. Higher power densities have been reported (2 A/cm/sup 2/ at 0.5 V) but only with high catalyst loading electrodes (2 mg/cm/sup 2/ and 4 mg/cm/sup 2/ at anode and cathode, respectively) and using a Dow membrane with a better conductivity and water retention characteristics. Work is in progress to ascertain performances of cells with Dow membrane impregnated electrodes and Dow membrane electrolytes. 5 refs., 6 figs.

  17. Three electrode measurements on solid electrolytes

    SciTech Connect

    Pham, A.Q.; Glass, R.S.

    1995-12-01

    AC impedance spectroscopy and chronopotentiometry have been used to study solid-state ionic conductors. Results obtained using three electrodes are compared to those using a two-electrode configuration. The uncompensated resistance was shown to depend strongly on the geometric placement of the electrodes. The optimal configuration for minimized uncompensated resistance effects is similar to the Luggin capillary arrangement in the liquid phase. The effect of non-negligible geometric capacitance on interpretation of results is discussed.

  18. Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions

    PubMed Central

    Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L.

    2016-01-01

    Ion transport–driven instabilities in electrodeposition of metals that lead to morphological instabilities and dendrites are receiving renewed attention because mitigation strategies are needed for improving rechargeability and safety of lithium batteries. The growth rate of these morphological instabilities can be slowed by immobilizing a fraction of anions within the electrolyte to reduce the electric field at the metal electrode. We analyze the role of elastic deformation of the solid electrolyte with immobilized anions and present theory combining the roles of separator elasticity and modified transport to evaluate the factors affecting the stability of planar deposition over a wide range of current densities. We find that stable electrodeposition can be easily achieved even at relatively high current densities in electrolytes/separators with moderate polymer-like mechanical moduli, provided a small fraction of anions are immobilized in the separator. PMID:27453943

  19. Elongated solid electrolyte cell configurations and flexible connections therefor

    DOEpatents

    Reichner, Philip

    1989-01-01

    A flexible, high temperature, solid oxide electrolyte electrochemical cell stack configuration is made, comprising a plurality of flattened, elongated, connected cell combinations 1, each cell combination containing an interior electrode 2 having a top surface and a plurality of interior gas feed conduits 3, through its axial length, electrolyte 5 contacting the interior electrode and exterior electrode 8 contacting electrolyte, where a major portion of the air electrode top surface 7 is covered by interconnection material 6, and where each cell has at least one axially elongated, electronically conductive, flexible, porous, metal fiber felt material 9 in electronic connection with the air electrode 2 through contact with a major portion of the interconnection material 6, the metal fiber felt being effective as a shock absorbent body between the cells.

  20. Elongated solid electrolyte cell configurations and flexible connections therefor

    DOEpatents

    Reichner, P.

    1989-10-17

    A flexible, high temperature, solid oxide electrolyte electrochemical cell stack configuration is made, comprising a plurality of flattened, elongated, connected cell combinations, each cell combination containing an interior electrode having a top surface and a plurality of interior gas feed conduits, through its axial length, electrolyte contacting the interior electrode and exterior electrode contacting electrolyte, where a major portion of the air electrode top surface is covered by interconnection material, and where each cell has at least one axially elongated, electronically conductive, flexible, porous, metal fiber felt material in electronic connection with the air electrode through contact with a major portion of the interconnection material, the metal fiber felt being effective as a shock absorbent body between the cells. 4 figs.

  1. Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions.

    PubMed

    Tikekar, Mukul D; Archer, Lynden A; Koch, Donald L

    2016-07-01

    Ion transport-driven instabilities in electrodeposition of metals that lead to morphological instabilities and dendrites are receiving renewed attention because mitigation strategies are needed for improving rechargeability and safety of lithium batteries. The growth rate of these morphological instabilities can be slowed by immobilizing a fraction of anions within the electrolyte to reduce the electric field at the metal electrode. We analyze the role of elastic deformation of the solid electrolyte with immobilized anions and present theory combining the roles of separator elasticity and modified transport to evaluate the factors affecting the stability of planar deposition over a wide range of current densities. We find that stable electrodeposition can be easily achieved even at relatively high current densities in electrolytes/separators with moderate polymer-like mechanical moduli, provided a small fraction of anions are immobilized in the separator. PMID:27453943

  2. Correlations Between Electrolyte Concentration and Solid Electrolyte Interphase Composition in Electrodeposited Lithium.

    PubMed

    Jeong, Soon-Ki; Kim, Jin Hee; Jeong, Yoon-Taek; Kim, Yang Soo

    2016-03-01

    This study examined the electrochemical deposition and dissolution of lithium on nickel electrodes in propylene carbonate (PC) electrolytes containing different concentrations of lithium salts, including LiN(SO2C2F5)2 or LiPF6. The electrode reactions were significantly affected by the electrolyte concentration. The cyclability of the electrodes was considerably improved by increasing the electrolyte concentration. X-ray photoelectron spectroscopy (XPS) showed that the composition of the solid electrolyte interphase (SEI) was also affected by the electrolyte concentration. The SEI formed in the 1st cycle consisted mainly of LiF in 1 and 2.15 M LiN(SO2C2F5)2/PC solutions. After the 30th cycle in the former solution, there was a large decrease in the amount of LiF and a large increase in the amount of LiOH. On the other hand, in the latter solution there was a smaller decrease and a smaller increase in the amount of LiF and LiOH, respectively, as compared to the former solution after the 30th cycle. PMID:27455758

  3. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes.

    PubMed

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

    2014-10-01

    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. PMID:25108613

  4. Solid polymer battery electrolyte and reactive metal-water battery

    DOEpatents

    Harrup, Mason K.; Peterson, Eric S.; Stewart, Frederick F.

    2000-01-01

    In one implementation, a reactive metal-water battery includes an anode comprising a metal in atomic or alloy form selected from the group consisting of periodic table Group 1A metals, periodic table Group 2A metals and mixtures thereof. The battery includes a cathode comprising water. Such also includes a solid polymer electrolyte comprising a polyphosphazene comprising ligands bonded with a phosphazene polymer backbone. The ligands comprise an aromatic ring containing hydrophobic portion and a metal ion carrier portion. The metal ion carrier portion is bonded at one location with the polymer backbone and at another location with the aromatic ring containing hydrophobic portion. The invention also contemplates such solid polymer electrolytes use in reactive metal/water batteries, and in any other battery.

  5. Design and manufacture of solid ZrO2 electrolyte

    NASA Technical Reports Server (NTRS)

    1988-01-01

    The following project assignment was given to the students: 'design and build a suitable YSZ solid electrolyte cell. Describe advantages of the design and fabrication method. Finally, to the limits of available resources, fabricate the design. Explain why it would be superior to other designs.' Clemson University students definitely benefitted from this experience with USRA/NASA. The challenge that this project gave the students was both exciting and attention-getting. Students spent far more time per credit hour on this project than on their other course. This project advanced the art of making efficient oxygen generators as well. Clemson students are now well on the way to designing a solid electrolyte with a large active surface area and comparatively small volume. Previous devices have had to endure the limitation of using only simple shapes such as tubes. The results of this project have demonstrated that better configurations are not only possible but practical.

  6. New solid electrolytes: substituted organic ammonium silver iodides

    SciTech Connect

    Ferraro, J.R.; Walling, P.L.; Sherren, A.T.

    1980-01-01

    Several new solid electrolytes were synthesized from the reaction of substituted organic ammonium hydroiodides (pyridinium and quinolinium type) and varying quantities of silver iodide. The inductive effects of nucleophilic and electrophilic substitution on the pyridinium or quinolinium ring, as well as substituent position on the ionic conductivity, were determined. Pressure and thermal studies were undertaken to determine if new nonambient conductive phases existed. 39 references, 4 figures, 2 tables.

  7. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Singh, Prabhakar; Vasilow, Theodore R.; Richards, Von L.

    1996-01-01

    The invention comprises of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb.sub.x Ta.sub.y Ce.sub.1-x-y O.sub.2 where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell (10), characterized by a first electrode (12); an electrically conductive interlayer (14) of niobium and/or tantalum doped cerium oxide deposited over at least a first portion (R) of the first electrode; an interconnect (16) deposited over the interlayer; a solid electrolyte (18) deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode (20) deposited over the solid electrolyte. The interlayer (14) is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode (12), an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer (18) is a dense yttria stabilized zirconium oxide, the interconnect layer (16) is a dense, doped lanthanum chromite, and the second electrode (20), a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell (10) can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy.

  8. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Singh, P.; Vasilow, T.R.; Richards, V.L.

    1996-05-14

    The invention is comprised of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb{sub x}Ta{sub y}Ce{sub 1{minus}x{minus}y}O{sub 2} where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same is also described. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell, characterized by a first electrode; an electrically conductive interlayer of niobium and/or tantalum doped cerium oxide deposited over at least a first portion of the first electrode; an interconnect deposited over the interlayer; a solid electrolyte deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode deposited over the solid electrolyte. The interlayer is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode, an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer is a dense yttria stabilized zirconium oxide, the interconnect layer is a dense, doped lanthanum chromite, and the second electrode, a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy. 5 figs.

  9. Amperometric Solid Electrolyte Oxygen Microsensors with Easy Batch Fabrication

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; Xu, Jennifer C.; Liu, ChungChiun

    2011-01-01

    An amperometric solid electrolyte oxygen (O2) microsensor using a novel and robust structure has been developed with a detection range of 0.025 to 21 percent of O2 concentration. The microsensor has a simple structure with a sensing area of 1.10 0.99 mm(exp 2), and is operated by applying voltage across the electrodes and measuring the resulting current flow at a temperature of 600 C.

  10. Oxygen production using solid-state zirconia electrolyte technology

    NASA Technical Reports Server (NTRS)

    Suitor, Jerry W.; Clark, Douglas J.

    1991-01-01

    High purity oxygen is required for a number of scientific, medical, and industrial applications. Traditionally, these needs have been met by cryogenic distillation or pressure swing adsorption systems designed to separate oxygen from air. Oxygen separation from air via solid-state zirconia electrolyte technology offers an alternative to these methods. The technology has several advantages over the traditional methods, including reliability, compactness, quiet operation, high purity output, and low power consumption.

  11. Enhanced piezoelectric and ferroelectric properties in the BaZrO3 substituted BiFeO3-PbTiO3

    NASA Astrophysics Data System (ADS)

    Fan, Longlong; Chen, Jun; Li, Sha; Kang, Huajun; Liu, Laijun; Fang, Liang; Xing, Xianran

    2013-01-01

    BiFeO3-PbTiO3 (BF-PT) compounds possess very high Curie temperature and tetragonality compared to other PbTiO3-based piezoceramics. The BaZrO3 (BZ), with weakly ferroelectric active cations, was introduced into the BiFeO3-PbTiO3 to reduce the tetragonality (c/a) and improve the piezoelectric property. For the (0.8-x)BiFeO3-0.2BaZrO3-xPbTiO3, the BaZrO3 substitution can effectively decrease the tetragonality (c/a) from 1.18 to 1.02 for those compositions near the morphotropic phase boundary. The piezoelectric property of BiFeO3-PbTiO3 can be much enhanced with an optimal piezoelectric constant ˜270 pC/N with a reduced TC of 270 °C. Both the temperature dependent dielectric properties and polarization loops verified the existence of antiferroelectric relaxor, which was not observed in previous reported BiFeO3-PbTiO3 based materials.

  12. Thermodynamic properties of neutral and charged oxygen vacancies in BaZrO3 based on first principles phonon calculations.

    PubMed

    Bjørheim, Tor S; Arrigoni, Marco; Gryaznov, Denis; Kotomin, Eugene; Maier, Joachim

    2015-08-28

    The structural, electronic and thermodynamic properties of neutral and positively doubly charged oxygen vacancies in BaZrO3 are addressed by first principles phonon calculations. The calculations are performed using two complementary first principles approaches and functionals; the linear combination of atomic orbitals (LCAO) within the hybrid Hartree-Fock and density functional theory formalism (HF-DFT), and the projector augmented plane wave approach (PAW) within DFT. Phonons are shown to contribute significantly to the formation energy of the charged oxygen vacancy at high temperatures (∼1 eV at 1000 K), due to both its large distortion of the local structure, and its large negative formation volume. For the neutral vacancy, the resulting lattice distortions, and thus the contributions from phonons to the free formation energy, are significantly smaller. As a result, phonons affect the relative stability of the two defects at finite temperatures and the charge transition level for oxygen vacancies (+2/0) changes from 0.42 to 0.83 eV below the conduction band bottom from 0 K to 1000 K. PMID:26211926

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

    NASA Astrophysics Data System (ADS)

    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. Improved solid oxide fuel cell performance with nanostructured electrolytes.

    PubMed

    Chao, Cheng-Chieh; Hsu, Ching-Mei; Cui, Yi; Prinz, Fritz B

    2011-07-26

    Considerable attention has been focused on solid oxide fuel cells (SOFCs) due to their potential for providing clean and reliable electric power. However, the high operating temperatures of current SOFCs limit their adoption in mobile applications. To lower the SOFC operating temperature, we fabricated a corrugated thin-film electrolyte membrane by nanosphere lithography and atomic layer deposition to reduce the polarization and ohmic losses at low temperatures. The resulting micro-SOFC electrolyte membrane showed a hexagonal-pyramid array nanostructure and achieved a power density of 1.34 W/cm(2) at 500 °C. In the future, arrays of micro-SOFCs with high power density may enable a range of mobile and portable power applications. PMID:21657222

  15. Nonstoichiometric fluorides—Solid electrolytes for electrochemical devices: A review

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.; Sobolev, B. P.

    2007-09-01

    The solid electrolytes with fluorine-ion conductivity that were revealed during the analysis of the phase diagrams of the MF m - RF n systems within the program of search for new multicomponent fluoride crystalline materials carried out at the Shubnikov Institute of Crystallography, Russian Academy of Sciences, are described. The most widespread and promising materials are the nonstoichiometric phases with fluorite (CaF2) and tysonite (LaF3) structures, which are formed in the MF2- RF3 systems ( M = Ca, Sr, Ba, Cd, or Pb; R = Sc, Y, or La-Lu). These phases have superionic fluorine conductivity due to the anion sublattice disorder. The ionic conductivity of crystals of both structure types has been studied and the limits of its change with composition and temperature are determined. Nonstoichiometric fluorides are used as solid electrolytes in chemical sensors, fluorine sources, and batteries. The prospects of the use of fluorine-ion conductors in solid-state electrochemical devices, principles of their operation, and the problems of optimization of their composition are discussed.

  16. Strength of an electrolyte supported solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    For the proper function of solid oxide fuel cells (SOFC) their structural integrity must be maintained during their whole lifetime. Any cell fracture would cause leakage and partial oxidization of the anode, leading to a reduced performance, if not catastrophic failure of the whole stack. In this study, the mechanical strength of a state of the art SOFC, developed and produced by Hexis AG/Switzerland, was investigated with respect to the influence of temperature and ageing, whilst for the anode side of the cell the strength was measured under reducing and oxidizing atmospheres. Ball-on-3-Ball bending strength tests and fractography conducted on anode and cathode half-cells revealed the underlying mechanisms, which lead to cell fracture. They were found to be different for the cathode and the anode side and that they change with temperature and ageing. Both anode and cathode sides exhibit the lowest strength at T = 850 °C, which is greatly reduced to the initial strength of the bare electrolyte. This reduction is the consequence of the formation of cracks in the electrode layer which either directly penetrate into the electrolyte (anode side) or locally increase the stress intensity level of pre-existing flaws of the electrolytes at the interface (cathode side).

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

    NASA Astrophysics Data System (ADS)

    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

  18. Advanced materials for high-temperature solid electrolyte applications

    SciTech Connect

    Bates, J.L.; Chick, L.A.; Weber, W.J.; Youngblood, G.E.

    1990-05-01

    Advanced materials for use as electrodes, interconnections, and electrolytes in high-temperature electrochemical applications are under investigation. The air sinterability of La{sub 1-x}Sr{sub x}CrO{sub 3} is highly dependent upon a synergistic relationship between the (La + Sr)/Cr ratio, cation volatility, and second phase formation and transformation. Electrical conductivity in the ZrO{sub 2}--Y{sub 2}O{sub 3}--CeO{sub 2} and ZrO{sub 2}--Y{sub 2}O{sub 3}--TiO{sub 2} systems is highly dependent on composition and atmosphere. The electrochemical processes that occur at the solid-solid-gas interfaces in La(Sr)MnO{sub 3}/ZrO{sub 2}(Y{sub 2}O{sub 3}) have been studied using an unbonded interface cell and impedance spectroscopy. 6 refs., 7 figs.

  19. Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Goldsby, John C.; Choi, Sung R.

    2004-01-01

    Tests have shown that modification of chemical compositions can increase the strengths and fracture toughnesses of solid oxide fuel-cell (SOFC) electrolytes. Heretofore, these solid electrolytes have been made of yttria-stabilized zirconia, which is highly conductive for oxygen ions at high temperatures, as needed for operation of fuel cells. Unfortunately yttria-stabilized zirconia has a high coefficient of thermal expansion, low resistance to thermal shock, low fracture toughness, and low mechanical strength. The lack of strength and toughness are especially problematic for fabrication of thin SOFC electrolyte membranes needed for contemplated aeronautical, automotive, and stationary power-generation applications. The modifications of chemical composition that lead to increased strength and fracture toughness consist in addition of alumina to the basic yttria-stabilized zirconia formulations. Techniques for processing of yttria-stabilized zirconia/alumina composites containing as much as 30 mole percent of alumina have been developed. The composite panels fabricated by these techniques have been found to be dense and free of cracks. The only material phases detected in these composites has been cubic zirconia and a alumina: this finding signifies that no undesired chemical reactions between the constituents occurred during processing at elevated temperatures. The flexural strengths and fracture toughnesses of the various zirconia-alumina composites were measured in air at room temperature as well as at a temperature of 1,000 C (a typical SOFC operating temperature). The measurements showed that both flexural strength and fracture toughness increased with increasing alumina content at both temperatures. In addition, the modulus of elasticity and the thermal conductivity were found to increase and the density to decrease with increasing alumina content. The oxygen-ion conductivity at 1,000 C was found to be unchanged by the addition of alumina.

  20. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    DOE PAGESBeta

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.

    2015-06-23

    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for furthermore » development of this new class of solid electrolytes.« less

  1. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    SciTech Connect

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.

    2015-06-23

    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for further development of this new class of solid electrolytes.

  2. Stability of the Solid Electrolyte Interface on the Li Electrode in Li-S Batteries.

    PubMed

    Zheng, Dong; Yang, Xiao-Qing; Qu, Deyang

    2016-04-27

    By means of high performance liquid chromatography-mass spectroscopy, the concentration of sulfur and polysulfides was determined in nonaqueous electrolytes. The stability of sulfur and Li in eight electrolytes was studied quantitatively. It was found that sulfur reacted with Li in most of the commonly used electrolytes for lithium-sulfur batteries. The reaction products between sulfur and Li were qualitatively identified. In some cases, the solid electrolyte interface on the Li can successfully prevent the interaction between S and Li; however, it was found that the solid electrolyte interface was damaged by polysulfide ions. PMID:27045986

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

    SciTech Connect

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

    1997-12-31

    The intent of this project with Federal Energy Technology Center (FETC)/Morgantown Energy Technology Center (METC) is to develop research infrastructure conductive to Fuel Cell research at Southern University and A and M College, Baton Route. A state of the art research laboratory (James Hall No.123 and No.114) for energy conversion and storage devices was developed during this project duration. The Solid State Ionics laboratory is now fully equipped with materials research instruments: Arbin Battery Cycling and testing (8 channel) unit, Electrochemical Analyzer (EG and G PAR Model 273 and Solartron AC impedance analyzer), Fuel Cell test station (Globe Tech), Differential Scanning Calorimeter (DSC-10), Thermogravimetric Analyzer (TGA), Scanning Tunneling Microscope (STM), UV-VIS-NIR Absorption Spectrometer, Fluorescence Spectrometer, FT-IR Spectrometer, Extended X-ray Absorption Fine Structure (EXAFS) measurement capability at Center for Advanced Microstructure and Devices (CAMD- a multimillion dollar DOE facility), Glove Box, gas hood chamber, high temperature furnaces, hydraulic press and several high performance computers. IN particular, a high temperature furnace (Thermodyne 6000 furnace) and a high temperature oven were acquired through this project funds. The PI Dr. R Bobba has acquired additional funds from federal agencies include NSF-Academic Research Infrastructure program and other DOE sites. They have extensively used the multimillion dollar DOE facility ''Center'' for Advanced Microstructures and Devices (CAMD) for electrochemical research. The students were heavily involved in the experimental EXAFS measurements and made use of their DCM beamline for EXAFS research. The primary objective was to provide hands on experience to the selected African American undergraduate and graduate students in experimental energy research.The goal was to develop research skills and involve them in the Preparation and Characterization of Solid Electrolytes. Ionically

  4. Dye-sensitized solar cell comprising polyethyl methacrylate doped with ammonium iodide solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Vivek Kr.; Bhattacharya, B.; Shukla, S.; Singh, Pramod K.

    2014-09-01

    The aim of the present work was to develop a new solid electrolyte polyethyl methacrylate doped with ammonium iodide polymer electrolyte and its application in dye-sensitized solar cell (DSSC). The electrical, structural and photoelectrochemical properties of polymer electrolytes are presented in detail. DSSCs have been fabricated and characterized. The polymer electrolyte film with maximum ionic conductivity shows maximum efficient DSSC of efficiency 0.43 % at 1 sun condition.

  5. Dye-sensitized solar cell comprising polyethyl methacrylate doped with ammonium iodide solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Vivek Kr.; Bhattacharya, B.; Shukla, S.; Singh, Pramod K.

    2015-03-01

    The aim of the present work was to develop a new solid electrolyte polyethyl methacrylate doped with ammonium iodide polymer electrolyte and its application in dye-sensitized solar cell (DSSC). The electrical, structural and photoelectrochemical properties of polymer electrolytes are presented in detail. DSSCs have been fabricated and characterized. The polymer electrolyte film with maximum ionic conductivity shows maximum efficient DSSC of efficiency 0.43 % at 1 sun condition.

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

    SciTech Connect

    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.

  7. High strength porous support tubes for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Rossing, Barry R.; Zymboly, Gregory E.

    1986-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having an electrode and a solid electrolyte disposed on a porous, sintered support material containing thermally stabilized zirconia powder particles and from about 3 wt. % to about 45 wt. % of thermally stable oxide fibers.

  8. Nanoscale electrochemistry using dielectric thin films as solid electrolytes.

    PubMed

    Valov, Ilia; Lu, Wei D

    2016-08-01

    It is now well known that at the nanoscale matters behave differently compared to bulk phases. Increased reactivity, deviations in structural, thermodynamic and kinetic properties make nanoscale materials and processes attractive for both fundamental research and applications. Here we show that nanometer thin films of materials with dielectric properties at the macroscopic level such as SiO2, Ta2O5 and HfO2 behave as solid electrolytes and exhibit evident ionic transport and electrochemical redox reactions. Experimental studies demonstrate that classical electrochemical potentiodynamic and steady state methods can be used to study the mass and charge transport at the nanoscale. We believe these reported properties of nanomatter open new opportunities for fundamental research and applications. PMID:27150952

  9. Dynamics and morphology of solid electrolyte interphase (SEI).

    PubMed

    Single, Fabian; Horstmann, Birger; Latz, Arnulf

    2016-07-21

    We develop a novel theory for the continuous electrochemical formation of porous films to study the solid electrolyte interphase (SEI) on lithium ion battery anodes. Existing SEI studies model a homogeneous morphology and a single relevant transport mechanism. Our approach, in contrast, is based on two transport mechanisms and enables us to track SEI porosity in a spatially resolved way. SEI thickness evolution agrees with existing studies and is validated with experiments. This consistent approach is unprecedented in SEI modeling. We predict a non-zero SEI porosity and the dependence of morphology on transport properties. Additionally, we capture dual-layer chemistry and morphology. Analytic expressions which describe the parameter dependence of all key properties are derived and discussed. PMID:27327841

  10. Electrical contact structures for solid oxide electrolyte fuel cell

    DOEpatents

    Isenberg, Arnold O.

    1984-01-01

    An improved electrical output connection means is provided for a high temperature solid oxide electrolyte type fuel cell generator. The electrical connection of the fuel cell electrodes to the electrical output bus, which is brought through the generator housing to be connected to an electrical load line maintains a highly uniform temperature distribution. The electrical connection means includes an electrode bus which is spaced parallel to the output bus with a plurality of symmetrically spaced transversely extending conductors extending between the electrode bus and the output bus, with thermal insulation means provided about the transverse conductors between the spaced apart buses. Single or plural stages of the insulated transversely extending conductors can be provided within the high temperatures regions of the fuel cell generator to provide highly homogeneous temperature distribution over the contacting surfaces.

  11. Solid State Electrolytes Prepared from PEO (360) Silanated Silica

    NASA Technical Reports Server (NTRS)

    Maitra, P.; Ding, J.; Liu, B.; Wunder, S. L.; Lin, H.-P.; Chua, D.; Salomon, M.

    2002-01-01

    All solid state composite electrolytes were prepared using fumed silica (SiO2) silanated with an oligomeric polyethylene oxide (PEO) silane containing 6-9 ethylene oxide repeat units, a PEO matrix and LiClO4 (8/1 O/Li). The PEO-silane covalently attached to the silica was amorphous, with a T(sub g) that increased from -90 C to -53 C after attachment. The conductivity of films prepared using the PEO-silanated silica increased to approx. 6 x 10(exp -5) S/cm at RT compared with approx. 1 x 10(-5) S/cm for films prepared with unsilanated SiO2.

  12. Robust solid polymer electrolyte for conducting IPN actuators

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    Linkous, C.A.

    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.

  14. Solid electrolytes and impact-resistant ceramics. [Progress report

    SciTech Connect

    Angell, C.A.

    1991-08-01

    In this proposal, we describe a program to exploit recent achievements in two distinct areas of materials science, both of them dependent on the independent motion of singly charged ions through an immobile matrix. The first is the area of non-crystalline solid electrolytes in which this laboratory has gained prominence over the past decade. The second is an area proposed for study in our previous proposal and now verified as a principle worthy of considerable further investigation: it involves the use of mobile ions for fast absorption of mechanical energy from short time impacts hence inhibition of crack nucleation and failure in glassy substances. In the first area, we will study both glassy and polymeric systems. For glassy solid electrolytes, we will perform the first electrochemical measurements of cation and anion self-diffusion coefficients in glasses, to provide data to compare with neutron scattering results and thereby to resolve a theoretical dispute. We will look for an important but so-far-unstudied relationship between conductivity/viscosity decoupling in fast ion glasses, and fragility of the liquid above the glass transition temperature. In polymer-salt systems, we will perform both diagnostic and developmental studies. We will try to demonstrate a continuity of behavior, as function of solvent content, between highly decoupled glass and over-coupled salt/polymer solution behavior. This will incorporate a study of polymer-salt liquid immiscibility at high temperatures to seek the relationship between salts and molecular diluent as additives to the polymer solvent. We propose also to study the effects of perfluorination on both polymer fragility and glass transition, and also on carboxylate basicity for possible improvements in overall polymer-salt performance.

  15. Support tube for high temperature solid electrolyte electrochemical cell

    DOEpatents

    Ruka, Roswell J.; Rossing, Barry R.

    1986-01-01

    Disclosed is a compound having a fluorite-like structure comprising a solid solution having the general formula [(ZrO.sub.2).sub.1-x (MO.sub.s).sub.x ].sub.1-y [(La.sub.m A.sub.1-m).sub.2-z (Mn.sub.n B.sub.1-n).sub.z O.sub.r ].sub.y where MO.sub.5 is an oxide selected from the group consisting of calcia, yttria, rare earth oxides, and mixtures thereof, x is about 0.1 to 0.3, y is about 0.005 to about 0.06, z is about 0.1 to about 1.9, A is yttrium, rare earth element, alkaline earth element, or mixture thereof, B is iron, nickel, cobalt, or mixture thereof, m is 0.3 to 1, n is 0.5 to 1, and r is 2 to 4. A porous tube made from such a composition can be coated with an electrically conducting mixed oxide electrode such as lanthanum manganite, and can be used in making high temperature electrochemical cells such as solid electrolyte fuel cells.

  16. Flexible solid polymer electrolyte membran formed by photopolymerization

    NASA Astrophysics Data System (ADS)

    Cao, Jinwei; Kyu, Thein

    2014-03-01

    Binary and ternary phase diagrams of poly(ethylene glycol) dimethacrylate (PEGDMA,succinonitrile(SCN), and bis(trifluoromethane)sulfonimide (LiTFSI) blends have been established to provide guidance to fabricationof polymer electrolyte membrane (PEM). The phase diagram of binary PEGDMA/SCN mixture is of a typical eutectic typ, whereas the binary PEGDMA/LiTFSI mixture reveals a eutectic trend exhibiting a wide single phase region at intermediate composition. Likewise, the ternary phase diagram of PEGDMA/SCN/LiTFSI mixture shows a wide isotropic regio. The PEM network, formed by UV-crosslinking of PEGDMA in the isotropic region, is a solid amorphous network, but flexible and stretchable. Ion conductivity of PEMwas measured as a function of temperature at different ratios of PEGDMA/SCN and SCN/LiTFSI. Of particular importance is that these PEM networks possessvery high roo-temperature ion conductivity on the order of 10-3 S cm-1, which reaches the level of 10-2 S cm-1 at elevated temperatures of 60-70 °C. The electrochemical stability of the solid PEM will be evaluated by cyclic voltammetry and its potential applicabilityinflexible lithium ion battery will be discussed.

  17. Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes.

    PubMed

    Michan, Alison L; Divitini, Giorgio; Pell, Andrew J; Leskes, Michal; Ducati, Caterina; Grey, Clare P

    2016-06-29

    The solid electrolyte interphase (SEI) of the high capacity anode material Si is monitored over multiple electrochemical cycles by (7)Li, (19)F, and (13)C solid-state nuclear magnetic resonance spectroscopies, with the organics dominating the SEI. Homonuclear correlation experiments are used to identify the organic fragments -OCH2CH2O-, -OCH2CH2-, -OCH2CH3, and -CH2CH3 contained in both oligomeric species and lithium semicarbonates ROCO2Li, RCO2Li. The SEI growth is correlated with increasing electrode tortuosity by using focused ion beam and scanning electron microscopy. A two-stage model for lithiation capacity loss is developed: initially, the lithiation capacity steadily decreases, Li(+) is irreversibly consumed at a steady rate, and pronounced SEI growth is seen. Later, below 50% of the initial lithiation capacity, less Si is (de)lithiated resulting in less volume expansion and contraction; the rate of Li(+) being irreversibly consumed declines, and the Si SEI thickness stabilizes. The decreasing lithiation capacity is primarily attributed to kinetics, the increased electrode tortuousity severely limiting Li(+) ion diffusion through the bulk of the electrode. The resulting changes in the lithiation processes seen in the electrochemical capacity curves are ascribed to non-uniform lithiation, the reaction commencing near the separator/on the surface of the particles. PMID:27232540

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    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.

  19. Solid-state thin-film supercapacitor with ruthenium oxide and solid electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Yoon, Y. S.; Cho, W. I.; Lim, J. H.; Choi, D. J.

    Direct current reactive sputtering deposition of ruthenium oxide thin films (bottom and top electrodes) at 400°C are performed to produce a solid-state thin-film supercapacitor (TFSC). The supercapacitor has a cell structure of RuO 2/Li 2.94PO 2.37N 0.75 (Lipon)/RuO 2/Pt. Radio frequency, reactive sputtering deposition of an Li 2.94PO 2.37N 0.75 electrolyte film is performed on the bottom RuO 2 film at room temperature to separate the bottom and top RuO 2 electrodes electrically. The stoichiometry of the RuO 2 thin film is investigated by Rutherford back-scattering spectrometry (RBS). X-ray diffraction (XRD) shows that the as-deposited RuO 2 thin film is an amorphous phase. Scanning electron microscopy (SEM) measurements reveal that the RuO 2/Lipon/RuO 2 hetero-interfaces have no inter-diffusion problems. Charge-discharge measurements with constant current at room temperature clearly reveal typical supercapacitor behaviour for a RuO 2/Lipon/RuO 2/Pt cell structure. Since the electrolyte thin film has low ionic mobility, the capacity and cycle performance are inferior to those of a bulk type of supercapacitor. These results indicate that a high performance, TFSC can be fabricated by a solid electrolyte thin film with high ionic conductivity.

  20. Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin films

    NASA Astrophysics Data System (ADS)

    West, W. C.; Whitacre, J. F.; Lim, J. R.

    Sputter deposition of LiPON films directly onto high Li + conductivity solid electrolyte plates has been investigated as a means to minimize the reactivity of the plates to metallic Li. The LiPON films were shown to effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal. The conductivity of the passivated solid electrolyte plates was measured to be 1.0×10 -4 S cm -1, with Arrhenius activation energy of 0.36 eV and an electrochemical stability window of at least 0-5.0 V versus Li/Li +. The passivated solid electrolyte was capable of supporting electrochemical plating and stripping of Li metal, as demonstrated by EIS and CV measurements. These high chemical stability, high Li + conductivity solid electrolyte plates will be useful for solid-state batteries employing Li anodes.

  1. Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

    NASA Technical Reports Server (NTRS)

    Isenberg, Arnold O.

    1989-01-01

    The development of the Three-Man (2.2 lb CO2/man-day) Solid Electrolyte CO2 Electrolysis Breadboard consisted of a Phase 1 and 2 effort. The Phase 1 effort constituted fabrication of three electrolysis cell types and performing parametric testing, off-design testing, and cell life testing. The Phase 2 consisted of the preliminary design, incorporation of palladium (Pd) tubes for hydrogen separation from the electrolyzer cathode feed gases, design support testing, final design, fabrication, and performance testing of the breadboard system. The results of performance tests demonstrated that CO2 electrolysis in an oxygen reclamation system for long duration space-based habitats is feasible. Closure of the oxygen system loop, therefore, can be achieved by CO2 electrolysis. In a two step process the metabolic CO2 and H2O vapor are electrolyzed into O2, H2, and CO. The CO can subsequently be disproportionated into carbon and CO2 in a carbon deposition reactor and the CO2 in turn be recycled and electrolyzed for total O2 recovery. The development effort demonstrated electrolyzer system can be designed and built to operate safely and reliably and the incorporation of Pd tubes for hydrogen diffusion can be integrated safely with predictable performance.

  2. Investigation of solid state electrolyte silver-zinc battery

    NASA Technical Reports Server (NTRS)

    1970-01-01

    Study of the solid electrolyte ZnCl2-2NH3 rechargeable silver zinc electrochemical cell by X-ray diffraction analysis of the reaction products led to the conclusion that some water is consumed when the cell is discharged. Replacement of ZnCl2-2NH3 by ZnCl2-4Zn(OH)2 gave cells with high internal resistance and limited capacity. The salt formed by exposing a fibrous membrane saturated with ZnCl2 solution to fumes from ammonium carbonate in a dry desiccator comprised ZnCl2-4Zn(OH)2, ZnCl2,3NH4Cl and a third unidentified component. The temperature coefficient of open circuit EMF was nearly zero over the range from -25 C to 50 C. The internal resistance and polarization increased substantially below -25 C. There is some indication that exposure to 50 C for 29 hours causes some deterioration.

  3. Separation of gases with solid electrolyte ionic conductors

    SciTech Connect

    Balachandran, U.; Dusek, J.T.; Maiya, P.S.; Mieville, R.L.; Ma, B.; Kleefisch, M.S.; Udovich, C.A.

    1996-11-01

    The authors have developed a novel method of gas separation based on electrolyte ionic membrane technology. Separation of one gas from another occurs through an ion-conducting membrane by the passage of selected ions. Most systems studied have focused on oxygen ion conduction for the separation of oxygen from air, although protonic and halide-conducting solid materials also exist. As an example of this system, this paper concentrates on a study of a membrane reactor used in the production of syngas (CO + H{sub 2}) from methane. The membrane material is a modified perovskite-type oxide exhibiting mixed (electronic/ionic) conductivity. Mixed-conductivity oxides are promising materials for oxygen-permeating membranes that can operate without electrodes or external electrical circuitry. Extruded tubes of this material have been evaluated in a reactor operating at {approx} 850 C for partial oxidation of methane into syngas in the presence of a reforming catalyst. Separated oxygen on one side of the reactor wall was obtained from air on the other side. Methane conversion efficiencies of > 99% were observed, and some of the reactor tubes have been operated for > 1,000 h. Membrane tubes were fabricated from calcined powders by a plastic extrusion technique. Characterization of the mechanical, physical, and chemical properties of this material confirmed the stability exhibited in the reactor.

  4. Adaption of kinetics to solid electrolyte interphase layer formation and application to electrolyte-soluble reaction products

    NASA Astrophysics Data System (ADS)

    Gourdin, Gerald; Zheng, Dong; Qu, Deyang

    2015-12-01

    During the electrochemical lithiation of a carbon electrode, carbonate-based electrolytes react with the electrode surface and undergo reductive decomposition to form a solid electrolyte interphase (SEI) layer that passivates the surface of the carbon electrode. In addition, reduction of the electrolyte also results in the generation of electrolyte-soluble products. Structural similarities between the soluble and insoluble products provide an opportunity to examine the formation kinetics of the SEI layer through an analysis of the kinetic behavior of the soluble products. In this work, the electrolyte-soluble products generated by reductive decomposition of a baseline electrolyte were analyzed at different stages and at different hold times during the initial lithiation of an amorphous carbon electrode. A statistical regression analysis of that data was used to produce a representative lithiation experiment from which was calculated the potential-dependent formation rates for the soluble decomposition products. The predicted formation rate data was fitted using an adapted rate equation that accounts for the effect of the SEI layer to obtain estimated formation rate constants and redox potentials.

  5. Investigation of solid polymer electrolyte gas sensor with different electrochemical techniques

    NASA Astrophysics Data System (ADS)

    Strzelczyk, A.; Jasinski, G.; Chachulski, B.

    2016-01-01

    In this work solid polymer electrolyte (SPE) amperometric sulphur dioxide sensor is investigated. Nafion was used as a membrane electrode and 1M sulphuric acid as an internal electrolyte. Sensor response to sulphur dioxide was measured. Besides traditional constant voltage amperometry also different electrochemical techniques were used. Results obtained by these methods are compared.

  6. Defect chemistry of a BaZrO3 Σ3 (111) grain boundary by first principles calculations and space-charge theory.

    PubMed

    Polfus, Jonathan M; Toyoura, Kazuaki; Oba, Fumiyasu; Tanaka, Isao; Haugsrud, Reidar

    2012-09-21

    Defect calculations from density functional theory are implemented with space-charge theory models to describe the equilibrium defect chemistry of a Σ3 (111) symmetric tilt boundary in BaZrO(3). As such, the space-charge potential and the concentrations of , , , NH and in the bulk, core and space-charge regions of the interface are calculated as a function of temperature and atmospheric conditions. Our results show that the core will be predominated by under hydrating conditions and that the space-charge potential increases with water vapor pressure. Under nitriding conditions, , NH and will predominate the core in different temperature regimes and effects of these defects on the space-charge properties are discussed. PMID:22864195

  7. Flux pinning properties of TFA-MOD (Y,Gd)Ba2Cu3Ox tapes with BaZrO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Awaji, Satoshi; Namba, Masafumi; Watanabe, Kazuo; Miura, Masashi; Yoshizumi, Masateru; Izumi, Teruo; Shiohara, Yuh

    2010-01-01

    A high critical current density Jc with a nearly isotropic angular dependence at 77.3 K was recently obtained by the introduction of nanoparticles to (Y,RE)Ba2Cu3Oy (RE123, RE = Sm, Gd)-coated conductors prepared by trifluoroacetate metal-organic deposition (TFA-MOD). The flux pinning properties were evaluated on the basis of detailed measurements of the upper critical field, the irreversibility field and the critical current density of the TFA-MOD RE123-coated conductor. We found that strong random pinning by the BaZrO3 nanoparticles and weak c-axis correlated pinning by twin boundaries functioned cooperatively in nanoparticles introduced to (Y, Gd)123-coated conductors prepared by TFA-MOD. The coexistence of two different pinning centers played an important role in the nearly isotropic angular dependence of Jc.

  8. In Situ AFM Imaging of Solid Electrolyte Interfaces on HOPG with Ethylene Carbonate and Fluoroethylene Carbonate-Based Electrolytes.

    PubMed

    Shen, Cai; Wang, Shuwei; Jin, Yan; Han, Wei-Qiang

    2015-11-18

    Chemical and morphological structure of solid electrolyte interphase (SEI) plays a vital role in lithium-ion battery (LIB), especially for its cyclability and safety. To date, research on SEI is quite limited because of the complexity of SEI and lack of effective in situ characterization techniques. Here, we present real-time views of SEI morphological evolution using electrochemical atomic force microscopy (EC-AFM). Complemented by an ex situ XPS analysis, fundamental differences of SEI formation from ethylene carbonate (EC) and fluoroethylene carbonate (FEC)-based electrolytes during first lithiation/delithiation cycle on HOPG electrode surface were revealed. PMID:26502161

  9. Development of rechargeable lithium-bromine batteries with lithium ion conducting solid electrolyte

    NASA Astrophysics Data System (ADS)

    Takemoto, Koshin; Yamada, Hirotoshi

    2015-05-01

    Electrochemical performances of a prototype lithium-bromine battery (LBB) employing a solid electrolyte is investigated. The discharge capacity decreases with repeating charge/discharge cycles. Electrochemical impedance analysis reveals that the capacity fading is mainly due to increase in the interfacial resistance between an aqueous active material solution and a solid electrolyte. Based on the results of symmetric cells and structural analysis of the surface of the solid electrolyte immersed in Br2 solutions, it is suggested that a Li+-depletion layer is formed on the surface of the solid electrolyte as a result of contact with bromine. Addition of tetraethylammonium bromide (TEABr) depresses the interfacial resistance, which results in improved cycleability. LBB with 1.0 M LiBr and 0.25 M TEABr shows discharge capacity of 139 mAh/g-LiBr and Coulombic efficiency of 99.6% at 5th cycle.

  10. Thermal Stability of Beta-Alumina Solid Electrolyte Under AMTEC Operating Conditions

    NASA Technical Reports Server (NTRS)

    Williams, R.; Homer, M.; Kulleck, J.; Lara, L.; Kisor, A.; Cortez, R.; Shields, V.; Ryan, M.

    1999-01-01

    A critical component of alkali metal thermal-to electric converter (AMTEC) devices for long duration space missions is the sodium beta-alumina solid electrolyte ceramic (BASE), for which there exists no substitute.

  11. Continuous cross-over from ferroelectric to relaxor state and piezoelectric properties of BaTiO3-BaZrO3-CaTiO3 single crystals

    NASA Astrophysics Data System (ADS)

    Benabdallah, F.; Veber, P.; Prakasam, M.; Viraphong, O.; Shimamura, K.; Maglione, M.

    2014-04-01

    Optimal properties like piezoelectricity can be found in polarizable materials for which the structure changes sharply under small composition variations in the vicinity of their morphotropic phase boundary or the triple point in their isobaric temperature-composition phase diagram. In the latter, lead-free (Ba0.850Ca0.150)(Ti0.900Zr0.100)O3 ceramics exhibit outstanding piezoelectric coefficients. For the first time, we report the growth of piezoelectric lead-free single crystals in the BaTiO3-BaZrO3-CaTiO3 pseudo-ternary system. The stoichiometry control in the CaO-BaO-TiO2-ZrO2 solid solution led to single crystals with various compositions ranging from (Ba0.857Ca0.143)(Ti0.928Zr0.072)O3 to (Ba0.953Ca0.047)(Ti0.427Zr0.573)O3. We evidenced a continuous cross-over from a ferroelectric state at high titanium content to a relaxor one on increasing the zirconium content. Such a property tuning is rather seldom observed in lead-free ferroelectrics and confirms what was already reported for ceramics. Single crystal with (Ba0.838Ca0.162)(Ti0.854Zr0.146)O3 composition, which has been grown and oriented along [001] crystallographic direction, displayed electromechanical coefficients d31 and k31 of 93 pC.N-1 and 0.18, respectively, near the room temperature (T = 305 K).

  12. CRACK GROWTH ANALYSIS OF SOLID OXIDE FUEL CELL ELECTROLYTES

    SciTech Connect

    S. Bandopadhyay; N. Nagabhushana

    2003-10-01

    Defects and Flaws control the structural and functional property of ceramics. In determining the reliability and lifetime of ceramics structures it is very important to quantify the crack growth behavior of the ceramics. In addition, because of the high variability of the strength and the relatively low toughness of ceramics, a statistical design approach is necessary. The statistical nature of the strength of ceramics is currently well recognized, and is usually accounted for by utilizing Weibull or similar statistical distributions. Design tools such as CARES using a combination of strength measurements, stress analysis, and statistics are available and reasonably well developed. These design codes also incorporate material data such as elastic constants as well as flaw distributions and time-dependent properties. The fast fracture reliability for ceramics is often different from their time-dependent reliability. Further confounding the design complexity, the time-dependent reliability varies with the environment/temperature/stress combination. Therefore, it becomes important to be able to accurately determine the behavior of ceramics under simulated application conditions to provide a better prediction of the lifetime and reliability for a given component. In the present study, Yttria stabilized Zirconia (YSZ) of 9.6 mol% Yttria composition was procured in the form of tubes of length 100 mm. The composition is of interest as tubular electrolytes for Solid Oxide Fuel Cells. Rings cut from the tubes were characterized for microstructure, phase stability, mechanical strength (Weibull modulus) and fracture mechanisms. The strength at operating condition of SOFCs (1000 C) decreased to 95 MPa as compared to room temperature strength of 230 MPa. However, the Weibull modulus remains relatively unchanged. Slow crack growth (SCG) parameter, n = 17 evaluated at room temperature in air was representative of well studied brittle materials. Based on the results, further work

  13. PEALD YSZ-based bilayer electrolyte for thin film-solid oxide fuel cells.

    PubMed

    Yu, Wonjong; Cho, Gu Young; Hong, Soonwook; Lee, Yeageun; Kim, Young Beom; An, Jihwan; Cha, Suk Won

    2016-10-14

    Yttria-stabilized zirconia (YSZ) thin film electrolyte deposited by plasma enhanced atomic layer deposition (PEALD) was investigated. PEALD YSZ-based bi-layered thin film electrolyte was employed for thin film solid oxide fuel cells on nanoporous anodic aluminum oxide substrates, whose electrochemical performance was compared to the cell with sputtered YSZ-based electrolyte. The cell with PEALD YSZ electrolyte showed higher open circuit voltage (OCV) of 1.0 V and peak power density of 182 mW cm(-2) at 450 °C compared to the one with sputtered YSZ electrolyte(0.88 V(OCV), 70 mW cm(-2)(peak power density)). High OCV and high power density of the cell with PEALD YSZ-based electrolyte is due to the reduction in ohmic and activation losses as well as the gas and electrical current tightness. PMID:27595193

  14. High-performance solid polymer electrolytes for lithium batteries operational at ambient temperature

    NASA Astrophysics Data System (ADS)

    Mindemark, Jonas; Sun, Bing; Törmä, Erik; Brandell, Daniel

    2015-12-01

    Incorporation of carbonate repeating units in a poly(ε-caprolactone) (PCL) backbone used as a host material in solid polymer electrolytes is found to not only suppress crystallinity in the polyester material, but also give higher ionic conductivity in a wide temperature range exceeding the melting point of PCL crystallites. Combined with high cation transference numbers, this electrolyte material has sufficient lithium transport properties to be used in battery cells that are operational at temperatures down to below 23 °C, thus clearly demonstrating the potential of using non-polyether electrolytes in high-performance all-solid lithium polymer batteries.

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

    NASA Technical Reports Server (NTRS)

    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.

  16. Copper sulfide solid-state electrolytic memory devices

    NASA Astrophysics Data System (ADS)

    You, Liang

    Copper sulfide thin films with electrical switching and memory effect were grown using a chemical vapor reaction apparatus. The formation of copper sulfide film undergoes a process which includes nucleation, growth of nucleation, coalescence into continuous film, and film thickening. The initial phase of the sulfide growth was reaction limited followed by a diffusion limited phase involving out-diffusion of copper. The thin film tends to nucleate and grow at energy favorable sites such as twinning boundary. Sulfidation of polycrystalline copper results in formation of voids at the interface between the copper and its sulfide. (111) copper has the highest sulfidation rate followed by (100) and (110) copper planes. Moreover, the sulfidation rate near the microfabricated plug edge was found to be faster than the rate at the center of the plug. A mechanism based on competing sulfidation sites due to the geometry difference between the plugs' center and their edge is presented to explain this phenomenon. We show for the first time that field-assisted solid-electrolyte copper sulfide thin film device can function as a switch by reversing the voltage polarity between copper and inert metal electrodes through a copper-sulfide layer in planar and vertical structures. The copper oxide at the top of copper sulfide greatly increased the turn-on voltage. The turn-on voltage depends linearly on the film thickness. Copper sulfide devices in micrometer dimension were microfabricated using IC compatible techniques and characterized showing the same switching effect. Electrode contact area effect on switching performance was investigated in term of turn-on voltage, turn-off voltage, on-state resistance and off-state resistance. Four-point resistance measurement unit, Hall Effect and transfer length measurement were also fabricated together with copper sulfide switching devices and they were studied in order to determine the CuxS carrier type, carrier concentration, film resistivity

  17. Optical and surface properties of optically transparent Li3 PO4 solid electrolyte layer for transparent solid batteries.

    PubMed

    Pat, Suat; Özen, Soner; Şenay, Volkan; Korkmaz, Şadan

    2016-07-01

    In this study, optical and surface properties of the optically transparent Li3 PO4 solid electrolyte layer for transparent solid battery have been investigated for the first time. To determine the optical properties, transmittance, absorbance, reflection, refractive index spectra, and optical band gap were determined by UV-Vis spectrophotometer and optical interferometer. The surface property of the transparent Li3 PO4 solid electrolyte was analyzed using atomic force microscopy. One another important parameter is contact angle (CA) surface free energy (SFE). CA and SFE were determined by optical tensiometer. These values probably are a most important parameter for polymer and hybrid battery performance. For the best performance, value of CA should be low. As a result, solid electrolyte layer is a highly transparent and it has a high wettability. SCANNING 38:317-321, 2016. © 2015 Wiley Periodicals, Inc. PMID:26435203

  18. Artificial Solid Electrolyte Interphase to Address the Electrochemical Degradation of Silicon Electrodes

    SciTech Connect

    Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu; Li, Juchuan

    2014-01-01

    Electrochemical degradation on Si anodes prevents them from being successfully used in lithium-ion full cells. Unlike the case of graphite anodes, natural solid electrolyte interphase (SEI) films generated from carbonate electrolyte do not self-passivate on Si and causes continuous electrolyte decomposition. In this work we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphor oxynitride (Lipon), that conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, significant effect is observed in suppressing the electrolyte decomposition, while Lipon of thinner than 40 nm has little effect. Ionic and electronic conductivity measurement reveals that the artificial SEI is effective when it is a pure ionic conductor, and the electrolyte decomposition is not suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40~50 nm. This work provides guidance for designing artificial SEI for high capacity lithium-ion battery electrodes using solid electrolyte materials.

  19. Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

    PubMed

    Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

    2014-07-01

    Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials. PMID:24926882

  20. Ionically conducting polymers: Principles and properties of solid electrolytes

    SciTech Connect

    Skotheim, T.; Okamoto, Y.

    1987-01-01

    The recent success in developing rechargeable lithium batteries incorporating polyether-based electrolytes has led to the anticipation of a wider use of polymer electrolytes in a host of different applications. The polymers with the best combinations of solvation power, conductivity and electrochemical stability are all based on either PEO or polymers incorporating a high density of EO units. PEO-based electrolytes still yield the highest conductivities at elevated temperatures (approx.100/sup 0/C) when it is completely amorphous. What has emerged during the last ten years of research on polymer electrolytes is the central importance of the amorphous state for high conductivity, where the ion mobility is governed by the mobility associated with a low glass transition temperature. The difference between polymer and liquid electrolytes is that in the former the solvating part does not migrate with the ions. There is, however, still some controversy concerning the nature of the ionic species, i.e. whether the salt is present in the form of associated ions. The intensive research of the last few years has led to a far better understanding of these polymer-ion complexes. Several different types of solvating polymers have been developed, in particular single ion conductors, which represent much of the future of ion conducting polymer research. 36 refs.

  1. Hybrid Lithium-Sulfur Batteries with a Solid Electrolyte Membrane and Lithium Polysulfide Catholyte.

    PubMed

    Yu, Xingwen; Bi, Zhonghe; Zhao, Feng; Manthiram, Arumugam

    2015-08-01

    Lithium-sulfur (Li-S) batteries are receiving great attention as the most promising next-generation power source with significantly high charge-storage capacity. However, the implementation of Li-S batteries is hampered by a critical challenge because of the soluble nature of the intermediate polysulfide species in the liquid electrolyte. The use of traditional porous separators unavoidably allows the migration of the dissolved polysulfide species from the cathode to the lithium-metal anode and results in continuous loss of capacity. In this study, a LiSICON (lithium super ionic conductor) solid membrane is used as a cation-selective electrolyte for lithium-polysulfide (Li-PS) batteries to suppress the polysulfide diffusion. Ionic conductivity issue at the lithium metal/solid electrolyte interface is successfully addressed by insertion of a "soft", liquid-electrolyte integrated polypropylene interlayer. The solid LiSICON lithium-ion conductor maintains stable ionic conductivity during the electrochemical cycling of the cells. The Li-PS battery system with a hybrid solid/liquid electrolyte exhibits significantly enhanced cyclability relative to the cells with the traditional liquid-electrolyte integrated porous separator. PMID:26161547

  2. A high-input impedance differential millivolt meter for use with solid ceramic oxygen electrolyte cells

    NASA Technical Reports Server (NTRS)

    Williams, R. J.; Mullins, O.; Quin, E.

    1975-01-01

    Design factors are given for a high-input impedance differential millivolt meter designed, built, and tested as an inexpensive solid-state electronic system for use in measuring the electromotive force from solid ceramic oxygen electrolyte cells. A schematic diagram is included.

  3. All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes.

    PubMed

    Lago, Nerea; Garcia-Calvo, Oihane; Lopez del Amo, Juan Miguel; Rojo, Teofilo; Armand, Michel

    2015-09-21

    Lithium-based rechargeable batteries offer superior specific energy and power, and have enabled exponential growth in industries focused on small electronic devices. However, further increases in energy density, for example for electric transportation, face the challenge of harnessing the lithium metal as negative electrode instead of limited-capacity graphite and its heavy copper current collector. All-solid-state batteries utilize solid polymer electrolytes (SPEs) to overcome the safety issues of liquid electrolytes. We demonstrate an all-solid-state lithium-ion battery by using plasticized poly(ethylene oxide)-based SPEs comprising anions grafted or co-grafted onto ceramic nanoparticles. This new approach using grafted ceramic nanoparticles enables the development of a new generation of nanohybrid polymer electrolytes with high ionic conductivity as well as high electrochemical and mechanical stability, enabling Li-ion batteries with long cycle life. PMID:26373359

  4. All-solid-state proton battery using gel polymer electrolyte

    SciTech Connect

    Mishra, Kuldeep; Pundir, S. S.; Rai, D. K.

    2014-04-24

    A proton conducting gel polymer electrolyte system; PMMA+NH{sub 4}SCN+EC/PC, has been prepared. The highest ionic conductivity obtained from the system is 2.5 × 10−4 S cm{sup −1}. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO{sub 4}⋅7H{sub 2}O anode and MnO{sub 2} cathode. The open circuit voltage of the battery is 1.4 V and the highest energy density is 5.7 W h kg−1 for low current drain.

  5. Thin-film electrolytes for reduced temperature solid oxide fuel cells

    SciTech Connect

    Visco, S.J.; Wang, L.S.; De Souza, S.; De Jonghe, L.C.

    1994-11-01

    Solid oxide fuel cells produce electricity at very high efficiency and have very low to negligible emissions, making them an attractive option for power generation for electric utilities. However, conventional SOFC`s are operated at 1000{degrees}C or more in order to attain reasonable power density. The high operating temperature of SOFC`s leads to complex materials problems which have been difficult to solve in a cost-effective manner. Accordingly, there is much interest in reducing the operating temperature of SOFC`s while still maintaining the power densities achieved at high temperatures. There are several approaches to reduced temperature operation including alternative solid electrolytes having higher ionic conductivity than yttria stabilized zirconia, thin solid electrolyte membranes, and improved electrode materials. Given the proven reliability of zirconia-based electrolytes (YSZ) in long-term SOFC tests, the use of stabilized zirconia electrolytes in reduced temperature fuel cells is a logical choice. In order to avoid compromising power density at intermediate temperatures, the thickness of the YSZ electrolyte must be reduced from that in conventional cells (100 to 200 {mu}m) to approximately 4 to 10 {mu}m. There are a number of approaches for depositing thin ceramic films onto porous supports including chemical vapor deposition/electrochemical vapor deposition, sol-gel deposition, sputter deposition, etc. In this paper we describe an inexpensive approach involving the use of colloidal dispersions of polycrystalline electrolyte for depositing 4 to 10 {mu}m electrolyte films onto porous electrode supports in a single deposition step. This technique leads to highly dense, conductive, electrolyte films which exhibit near theoretical open circuit voltages in H{sub 2}/air fuel cells. These electrolyte films exhibit bulk ionic conductivity, and may see application in reduced temperature SOFC`s, gas separation membranes, and fast response sensors.

  6. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    DOE PAGESBeta

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; Herbert, Erik G.; Dudney, Nancy J.; Wolfenstine, Jeff; Sakamoto, Jeff; Seigel, Donald

    2015-12-16

    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 barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte s shear modulus increases. Inmore » the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.« less

  7. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    SciTech Connect

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; Herbert, Erik G.; Dudney, Nancy J.; Wolfenstine, Jeff; Sakamoto, Jeff; Seigel, Donald

    2015-12-16

    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 barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte s shear modulus increases. In the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.

  8. Metallization pattern on solid electrolyte or porous support of sodium battery process

    DOEpatents

    Kim, Jin Yong; Li, Guosheng; Lu, Xiaochuan; Sprenkle, Vincent L.; Lemmon, John P.

    2016-05-31

    A new battery configuration and process are detailed. The battery cell includes a solid electrolyte configured with an engineered metallization layer that distributes sodium across the surface of the electrolyte extending the active area of the cathode in contact with the anode during operation. The metallization layer enhances performance, efficiency, and capacity of sodium batteries at intermediate temperatures at or below about 200.degree. C.

  9. Lithium dendrite growth through solid polymer electrolyte membranes

    NASA Astrophysics Data System (ADS)

    Harry, Katherine; Schauser, Nicole; Balsara, Nitash

    2015-03-01

    Replacing the graphite-based anode in current batteries with a lithium foil will result in a qualitative increase in the energy density of lithium batteries. The primary reason for not adopting lithium-foil anodes is the formation of dendrites during cell charging. In this study, stop-motion X-ray microtomography experiments were used to directly monitor the growth of lithium dendrites during electrochemical cycling of symmetric lithium-lithium cells with a block copolymer electrolyte. In an attempt to understand the relationship between viscoelastic properties of the electrolyte on dendrite formation, a series of complementary experiments including cell cycling, tomography, ac impedance, and rheology, were conducted above and below the glass transition temperature of the non-conducting poly(styrene) block; the conducting phase is a mixture of rubbery poly(ethylene oxide) and a lithium salt. The tomography experiments enable quantification of the evolution of strain in the block copolymer electrolyte. Our work provides fundamental insight into the dynamics of electrochemical deposition of metallic films in contact with high modulus polymer electrolytes. Rational approaches for slowing down and, perhaps, eliminating dendrite growth are proposed.

  10. A hybrid gel-solid-state polymer electrolyte for long-life lithium oxygen batteries.

    PubMed

    Luo, Wen-Bin; Chou, Shu-Lei; Wang, Jia-Zhao; Kang, Yong-Mook; Zhai, Yu-Chun; Liu, Hua-Kun

    2015-05-14

    A hybrid gel-solid-state polymer electrolyte has been used as the separator and an electrolyte for lithium oxygen batteries. It can not only avoid electrolyte evaporation but also protect the lithium metal anode during reactions over long-term cycling. Due to its high ionic conductivity and low activation energy, excellent cycling performance is demonstrated, in which the terminal voltage is higher than 2.2 V after 140 cycles at 0.4 mA cm(-2), with a capacity of 1000 mA h g(composite)(-1). PMID:25874974

  11. Electrolytes

    MedlinePlus

    ... part of blood that doesn't contain cells. Sodium, potassium, and chloride levels can also be measured as part of ... in urine. It test the levels of calcium, chloride, potassium, sodium, and other electrolytes.

  12. Electrolytes

    MedlinePlus

    ... part of blood that doesn't contain cells. Sodium, potassium, and chloride levels can also be measured as part of ... in urine. It test the levels of calcium, chloride, potassium, sodium, and other electrolytes. References Chernecky CC, Berger BJ. ...

  13. Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

    PubMed

    Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

    2014-12-01

    Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers. PMID:25971069

  14. Modeling solid electrolyte/electrode interface stability using first principles calculations

    NASA Astrophysics Data System (ADS)

    Lepley, Nicholas; Holzwarth, N. A. W.

    2015-03-01

    The formation of a stable interface between electrode and electrolyte materials is a necessary property for batteries in general and for Li-ion batteries in particular. We present a framework for understanding and predicting the electrochemical stability of electrode/electrolyte interfaces based on density functional theory calculations. Within this framework, we have extended our previous work to include quantitative results for the solid-solid interface energy of the Li3PS4/Li, Li3PO4/Li, Li2S/Li, Li2O/Li, and Li3PS4/Li2S interfaces. We show that under local equilibrium conditions the interface energy appears to be a good indicator of the stability of the interface. While the results we present are focused on the interface between Li-ion solid electrolytes and Li metal we expect the method to be applicable to other interface systems. Supported by NSF Grant DMR-1105485.

  15. Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Manko, David J.; Koch, Hermann; Enayetullah, Mohammad A.; Appleby, A. John

    1989-01-01

    Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.

  16. Isn't the space-charge potential in ceria-based solid electrolytes largely overestimated?

    PubMed

    Kim, Sangtae

    2016-07-20

    The effective ionic conductivity of polycrystalline solid electrolytes that conduct oxide ions or protons is known to be markedly below those of the corresponding single crystals due to substantial current obstruction across the grain boundary. Numerous studies have previously demonstrated that the ionic charge carriers deplete in the vicinity of the grain boundary to form a potential barrier at the grain boundary, which further impedes the current across the grain boundary. Hence an accurate estimation of the barrier height is essential to acquire a comprehensive and precise mechanistic picture of the ionic current in solid electrolytes. The values of the potential barrier height, i.e. equivalent to the equilibrium space-charge potential with the opposite sign, in prominent solid electrolytes such as ceria solid solutions are available in the literature and were determined exclusively from the ratio of the resistivity of the grain boundary to that of the crystal interior. Here I present the results clearly demonstrating that the resistivity ratio yields considerable overestimation of the barrier height even in relatively diluted solid solutions of ceria. These results imply that the space charge is unlikely the sole origin of the large current obstruction across the grain boundary in ceria-based solid electrolytes. PMID:27388961

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

    NASA Astrophysics Data System (ADS)

    de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

    2016-03-01

    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 with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid 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.

  18. Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures.

    PubMed

    Zhang, Jinshui; Bai, Ying; Sun, Xiao-Guang; Li, Yunchao; Guo, Bingkun; Chen, Jihua; Veith, Gabriel M; Hensley, Dale K; Paranthaman, Mariappan Parans; Goodenough, John B; Dai, Sheng

    2015-05-13

    The growth and proliferation of lithium (Li) dendrites during cell recharge are currently unavoidable, which seriously hinders the development and application of rechargeable Li metal batteries. Solid electrolytes with robust mechanical modulus are regarded as a promising approach to overcome the dendrite problems. However, their room-temperature ionic conductivities are usually too low to reach the level required for normal battery operation. Here, a class of novel solid electrolytes with liquid-like room-temperature ionic conductivities (>1 mS cm(-1)) has been successfully synthesized by taking advantage of the unique nanoarchitectures of hollow silica (HS) spheres to confine liquid electrolytes in hollow space to afford high conductivities (2.5 mS cm(-1)). In a symmetric lithium/lithium cell, the solid-like electrolytes demonstrate a robust performance against the Li dendrite problem, preventing the cell from short circuiting at current densities ranging from 0.16 to 0.32 mA cm(-2) over an extended period of time. Moreover, the high flexibility and compatibility of HS nanoarchitectures, in principle, enables broad tunability to choose desired liquids for the fabrication of other kinds of solid-like electrolytes, such as those containing Na(+), Mg(2+), or Al(3+) as conductive media, providing a useful alternative strategy for the development of next generation rechargeable batteries. PMID:25844598

  19. Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures

    SciTech Connect

    Zhang, Jinshui; Bai, Ying; Sun, Xiao-Guang; Li, Yunchao; Guo, Bingkun; Chen, Jihua; Veith, Gabriel M; Hensley, Dale K; Paranthaman, Mariappan Parans; Goodenough, John B; Dai, Sheng

    2015-01-01

    The growth and proliferation of lithium (Li) dendrites during cell recharge is unavoidable, which seriously hinders the development and application of rechargeable Li metal batteries. Solid electrolytes with robust mechanical modulus are regarded as a promising approach to overcome the dendrite problems. However, their room-temperature ionic conductivities are usually too low to reach the level required for normal battery operation. Here, a class of novel solid electrolytes with liquid-like room-temperature ionic conductivities (> 1 mS cm-1) has been successfully synthesized by taking advantage of the unique nanoarchitectures of hollow silica (HS) spheres to confine liquid electrolytes in hollow space to afford high conductivities. In a symmetric lithium/lithium cell, such kind of solid-like electrolytes demonstrates a robust performance against Li dendrite problems, well stabilizing the cell system from short circuiting in a long-time operation at current densities ranging from 0.16 to 0.32 mA cm-2. Moreover, the high flexibility and compatibility of HS nanoarchitectures, in principle, enables broad tunability to choose desired liquids for the fabrication of other kinds of solid-like electrolytes, such as those containing Na+, Mg2+ or Al3+ as conductive media, providing a useful alternative strategy for the development of next generation rechargeable batteries.

  20. Epitaxial thin-film growth of Ruddlesden-Popper-type Ba3Zr2O7 from a BaZrO3 target by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Butt, Shariqa Hassan; Rafique, M. S.; Siraj, K.; Latif, A.; Afzal, Amina; Awan, M. S.; Bashir, Shazia; Iqbal, Nida

    2016-07-01

    Ruddlesden-Popper Ba3Zr2O7 thin films have been synthesized via pulsed laser deposition (PLD) technique. The optimization of deposition parameters in PLD enables the formation of thin film of metastable Ba3Zr2O7 phase from BaZrO3 target. In order to see the post-annealing effects on the structural and optical properties, the deposited Ba3Zr2O7 thin films were annealed at 500, 600 and 800 °C. X-ray diffraction (XRD) reveals the formation of Ba3Zr2O7 phase with tetragonal structure. The changes in the surface of the deposited films were analysed by FE-SEM and AFM. The thin film post-annealed at 500 °C exhibited the best structural, optical and surface properties. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Zr and O exist mainly in the form of Ba3Zr2O7 Ruddlesden-Popper-type perovskite structure.

  1. Isotropic and anisotropic pinning in TFA-grown YBa2Cu3O7 - x films with BaZrO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Palau, A.; Bartolomé, E.; Llordés, A.; Puig, T.; Obradors, X.

    2011-12-01

    YBCO films grown by the trifluoroacetate (TFA) method with increasing number of BaZrO3 (BZO) nanoparticles have been measured by in-field angular transport measurements to investigate changes in the pinning landscape. The isotropic and anisotropic contributions to the critical current density, Jc(H), with the magnetic field applied in H\\parallel c and H\\parallel ab orientation have been determined, allowing us to characterize the population of isotropic and correlated defects along the c axis and ab planes. First, the influence of the YBCO oxygenation process on the formation of different sorts of anisotropic defects in standard films is demonstrated. Next, we show that the addition of non-coherent BZO nanoparticles to the YBCO matrix produces an expansion of the single-vortex pinning regime toward higher fields, due to the presence of isotropic pinning centers. Moreover, by increasing the amount of isotropic defects in the BZO nanocomposites it is possible to extend the region dominated by strong isotropic pinning centers to large magnetic fields and thus enhance the irreversibility line.

  2. Controlling BaZrO3 nanostructure orientation in YBa2Cu3O{}_{7-\\delta } films for a three-dimensional pinning landscape

    NASA Astrophysics Data System (ADS)

    Wu, J. Z.; Shi, J. J.; Baca, F. J.; Emergo, R.; Wilt, J.; Haugan, T. J.

    2015-12-01

    The orientation phase diagram of self-assembled BaZrO3 (BZO) nanostructures in c-oriented YBa2Cu3O{}7-δ (YBCO) films on flat and vicinal SrTiO3 substrates was studied experimentally with different dopant concentrations and vicinal angles and theoretically using a micromechanical model based on the theory of elasticity. The organized BZO nanostructure configuration was found to be tunable, between c-axis to ab-plane alignment, by the dopant concentration in the YBCO film matrix strained via lattice mismatched substrates. The correlation between the local strain caused by the BZO doping and the global strain on the matrix provides a unique approach for controllable growth of dopant nanostructure landscapes. In particular, a mixed phase of the c-axis-aligned nanorods and the ab-plane-aligned planar nanostructures can be obtained, leading to a three-dimensional pinning landscape with single impurity doping and much improved J c in almost all directions of applied magnetic field.

  3. Thin Film Electrodes with an Integral Current Collection Grid for Use with Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    Ryan, M. A.; Kisor, A.; Williams, R. M.; Jeffries-Nakamura, B.; O'Connor, D.

    1994-01-01

    Thin film, high performance electrodes which can operate in high temperature environments are necessary for many devices which use a solid electrolyte. Electrodes of rhodium-tungsten alloy have been deposited on solid electrolyte using photolytic chemical vapor deposition (PCVD). A technique for depositing electrodes and current collection grids simultaneously has been developed using the prenucleation characteristics of PCVD. This technique makes it possible to fabricate electrodes which allow vapor transport through the thin (<1 (micro)m) portions of the electrode while integral thick grid lines improve the electronic conductivity of the electrode, thus improving overall performance.

  4. Electromotive force measurements on cells involving beta-alumina solid electrolyte

    NASA Technical Reports Server (NTRS)

    Choudhury, N.

    1973-01-01

    Open circuit emf measurements have been made to demonstrate that a two-phase, polycrystalline mixture of beta- alumina and alpha-alumina could be used as a solid electrolyte in galvanic cells with reversible electrodes fixing oxygen or aluminum chemical potentials. These measurements indicate that such a two phase solid electrolyte can be used to monitor oxygen chemical potentials as low as that corresponding to Al, Al2O3 coexistence. The activity of Na2O in beta-alumina in coexistence with alpha-alumina was also determined by emf measurements.

  5. Electromotive force measurements on cells involving beta-alumina solid electrolyte

    NASA Technical Reports Server (NTRS)

    Choudhury, N. S.

    1973-01-01

    Open-circuit emf measurements have been made to demonstrate that a two-phase, polycrystalline mixture of beta-alumina and alpha-alumina could be used as a solid electrolyte in galvanic cells with reversible electrodes fixing oxygen or aluminum chemical potentials. These measurements indicate that such a two-phase solid electrolyte may be used to monitor oxygen chemical potentials as low as that corresponding to Al and Al2O3 coexistence (potentials of about 10 to the minus 47th power atm at 1000 K). The activity of Na2O in beta-alumina in coexistence with alpha-alumina was also determined by emf measurements.

  6. Bipolar switching polarity reversal by electrolyte layer sequence in electrochemical metallization cells with dual-layer solid electrolytes.

    PubMed

    Soni, Rohit; Meuffels, Paul; Petraru, Adrian; Hansen, Mirko; Ziegler, Martin; Vavra, Ondrej; Kohlstedt, Hermann; Jeong, Doo Seok

    2013-12-21

    Bipolar switching behaviours of electrochemical metallization (ECM) cells with dual-layer solid electrolytes (SiOx-Ge0.3Se0.7) were analyzed. Type 1 ECM cell, Pt (bottom electrode)/SiOx/Ge0.3Se0.7/Cu (top electrode), exhibited typical eightwise current-voltage (I-V) hysteresis of ECM cells whereas Type 2 ECM cell, Pt (bottom electrode)/Ge0.3Se0.7/SiOx/Cu(top electrode), showed counter-eightwise hysteresis. In addition, absolute off-switching voltage in Type 2 cell is lower than that in Type 1 cell while on-switching voltage in both cells is almost the same. An attempt to understand this electrolyte-stack-sequence-depending switching polarity reversal was made in terms of the ECM cell potential change upon the electrolyte stack sequence and the consequent change in Cu filament growth direction. Relevant experimental evidence for the hypothesis was obtained regarding the switching behaviours. Furthermore, given the switching polarity reversal, feasibility of serial complementary resistive switches was also demonstrated. PMID:24177268

  7. The formation and stability of the solid electrolyte interface on the graphite anode

    NASA Astrophysics Data System (ADS)

    Agubra, Victor A.; Fergus, Jeffrey W.

    2014-12-01

    The solid electrolyte interface (SEI) layer plays a critical role in the cycle life of Li-ion batteries. The potential difference across the SEI during charging results in the potential for Li+ intercalation at the graphite-SEI interface to be lower than the potential at the SEI-electrolyte interface, which can prevent electrolyte reduction and decomposition. The stability of the SEI layer at certain critical battery operating conditions remains a challenge in the performance of lithium ion batteries. Electrolyte additives and surface modification of the anode electrode have been shown to improve the formation of an effective SEI layer. However, there is still a need for improving the robustness of the SEI to withstand extreme battery operating conditions. In this paper, the formation and stability of the SEI layer for lithium ion batteries is reviewed. This review includes discussion of the formation, growth and stability of the SEI on graphite anode materials.

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

    SciTech Connect

    Schroeder, D.J.; Hubaud, A.A.; Vaughey, J.T.

    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.

  9. Comparative determination of effective transport numbers in solid lithium electrolytes

    NASA Astrophysics Data System (ADS)

    Fritz, H. P.; Kuhn, A.

    A comparison of the effective transport numbers t+ of the lithium cation in immobilized liquid electrolytes, obtained by mixing molar solutions of LiClO 4 in propylene carbonate with varying amounts and types of highly-dispersed pyrogenic silica is presented. The results vary from 0.1 to 0.4 as determined by (i) a.c. complex impedance spectroscopy; (ii) isothermal transient ionic current method; (iii) steady-state current method, and (iv) Tubandt method. Main object of this study was to evaluate the value of the four methods as simple, practiclly useful measn to check effective cationic transport numbers of ionic conductors without extensive ion aggregation.

  10. Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

    2014-03-01

    With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  12. A new look at the solid electrolyte interphase on graphite anodes in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Edström, Kristina; Herstedt, Marie; Abraham, Daniel P.

    The solid electrolyte interphase (SEI) of graphite electrodes has been extensively studied using surface sensitive techniques such as photoelectron spectroscopy (PES) and soft X-ray spectroscopy. By combining measurements of reference compounds with graphite electrodes cycled in different electrolytes and under different conditions, knowledge of the solid electrolyte interphase (SEI) chemistry can be obtained. In this article, conclusive results concerning the chemical composition of the inorganic part of the SEI is described. The results show that Li 2O often reported to be present in the SEI could be an artifact from abusive Ar + sputtering. The presence of Li 2CO 3 is a matter of debate; the compound is not observed in anodes extracted from hermetically sealed cells that are never exposed to air. The results show that cell-design and sample handling are crucial to the observed chemical composition of the SEI.

  13. Basic investigation into the production of oxygen in a solid electrolyte process

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1981-01-01

    Mission analyses indicated that by extracting oxygen from the Martian atmosphere, which consists primarily of carbon dioxide, the launch mass of a spacecraft can be reduced by such an amount that samples from the planet can be returned to earth. The solid electrolyte process for producing O2 from CO2 was investigated. A model of the thermodynamic and electrochemical processes in the electrolyte cell was postulated, thereby establishing the parameters influencing the effectiveness and efficiency of an in situ O2 production system. The major operating parameters were investigated over a wide range of temperature and pressure. Operating limits imposed by the solid electrolyte material, 8% yttria stabilized zirconia, were determined as a function of the operating temperature.

  14. [Some aspects of water electrolysis with the use of a solid polymer electrolyte].

    PubMed

    Zorina, N G

    2006-01-01

    Electrochemical process in cells with a solid polymer electrolyte is dependent on catalyst durability in harsh environments and catalyst sputtering technology to ensure efficient power consumption. Active polymer electrolytes will permit to reduce substantially non-productive layouts and design a cost-effective, compact and safe system generator of high-purity oxygen and hydrogen. The existing designs of combined oxide systems integrating rear-earth and earth metals with a structure of Ln3+x Me2+1-x CoO3 containing perofskites were shown to be active catalysts in cells with a solid polymer electrolyte, and the sputtering technology was proven to reduce non-productive layouts in 2 or 2.5 times. PMID:17405280

  15. Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

    2002-01-01

    Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

  16. Gas-potentiometric method with solid electrolyte oxygen sensors for the investigation of combustion.

    PubMed

    Lorenz, H; Tittmann, K; Sitzki, L; Trippler, S; Rau, H

    1996-09-01

    Gas-potentiometric analysis using oxide-ion-conducting solid electrolytes as stabilized zirconia is a worthwhile method for the investigation of combustion processes. In the case of gas and oil flames specific parameters like the flame contour, the degree of burn-out and mixing can be determined and information about flame turbulence and reaction density can be gained from the temporal resolution of the sensor signal. Measurements carried out with solid electrolyte oxygen sensors in a fluidized bed show that combustion processes of solid fuels are also analyzable. This analysis results in fuel specific burn-out curves finally leading to burn-out times and to parameters of a macrokinetics of the combustion process as well as to ideas about the burn-out mechanism. From the resulting constants of the effective reaction rate a reactivity relative to bituminous coal coke can be given for any solid fuel. PMID:15048356

  17. Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lü, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B

    2016-08-16

    A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles. PMID:27356953

  18. First Principles Study of Electrochemical and Chemical Stability of the Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yizhou; He, Xingfeng; Mo, Yifei

    All-solid-state Li-ion battery is a promising next-generation energy-storage technology. Using novel ceramic solid electrolyte materials, all-solid-state battery has advantages of intrinsic safety and high energy density compared to current Li-ion batteries based on organic liquid electrolyte. However, the power density achieved in all-solid-state battery is still unsatisfactory. The high interfacial resistance at electrode-electrolyte interface is one of the major limiting factors. Here we demonstrated a computational approach based on first principles calculation to systematically investigate the chemical and electrochemical stability of solid electrolyte materials, and provide insightful understanding of the degradation and passivation mechanisms at the interface. Our calculation revealed that the intrinsic stability of solid electrolyte materials and solid electrolyte-electrode interfaces is limited and the formation of interphase layers are thermodynamically favorable. Our study demonstrated a computational scheme to evaluate the electrochemical and chemical stability of the solid interfaces. Our newly gained understanding provided principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries. This work was supported by Office of Energy Efficiency and Renewable Energy (DE-EE0006860).

  19. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes.

    PubMed

    Tselev, Alexander; Morozovska, Anna N; Udod, Alexei; Eliseev, Eugene A; Kalinin, Sergei V

    2014-11-01

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann-Planck-Nernst-Einstein theory and Vegard's law while taking account of the electromigration and diffusion. The characteristic time scales involved in the formation of the ESM response were identified. It was found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces can be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid. PMID:25302673

  20. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

    DOE PAGESBeta

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; Eliseev, Eugene A.; Kalinin, Sergei V.

    2014-10-10

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces canmore » be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.« less

  1. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

    SciTech Connect

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; Eliseev, Eugene A.; Kalinin, Sergei V.

    2014-10-10

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces can be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.

  2. High voltage electric double layer capacitor using a novel solid-state polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Sato, Takaya; Marukane, Shoko; Morinaga, Takashi; Kamijo, Toshio; Arafune, Hiroyuki; Tsujii, Yoshinobu

    2015-11-01

    We designed and fabricated a bipolar-type electric double layer capacitor (EDLC) with a maximum 7.5 V operating voltage using a new concept in solid electrolytes. A cell having a high operating voltage, that is free from liquid leakage and is non-flammable is achieved by a bipolar design utilizing a solid polymer electrolyte made up of particles in a three-dimensional array, such as crystals composed of 75 wt% of hybrid particles decorated with a concentrated ionic liquid polymer brush (PSiP) and 25wt% of an ionic liquid (IL). The resulting solid film had sufficient physical strength and a high enough ionic conductivity to function as an electrolyte. Solidification as well as ionic conduction is due to the regular array of PSiPs, thereby producing a high ion-conductivity from a networked path between cores containing an appropriate amount of IL as a plasticizer. The demonstration cell shows a relatively good cycle durability and rate properties up to a 10C discharge process. It also has a very small leakage current in continuous charging and better self-discharge properties, even at 60 °C, compared with conventional cells. This paper demonstrates the first successful fabrication of a bipolar EDLC in a simple structure using this novel polymer solid electrolyte.

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

    DOEpatents

    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.

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

    DOEpatents

    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. Status of the development of solid polymer electrolyte water electrolysis for large scale hydrogen generation

    NASA Astrophysics Data System (ADS)

    Russell, J. H.

    1982-02-01

    Solid polymer electrolyte water electrolysis for large scale hydrogen generation is reported. The program was aimed at performance improvement. Reductions in cell impedance were demonstrated which improve cell performance by over 100 mV. A prototype 500 SCFH system for field evaluation was developed.

  6. An update of solid polymer electrolyte water electolysis programs at General Electric

    NASA Astrophysics Data System (ADS)

    Russell, J. H.

    At the previous two world hydrogen energy conferences in 1976 and 1978 the status of General Electric solid polymer electrolyte water electrolysis development program for large scale hydrogen generator was presented (Nuttall 1976, 1978). This paper updates the progress of this ongoing development program and also describes several new associated programs aimed at gaining early field experience on prototype systems.

  7. Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin film

    NASA Technical Reports Server (NTRS)

    West, W. C.; Whitacre, J. F.; Lim, J. R.

    2004-01-01

    Sputter deposition of LiPON films directly onto high Li+ conductivity solid electrolyte plates has been investigated as a means to minimize the reactivity of the plates to metallic Li. The LiPON films were shown to effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal.

  8. Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts.

    PubMed

    Busche, Martin R; Drossel, Thomas; Leichtweiss, Thomas; Weber, Dominik A; Falk, Mareike; Schneider, Meike; Reich, Maria-Louisa; Sommer, Heino; Adelhelm, Philipp; Janek, Jürgen

    2016-05-01

    The discharging and charging of batteries require ion transfer across phase boundaries. In conventional lithium-ion batteries, Li(+) ions have to cross the liquid electrolyte and only need to pass the electrode interfaces. Future high-energy batteries may need to work as hybrids, and so serially combine a liquid electrolyte and a solid electrolyte to suppress unwanted redox shuttles. This adds new interfaces that might significantly decrease the cycling-rate capability. Here we show that the interface between a typical fast-ion-conducting solid electrolyte and a conventional liquid electrolyte is chemically unstable and forms a resistive solid-liquid electrolyte interphase (SLEI). Insights into the kinetics of this new type of interphase are obtained by impedance studies of a two-chamber cell. The chemistry of the SLEI, its growth with time and the influence of water impurities are examined by state-of-the-art surface analysis and depth profiling. PMID:27102676

  9. Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts

    NASA Astrophysics Data System (ADS)

    Busche, Martin R.; Drossel, Thomas; Leichtweiss, Thomas; Weber, Dominik A.; Falk, Mareike; Schneider, Meike; Reich, Maria-Louisa; Sommer, Heino; Adelhelm, Philipp; Janek, Jürgen

    2016-05-01

    The discharging and charging of batteries require ion transfer across phase boundaries. In conventional lithium-ion batteries, Li+ ions have to cross the liquid electrolyte and only need to pass the electrode interfaces. Future high-energy batteries may need to work as hybrids, and so serially combine a liquid electrolyte and a solid electrolyte to suppress unwanted redox shuttles. This adds new interfaces that might significantly decrease the cycling-rate capability. Here we show that the interface between a typical fast-ion-conducting solid electrolyte and a conventional liquid electrolyte is chemically unstable and forms a resistive solid-liquid electrolyte interphase (SLEI). Insights into the kinetics of this new type of interphase are obtained by impedance studies of a two-chamber cell. The chemistry of the SLEI, its growth with time and the influence of water impurities are examined by state-of-the-art surface analysis and depth profiling.

  10. Air-Stable, High-Conduction Solid Electrolytes of Arsenic-Substituted Li4SnS4

    SciTech Connect

    Sahu, Gayatri; Lin, Zhan; Li, Juchuan; Liu, Zengcai; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    Lithium-ion-conducting solid electrolytes show promise for enabling high-energy secondary battery chemistries and solving safety issues associated with conventional lithium batteries. Achieving the combination of high ionic conductivity and outstanding chemical stability in solid electrolytes is a grand challenge for the synthesis of solid electrolytes. Herein we report the design of aliovalent substitution of Li4SnS4 to achieve high conduction and excellent air stability based on the hard and soft acids and bases theory. The composition of Li3.833Sn0.833As 0.166S4 has a high ionic conductivity of 1.39 mS/cm 1 at 25 C. Considering the high Li+ transference number, this phase conducts Li+ as well as carbonate-based liquid electrolytes. This research also addresses the compatibility of the sulfide-based solid electrolytes through chemical passivation.

  11. Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

    PubMed

    Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

    2014-02-12

    Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities. PMID:24444763

  12. 'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film

    SciTech Connect

    Parthasarathy, Meera; Pillai, Vijayamohanan K. Mulla, Imtiaz S.; Shabab, Mohammed; Khan, M.I.

    2007-12-07

    Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe{sup 2+}-form of the entrapped protein is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.

  13. A solid ceramic electrolyte system for measuring redox conditions in high temperature gas mixing studies

    NASA Technical Reports Server (NTRS)

    Williams, R. J.

    1972-01-01

    The details of the construction and operation of a gas mixing furnace are presented. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a standard vertical-quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the highinput impedance electronics necessary for measurements and a simplified version of standard gas mixing apparatus. The calibration and maintenance of the system are discussed.

  14. Development status of the General Electric solid polymer electrolyte water electrolysis technology

    NASA Astrophysics Data System (ADS)

    Nuttall, L. J.

    The solid polymer electrolyte used by the considered technology is a thin sheet (5 to 10 mil thickness) of a sulfonated fluoropolymer. It is a high strength plastic material which serves as the sole electrolyte, and also forms a rugged barrier between the hydrogen and oxygen chambers. The electrodes consist of a thin catalyst layer bonded to the surfaces of the plastic sheet. A description is presented of a 60-cell module, operating at the normal design point of 1000 amps per square foot. The module generates more than 2000 standard cubic feet per hour of hydrogen at a pressure of approximately 100 psig. Performance and cost projections are discussed.

  15. Role of the solid electrolyte interphase on a Li metal anode in a dimethylsulfoxide-based electrolyte for a lithium-oxygen battery

    NASA Astrophysics Data System (ADS)

    Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

    2015-10-01

    The effect of the solid electrolyte interphase (SEI) on a Li anode on the charge-discharge cycling performance in 1 M LiTFSI/dimethylsulfoxide electrolyte solution is examined by using charge-discharge cycling. The chemical structure of the surface and interior of the SEI strongly affects the cycling performance of the anode. The observed coulombic efficiency is low (<45%) when organic compounds such as lithium alkyl carbonates and polycarbonate form predominantly on the surface and interior. However, when inorganic compounds such as Li2CO3, Li2O, and LiF form instead, the coulombic efficiency increases to >85%. This enhanced efficiency remains constant regardless of the O2 content and despite <1000 ppm concentration of the contaminant H2O in the electrolyte. Thus, the lithium surface should be protected by inorganic compounds prior to cycling to prevent it from undergoing side reactions with the electrolyte during cycling in the electrolyte.

  16. Non-traditional approaches to solid-electrolyte interfaces: Trends and prospects

    NASA Astrophysics Data System (ADS)

    Duke, C. B.

    1980-12-01

    This paper is a synopsis of the "summing-up" lecture presented at the International Conference on Non-Traditional Approaches to the Study of the Solid-Electrolyte Interface. The major issue addressed at this conference was the determination of the structure of the solid-electrolyte interface at the microscopic level (e.g., elemental composition, atomic geometry) as opposed to the phenomenological level (e.g., average local electrostatic potentials and dielectric functions). Studies reported at the conference and in the recent literature may be collected into three groups: (1) the development of new experimental methods to determine the interface structure, (2) the construction of new theoretical models either to interpret the experimental measurements or to predict interface structure, and (3) the study of new materials for electrodes, electrolytes, and complete electrochemical cells. In each of these three areas major trends in current research are delineated. Current work is compared with the goal, articulated by the conference organizers, of achieving an experimental determination of the microscopic structure of the solid-electrolyte interface via in situ methods. This comparison suggests that whereas the reproducibility of the preparation and characterization of these interfaces seem adequate for the intended purpose, suitable in situ structure-sensitive experimental methods have not yet been demonstrated. It is proposed that the status of the characterization of solid-electrolyte interfaces today is roughly comparable to that of solidvacuum interfaces in the early 1970's. Examination of the history of the development of solid-vacuum interface characterization from this perspective further suggests that improved collaboration between theorists and experimentalists as well as more substantial investments in new apparatus and computation for data analysis will be required if the goal of the characterization at a microscopic level of the solid-electrolyte

  17. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction.

    PubMed

    Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis; Chang, Hao-Hsun; Pour, Nir; Lux, Simon F; Paschos, Odysseas; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Giordano, Livia; Shao-Horn, Yang

    2016-01-13

    This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochemical energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the conductivity through interfacial effects-specifically controlling grain boundaries and strain at the interfaces-is introduced. High-frequency dielectric constants and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Experimental studies and theoretical results are discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present Review aims to provide insight into the physical parameters affecting the diffusion process, to allow for more efficient and target-oriented research on improving solid-state ion conductors. PMID:26713396

  18. Solid Electrolyte/Electrode Interfaces: Atomistic Behavior Analyzed Via UHV-AFM, Surface Spectroscopies, and Computer Simulations Computational and Experimental Studies of the Cathode/Electrolyte Interface in Oxide Thin Film Batteries

    SciTech Connect

    Garofalini, Stephen H

    2012-03-21

    The goals of the research were to understand the structural, dynamic, and chemical properties of solid electrolyte surfaces and the cathode/electrolyte interface at an atomistic and nanometer level using both computational and experimental techniques.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

    2016-01-01

    Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

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

    SciTech Connect

    Raza, Rizwan; Ahmed, Akhlaq; Akram, Nadeem; Saleem, Muhammad; Niaz Akhtar, Majid; Ajmal Khan, M.; Abbas, Ghazanfar; Alvi, Farah; Yasir Rafique, M.; Sherazi, Tauqir A.; Shakir, Imran; Mohsin, Munazza; Javed, Muhammad Sufyan; Zhu, Bin E-mail: zhubin@hubu.edu.cn

    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.

  2. Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Li, Qin; Ardebili, Haleh

    2016-01-01

    The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

  3. Operando X-ray Investigation of Electrode/Electrolyte Interfaces in Model Solid Oxide Fuel Cells

    PubMed Central

    2016-01-01

    We employed operando anomalous surface X-ray diffraction to investigate the buried interface between the cathode and the electrolyte of a model solid oxide fuel cell with atomic resolution. The cell was studied under different oxygen pressures at elevated temperatures and polarizations by external potential control. Making use of anomalous X-ray diffraction effects at the Y and Zr K-edges allowed us to resolve the interfacial structure and chemical composition of a (100)-oriented, 9.5 mol % yttria-stabilized zirconia (YSZ) single crystal electrolyte below a La0.6Sr0.4CoO3−δ (LSC) electrode. We observe yttrium segregation toward the YSZ/LSC electrolyte/electrode interface under reducing conditions. Under oxidizing conditions, the interface becomes Y depleted. The yttrium segregation is corroborated by an enhanced outward relaxation of the YSZ interfacial metal ion layer. At the same time, an increase in point defect concentration in the electrolyte at the interface was observed, as evidenced by reduced YSZ crystallographic site occupancies for the cations as well as the oxygen ions. Such changes in composition are expected to strongly influence the oxygen ion transport through this interface which plays an important role for the performance of solid oxide fuel cells. The structure of the interface is compared to the bare YSZ(100) surface structure near the microelectrode under identical conditions and to the structure of the YSZ(100) surface prepared under ultrahigh vacuum conditions. PMID:27346923

  4. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

    PubMed Central

    Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

    2016-01-01

    Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

  5. Evaporation-Induced Self-Assembly of Nano-flaky Li3PS4 for Ultra thin Solid Electrolyte Membrane

    SciTech Connect

    Wang, Hui; Liang, Chengdu; Hood, Zachary; Hood, Zachary D; Xia, Younan

    2016-01-01

    Energy storage system is a critical technology to achieve efficient delivery and a steady supply of energy from intermittent sustainable sources (e.g. solar, wind). Lithium (Li) solid-state batteries are attractive candidates for next-generation batteries that require high energy density and stringent safety. In solid-state batteries, sulfides solid electrolytes are very promising to construct a large scale energy storage system. However, sulfide solid electrolyte pallets usually have an average thickness of 500-2000 m, which is 50 times that of the separators in conventional Li-ion batteries pose a huge challenge for their practical applications. Furthermore, the preparation of ultra-thin sulfide solid electrolyte membranes is difficult mainly due to the lack of efficient, low-cost solid electrolyte processing methods. Herein, we propose to use an evaporation-induced self-assembly (EISA) technique to produce ultra-thin sulfide solid electrolyte membranes. We designed and synthesized nano-flaky structured -Li3PS4 with high ionic conductivity, employed EISA method to produce ultra-thin -Li3PS4 membranes as thin as 8 m plus controllable thickness. It was clearly demonstrated that EISA method could be an facile approach to prepare solid electrolyte membranes.

  6. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman; Keith L. Duncan

    2002-03-31

    Solid oxide fuel cells (SOFCs) are the future of energy production in America. They offer great promise as a clean and efficient process for directly converting chemical energy to electricity while providing significant environmental benefits (they produce negligible hydrocarbons, CO, or NO{sub x} and, as a result of their high efficiency, produce about one-third less CO{sub 2} per kilowatt hour than internal combustion engines). Unfortunately, the current SOFC technology, based on a stabilized zirconia electrolyte, must operate in the region of 1000 C to avoid unacceptably high ohmic losses. These high temperatures demand (a) specialized (expensive) materials for the fuel cell interconnects and insulation, (b) time to heat up to the operating temperature and (c) energy input to arrive at the operating temperature. Therefore, if fuel cells could be designed to give a reasonable power output at low to intermediate temperatures tremendous benefits may be accrued. At low temperatures, in particular, it becomes feasible to use ferritic steel for interconnects instead of expensive and brittle ceramic materials such as those based on LaCrO{sub 3}. In addition, sealing the fuel cell becomes easier and more reliable; rapid startup is facilitated; thermal stresses (e.g., those caused by thermal expansion mismatches) are reduced; radiative losses ({approx}T{sup 4}) become minimal; electrode sintering becomes negligible and (due to a smaller thermodynamic penalty) the SOFC operating cycle (heating from ambient) would be more efficient. Combined, all these improvements further result in reduced initial and operating costs. The problem is, at lower temperatures the conductivity of the conventional stabilized zirconia electrolyte decreases to the point where it cannot supply electrical current efficiently to an external load. The primary objectives of the proposed research is to develop a stable high conductivity (> 0.05 S cm{sup -1} at {le} 550 C) electrolyte for lower

  7. Effective solid electrolyte based on benzothiazolium for dye-sensitized solar cells.

    PubMed

    Han, Lu; Wang, Ye Feng; Zeng, Jing Hui

    2014-12-24

    Thiaozole/benzothiaozole-based dicationic conductors were synthesized and applied as solid-state electrolyte in dye-sensitized solar cells (DSSCs). X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, steady-state voltammogram, photocurrent intensity-photovoltage test, and electrochemical impedance spectroscopy are used to characterize the materials and the mechanism of the cell performance. Compared to the traditional monocationic crystals, the dicationic crystals have a larger size and can provide more opportunities to fine-tune their physical/chemical properties. As a consequence, this solid-state electrolyte-based DSSC achieved photoelectric conversion efficiency of 7.90% under full air-mass (AM 1.5) sunlight (100 mW·cm(-2)). PMID:25469936

  8. Obtention and evaluation of polyethylene-based solid polymer electrolyte membranes fro hydrogen production

    NASA Astrophysics Data System (ADS)

    Masson, J. P.; Molina, R.; Roth, E.; Gaussens, G.; Lemaire, F.

    The fabrication and testing of a polyethylene-based solid polymer electrolyte for use in hydrogen production by water electrolysis are discussed. The fabrication process involves the radiation grafting of styrene groups onto a polyethylene matrix, followed by the chemical sulphonation of the resulting polymer. The membrane produced has exhibited resistivities as low as 60 ohm cm for a 1-mm thickness, and other properties of the same order of magnitude as those of the commercially available but more expensive Nafion 014 membrane. Life tests carried out at a current density of 2 kA/sq m in single-cell modules with 10-sq cm active surface have revealed no noticeable degradation in membrane mechanical or electrical properties after 3000 hours for membranes reinforced by an organic polymer fabric. The development of an electrolyzer specifically designed for operation with a solid polymer electrolyte is currently under way.

  9. Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

  10. Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

    DOE PAGESBeta

    Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; Fang, Youxing; Veith, Gabriel M.; Sun, Xiao-Guang; Dai, Sheng

    2015-11-02

    Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10-3 S cm-1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

  11. Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

    SciTech Connect

    Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; Fang, Youxing; Veith, Gabriel M.; Sun, Xiao-Guang; Dai, Sheng

    2015-11-02

    Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10-3 S cm-1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

  12. Polymerized Ionic Networks with High Charge Density: Quasi-Solid Electrolytes in Lithium-Metal Batteries.

    PubMed

    Zhang, Pengfei; Li, Mingtao; Yang, Bolun; Fang, Youxing; Jiang, Xueguang; Veith, Gabriel M; Sun, Xiao-Guang; Dai, Sheng

    2015-12-22

    Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10(-3) S cm(-1) at 22°C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes. PMID:26523468

  13. Solid polymer electrolyte (SPE) fuel cell technology program, phase 1/1A. [design and fabrication

    NASA Technical Reports Server (NTRS)

    1975-01-01

    A solid polymer electrolyte fuel cell was studied for the purpose of improving the characteristics of the technology. Several facets were evaluated, namely: (1) reduced fuel cell costs; (2) reduced fuel cell weight; (3) improved fuel cell efficiency; and (4) increased systems compatibility. Demonstrated advances were incorporated into a full scale hardware design. A single cell unit was fabricated. A substantial degree of success was demonstrated.

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

    SciTech Connect

    Liaw, B.Y.; Song, S.Y.

    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.

  15. Superionic solid-state polymer electrolyte membrane for high temperature applications

    NASA Astrophysics Data System (ADS)

    Kyu, Thein; He, Ruixuan; Cao, Jinwei

    2015-03-01

    Completely amorphous, flexible, solid-state polymer electrolyte membranes (ss-PEM) consisted of polyethylene glycol diacrylate /succinonitrile plasticizer (SCN)/lithium trifluorosulfonyl imide were fabricated via UV polymerization. The room temperature ionic conductivity of our ss-PEM is extremely high (i.e., 10-3S/cm), which is already in the superionic conductor range of inorganic and/or liquid electrolyte counterparts. Of particular interest is that our ss-PEM is thermally stable up to 140°C, which is superior to the liquid electrolyte counterpart that degrades above 80°C. The ss-PEM exhibits cyclic stability in both LiFePO4/Li and Li4Ti5O12 /Li half-cells up to 50 cycles tested. The trend of conductivity enhancement with temperature is reproducible in the repeated cycles, showing melting transitions of the SCN plastic crystals. In the compositions close to the solid (SCN plastic crystal)-liquid coexistence line, polymerization-induced crystallization occurs during photo-curing. The effect of solid-liquid segregation on ionic conductivity behavior is discussed. Supported by NSF-DMR 1161070.

  16. Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

    SciTech Connect

    Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; Ren, Fei; Keum, Jong Kahk; Ahn, Suk-Kyun; Li, Dawen; Chen, Jihua

    2015-08-06

    Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition that is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.

  17. Strength and Fracture Toughness of Solid Oxide Fuel Cell Electrolyte Material Improved

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2002-01-01

    Solid oxide fuel cells (SOFC) are being developed for various applications in the automobile, power-generation, and aeronautics industries. Recently, the NASA Glenn Research Center has been exploring the possibility of using SOFC's for aeropropulsion under its Zero Carbon Dioxide Emission Technology (ZCET) Program. 10-mol% yttriastabilized zirconia (10YSZ) is a very good anionic conductor at high temperatures and is, therefore, used as an oxygen solid electrolyte in SOFC. However, it has a high thermal expansion coefficient, low thermal shock resistance, low fracture toughness, and poor mechanical strength. For aeronautic applications, the thin ceramic electrolyte membrane of the SOFC needs to be strong and tough. Therefore, we have been investigating the possibility of enhancing the strength and fracture toughness of the 10YSZ electrolyte without degrading its electrical conductivity to an appreciable extent. We recently demonstrated that the addition of alumina to zirconia electrolyte increases its strength as well as its fracture toughness. Zirconia-alumina composites containing 0 to 30 mol% of alumina were fabricated by hot pressing. The hot pressing procedure was developed and various hot pressing parameters were optimized, resulting in dense, crackfree panels of composite materials. Cubic zirconia and a-alumina were the only phases detected, indicating that there was no chemical reaction between the constituents during hot pressing at elevated temperatures. Flexure strength sf and fracture toughness K(sub IC) of the various zirconia-alumina composites were measured at room temperature as well as at 1000 C in air. Both properties showed systematic improvement with increased alumina addition at room temperature and at 1000 C. Use of these modified electrolytes with improved strength and fracture toughness should prolong the life and enhance the performance of SOFC in aeronautics and other applications.

  18. Carbon dioxide sensing mechanisms of an electrocatalytic sensor/cell based on a tungsten stabilized bismuth oxide solid electrolyte

    NASA Astrophysics Data System (ADS)

    Shoemaker, Erika Leigh

    This work describes the specific O2/CO2 sensing mechanisms of a solid-state, thick-film, electrocatalytic cermet (ceramic/metallic) gas sensor based on a tungsten stabilized bismuth oxide (WBO) solid electrolyte. The sensors embody the same configuration of classical planar oxygen sensors with two catalytic electrodes sandwiching an oxygen ion conducting solid electrolyte and a buried metal oxide reference. The technique of cyclic voltammetry is used where a cyclic voltage is ramped across the electrodes to promote electrochemical reactions on the surface of the sensor. These reactions alter the ionic current flow through the solid electrolyte, generating voltage-current related responses (voltammograms) which are gas specific. The WBO sensors have the identical configuration of previously investigated sensors of this type based on a yttria stabilized zirconia (YSZ) solid electrolyte which show good response to O 2 but do not respond to CO2 to any degree. This dissertation examines the specific function of each solid electrolyte layer and relates them to both the WBO sensors ability to respond uniquely to CO2 and the YSZ sensors incapability to respond to CO2. The research suggests that the tungsten component of the WBO electrolyte along with the porosity of the WBO layer together are responsible for the unique CO 2 response of this sensor.

  19. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman; Keith L. Duncan

    2001-09-30

    Solid oxide fuel cells (SOFCs) are the future of energy production in America. They offer great promise as a clean and efficient process for directly converting chemical energy to electricity while providing significant environmental benefits (they produce negligible hydrocarbons, CO, or NO{sub x} and, as a result of their high efficiency, produce about one-third less CO{sub 2} per kilowatt hour than internal combustion engines). Unfortunately, the current SOFC technology, based on a stabilized zirconia electrolyte, must operate in the region of 1000 C to avoid unacceptably high ohmic losses. These high temperatures demand (a) specialized (expensive) materials for the fuel cell interconnects and insulation, (b) time to heat up to the operating temperature and (c) energy input to arrive at the operating temperature. Therefore, if fuel cells could be designed to give a reasonable power output at low to intermediate1 temperatures tremendous benefits may be accrued. At low temperatures, in particular, it becomes feasible to use ferritic steel for interconnects instead of expensive and brittle ceramic materials such as those based on LaCrO{sub 3}. In addition, sealing the fuel cell becomes easier and more reliable; rapid start-up is facilitated; thermal stresses (e.g., those caused by thermal expansion mismatches) are reduced; radiative losses ({approx}T{sup 4}) become minimal; electrode sintering becomes negligible and (due to a smaller thermodynamic penalty) the SOFC operating cycle (heating from ambient) would be more efficient. Combined, all these improvements further result in reduced initial and operating costs. The problem is, at lower temperatures the conductivity of the conventional stabilized zirconia electrolyte decreases to the point where it cannot supply electrical current efficiently to an external load. The primary objectives of the proposed research are to develop a stable high conductivity (> 0.05 S cm{sup -1} at {le} 550 C) electrolyte for lower

  20. Evaporation-Induced Self-Assembly of Nano-flaky Li3PS4 for Ultra thin Solid Electrolyte Membrane

    DOE PAGESBeta

    Wang, Hui; Liang, Chengdu; Hood, Zachary; Hood, Zachary D; Xia, Younan

    2016-01-01

    Energy storage system is a critical technology to achieve efficient delivery and a steady supply of energy from intermittent sustainable sources (e.g. solar, wind). Lithium (Li) solid-state batteries are attractive candidates for next-generation batteries that require high energy density and stringent safety. In solid-state batteries, sulfides solid electrolytes are very promising to construct a large scale energy storage system. However, sulfide solid electrolyte pallets usually have an average thickness of 500-2000 m, which is 50 times that of the separators in conventional Li-ion batteries pose a huge challenge for their practical applications. Furthermore, the preparation of ultra-thin sulfide solid electrolytemore » membranes is difficult mainly due to the lack of efficient, low-cost solid electrolyte processing methods. Herein, we propose to use an evaporation-induced self-assembly (EISA) technique to produce ultra-thin sulfide solid electrolyte membranes. We designed and synthesized nano-flaky structured -Li3PS4 with high ionic conductivity, employed EISA method to produce ultra-thin -Li3PS4 membranes as thin as 8 m plus controllable thickness. It was clearly demonstrated that EISA method could be an facile approach to prepare solid electrolyte membranes.« less

  1. Conductivity and electrical studies of plasticized carboxymethyl cellulose based proton conducting solid biopolymer electrolytes

    NASA Astrophysics Data System (ADS)

    Isa, M. I. N.; Noor, N. A. M.

    2015-12-01

    In this paper, a proton conducting solid biopolymer electrolytes (SBE) comprises of carboxymethyl cellulose (CMC) as polymer host, ammonium thiocyanate (NH4SCN) as doping salt and ethylene carbonate (EC) as plasticizer has been prepared via solution casting technique. Electrical Impedance Spectroscopy (EIS) was carried out to study the conductivity and electrical properties of plasticized CMC-NH4SCN SBE system over a wide range of frequency between 50 Hz and 1 MHz at temperature range of 303 to 353 K. Upon addition of plasticizer into CMC-NH4SCN SBE system, the conductivity increased from 10-5 to 10-2 Scm-1. The highest conductivity was obtained by the electrolyte containing 10 wt.% of EC. The conductivity of plasticized CMC-NH4SCN SBE system by various temperatures obeyed Arrhenius law where the ionic conductivity increased as the temperature increased. The activation energy, Ea was found to decrease with enhancement of EC concentration. Dielectric studies for the highest conductivity electrolyte obeyed non-Debye behavior. The conduction mechanism for the highest conductivity electrolyte was determined by employing Jonsher's universal power law and thus, can be represented by the quantum mechanical tunneling (QMT) model.

  2. Lithium cell having a solid electrolyte constituted by a conductive vitreous compound

    SciTech Connect

    Gabano, J.P.; Duchange, J.P.

    1984-10-23

    The electrolyte is constituted by a conductive vitreous compound having the formula aP/sub 2/S/sub 5/, bLi/sub 2/S, cLiX, where X represents chlorine, bromine, or iodine, and where a, b, and c are numbers chosen so that the ratio b/(a+b) lies between 0.61 and 0.70, and so that the ratio c/(a+b+c) is less than or equal to a limit corresponding to the solubility in vitreous phase of LiX in the compound aP/sub 2/S/sub 5/, bLi/sub 2/S, with the positive active material comprising 20% to 80% by volume solid electrolyte together with an electron conductor, the improvement wherein a substance chosen from the halogens and the chalcogens is included in the electrolyte in order to produce an in situ chemical reaction at the lithium electrolyte interface thereby creating an ionically conductive bonding layer comprising a lithium halogenide or chalcogenide.

  3. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    DOE PAGESBeta

    Wang, Hui; Hood, Zachary D.; Xia, Younan; Liang, Chengdu

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achievemore » ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

  4. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10‑4 S cm‑1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  5. Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane

    NASA Technical Reports Server (NTRS)

    Surampudi, Subbarao (Inventor); Narayanan, Sekharipuram R. (Inventor); Vamos, Eugene (Inventor); Frank, Harvey A. (Inventor); Halpert, Gerald (Inventor); Olah, George A. (Inventor); Prakash, G. K. Surya (Inventor)

    1997-01-01

    A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

  6. In-situ, non-destructive acoustic characterization of solid state electrolyte cells

    NASA Astrophysics Data System (ADS)

    Schmidt, Robert D.; Sakamoto, Jeffrey

    2016-08-01

    Solid-state electrolytes such as cubic Li6.25Al0.25La3Zr2O12 (LLZO) can enable solid-state batteries, metallic lithium anodes and higher voltage cathodes. However, the stability of cubic LLZO is affected by current density. In beta alumina solid electrolyte, microstructural failure was caused by Na dendrite penetration, and was shown to be a function of the fracture toughness, KIC. The relationship between dendrite penetration and KIC indicates electronic failure is related to creation of microstructural damage, and the microstructural damage may be used as an indicator of imminent electronic failure. To monitor microstructural damage during cycling, we developed a non-invasive, in-situ cell monitoring apparatus to help to correlate mechanical stability with Li-ion current density in LLZO. A pulse-echo transducer was integrated into all solid-state Li-LLZO-Li cells. The capability enables the characterization of microscopic inhomogeneities through the careful measurement of changes to the elastic moduli. The elastic moduli and fracture toughness have been previously reported for dense (>99%) specimens, but monitoring of the relative change in moduli during cycling has not been explored. In this study, an acoustic monitoring method is presented to monitor LLZO specimens during cycling.

  7. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman

    2000-10-01

    Solid oxide fuel cells (SOFCs) are the future of energy production in America. They offer great promise as a clean and efficient process for directly converting chemical energy to electricity while providing significant environmental benefits (they produce negligible CO, HC, or NOx and, as a result of their high efficiency, produce about one-third less CO{sub 2} per kilowatt hour than internal combustion engines). Unfortunately, the current SOFC technology, based on a stabilized zirconia electrolyte, must operate in the region of 1000 C to avoid unacceptably high ohmic losses. These high temperatures demand (a) specialized (expensive) materials for the fuel cell interconnects and insulation, (b) time to heat up to the operating temperature and (c) energy input to arrive at the operating temperature. Therefore, if fuel cells could be designed to give a reasonable power output at lower temperatures tremendous benefits may be accrued, not the least of which is reduced cost. The problem is, at lower temperatures the conductivity of the conventional stabilized zirconia electrolyte decreases to the point where it cannot supply electrical current efficiently to an external load. The primary objectives of the proposed research is to develop a stable high conductivity (>0.05 S cm{sup -1} at 550 C) electrolyte for lower temperature SOFCs. This objective is specifically directed toward meeting the lowest (and most difficult) temperature criteria for the 21st Century Fuel Cell Program. Meeting this objective provides a potential for future transportation applications of SOFCs, where their ability to directly use hydrocarbon fuels could permit refueling within the existing transportation infrastructure. In order to meet this objective we are developing a functionally gradient bilayer electrolyte comprised of bismuth oxide on the air side and ceria on the fuel side. Bismuth oxide and doped ceria are among the highest ionic conducting electrolytes and in fact bismuth oxide based

  8. A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

    PubMed

    Yi, Jin; Zhou, Haoshen

    2016-09-01

    In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application. PMID:27487523

  9. Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

    2016-05-01

    Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) 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 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

  10. Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus

    DOEpatents

    Zaromb, S.

    1994-06-21

    Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity [>=]10[sup [minus]4] (ohm-cm)[sup [minus]1], and preferably [>=]0.01 (ohm-cm)[sup [minus]1]. The conductivity may be due predominantly to Ag[sup +] ions, as in Ag[sub 2]WO[sub 4], or to F[sup [minus

  11. Electrode assembly for use in a solid polymer electrolyte fuel cell

    DOEpatents

    Raistrick, Ian D.

    1989-01-01

    A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

  12. Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

    DOEpatents

    Wiers, Brian M.; Balsara, Nitash P.; Long, Jeffrey R.

    2016-03-29

    Various embodiments of the invention disclose that the uptake of LiO.sup.iPr in Mg.sub.2(dobdc) (dobdc.sup.4-=1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg.sub.2(dobdc).0.35LiO.sup.iPr.0.25LiBF.sub.4.EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1.times.10.sup.-4 S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

  13. Communication: Conductivity enhancement in plastic-crystalline solid-state electrolytes

    NASA Astrophysics Data System (ADS)

    Geirhos, K.; Lunkenheimer, P.; Michl, M.; Reuter, D.; Loidl, A.

    2015-08-01

    Finding new ionic conductors that enable significant advancements in the development of energy-storage devices is a challenging goal of current material science. Aside of material classes as ionic liquids or amorphous ion conductors, the so-called plastic crystals (PCs) have been shown to be good candidates combining high conductivity and favorable mechanical properties. PCs are formed by molecules whose orientational degrees of freedom still fluctuate despite the material exhibits a well-defined crystalline lattice. In the present work, we show that the conductivity of Li+ ions in succinonitrile, the most prominent molecular PC electrolyte, can be enhanced by several decades when replacing part of the molecules in the crystalline lattice by larger ones. Dielectric spectroscopy reveals that this is accompanied by a stronger coupling of ionic and reorientational motions. These findings, which can be understood in terms of an optimized "revolving door" mechanism, open a new path towards the development of better solid-state electrolytes.

  14. Hollow Structured Silicon Anodes with Stabilized Solid Electrolyte Interphase Film for Lithium-Ion Batteries.

    PubMed

    Lv, Qiuliang; Liu, Yuan; Ma, Tianyi; Zhu, Wentao; Qiu, Xinping

    2015-10-28

    Silicon has been considered as a promising anode material for the next generation of lithium-ion batteries due to its high specific capacity. Its huge volume expansion during the alloying reaction with lithium spoils the stability of the interface between electrode and electrolyte, resulting in capacity degradation. Herein, we synthesized a novel hollow structured silicon material with interior space for accumulating the volume change during the lithiation. The as-prepared material shows excellent cycling stability, with a reversible capacity of ∼1650 m Ah g(-1) after 100 cycles, corresponding to 92% retention. The electrochemical impedance spectroscopy and differential scanning calorimetry were carried out to monitor the growth of SEI film, and the results confirm the stable solid electrolyte interphase film on the surface of hollow structured silicon. PMID:26402521

  15. Jumping liquid metal droplet in electrolyte triggered by solid metal particles

    NASA Astrophysics Data System (ADS)

    Tang, Jianbo; Wang, Junjie; Liu, Jing; Zhou, Yuan

    2016-05-01

    We report the electron discharge effect due to point contact between liquid metal and solid metal particles in electrolyte. Adding nickel particles induces drastic hydrogen generating and intermittent jumping of a sub-millimeter EGaIn droplet in NaOH solution. Observations from different orientations disclose that such jumping behavior is triggered by pressurized bubbles under the assistance of interfacial interactions. Hydrogen evolution around particles provides clear evidence that such electric instability originates from the varied electric potential and morphology between the two metallic materials. The point-contact-induced charge concentration significantly enhances the near-surface electric field intensity at the particle tips and thus causes electric breakdown of the electrolyte.

  16. Control ion transport by tuning the crystalline morphology in polyethylene oxide-based solid electrolyte

    NASA Astrophysics Data System (ADS)

    Cheng, Shan; Li, Christopher; Smith, Derrick

    2013-03-01

    The crystalline structure of polyethylene oxide (PEO) strongly affects the ion transport in solid PEO-Lithium salt electrolytes. Four possible phases can exist in a PEO-LiClO4 electrolyte membrane, e.g. crystalline PEO, amorphous PEO, amorphous PEO-Li complex and crystalline PEO-Li complex. It has been widely accepted so far that ion can transport through either amorphous PEO phase or PEO-Li crystalline complex phase. The ion conduction mechanism of the former is based on ion hopping as well as PEO segment motion. In the latter case two PEO chains form cylindrical channels within which Lithium cation can transport. In this presentation, we will show that tuning the crystalline morphology can optimize ion conduction. This can be achieved by controlling the orientation of the PEO lamellae as well as PEO-Li crystalline complex to optimize the ion conducting pathways.

  17. Evaluation of lanthanum tungstates as electrolytes for proton conductors Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Zayas-Rey, M. J.; dos Santos-Gómez, L.; Porras-Vázquez, J. M.; Losilla, E. R.; Marrero-López, D.

    2015-10-01

    La27W4NbO55-δ (LWNO) has been tested as electrolyte for proton conductor Solid Oxide Fuel Cells (PC-SOFCs). For this purpose, different electrodes and composite electrodes are considered, including: La0.8Sr0.2MnO3-δ, La0.6Sr0.4Co1-xFexO3-δ, La0.75Sr0.25Cr0.5Mn0.5O3-δ, SrFe0.75Nb0.25O3-δ and NiO. Chemical compatibility between the cell components is investigated by X-ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS). Furthermore, area specific resistance (ASR) for the different electrodes is determined in symmetrical cells by impedance spectroscopy. XRPD and EDS analysis does not reveal significant bulk reactivity between most of these electrodes and LWNO electrolyte in the typical operating temperature range of an SOFC (600-900 °C). However, minor interdiffusion of elements at the electrolyte/electrode interface has negative effects on both the ohmic losses and electrode polarization of the cells. ASR values are significantly improved by using a porous buffer layer of Ce0.8Gd0.2O1.9 (CGO), deposited between the electrolyte and electrode materials, to prevent reactivity. A single cell with a 350 μm-thick electrolyte, NiO-CGO and La0.6Sr0.4Co0.8Fe0.2O3-δ-CGO composite as anode and cathode, respectively, generates maximum power densities of 140 and 18 mWcm-2 at 900 and 650 °C, respectively.

  18. Solid-state sodium batteries using polymer electrolytes and sodium intercalation electrode materials

    SciTech Connect

    Ma, Y. |

    1996-08-01

    Solid-state sodium cells using polymer electrolytes (polyethylene oxide mixed with sodium trifluoromethanesulfonate: PEO{sub n}NaCF{sub 3}SO{sub 3}) and sodium cobalt oxide positive electrodes are characterized in terms of discharge and charge characteristics, rate capability, cycle life, and energy and power densities. The P2 phase Na{sub x}CoO{sub 2} can reversibly intercalate sodium in the range of x = 0.3 to 0.9, giving a theoretical specific energy of 440 Wh/kg and energy density of 1,600 Wh/l. Over one hundred cycles to 60% depth of discharge have been obtained at 0.5 mA/cm{sup 2}. Experiments show that the electrolyte/Na interface is stable and is not the limiting factor to cell cycle life. Na{sub 0.7}CoO{sub 2} composite electrodes containing various amounts of carbon black additive are investigated. The transport properties of polymer electrolytes are the critical factors for performance. These properties (the ionic conductivity, salt diffusion coefficient, and ion transference number) are measured for the PEO{sub n}NaCF{sub 3}SO{sub 3} system over a wide range of concentrations at 85 C. All the three transport properties are very salt-concentration dependent. The ionic conductivity exhibits a maximum at about n = 20. The transference number, diffusion coefficient, and thermodynamic factor all vary with salt concentration in a similar fashion, decreasing as the concentration increases, except for a local maximum. These results verify that polymer electrolytes cannot be treated as ideal solutions. The measured transport-property values are used to analyze and optimize the electrolytes by computer simulation and also cell testing. Salt precipitation is believed to be the rate limiting process for cells using highly concentrated solutions, as a result of lower values of these properties, while salt depletion is the limiting factor when a dilute solution is used.

  19. Studies on the enhancement of solid electrolyte interphase formation on graphitized anodes in LiX-carbonate based electrolytes using Lewis acid additives for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Li, L. F.; Xie, B.; Lee, H. S.; Li, H.; Yang, X. Q.; McBreen, J.; Huang, X. J.

    The new electrolyte systems utilizing one type of Lewis acids, the boron based anion receptors (BBARs) with LiF, Li 2O, or Li 2O 2 in carbonate solutions have been developed and reported by us. These systems open up a new approach in developing non-aqueous electrolytes with higher operating voltage and less moisture sensitivity for lithium-ion batteries. However, the formation of a stable solid electrolyte interphase (SEI) layer on the graphitized anodes is a serious problem needs to be solved for these new electrolyte systems, especially when propylene carbonate (PC) is used as a co-solvent. Using lithium bis(oxalato)borate (LiBOB) as an additives, the SEI layer formation on mesophase carbon microbeads (MCMB) anode is significantly enhanced in these new electrolytes containing boron-based anion receptors, such as tris(pentafluorophenyl) borane, and lithium salt such as LiF, or lithium oxides such as Li 2O or Li 2O 2 in PC and dimethyl carbonate (DMC) solvents. The cells using these electrolytes and MCMB anodes cycled very well and the PC co-intercalation was suppressed. Fourier transform infrared spectroscopy (FTIR) studies show that one of the electrochemical decomposition products of LiBOB, lithium carbonate (Li 2CO 3), plays a quite important role in the stablizing SEI layer formation.

  20. Use of nafion as a solid polymer electrolyte for the electroreduction of tungsten (VI) fluoride

    SciTech Connect

    Bettelheim, A.; Raven, A.; Polak, M.; Ozer, D. )

    1992-01-01

    In this paper a new method is described in which WF{sub 6} is electroreduced in a solid-state cell configuration with a Nafion membrane serving as a solid polymer electrolyte. Cyclic voltammetry indicates a behavior similar to that of metallic tungsten for coatings obtained at dry conditions and similar to that of tungsten oxide species when water vapor is not totally expelled. Surface analysis using Auger electroscope and x-ray photoelectron spectroscopy shows that solid-state electro-reduction of WF{sub 6} in dry conditions yields coatings free of fluorine, which contain much less oxygen than electrodeposits obtained from aqueous solutions. However, due to possible oxidation and reduction reactions occurring before and during the surface-analysis process, it is not possible at this state to determine the exact content of metallic and oxide species in the deposits obtained by the present method.

  1. All solid state lithium batteries based on lamellar garnet-type ceramic electrolytes

    NASA Astrophysics Data System (ADS)

    Du, Fuming; Zhao, Ning; Li, Yiqiu; Chen, Cheng; Liu, Ziwei; Guo, Xiangxin

    2015-12-01

    All solid-state lithium batteries are constructed by using highly conducting Ta-doped Li7La3Zr2O12 (LLZTO) as the solid electrolytes as well as the supports, coated with composite cathodes consisting of poly(vinylidene fluoride) (PVdF):LiTFSI, Ketjen Black, and carbon-coated LiFePO4 on one side and attached with Li anode on the other side. At 60 °C, the batteries show the first discharge capacity of 150 mAh g-1 at 0.05 C and 93% capacity retention after 100 cycles. As the current density increases from 0.05 C to 1 C, the specific capacity decreases from 150 mAh g-1 to 100 mAh g-1. Further elevated temperature up to 100 °C leads to further improved performance, i.e. 126 mAh g-1 at 1 C and 99% capacity retention after 100 cycles. This good performance can be attributed to the highly conducting ceramic electrolytes, the optimum electronic and ionic conducting networks in the composite cathodes, and closely contacted cathode/LLZTO interface. These results indicate that the present strategy is promising for development of high-performance solid-state Li-ion batteries operated at medium temperature.

  2. Direct Electrolytic Reduction of Solid Ta2O5 to Ta with SOM Process

    NASA Astrophysics Data System (ADS)

    Chen, Chaoyi; Yang, Xiaqiong; Li, Junqi; Lu, Xionggang; Yang, Shufeng

    2016-06-01

    A process that uses the solid-oxide-oxygen-ion conducting membrane has been investigated to produce tantalum directly from solid Ta2O5 in molten CaCl2 or a molten mixture of 55.5MgF2-44.5CaF2 (in wt pct). The sintered porous Ta2O5 pellet was employed as the cathode, while the liquid copper alloy, saturated with graphite powder and encased in a one-end-closed yttria-stabilized-zirconia (YSZ) tube, acted as the anode. The electrolysis potential in this method is higher than that of the Fray-Farthing-Chen Cambridge process because the YSZ membrane tube blocks the melts to electrolyze, and only Ta2O5 is will be electrolyzed. The microstructures of reduced pellets and a cyclic voltammogram of solid Ta2O5 in molten CaCl2 were analyzed. In addition, the influence of particle size and porosity of the cathode pellets on metal-oxide-electrolyte, three-phase interlines was also discussed. The results demonstrate that the sintering temperature of cathode pellets and electrolytic temperature play important roles in the electrochemical process. Furthermore, this process can be used to produce Ta metal efficiently without the expensive cost of pre-electrolysis and generation of harmful by-products.

  3. All Solid-State Lithium Metal Batteries Using Cross-linked Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Pan, Qiwei; Li, Christopher; Soft Materials Team

    Nowadays, to prepare all solid-state lithium metal batteries with high rate capability and stability using solid polymer electrolytes (SPEs) is still a grand challenge because of the interfaces between the SPE and the electrodes. In this presentation, we report a series of hybrid SPEs with controlled network structures by using POSS as cross-linker. These hybrid network SPEs show promising ionic conductivity, mechanical properties, and lithium dendrite growth resistance. All solid-state LiFePO4/Li batteries were also prepared using these SPEs as the electrolytes to study the effect of conductivity and mechanical properties of the SPEs on the performance of the batteries. At 90 °C, the prepared cells show high rate capability and stability. Capacity up to 160 mAh/g can be obtained at a C/2 rate during the galvanostatic cycling. Capacity retention of the cells is higher than 80% after 250 cycles. Battery performance at 60 °C and decay mechanism of the batteries will also be discussed.

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

    NASA Technical Reports Server (NTRS)

    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.

  5. Method for forming thin composite solid electrolyte film for lithium batteries

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan (Inventor); Attia, Alan I. (Inventor)

    1994-01-01

    A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

  6. Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

    NASA Astrophysics Data System (ADS)

    Cheng, Hua; Scott, Keith

    The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

  7. Surface engineering of nanoporous substrate for solid oxide fuel cells with atomic layer-deposited electrolyte

    PubMed Central

    Ji, Sanghoon; Tanveer, Waqas Hassan; Yu, Wonjong; Kang, Sungmin; Cho, Gu Young; Kim, Sung Han

    2015-01-01

    Summary Solid oxide fuel cells with atomic layer-deposited thin film electrolytes supported on anodic aluminum oxide (AAO) are electrochemically characterized with varying thickness of bottom electrode catalyst (BEC); BECs which are 0.5 and 4 times thicker than the size of AAO pores are tested. The thicker BEC ensures far more active mass transport on the BEC side and resultantly the thicker BEC cell generates ≈11 times higher peak power density than the thinner BEC cell at 500 °C. PMID:26425432

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Method for forming thin composite solid electrolyte film for lithium batteries

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan (Inventor); Attia, Alan I. (Inventor)

    1997-01-01

    A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

  10. General method to predict voltage-dependent ionic conduction in a solid electrolyte coating on electrodes

    NASA Astrophysics Data System (ADS)

    Pan, Jie; Cheng, Yang-Tse; Qi, Yue

    2015-04-01

    Understanding the ionic conduction in solid electrolytes in contact with electrodes is vitally important to many applications, such as lithium ion batteries. The problem is complex because both the internal properties of the materials (e.g., electronic structure) and the characteristics of the externally contacting phases (e.g., voltage of the electrode) affect defect formation and transport. In this paper, we developed a method based on density functional theory to study the physics of defects in a solid electrolyte in equilibrium with an external environment. This method was then applied to predict the ionic conduction in lithium fluoride (LiF), in contact with different electrodes which serve as reservoirs with adjustable Li chemical potential (μLi) for defect formation. LiF was chosen because it is a major component in the solid electrolyte interphase (SEI) formed on lithium ion battery electrodes. Seventeen possible native defects with their relevant charge states in LiF were investigated to determine the dominant defect types on various electrodes. The diffusion barrier of dominant defects was calculated by the climbed nudged elastic band method. The ionic conductivity was then obtained from the concentration and mobility of defects using the Nernst-Einstein relationship. Three regions for defect formation were identified as a function of μLi: (1) intrinsic, (2) transitional, and (3) p -type region. In the intrinsic region (high μLi, typical for LiF on the negative electrode), the main defects are Schottky pairs and in the p -type region (low μLi, typical for LiF on the positive electrode) are Li ion vacancies. The ionic conductivity is calculated to be approximately 10-31Scm-1 when LiF is in contact with a negative electrode but it can increase to 10-12Scm-1 on a positive electrode. This insight suggests that divalent cation (e.g., Mg2+) doping is necessary to improve Li ion transport through the engineered LiF coating, especially for LiF on negative

  11. Modeling of liquid electrolyte films on non-uniformly charged solid substrates

    NASA Astrophysics Data System (ADS)

    Jutley, Mahnprit; Ajaev, Vladimir

    2015-11-01

    We consider a thin electrolyte film on a solid substrate characterized by a space-dependent electrical charge density. Using the Debye-Hückel equation to model the electrostatic potential and the Navier-Stokes equations for fluid flow, we consider both steady-state interface shapes and their stability resulting from small perturbations of arbitrary wavelength. Calculations are carried out by two different approaches: Fourier expansion of all terms is used and the corresponding coefficients of the first order correction to the interface shape are found, and, secondly, an evolution equation is obtained within the framework of a lubrication-type model. Stability analysis of the linearized problem is conducted.

  12. Properties of a lithium solid electrolyte gas sensor based on reaction kinetics

    NASA Astrophysics Data System (ADS)

    Jasinski, Grzegorz; Jasinski, Piotr; Nowakowski, Antoni; Chachulski, Bogdan

    2006-01-01

    Principle of operation, construction and properties of a gas sensor based on lithium ion-conductor solid electrolyte (Lisicon) are presented. The sensor has been prepared using thick film technology. Its working principle is based on electric current acquisition, while a voltage ramp is applied to the sensor. The current-voltage plot has a unique shape, which depends on the surrounding gas type and its concentration. Results of measurements conducted in mixtures of high purity gases—nitrogen dioxide, sulfur dioxide, carbon dioxide and synthetic air of controlled concentration—over a wide range of temperatures are presented and discussed.

  13. Tritiated water processing using liquid phase catalytic exchange and solid oxide electrolyte cell

    SciTech Connect

    Yamai, H.; Konishi, S.; Hara, M.; Okuno, K.; Yamamoto, I.

    1995-10-01

    Liquid phase catalytic exchange (LPCE) is an effective method for enrichment and removal of tritium from tritiated water. Combined electrolysis catalytic exchange (CECE) process is an attractive application of a LPCE column. We proposed a new process that improves the CECE process. Using a solid oxide electrolyte (SOE) cell for electrolysis makes the CECE process more energy efficient and eliminates other disadvantages such as large tritium inventory and extremely slow system response. When the cell is used for recombination, the system becomes even more simple, efficiently, reliable and safe. 21 refs., 9 figs.

  14. Surface engineering of nanoporous substrate for solid oxide fuel cells with atomic layer-deposited electrolyte.

    PubMed

    Ji, Sanghoon; Tanveer, Waqas Hassan; Yu, Wonjong; Kang, Sungmin; Cho, Gu Young; Kim, Sung Han; An, Jihwan; Cha, Suk Won

    2015-01-01

    Solid oxide fuel cells with atomic layer-deposited thin film electrolytes supported on anodic aluminum oxide (AAO) are electrochemically characterized with varying thickness of bottom electrode catalyst (BEC); BECs which are 0.5 and 4 times thicker than the size of AAO pores are tested. The thicker BEC ensures far more active mass transport on the BEC side and resultantly the thicker BEC cell generates ≈11 times higher peak power density than the thinner BEC cell at 500 °C. PMID:26425432

  15. Enhanced electrical transport in ionic liquid dispersed TMAI-PEO solid polymer electrolyte

    SciTech Connect

    Gupta, Neha; Rathore, Munesh Dalvi, Anshuman; Kumar, Anil

    2014-04-24

    A polymer composite is prepared by dispersing ionic liquid [Bmim][BF{sub 4}] in Polyethylene oxide-tetra methyl ammonium iodide composite and subsequent microwave treatment. X-ray diffraction patterns confirm the composite nature. To explore possibility of proton conductivity in these films, electrical transport is studied by impedance spectroscopy and DC polarization. It is revealed that addition of ionic liquid in host TMAI-PEO solid polymer electrolyte enhances the conductivity by ∼ 2 orders of magnitude. Polarization measurements suggest that composites are essentially ion conducting in nature. The maximum ionic conductivity is found to be ∼2 × 10{sup −5} for 10 wt % ionic liquid.

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

    NASA Technical Reports Server (NTRS)

    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.

  17. Solid polymer electrolytes derived from polyphenols. Final report, 28 April--27 October 1998

    SciTech Connect

    Filler, R.

    1998-11-09

    In the Phase-1 study, Tech Drive synthesized several phenol monomers. Two of these monomers, one of which is new, were converted to phenolic polymers by enzymatic means, using horseradish peroxidase and hydrogen peroxide. The monomers and polymers were fully characterize using thin layer chromatography, FT-IR and NMR spectroscopy, gel permeation chromatography and light scattering analyses. Solid polymeric electrolytes (SPEs) were formulated using the processable polyphenols. Ionic conductivity measurements of one of the SPEs based on a substituted polyphenol showed promising levels of ionic conductivity. Addition of a plasticizer dramatically improved the room temperature conductivity of the SPE film. Laboratory cells, fabricated using the SPEs, gave very promising results.

  18. Oxygen substitution effects in Li10GeP2S12 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Sun, Yulong; Suzuki, Kota; Hara, Kosuke; Hori, Satoshi; Yano, Taka-aki; Hara, Masahiko; Hirayama, Masaaki; Kanno, Ryoji

    2016-08-01

    For the lithium super-ionic conductor Li10GeP2S12, the partial substitution of sulfur by oxygen is achieved via a solid-state reaction. The solid-solution range of oxygen is found to be 0 ≤ x < 0.9 in Li10GeP2S12-xOx. Structure refinements using synchrotron X-ray diffraction data confirm the preference for oxygen substitution in the PS4 tetrahedra. The local structural change in the P(S/O)4 tetrahedra upon substitution is also indicated by Raman spectroscopy. Ionic conduction properties are maintained even after the oxygen substitution in Li10GeP2S12; the ionic conductivity of Li10GeP2S12-xOx (0.3 ≤ x ≤ 0.6) ranges from 1.03 × 10-2 to 8.43 × 10-3 S cm-1 at 298 K. No redox current is observed by cyclic voltammetry from nearly 0 to 10 V versus Li/Li+ except for that due to the lithium deposition/dissolution reactions. All-solid-state batteries using Li10GeP2S12-xOx (x = 0.3 and 0.6) as solid electrolytes with Li metal anodes show discharge capacities exceeding 100 mAh g-1 and better cycling performance compared to batteries using the original Li10GeP2S12. The partial substitution of oxygen for sulfur in Li10GeP2S12 affords a novel solid electrolyte, Li10GeP2S12-xOx, with high conductive properties and electrochemical stability.

  19. High performance zirconia-bismuth oxide nanocomposite electrolytes for lower temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Joh, Dong Woo; Park, Jeong Hwa; Kim, Do Yeub; Yun, Byung-Hyun; Lee, Kang Taek

    2016-07-01

    We develop a novel nanocomposite electrolyte, consisting of yttria-stabilized zirconia (YSZ) and erbia-stabilized bismuth oxide (ESB). The 20 mol% ESB-incorporated YSZ composite (20ESB-YSZ) achieves the high density (>97%) at the low sintering temperature of 800 °C. The microstructural analysis of 20ESB-YSZ reveals the characteristic nanocomposite structure of the highly percolated ESB phase at the YSZ grain boundaries (a few ∼ nm thick). The ionic conductivity of 20ESB-YSZ is increased by 5 times compared to that of the conventional YSZ due to the fast oxygen ion transport along the ESB phase. Moreover, this high conductivity is maintained up to 580 h, indicating high stability of the ESB-YSZ nanocomposite. In addition, the oxygen reduction reaction at the composite electrolyte/cathode interface is effectively enhanced (∼70%) at the temperature below 650 °C, mainly due to the fast dissociative oxygen adsorption on the ESB surface as well as the rapid oxygen ion incorporation into the ESB lattice. Thus, we believe this ESB-YSZ nanocomposite is a promising electrolyte for high performance solid oxide fuel cells at reduced temperatures.

  20. First-principles material modeling of solid-state electrolytes with the spinel structure.

    PubMed

    Mees, Maarten J; Pourtois, Geoffrey; Rosciano, Fabio; Put, Brecht; Vereecken, Philippe M; Stesmans, André

    2014-03-21

    Ionic diffusion through the novel (AlxMg1-2xLix)Al2O4 spinel electrolyte is investigated using first-principles calculations, combined with the Kinetic Monte Carlo algorithm. We observe that the ionic diffusion increases with the lithium content x. Furthermore, the structural parameters, formation enthalpies and electronic structures of (AlxMg1-2xLix)Al2O4 are calculated for various stoichiometries. The overall results indicate the (AlxMg1-2xLix)Al2O4 stoichiometries x = 0.2…0.3 as most promising. The (AlxMg1-2xLix)Al2O4 electrolyte is a potential candidate for the all-spinel solid-state battery stack, with the material epitaxially grown between well-known spinel electrodes, such as LiyMn2O4 and Li4+3yTi5O12 (y = 0…1). Due to their identical crystal structure, a good electrolyte-electrode interface is expected. PMID:24503944

  1. Effect of water on solid electrolyte interphase formation in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Saito, M.; Fujita, M.; Aoki, Y.; Yoshikawa, M.; Yasuda, K.; Ishigami, R.; Nakata, Y.

    2016-03-01

    Time-of-flight-elastic recoil detection analysis (TOF-ERDA) with 20 MeV Cu ions has been applied to measure the depth profiles of solid electrolyte interphase (SEI) layers on the negative electrode of lithium ion batteries (LIB). In order to obtain quantitative depth profiles, the detector efficiency was first assessed, and the test highlighted a strong mass and energy dependence of the recoiled particles, especially H and He. Subsequently, we prepared LIB cells with different water contents in the electrolyte, and subjected them to different charge-discharge cycle tests. TOF-ERDA, X-ray photoelectron spectrometry (XPS), gas chromatography (GC), ion chromatography (IC), and 1H nuclear magnetic resonance (1H NMR) were applied to characterize the SEI region of the negative electrode. The results showed that the SEI layer is formed after 300 cycle tests, and a 500 ppm water concentration in the electrolyte does not appear to cause significant differences in the elemental and organic content of the SEI.

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

    NASA Astrophysics Data System (ADS)

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

    NASA Astrophysics Data System (ADS)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  4. Multifunctional graphene incorporated polyacrylamide conducting gel electrolytes for efficient quasi-solid-state quantum dot-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Duan, Jialong; Tang, Qunwei; Li, Ru; He, Benlin; Yu, Liangmin; Yang, Peizhi

    2015-06-01

    Pursuit of a high efficiency and stability has been a persistent objective for quantum dot-sensitized solar cells (QDSCs). Here we launch a strategy of synthesizing graphene implanted polyacrylamide (PAAm-G) conducting gel electrolytes for quasi-solid-state QDSCs. With an aim of elevating the dosage of S2-/Sx2- redox couples and therefore charge-transfer ability, both osmotic press across the PAAm-G and capillary force within the three-dimensional micropores are utilized as driving forces. A promising power conversion efficiency of 2.34% is recorded for the QDSCs by optimizing graphene dosage in the conducting gel electrolyte. The enhanced conversion efficiency of solar cell is attributed to the expanded catalytic area from counter electrolyte/electrolyte interface to both interface and the conducting gel electrolyte.

  5. Structural and transport properties of PVC blend PEG doped with Mg(ClO4)2 solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Ramesh, C. H.; Reddy, M. Jaipal; Kumar, J. Siva; Reddy, K. Narasimha

    2014-04-01

    An attempt was made to investigate the effect of Mg(ClO4)2 concentration in PVC-PEG blend polymer electrolyte system. Solid polymer electrolyte films of PVC-PEG-Mg(ClO4)2 have been prepared by using solution - casting process. Structural and transport properties have been studied by employing experimental tools like XRD, FT-IR and DC electrical conductivity. The XRD, FTIR studies were confirmed the formation of a polymer-salt complex. The conductivity results indicated that the incorporation of Mg(ClO4)2 salt into PVC-PEG polymer; at low concentrations the increase in the conductivity is large, but at higher concentrations the increase in conductivity is modest. Using this electrolyte, an electrochemical cells have been fabricated with the configuration Mg/ (PVC-PEG-Mg(ClO4)2) electrolyte / (I2 + C + electrolyte) and its discharge characteristics were determined.

  6. Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy

    SciTech Connect

    Unocic, Raymond R.; Sun, Xiao-Guang; Sacci, Robert L.; Adamczyk, Leslie A.; Alsem, Daan Hein; Dai, Sheng; Dudney, Nancy J.; More, Karren Leslie

    2014-08-01

    Complex, electrochemically driven transport processes form the basis of electrochemical energy storage devices. The direct imaging of electrochemical processes at high spatial resolution and within their native liquid electrolyte would significantly enhance our understanding of device functionality, but has remained elusive. In this work we use a recently developed liquid cell for in situ electrochemical transmission electron microscopy to obtain insight into the electrolyte decomposition mechanisms and kinetics in lithium-ion (Li-ion) batteries by characterizing the dynamics of solid electrolyte interphase (SEI) formation and evolution. Here we are able to visualize the detailed structure of the SEI that forms locally at the electrode/electrolyte interface during lithium intercalation into natural graphite from an organic Li-ion battery electrolyte. We quantify the SEI growth kinetics and observe the dynamic self-healing nature of the SEI with changes in cell potential.

  7. Addition of a thin-film inorganic solid electrolyte (Lipon) as a protective film in lithium batteries with a liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Dudney, Nancy J.

    Three rechargeable lithium cells have been fabricated using thin films of Li and sputter-deposited Li xMn 2- yO 4 as the electrodes, and a LiPF 6 organic liquid electrolyte. Cells were cycled up to 18 times between 4.5 and 2.5 V at 25°C both with and without the addition of the thin-film lithium phosphorus oxynitride solid electrolyte, known as Lipon. Of the cells tested, the Lipon film was most effective in maximizing the capacity and cycling efficiency when deposited in direct contact with the cathode; however, a significant improvement over the Lipon-free cell was also observed with Lipon sandwiched between layers of the liquid electrolyte. In the latter case, the Lipon was deposited onto a microporous polypropylene separator membrane.

  8. A High-Conduction Ge Substituted Li3AsS4 Solid Electrolyte with Exceptional Low Activation Energy

    SciTech Connect

    Sahu, Gayatri; Rangasamy, Ezhiylmurugan; Li, Juchuan; Chen, Yan; An, Ke; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    Lithium-ion conducting solid electrolytes show potential to enable high-energy-density secondary batteries and offer distinctive safety features as an advantage over traditional liquid electrolytes. Achieving the combination of high ionic conductivity, low activation energy, and outstanding electrochemical stability in crystalline solid electrolytes is a challenge for the synthesis of novel solid electrolytes. Herein we report an exceptionally low activation energy (Ea) and high room temperature superionic conductivity via facile aliovalent substitution of Li3AsS4 by Ge, which increased the conductivity by two orders of magnitude as compared to the parent compound. The composition Li3.334Ge0.334As0.666S4 has a high ionic conductivity of 1.12 mScm-1 at 27oC. Local Li+ hopping in this material is accompanied by distinctive low activation energy Ea of 0.17 eV being the lowest of Li+ solid conductors. Furthermore, this study demonstrates the efficacy of surface passivation of solid electrolyte to achieve compatibility with metallic lithium electrodes.

  9. Thin and flexible solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes for device applications.

    PubMed

    Howlett, Patrick C; Ponzio, Florian; Fang, Jian; Lin, Tong; Jin, Liyu; Iranipour, Nahid; Efthimiadis, Jim

    2013-09-01

    All solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes are described for the first time. The new composite materials exhibit enhanced conductivity, excellent thermal, mechanical and electrochemical stability and allow the production of optically transparent, free-standing, flexible, thin film electrolytes (10's μms thick) for application in electrochemical devices. Stable cycling of a lithium cell incorporating the new composite electrolyte is demonstrated, including cycling at lower temperatures than previously possible with the pure material. PMID:23753038

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

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

    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{sub 0.9}Gd{sub 0.1}O{sub 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{sup 4+} and Ce{sup 3+} states. Presence of Ce{sup 3+} state was ascribed to the differential yield of oxygen atoms in the sputtering process.

  11. Advanced materials and electrochemical processes in high-temperature solid electrolytes

    SciTech Connect

    Bates, J.L.; Chick, L.A.; Youngblood, G.E.; Weber, W.J.

    1990-10-01

    Fuel cells for the direct conversion of fossil fuels to electric energy necessitates the use of high-temperature solid electrodes. This study has included: (1) determination of electrical transport, thermal and electrical properties to illucidate the effects of microstructure, phase equilibria, oxygen partial pressure, additives, synthesis and fabrication on these properties; (2) investigation of synthesis and fabrication of advanced oxide materials, such as La{sub 0.9}Sn{sub 0.1}MnO{sub 3}; and (3) application of new analytical techniques using complex impedance coupled with conventional electrochemical methods to study the electrochemical processes and behavior of materials for solid oxide fuel cells and other high-temperature electrolyte electrochemical process. 15 refs., 10 figs., 2 tabs. (BM)

  12. Application of solid polymer electrolyte to lithium/polypyrrole secondary battery system

    SciTech Connect

    Osaka, Tetsuya; Momma, Toshiyuki; Nishimura, Ken; Kakuda, Satoko; Ishii, Takayuki . Dept. of Applied Chemistry)

    1994-08-01

    An all solid-state lithium/polypyrrole (PPy) battery using polyethylene oxide (PEO)-LiClO[sub 4] as a solid polymer electrolyte was assembled, and the effects of the morphology of the PPy film and the concentration of LiClO[sub 4] on battery performance were investigated. Optimum conditions for the redox properties of PPy films in PEO-LiClO[sub 4] at 80 C were obtained with an LiClO[sub 4] concentration of n = 8 [approximately] 20 (n=[EO]/[Li]) when using rough PPy film. A Li/PPy battery using PEO-LiClO[sub 4] with optimized conditions exhibited high coulombic efficiency, above 90% at 0.1 mA cm [sup [minus]2] at 80 C. Cyclability of 1,400 cycles with high coulombic efficiency was attained.

  13. The NASA "PERS" Program: Solid Polymer Electrolyte Development for Advanced Lithium-Based Batteries

    NASA Technical Reports Server (NTRS)

    Baldwin, Richard S.; Bennett, William R.

    2007-01-01

    In fiscal year 2000, The National Aeronautics and Space Administration (NASA) and the Air Force Research Laboratory (AFRL) established a collaborative effort to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The ultimate objective of this development program, which was referred to as the Polymer Energy Rechargeable System (PERS), was to establish a world-class technology capability and U.S. leadership in polymer-based battery technology for aerospace applications. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. Out of a total of 38 proposals received in response to a NASA Research Announcement (NRA) solicitation, 18 proposals (13 contracts and 5 grants) were selected for initial award to address these technical challenges. Brief summaries of technical approaches, results and accomplishments of the PERS Program development efforts are presented. With Agency support provided through FY 2004, the PERS Program efforts were concluded in 2005, as internal reorganizations and funding cuts resulted in shifting programmatic priorities within NASA. Technically, the PERS Program participants explored, to various degrees over the lifetime of the formal program, a variety of conceptual approaches for developing and demonstrating performance of a viable advanced solid polymer electrolyte possessing the desired attributes, as well as several participants addressing all components of an integrated cell configuration. Programmatically, the NASA PERS Program was very successful, even though the very challenging technical goals for achieving a viable solid polymer electrolyte material or

  14. Effect of surface microstructure on electrochemical performance of garnet solid electrolytes.

    PubMed

    Cheng, Lei; Chen, Wei; Kunz, Martin; Persson, Kristin; Tamura, Nobumichi; Chen, Guoying; Doeff, Marca

    2015-01-28

    Cubic garnet phases based on Al-substituted Li7La3Zr2O12 (LLZO) have high ionic conductivities and exhibit good stability versus metallic lithium, making them of particular interest for use in next-generation rechargeable battery systems. However, high interfacial impedances have precluded their successful utilization in such devices until the present. Careful engineering of the surface microstructure, especially the grain boundaries, is critical to achieving low interfacial resistances and enabling long-term stable cycling with lithium metal. This study presents the fabrication of LLZO heterostructured solid electrolytes, which allowed direct correlation of surface microstructure with the electrochemical characteristics of the interface. Grain orientations and grain boundary distributions of samples with differing microstructures were mapped using high-resolution synchrotron polychromatic X-ray Laue microdiffraction. The electrochemical characteristics are strongly dependent upon surface microstructure, with small grained samples exhibiting much lower interfacial resistances and better cycling behavior than those with larger grain sizes. Low area specific resistances of 37 Ω cm(2) were achieved; low enough to ensure stable cycling with minimal polarization losses, thus removing a significant obstacle toward practical implementation of solid electrolytes in high energy density batteries. PMID:25563572

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

    SciTech Connect

    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.

  16. Solid oxide fuel cell electrolytes produced via very low pressure suspension plasma spray and electrophoretic deposition

    NASA Astrophysics Data System (ADS)

    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

  17. Flexible thin-film battery based on graphene-oxide embedded in solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Kammoun, M.; Berg, S.; Ardebili, H.

    2015-10-01

    Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method that is economical and scalable. The laminated battery shows robust mechanical flexibility over 6000 bending cycles and excellent electrochemical performance in both flat and bent configurations. Finite element analysis (FEA) of the LIB provides critical insights into the evolution of mechanical stresses during lamination and bending.Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method

  18. A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries.

    PubMed

    Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

    2016-01-01

    Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm(-1) at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface. PMID:27146645

  19. A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

    2016-05-01

    Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm‑1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface.

  20. Graphene-Analogues Boron Nitride Nanosheets Confining Ionic Liquids: A High-Performance Quasi-Liquid Solid Electrolyte.

    PubMed

    Li, Mingtao; Zhu, Wenshuai; Zhang, Pengfei; Chao, Yanhong; He, Qian; Yang, Bolun; Li, Huaming; Borisevich, Albinab; Dai, Sheng

    2016-07-01

    Solid electrolytes are one of the most promising electrolyte systems for safe lithium batteries, but the low ionic conductivity of these electrolytes seriously hinders the development of efficient lithium batteries. Here, a novel class of graphene-analogues boron nitride (g-BN) nanosheets confining an ultrahigh concentration of ionic liquids (ILs) in an interlayer and out-of-layer chamber to give rise to a quasi-liquid solid electrolyte (QLSE) is reported. The electron-insulated g-BN nanosheet host with a large specific surface area can confine ILs as much as 10 times of the host's weight to afford high ionic conductivity (3.85 × 10(-3) S cm(-1) at 25 °C, even 2.32 × 10(-4) S cm(-1) at -20 °C), which is close to that of the corresponding bulk IL electrolytes. The high ionic conductivity of QLSE is attributed to the enormous absorption for ILs and the confining effect of g-BN to form the ordered lithium ion transport channels in an interlayer and out-of-layer of g-BN. Furthermore, the electrolyte displays outstanding electrochemical properties and battery performance. In principle, this work enables a wider tunability, further opening up a new field for the fabrication of the next-generation QLSE based on layered nanomaterials in energy conversion devices. PMID:27225944

  1. A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

    PubMed Central

    Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

    2016-01-01

    Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm−1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface. PMID:27146645

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

    PubMed

    Zhu, Zihua; Zhou, Yufan; Yan, Pengfei; Vemuri, Rama Sesha; Xu, Wu; Zhao, Rui; Wang, Xuelin; Thevuthasan, Suntharampillai; Baer, Donald R; Wang, Chong-Min

    2015-09-01

    Dynamic structural and chemical evolution at solid-liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe a solid-liquid interface under reaction conditions. We describe the creation and usage of in situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid-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 be depleted of the salt anions and with reduced concentration of Li(+) ions, essentially leading to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributing to the overpotential of the cell. This observation provides unprecedented molecular level dynamic information on the initial formation of the solid electrolyte interphase (SEI) layer. The present work also ultimately opens new avenues for implanting the in situ liquid SIMS concept to probe the chemical reaction process that intimately involves solid-liquid interface, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization. PMID:26287361

  3. Energetics of Intermediate Temperature Solid Oxide Fuel Cell Electrolytes: Singly and Doubly doped Ceria Systems

    NASA Astrophysics Data System (ADS)

    Buyukkilic, Salih

    Solid oxide fuel cells (SOFCs) have potential to convert chemical energy directly to electrical energy with high efficiency, with only water vapor as a by-product. However, the requirement of extremely high operating temperatures (~1000 °C) limits the use of SOFCs to only in large scale stationary applications. In order to make SOFCs a viable energy solution, enormous effort has been focused on lowering the operating temperatures below 700 °C. A low temperature operation would reduce manufacturing costs by slowing component degradation, lessening thermal mismatch problems, and sharply reducing costs of operation. In order to optimize SOFC applications, it is critical to understand the thermodynamic stabilities of electrolytes since they directly influence device stability, sustainability and performance. Rare-earth doped ceria electrolytes have emerged as promising materials for SOFC applications due to their high ionic conductivity at the intermediate temperatures (500--700 °C). However there is a fundamental lack of understanding regarding their structure, thermodynamic stability and properties. Therefore, the enthalpies of formation from constituent oxides and ionic conductivities were determined to investigate a relationship between the stability, composition, structural defects and ionic conductivity in rare earth doped ceria systems. For singly doped ceria electrolytes, we investigated the solid solution phase of bulk Ce1-xLnxO2-0.5x where Ln = Sm and Nd (0 ≤ x ≤ 0.30) and analyzed their enthalpies of formation, mixing and association, and bulk ionic conductivities while considering cation size mismatch and defect associations. It was shown that for ambient temperatures in the dilute dopant region, the positive heat of formation reaches a maximum as the system becomes increasingly less stable due to size mismatch. In concentrated region, stabilization to a certain solubility limit was observed probably due to the defect association of trivalent cations

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

    NASA Astrophysics Data System (ADS)

    Esposito, Vincenzo; Gadea, Christophe; Hjelm, Johan; Marani, Debora; Hu, Qiang; Agersted, Karsten; Ramousse, Severine; Jensen, Søren Højgaard

    2015-01-01

    In this work, we present how a low-cost HP Deskjet 1000 inkjet printer was used to fabricate a 1.2 μm thin, dense and gas tight 16 cm2 solid oxide fuel cells (SOFC) electrolyte. The electrolyte was printed using an ink made of highly diluted (<4 vol.%) nanometric yttria stabilized zirconia (YSZ) powders (50 nm in size) in an aqueous medium. The ink was designed to be a highly dispersed, long term stable colloidal suspension, with optimal printability characteristics. The electrolyte was made by a multiple printing procedure, which ensures coverage of the several flaws occurring in a single printing pass. Together with an optimized sintering procedure this resulted in good adhesion and densification of the electrolyte. The SOFC exhibited a close-to-theoretical open circuit voltage and a remarkable peak power density above 1.5 W cm-2 at 800 °C.

  5. Effect of Eutectic Concentration on Conductivity in PEO:LiX Based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Zhan, Pengfei; Ganapatibhotla, Lalitha; Maranas, Janna

    Polyethylene oxide (PEO) and lithium salt based solid polymer electrolytes (SPEs) have been widely proposed as a substitution for the liquid electrolyte in Li-ion batteries. As salt concentration varies, these systems demonstrate rich phase behavior. Conductivity as a function of salt concentration has been measured for decades and various concentration dependences have been observed. A PEO:LiX mixture can have one or two conductivity maximums, while some mixtures with salt of high ionic strength will have higher conductivity as the salt concentration decrease. The factors that affect the conductivity are specific for each sample. The universal factor that affects conductivity is still not clear. In this work, we measured the conductivity of a series of PEO:LiX mixtures and statistical analysis shows conductivity is affected by the concentration difference from the eutectic concentration (Δc). The correlation with Δc is stronger than the correlation with glass transition temperature. We believe that at the eutectic concentration, during the solidification process, unique structures can form which aid conduction. Currently at Dow Chemical.

  6. Lithium dendrite and solid electrolyte interphase investigation using OsO4

    NASA Astrophysics Data System (ADS)

    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.

  7. Electrochemical redox properties of polypyrrole/Nafion composite film in a solid polymer electrolyte battery

    SciTech Connect

    Momma, Toshiyuki; Kakuda, Satoko; Yarimizu, Hideki; Osaka, Tetsuya

    1995-06-01

    Nafion{reg_sign} was introduced into a polypyrrole (PPy) matrix, and the redox performance of the PPy/Nafion electrode was investigated in a polyethylene oxide (PEO)-LiClO{sub 4} electrolyte. A rougher interface between polymer cathode and polymer electrolyte is usually needed for an all-solid battery, however, the PPy/Nafion cathode works well regardless of the flat surface of the PPy/Nafion film. When compared to a PPy film doped with ClO{sub 4}{sup {minus}} anions with a similar morphology, the PPy/Nafion film showed better redox performance. The results of the impedance spectroscopy and potential-step chronoamperometry confirmed that the improvement in the redox reaction of the PPy/Nafion film was due to the enhancement of the ion diffusion rate in the film. Thus, the PPy/Nafion film showed good charging-discharging properties in a rechargeable Li/PEO-LiClO{sub 4}/(PPy/Nafion) battery.

  8. High temperature mechanical properties of zirconia tapes used for electrolyte supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    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.

  9. Transport properties of the solid polymer electrolyte system P(EO){sub n}LiTFSI

    SciTech Connect

    Edman, L.; Doeff, M.M.; Ferry, A.; Kerr, J.; De Jonghe, L.C.

    2000-04-20

    Values for the lithium ion transference number ({tau}{sub +}{sup 0}) are reported for the solid polymer electrolyte system poly(ethylene oxide) (PEO) complexed with Li(CF{sub 3}SO{sub 2}){sub 2}N (LiTFSI). {tau}{sub +}{sup 0} ranges from 0.17 {+-} 0.17 to 0.60 {+-} 0.03 in the salt concentration (c) region of 742 to 2,982 mol/m{sup 3} at 85 C. The concentration dependence of {tau}{sub +}{sup 0} and the molar ionic conductivity ({Lambda}) are shown to be in good agreement with a free volume approach over the salt-rich composition range investigated. The present {tau}{sub +}{sup 0} results were obtained using an electrochemical technique based on concentrated solution theory. This experimentally straightforward method is herein demonstrated to give accurate results for a highly concentrated SPE system, without relying on any dubious simplifications regarding the state of the electrolyte.

  10. Formation, dynamics, and implication of solid electrolyte interphase in high voltage reversible conversion fluoride nanocomposites

    SciTech Connect

    Gmitter, Andrew J.; Badway, Fadwa; Rangan, Sylvie; Bartynski, Robert A.; Halajko, Anna; Pereira, Nathalie; Amatucci, Glenn G.

    2010-01-01

    Metal fluoride nanocomposites are uniquely suited as an alternative pathway to provide very high energy density cathodes for lithium batteries. Contrasted with modern intercalation compounds, they undergo conversion upon discharge into nanodomains of lithium fluoride and highly active metal. The nanosized metal formed during the discharge process along with the dynamic nature of the crystal structure may have considerable impact on the stability of any solid state interphase formed through reaction with the electrolyte. This is in contrast to the more macrocrystalline and stable crystal structure of traditional intercalation compounds. It has been found that the cyclic carbonates are susceptible to decomposition on the nanometal surfaces at potentials as high as 2.00 V vs. Li, and the products have been identified with Field Emission Scanning Electron Microscopy (FESEM), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and X-ray Photoelectron Spectroscopy (XPS) as lithium carbonate species. Of greater importance is the impact of these decomposition products on the reversible cycling of the metal fluoride. Through a series of potentiodynamic and galvanostatic cycling trials, a clear relationship has been developed for the bismuth fluoride nanocomposites, the decomposition of the electrolyte solvent, and the cycle life. Acyclic organic carbonate solvents have been found to have minimal interaction and exhibited better long-term cycling performance than cyclic solvents.

  11. High performance Bi-layered electrolytes via atomic layer deposition for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Jee, Youngseok; Cho, Gu Young; An, Jihwan; Kim, Hae-Ryoung; Son, Ji-Won; Lee, Jong-Ho; Prinz, Fritz B.; Lee, Min Hwan; Cha, Suk Won

    2014-05-01

    This study investigates the functionality of bi-layered electrolytes in intermediate temperature solid oxide fuel cells. A thin yttria-stabilized zirconia (YSZ) layer is expected to protect the underlying gadolinia doped ceria (GDC) electrolyte from being chemically reduced and significantly improve cell stability and durability. Although a thinner YSZ layer is preferable to minimize ohmic loss, there are limitations as to how thin the YSZ film can be and still serves as a valid protection layer. The limitation is partially attributed to the inter-diffusion and significant morphological changes during the high temperature sintering processes. In this study, a stable operation was demonstrated for extended duration (>80 h) with only a 28 nm YSZ layer (corresponding to a YSZ/GDC thickness ratio of 6.5 × 10-5) when limitations in both fabrication (<∼800 °C) and operating conditions (<∼600 °C, dry H2) were imposed. Furthermore, the functionality of a protection layer with a given thickness was found to strongly depend on the method of depositing the protective layer. Protective layers deposited by atomic layer deposition (ALD) can be much thinner than those prepared by physical vapor deposition; the YSZ/GDC thickness ratio for a stable operation approached close to a theoretical value when the ALD was used.

  12. Aging formula for lithium ion batteries with solid electrolyte interphase layer growth

    NASA Astrophysics Data System (ADS)

    Tanim, Tanvir R.; Rahn, Christopher D.

    2015-10-01

    Hybrid Electric Vehicle (HEV) current profiles are dynamic, consisting of repeated charge and discharge pulses. Accurate prediction of the battery response to these inputs requires models with open circuit voltage and Butler-Volmer kinetic nonlinearities. This paper derives a nonlinear, electrolyte-enhanced, single particle model (NESPM) that includes aging due to solid electrolyte interphase layer growth. The model is validated with experimental full charge, discharge, HEV cycle, and aging data from 4.5 Ah graphite/LiFePO4 cells. The NESPM is capable of operating up to 3C constant charge-discharge cycles and up to 25C and 10 s charge-discharge pulses within 35-65% state of charge (SOC) with less than 2% error. The NESPM aging model is then simplified to obtain explicit formulas for capacity fade and impedance rise that depend on the battery parameters and current input history. The formulas show that aging increases with SOC, operating temperature, time, and root mean square (RMS) current. The formula predicts that HEV current profiles with the (i) same average SOC, (ii) small SOC swing, (iii) same operating temperature, (iv) same cycle length, and (v) same RMS current, will have the same cell capacity fade.

  13. Advances in solid polymer electrolyte fuel cell technology with low-platinum-loading electrodes

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Ticianelli, E. A.; Derouin, C. R.; Redondo, A.

    1987-01-01

    The Gemini Space program demonstrated the first major application of fuel cell systems. Solid polymer electrolyte fuel cells were used as auxiliary power sources in the spacecraft. There has been considerable progress in this technology since then, particularly with the substitution of Nafion for the polystyrene sulfonate membrane as the electrolyte. Until recently the performance was good only with high platinum loading (4 mg/sq cm) electrodes. Methods are presented to advance the technology by (1) use of low platinum loading (0.35 mg/sq cm) electrodes; (2) optimization of anode/membrane/cathode interfaces by hot pressing; (3) pressurization of reactant gases, which is most important when air is used as cathodic reactant; and (4) adequate humidification of reactant gases to overcome the water management problem. The high performance of the fuel cell with the low loading of platinum appears to be due to the extension of the three dimensional reaction zone by introduction of a proton conductor, Nafion. This was confirmed by cyclic voltammetry.

  14. Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus and methods

    DOEpatents

    Zaromb, Solomon

    2001-01-01

    Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity .gtoreq.10.sup.-4 (ohm-cm).sup.-1, and preferably .gtoreq.0.01 (ohm-cm).sup.-1. The conductivity may be due predominantly to Ag+ ions, as in Ag.sub.2 WO.sub.4.4AgI, or to F- ions, as in Ce.sub.0.95 Ca.sub.0.05 F.sub.2.95. Electrical contacts serve to connect the electrodes to potentiostating and detecting circuitry which controls the potential of the sensing electrode relative to the reference electrode, detects the signal generated by the sensor, and indicates the detected signal.

  15. Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus

    DOEpatents

    Zaromb, Solomon

    1994-01-01

    Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity .gtoreq.10.sup.-4 (ohm-cm).sup.-1, and preferably .gtoreq.0.01 (ohm-cm).sup.-1. The conductivity may be due predominantly to Ag+ ions, as in Ag.sub.2 WO.sub.4.4AgI, or to F- ions, as in Ce.sub.0.95 Ca.sub.0.05 F.sub.2.95. Electrical contacts serve to connect the electrodes to potentiostating and detecting circuitry which controls the potential of the sensing electrode relative to the reference electrode, detects the signal generated by the sensor, and indicates the detected signal.

  16. Bubble Growth and Dynamics in a Strongly Superheated Electrolyte within a Solid-State Nanopore

    NASA Astrophysics Data System (ADS)

    Levine, Edlyn; Nagashima, Gaku; Burns, Michael; Golovchenko, Jene

    2015-03-01

    Extreme localized superheating and homogeneous vapor bubble nucleation have recently been demonstrated in a single nanopore in thin, solid state membranes. Aqueous electrolytic solution within the pore is superheated to well above its boiling point by Joule heating from ionic current driven through the pore. Continued heating of the metastable liquid leads to nucleation of a vapor bubble in the pore followed by explosive growth. Here we report on the growth dynamics of the vapor bubble after nucleation in the strongly superheated liquid. The process is modeled by numerically solving the Rayleigh-Plesset equation coupled with energy conservation and a Stefan boundary condition. The initial temperature distribution, peaked at the pore center, is taken to be radially symmetric. Energy conservation includes a Joule heating source term dependent on the bubble radius, which grows to constrict ionic current through the nanopore. Temperature-dependent properties of the electrolyte and the vapor are incorporated in the calculation. Comparison of the model to experimental results shows an initial bubble growth velocity of 50m/s and total bubble lifetime of 16ns. This work was supported by NIH Grant #5R01HG003703 to J.A. Golovchenko.

  17. Defect Physics and Ionic conduction in Solid Electrolyte Interphase for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Pan, Jie; Cheng, Yang-Tse; Qi, Yue

    The ionic conduction through the solid electrolyte interphase (SEI) is important to the rate capability of the battery. The origin of ionic conduction in the SEI is defect formation and transport. In this study, we developed a theoretical method based on density functional theory to calculate the ionic conductivity in LiF, an important SEI component, in contact with electrode materials. Seventeen native defects with their relevant charge states were investigated to determine the dominant defects on various electrodes. The contacted electrode serves as a Li reservoir with adjustable Li chemical potential (μLi) for defect formation. The formation energy and diffusion barrier of defects were mapped to ionic conductivity by the Nernst-Einstein relationship. The main defect is Schottky pair in the intrinsic region and Li ion vacancy in the p-type region. The ionic conductivity is calculated to be approximately 10-31 S/cm when LiF is in contact with an anode but it can increase to 10-12 S/cm on a cathode. Comparing with other SEI components, the ionic conductivity is very low in LiF if it is coated on an anode surface. However, due to the low concentration of electronic carriers, LiF can act as a good passivation layer on the electrode and prevent further electrolyte decomposition. This work is supported by Department of Energy and National Science Foundation.

  18. Ionic conductivity studies of solid oxide fuel cell electrolytes and theoretical modeling of an entire solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Pornprasertsuk, Rojana

    Because of the steep increase in oil prices, the global warming effect and the drive for energy independence, alternative energy research has been encouraged worldwide. The sustainable fuels such as hydrogen, biofuel, natural gas, and solar energy have attracted the attention of researchers. To convert these fuels into a useful energy source, an energy conversion device is required. Fuel cells are one of the energy conversion devices which convert chemical potentials into electricity. Due to their high efficiency, the ease to scale from 1 W range to megawatts range, no recharging requirement and the lack of CO2 and NOx emission (if H2 and air/O 2 are used), fuel cells have become a potential candidate for both stationary power generators and portable applications. This thesis has been focused primarily on solid oxide fuel cell (SOFC) studies due to its high efficiency, varieties of fuel choices, and no water management problem. At the present, however, practical applications of SOFCs are limited by high operating temperatures that are needed to create the necessary oxide-ion vacancy mobility in the electrolyte and to create sufficient electrode reactivities. This thesis introduces several experimental and theoretical approaches to lower losses both in the electrolyte and the electrodes. Yttria stabilized zirconia (YSZ) is commonly used as a solid electrolyte for SOFCs due to its high oxygen-ion conductivity. To improve the ionic conductivity for low temperature applications, an approach that involves dilating the structure by irradiation and introducing edge dislocations into the electrolyte was studied. Secondly, to understand the activation loss in SOFC, the kinetic Monte Carlo (KMC) technique was implemented to model the SOFC operation to determining the rate-limiting step due to the electrodes on different sizes of Pt catalysts. The isotope exchange depth profiling technique was employed to investigate the irradiation effect on the ionic transport in different

  19. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    NASA Astrophysics Data System (ADS)

    Manjunatha, H.; Damle, R.; Kumaraswamy, G. N.

    2016-05-01

    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 10-1 - 10-3 Scm-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 PEOxNaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O+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.

  20. A formalism for modeling solid electrolyte/electrode interfaces using first principles methods

    NASA Astrophysics Data System (ADS)

    Lepley, Nicholas; Holzwarth, Natalie

    We describe a scheme based on the interface energy for analyzing interfaces between crystalline solids, quantitatively including the effect of lattice strain. This scheme is applied to the modeling of likely interface geometries of several solid state battery materials including Li metal, Li3PO4, Li3PS4, Li2O, and Li2S. We find that all of the interfaces in this study are stable with the exception of Li3PS4/Li. For this chemically unstable interface, the partial density of states helps to identify mechanisms associated with the interface reactions. We also consider the case of charged defects at the interface, and show that accurately modeling them requires a careful treatment of the resulting electric fields. Our energetic measure of interfaces and our analysis of the band alignment between interface materials indicate multiple factors which may be predictors of interface stability, an important property of solid electrolyte systems. Supported by NSF Grant DMR-1105485 and DMR-1507942.

  1. Ceramic distribution members for solid state electrolyte cells and method of producing

    NASA Technical Reports Server (NTRS)

    Clark, Douglas J. (Inventor); Galica, Leo M. (Inventor); Losey, Robert W. (Inventor); Suitor, Jerry W. (Inventor)

    1993-01-01

    A solid state electrolyte cells apparatus and method of producing is disclosed. The apparatus can be used for separating oxygen from an oxygen-containing feedstock or as a fuel cell for reacting fluids. Cells can be stacked so that fluids can be introduced and removed from the apparatus through ceramic distribution members having ports designed for distributing the fluids in parallel flow to and from each cell. The distribution members can also serve as electrodes to membranes or as membrane members between electrodes. The distribution member design does not contain any horizontal internal ports which allows the member to be thin. A method of tape casting in combination with an embossing method allows intricate radial ribs and bosses to be formed on each distribution member. The bosses serve as seals for the ports and allow the distribution members to be made without any horizontal internal ports.

  2. Toward fast and cost-effective ink-jet printing of solid electrolyte for lithium microbatteries

    NASA Astrophysics Data System (ADS)

    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.

  3. Characterisation of the solid electrolyte interface during lithiation/delithiation of germanium in an ionic liquid.

    PubMed

    Lahiri, Abhishek; Borisenko, Natalia; Borodin, Andriy; Olschewski, Mark; Endres, Frank

    2016-02-21

    In this paper, we present investigations of the interface of electrodeposited Ge during lithiation/delithiation in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide containing 0.5 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI/[Py1,4]TFSI). Cyclic voltammetry (CV) and infrared spectroscopy were used to study the electrochemistry and the changes in the electrolyte during the Li intercalation/deintercalation processes. From infrared spectroscopic analysis, it was found that the TFSI(-) anion decomposes during the lithiation process, resulting in the formation of a solid-liquid interface (SEI) layer. X-ray photoelectron spectroscopy was used to analyse the composition of the SEI layer and the changes in the electrodeposited germanium. Furthermore, atomic force microscopy (AFM) was used to evaluate the changes in the SEI layer which showed that the SEI layer was inhomogenous and changed during the lithiation/delithiation processes. PMID:26863589

  4. Development status of solid polymer electrolyte water electrolysis for manned spacecraft life support systems

    NASA Technical Reports Server (NTRS)

    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.

  5. Solid polymer electrolyte water electrolysis system development. [to generate oxygen for manned space station applications

    NASA Technical Reports Server (NTRS)

    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.

  6. B₂O₃-added lithium aluminium germanium phosphate solid electrolyte for Li-O₂ rechargeable batteries.

    PubMed

    Jadhav, Harsharaj S; Kalubarme, Ramchandra S; Jang, Seong-Yong; Jung, Kyu-Nam; Shin, Kyoung-Hee; Park, Chan-Jin

    2014-08-14

    B2O3-added Li(1.5)Al(0.5)Ge(1.5)(PO4)3 (LAGP) glass ceramics showing a room temperature ionic conductivity of 0.67 mS cm(-1) have been synthesized by using a melt-quenching method. The prepared glass ceramics are observed to be stable in tetraethylene glycol dimethyl ether containing lithium bis(trifluoromethane) sulfonamide. The augmented conductivity of the B2O3-added LAGP glass ceramic has improved the plateau potential during discharge. Furthermore, the B2O3-added LAGP glass ceramics are successfully employed as a solid electrolyte in a Li-O2 battery to obtain a stable cycling lifetime of up to 15 cycles with the limited capacity protocol. PMID:24953185

  7. Development of solid electrolytes for water electrolysis at intermediate temperatures. Task 3 report; Annual report

    SciTech Connect

    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.

  8. Fast Na/+/-ion transport in skeleton structures. [solid electrolyte applications

    NASA Technical Reports Server (NTRS)

    Goodenough, J. B.; Hong, H. Y.-P.; Kafalas, J. A.

    1976-01-01

    The skeleton structures considered in the investigations consist of a rigid subarray with an interconnected interstitial space in which ions move in three dimensions. The classes of skeleton structures investigated include the Im3 phase of high-pressure KSbO3, the defect-pyrochlore structure illustrated by RbMgAlF6, and the carnegieite structure of high-temperature NaAlSiO4. A description is given of the results obtained in transport measurements involving dense polycrystalline ceramic disks. Results obtained in the case of the Na(+)-ion transport in Na3Zr2PSi2O12 appear particularly promising concerning the possible use of such substances in solid-electrolyte applications.

  9. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface

    NASA Astrophysics Data System (ADS)

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-07-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01-1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica.

  10. Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

    SciTech Connect

    Richardson, Thomas J.; Ross, Philip N.

    1999-01-01

    A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85.degree. C. or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1.times.10.sup.-8 cm.sup.2 /second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

  11. Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

    SciTech Connect

    Richardson, T.J.; Ross, P.N.

    1999-12-21

    A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85 C or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1 {times} 10{sup {minus}8}cm{sup 2}/second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

  12. Nanostructured Gd-CeO2 electrolyte for solid oxide fuel cell by aqueous tape casting

    NASA Astrophysics Data System (ADS)

    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.

  13. Thermodynamics of solid electrolytes and related oxide ceramics based on the fluorite structure

    SciTech Connect

    Navrotsky, Alexandra

    2010-01-01

    Oxides based on the fluorite structure are important as electrolytes in solid oxide fuel cells, thermal barrier coatings, gate dielectrics, catalysts, and nuclear materials. Though the parent fluorite structure is simple, the substitution of trivalent for tetravalent cations, coupled with the presence of charge-balancing oxygen vacancies, leads to a wealth of short-range and long-range ordered structures and complex thermodynamic properties. The location of vacancies and the nature of clusters affect the energetics of mixing in rare earth doped zirconia, hafnia, ceria, urania, and thoria, with systematic trends in energetics as a function of cation radius. High temperature oxide melt solution calorimetry has provided direct measurement of formation enthalpies of these refractory materials. Surface and interfacial energies have also been measured in yttria stabilized zirconia (YSZ) nanomaterials. Other ionic conductors having perovskite, apatite, and mellilite structures are discussed briefly.

  14. Electrolytes at Solid-Water Interfaces: Theoretical Studies for Practical Applications

    SciTech Connect

    Striolo, Alberto

    2013-09-23

    The goal of this research program was to determine how a solid substrate affects structure and dynamics of aqueous electrolyte solutions. From fundamental observations, we seek to improve practical applications. Of particular interest at the project inset were carbon nanotube separation, electric double layer capacitors, and water desalination. As time progresses, we became interested in sub-surface water transport and fate, and in hydraulic fracturing. We employed an arsenal of techniques based on atomistic molecular dynamics simulations. We validated our methods using experimental data, to propose practical improvements. Some experiments were conducted in house. We established valuable collaborations with experienced scientists at National Laboratories to provide information not attainable with our in-house resources.

  15. Method of producing ceramic distribution members for solid state electrolyte cells

    NASA Technical Reports Server (NTRS)

    Clark, Douglas J. (Inventor); Galica, Leo M. (Inventor); Losey, Robert W. (Inventor); Suitor, Jerry W. (Inventor)

    1995-01-01

    A solid state electrolyte cells apparatus and method of producing is disclosed. The apparatus can be used for separating oxygen from an oxygen-containing feedstock or as a fuel cell for reacting fluids. Cells can be stacked so that fluids can be introduced and removed from the apparatus through ceramic distribution members having ports designed for distributing the fluids in parallel flow to and from each cell. The distribution members can also serve as electrodes to membranes or as membrane members between electrodes, The distribution member design does not contain any horizontal internal ports which allows the member to be thin. A method of tape casting in combination with an embossing method allows intricate radial ribs and bosses to be formed on each distribution member. The bosses serve as seals for the ports and allow the distribution members to be made without any horizontal internal ports.

  16. Morphology and conductivity study of solid electrolyte Li3PO4

    NASA Astrophysics Data System (ADS)

    Prayogi, Lugas Dwi; Faisal, Muhamad; Kartini, Evvy; Honggowiranto, Wagiyo; Supardi

    2016-02-01

    The comparison between two different methods of synthesize of solid electrolyte Li3PO4 as precursor material for developing lithium ion battery, has been performed. The first method is to synthesize Li3PO4 prepared by wet chemical reaction from LiOH and H3PO4 which provide facile, abundant available resource, low cost, and low toxicity. The second method is solid state reaction prepared by Li2CO3 and NH4H2PO4. 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 Li3PO4 powder products from two different reaction are characterized by SEM, EDS, and EIS. The Li3PO4 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 Li3PO4 prepared by wet chemical reaction is 2.238 gr/cm3, little bit lower than the sample prepared by solid state reaction which density is 2.3560 gr/cm3. The EIS measurement result shows that the conductivity of Li3PO4 is 1.7 x 10-9 S.cm-1 for wet chemical reaction and 1.8 x 10-10 S.cm-1 for solid state reaction. The conductivity of Li3PO4 is not quite different between those two samples even though they were prepared by different method of synthesize.

  17. Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

    PubMed

    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

  18. Solid Polymer Electrolytes Based on Functionalized Tannic Acids from Natural Resources for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Shim, Jimin; Bae, Ki Yoon; Kim, Hee Joong; Lee, Jin Hong; Kim, Dong-Gyun; Yoon, Woo Young; Lee, Jong-Chan

    2015-12-21

    Solid polymer electrolytes (SPEs) for all-solid-state lithium-ion batteries are prepared by simple one-pot polymerization induced by ultraviolet (UV) light using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as an ion-conducting monomeric unit and tannic acid (TA)-based crosslinking agent and plasticizer. The crosslinking agent and plasticizer based on natural resources are obtained from the reaction of TA with glycidyl methacrylate and glycidyl poly(ethylene glycol), respectively. Dimensionally stable free-standing SPE having a large ionic conductivity of 5.6×10(-4)  Scm(-1) at room temperature can be obtained by the polymerization of PEGMA into P(PEGMA) with a very small amount (0.1 wt %) of the crosslinking agent and 2.0 wt % of the plasticizer. The ionic conductivity value of SPE with a crosslinked structure is one order of magnitude larger than that of linear P(PEGMA) in the waxy state. PMID:26609912

  19. Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

    PubMed Central

    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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  2. Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing

    SciTech Connect

    Chiu, K.-F.; Chen, C. C.; Lin, K. M.; Lo, C. C.; Lin, H. C.; Ho, W.-H.; Jiang, C. S.

    2010-07-15

    Amorphous lithium phosphorus oxynitride (LiPON) solid-state thin-film electrolyte has been deposited and characterized. The thin films were prepared by rf magnetron sputtering under various substrate biases. By fabricating under different substrate biases and applying low temperature annealing (473 K), the properties of the LiPON thin-film electrolytes and the electrolyte/cathode interfaces were modified. The ionic conductivity as high as 9.4x10{sup -4} S m{sup -1} can be obtained by depositing at optimal bias. The performances of the consequently fabricated SnO{sub 2}/LiPON/LiMn{sub 2}O{sub 4} all-solid-state lithium ion thin-film batteries were improved using the bias sputtering technique, due to the enhanced the ionic conductivity and uniform interface.

  3. Engineered interfaces and nano-scale thin films for solid oxide fuel cell electrolytes

    NASA Astrophysics Data System (ADS)

    Nandasiri, Manjula I.

    Solid state electrolytes with high oxygen ionic conductivity at low temperatures are required to develop cost effective and efficient solid oxide fuel cells. This study investigates the influence of engineered interfaces on the oxygen ionic conductivity of nano-scale multilayer thin film electrolytes. The epitaxial Sm2O3 doped CeO2 (SDC) and Sc2O3 stabilized ZrO2 (ScSZ) are selected as the alternative layers for the proposed multilayer thin film electrolyte based on the optimum structural, chemical, and electrical properties reported in the previous studies. The epitaxial SDC(111)/ScSZ(111) multilayer thin films are grown on high purity Al2O3(0001) substrates by oxygen-plasma assisted molecular beam epitaxy. Prior to the deposition of multilayers, the growth parameters are optimized for epitaxial CeO 2, ZrO2, SDC, and ScSZ thin films. The epitaxial orientation and surface morphology of CeO2 thin films shows dependency on the growth rate. Epitaxial CeO2(111) is obtained at relatively high growth rates (>9 A/min) at a substrate temperature of 650°C and an oxygen partial pressure of 2 x 10 -5 Torr. The same growth parameters are used for the deposition of ZrO2 thin films. ZrO2 exhibits both monoclinic and cubic phases, which is stabilized in the cubic structure by doping with Sc 2O3. The Sm and Sc evaporation rates are varied during the growth to obtain thin films of 15 mol % SmO1.5 doped CeO2 and 20 mol % ScO1.5 stabilized ZrO2, respectively. The SDC/ScSZ multilayer thin films are grown using the same growth parameters by varying the number of layers. The SDC/ScSZ multilayer thin films show significant enhancement in the oxygen ionic conductivity in comparison to single layer SDC and ScSZ thin films. The increase in the oxygen ionic conductivity with the increase in number of layers can be attributed to lattice mismatch induced ionic conductivity along the interfaces. The 8-layer film exhibits the maximum oxygen ionic conductivity with one order of magnitude

  4. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    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.

  5. Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

    DOE PAGESBeta

    Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; Ren, Fei; Keum, Jong Kahk; Ahn, Suk-Kyun; Li, Dawen; Chen, Jihua

    2015-08-06

    Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition thatmore » is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.« less

  6. Development of a solid polymer electrolyte electrolysis cell module and ancillary components for a breadboard water electrolysis system

    NASA Technical Reports Server (NTRS)

    Porter, F. J., Jr.

    1972-01-01

    Solid polymer electrolyte technology in a water electrolysis system along with ancillary components to generate oxygen and hydrogen for a manned space station application are considered. Standard commercial components are utilized wherever possible. Presented are the results of investigations, surveys, tests, conclusions and recommendations for future development efforts.

  7. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

    2016-02-01

    The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

  8. A room temperature Na/S battery using a β″ alumina solid electrolyte separator, tetraethylene glycol dimethyl ether electrolyte, and a S/C composite cathode

    NASA Astrophysics Data System (ADS)

    Kim, Icpyo; Park, Jin-Young; Kim, Chang Hyeon; Park, Jin-Woo; Ahn, Jae-Pyoung; Ahn, Jou-Hyeon; Kim, Ki-Won; Ahn, Hyo-Jun

    2016-01-01

    To realize a high-performance room temperature Na/S battery with an elemental sulfur cathode, it is important that sodium polysulfides stay within the cathode and that they have room enough to react freely. In this work, sodium polysulfides are confined to the cathode using a β″ alumina solid electrolyte separator and an optimal amount of tetraethylene glycol dimethyl ether (TEGDME) electrolyte. In addition, an activated carbon material, in the form of a sulfur/carbon (S/C) composite, with high surface area, porosity, and pore volume is employed in the cathode. The resulting Na/S battery shows a high first discharge capacity of 855 mAh g-1 and coulombic efficiency close to 100%, as well as stable cyclability, with a discharge capacity of 521 mAh g-1 at the 104th discharge.

  9. Interface stability of a TiO₂/3-methoxypropionitrile-based electrolyte: first evidence for solid electrolyte interphase formation and implications.

    PubMed

    Flasque, Miguel; Van Nhien, Albert Nguyen; Swiatowska, Jolanta; Seyeux, Antoine; Davoisne, Carine; Sauvage, Frédéric

    2014-04-14

    We report an in-depth study focusing on the stability of a benchmark electrolyte composition based on a low-volatile 3-methoxypropionitrile (MPN) solvent employed in dye-sensitized solar cells. In the presence of TiO2, the semi-conductor surface plays a catalytic role in the thermal degradation of the electrolyte, which induces, among other effects, the nucleation and growth of a uniform solid electrolyte interphase (SEI) layer that wraps TiO2. On the basis of our actual understanding, we argue that SEI formation is responsible for triiodide depletion in the electrolyte during ageing and also has a simultaneous impact on TiO2 optoelectronic properties through the onset of a visible-light absorption tail, energy modification of intraband trap states, and the induction of an increase in both electron lifetime and transport time in TiO2. In-depth characterization of this layer by using XPS and ToF-SIMS indicates that the chemical composition of this SEI results from solvent and additive degradation, that is, iodide, sulfur, cyano, nitrogen, carbon, and imidazolium rings. The SEI thickness, its content, and the concentration profile strongly vary depending on the ageing conditions. The outcome of this new finding is discussed in comparison with literature observations and stresses the difficulties in reaching long-term stability at 85 °C by using MPN-based electrolytes unless new interfacial engineering is accomplished to impede pinholes between dye molecules on TiO2. PMID:24446189

  10. Solid oxide fuel cell electrolytes produced by a combination of suspension plasma spray and very low pressure plasma spray.

    SciTech Connect

    Slamovich, Elliot; Fleetwood, James; McCloskey, James F.; Hall, Aaron Christopher; Trice, Rodney Wayne

    2010-07-01

    Plasma spray coating techniques allow unique control of electrolyte microstructures and properties as well as facilitating deposition on complex surfaces. This can enable significantly improved solid oxide fuel cells (SOFCs), including non-planar designs. SOFCs are promising because they directly convert the oxidization of fuel into electrical energy. However, electrolytes deposited using conventional plasma spray are porous and often greater than 50 microns thick. One solution to form dense, thin electrolytes of ideal composition for SOFCs is to combine suspension plasma spray (SPS) with very low pressure plasma spray (VLPPS). Increased compositional control is achieved due to dissolved dopant compounds in the suspension that are incorporated into the coating during plasma spraying. Thus, it is possible to change the chemistry of the feed stock during deposition. In the work reported, suspensions of sub-micron diameter 8 mol.% Y2O3-ZrO2 (YSZ) powders were sprayed on NiO-YSZ anodes at Sandia National Laboratories (SNL) Thermal Spray Research Laboratory (TSRL). These coatings were compared to the same suspensions doped with scandium nitrate at 3 to 8 mol%. The pressure in the chamber was 2.4 torr and the plasma was formed from a combination of argon and hydrogen gases. The resultant electrolytes were well adhered to the anode substrates and were approximately 10 microns thick. The microstructure of the resultant electrolytes will be reported as well as the electrolyte performance as part of a SOFC system via potentiodynamic testing and impedance spectroscopy.

  11. Conducting gel electrolytes with microporous structures for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Yuan, Shuangshuang; Tang, Qunwei; He, Benlin; Yu, Liangmin

    2015-01-01

    Conducting gel electrolytes from poly(acrylic acid)-cetyltrimethylammonium bromide/polyaniline (PAA-CTAB/PANi) and poly(acrylic acid)-cetyltrimethylammonium bromide/polypyrrole (PAA-CTAB/PPy) are synthesized under driving forces of both osmotic pressure and capillary force within microporous PAA-CTAB matrix. The as-synthesized PAA-CTAB/PANi or PAA-CTAB/PPy can extend the reduction reaction of triiodides from gel electrolyte/Pt counter electrode interface to both interface and three-dimensional framework of conducting gel electrolyte due to the electrical conduction of PANi or PPy toward reflux electrons (electrons from external circuit to Pt counter electrode). The enhanced kinetics for triiodides → iodide conversion is promising in elevating photovoltaic performances of quasi-solid-state dye-sensitized solar cells (DSSCs). Driving forces by both osmotic pressure across PAA-CTAB matrix and capillary force presenting in micropores can elevate the loading of PANi or PPy incorporated liquid electrolyte in per unit volume, leading to further enhancement in charge transfer and electrocatalytic activity. The total power conversion efficiencies of 7.11% and 6.39% are recorded in the solar cells with PAA-CTAB/PANi and PAA-CTAB/PPy electrolytes under one sun irradiation, respectively, whereas it is 6.07% for the cell device with pure PAA-CTAB gel electrolyte. Electrical and electrochemical characterizations reveal that the electrical conduction and electrocatalytic performances have been significantly enhanced by incorporating electrical conducting PANi or PPy into microporous PAA-CTAB matrix. The concept opens a new approach of fabricating efficient polymer gel electrolytes for robust quasi-solid-state DSSC applications.

  12. Cross-linking of Ordered Pluronic/Ionic Liquid Blends for Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Miranda, Daniel; Versek, Craig; Tuominen, Mark; Watkins, James; Russell, Thomas

    2012-02-01

    Ion gels were fabricated by cross-linking PPO-PEO-PPO triblock copolymers swollen in a room temperature ionic liquid (IL). The copolymers are modified by esterification to replace the terminal hydroxyl endgroups with methacrylate endgroups. This allows the copolymer/IL blends to be cross-linked by a UV cure, forming a gel. The strong interaction of the IL with the PEO block suppresses PEO crystallization which is necessary for good ion conduction. In addition, the interaction between the IL and PEO is strongly selective for PEO, strengthening microphase separation. Despite this, the low molecular weight copolymers remain disordered in the melt even when blended with the IL. However, high molecular weight copolymers are capable of microphase separating into highly ordered block copolymer morphologies. This difference allows the effect of microphase separation on ion transport to be studied. The effect of block copolymer composition is also studied, by varying the PEO fraction of the copolymer. The resultant gels show high ionic conductivity and solid-like behavior, indicating that these materials may be effective as solid polymer electrolytes.

  13. Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

    DOEpatents

    Kuo, L.J.H.; Singh, P.; Ruka, R.J.; Vasilow, T.R.; Bratton, R.J.

    1997-11-11

    A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators. 4 figs.

  14. Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations.

    PubMed

    Sun, Bing; Mindemark, Jonas; V Morozov, Evgeny; Costa, Luciano T; Bergman, Martin; Johansson, Patrik; Fang, Yuan; Furó, István; Brandell, Daniel

    2016-03-30

    Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with ε-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li(+) and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li(+)-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments. PMID:26984668

  15. Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

    DOEpatents

    Kuo, Lewis J. H.; Singh, Prabhakar; Ruka, Roswell J.; Vasilow, Theodore R.; Bratton, Raymond J.

    1997-01-01

    A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators.

  16. Structure and Ion Transport Studies of PEO-Based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Karlinsey, Robert L.; Aravinda Narayanan, R.; Bronstein, Lyudmila M.; Zwanziger, Josef W.

    2003-03-01

    X-ray and conductivity experiments have been performed to understand cation transport in polyethylene (PEO)-based organic-inorganic nanocomposite (OIC) solid polymer electrolytes [1], (PEO)14LiTf + OIC. X-ray diffraction patterns show that the addition of OIC enhances amorphicity, which is thought to aid ionic conduction [2]. The resulting disorder is reflected in changes in intensity and width of the prominent PEO peaks, d120 and d014, which are correlated with the observed maximum in conductivity near 40Further support for the correlation between structure and dynamics is provided by Raman, IR, and DSC measurements. The results are also likely to bear upon the existing theories to understand ionic conduction in crystalline [3] and amorphous [2] phases of materials. This work was funded by a NASA grant (NAG3-2588). [1] L.M. Bronstein, C. Joo, R.L. Karlinsey, A. Ryder, J.W.Zwanziger, Chem. Mat. 13 (2001) 3678. [2] C. Berthier, W. Gorecki, M. Minier, M.B. Armand, J.M. Chabagno, P. Rigaud, Solid State Ionics 11 (1983) 91. [3] J. Gadjourva, Y.G. Andreev, D.P. Tunstall, P.G. Bruce, Nature 412 (2001) 520.

  17. Co-sinterable lithium garnet-type oxide electrolyte with cathode for all-solid-state lithium ion battery

    NASA Astrophysics Data System (ADS)

    Ohta, Shingo; Seki, Juntaro; Yagi, Yusuke; Kihira, Yuki; Tani, Takao; Asaoka, Takahiko

    2014-11-01

    We investigated the development of a novel lithium garnet-type oxide electrolyte, which is co-sinterable with a metal oxide cathode, for practical all-solid-state lithium ion batteries using metal oxide electrolytes. The sintering temperature of Li6.8(La2.95,Ca0.05)(Zr1.75,Nb0.25)O12 was found to significantly lower to 790 °C by addition of Li3BO3 and Al2O3, due to simultaneous interdiffusion of Al and Ca elements between garnet-type oxide and additives. The sintered electrolyte exhibited high lithium ion conductivity of 0.36 mS cm-1 at 25 °C despite of the low sintering temperature. An all-solid-state lithium ion battery was successfully prepared by co-sintering of the electrolyte and LiCoO2 (cathode), followed by coating of Li metal (anode), and confirmed to function well as a secondary battery with charge and discharge capacities of 98 and 78 mAh g-1, respectively. These results opened the potential for fabrication of all-solid-state lithium ion batteries by a simple and well-established co-sintering process.

  18. Stable, High-Efficiency Pyrrolidinium-Based Electrolyte for Solid-State Dye-Sensitized Solar Cells.

    PubMed

    He, Tong; Wang, Ye Feng; Zeng, Jing Hui

    2015-09-30

    We synthesized a series of pyrrolidinium based dicationic ionic crystals with high melting point and good thermal stability. Research on the crystal structure shows that there are ordered three-dimensional ionic channels in these crystals which is favorable for the ionic conductor to achieve high conductivity and diffusion coefficient. These ionic crystals are applied to electrolyte as matrix in dye sensitized solar cells, and the influence of crystal structure (including the alkylene chain separating two pyrrolidinium rings and anion) versus the device performances are studied by steady-state voltammography, current-voltage trace, and electrochemical impedance spectroscopy. As the solid state electrolyte, an optimized efficiency of 6.02% have achieved under full sunlight irradiation using ionic crystal [C6BEP][TFSI]2. And the device based on this solid electrolyte shows the excellent long-term stability, maintaining 92% of the initial efficiency after 960 h. This study elucidates fundamental the structure of dicationic crystal and provide useful clues for further improvement of solid-state electrolytes in DSSC. PMID:26336080

  19. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    SciTech Connect

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquid cell.

  20. Applications of ceramic electrolytes and electrodes in the beta battery and solid oxide fuel cell: Current assessment

    SciTech Connect

    Gordon, R.S.; Fischer, W.; Virkar, A.V.

    1996-12-31

    The use of ceramics as electrolytes, electrodes, cell interconnects and other structural components will be reviewed for two advanced electrochemical systems: (1) the beta battery for electric vehicle and utility load leveling applications and (2) the solid oxide fuel cell (SOFC) for power generation. Specific attention will be given to the processing and properties of the beta{double_prime}-alumina ceramic electrolyte, the heart of the beta battery, and stabilized zirconia, the key element in the SOFC. Thin film component fabrication, as an approach to lowering the operational temperature of the SOFC, will be discussed. The current state of development of these two electro-chemical systems will be assessed.

  1. A system using solid ceramic oxygen electrolyte cells to measure oxygen fugacities in gas-mixing systems

    NASA Technical Reports Server (NTRS)

    Williams, R. J.; Mullins, O.

    1976-01-01

    Details are given for the construction and operation of a 101.3 kN/sq m (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the high input impedance electronics necessary for measurements, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change relative to temperature and redox state. The calibration and maintenance of the system are discussed.

  2. JSC systems using solid ceramic oxygen electrolyte cells to measure oxygen fugacites in gas-mixing systems

    NASA Technical Reports Server (NTRS)

    Williams, R. J.; Mullins, O.

    1981-01-01

    Details are given for the construction and operation of a 101.3 KN/sq meter (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change of temperature. A thermogravimetric analysis system employing these techniques of redox control and measurement is also described. The calibration and maintenance of the system are discussed.

  3. Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

    NASA Astrophysics Data System (ADS)

    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.

  4. Effect of electrolytes on the structure and evolution of the solid electrolyte interphase (SEI) in Li-ion batteries: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Pil; Duin, Adri C. T. van; Shenoy, Vivek B.

    2011-10-01

    We have studied the formation and growth of solid-electrolyte interphase (SEI) for the case of ethylene carbonate (EC), dimethyl carbonate (DMC) and mixtures of these electrolytes using molecular dynamics simulations. We have considered SEI growth on both Li metal surfaces and using a simulation framework that allows us to vary the Li surface density on the anode surface. Using our simulations we have obtained the detailed structure and distribution of different constituents in the SEI as a function of the distance from the anode surfaces. We find that SEI films formed in the presence of EC are rich in Li2CO3 and Li2O, while LiOCH3 is the primary constituent of DMC films. We find that dilithium ethylene dicarbonate, LiEDC, is formed in the presence of EC at low Li surface densities, but it quickly decomposes to inorganic salts during subsequent growth in Li rich environments. The surface films formed in our simulations have a multilayer structure with regions rich in inorganic and organic salts located near the anode surface and the electrolyte interface, respectively, in agreement with depth profiling experiments. Our computed formation potentials 1.0 V vs. Li/Li+ is also in excellent accord with experimental measurements. We have also calculated the elastic stiffness of the SEI films; we find that they are significantly stiffer than Li metal, but are somewhat more compliant compared to the graphite anode.

  5. Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices

    NASA Astrophysics Data System (ADS)

    Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

    2016-07-01

    Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices.Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength

  6. Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Manko, David J.; Enayatullah, Mohammad; Appleby, A. John

    1989-01-01

    High power density fuel cell systems for defense and civilian applications are being developed. Taking into consideration the main causes for efficiency losses (activation, mass transport and ohmic overpotentials) the only fuel cell systems capable of achieving high power densities are the ones with alkaline and solid polymer electrolyte. High power densities (0.8 W/sq cm at 0.8 V and 1 A/sq cm with H2 and O2 as reactants), were already used in NASA's Apollo and Space Shuttle flights as auxiliary power sources. Even higher power densities (4 W/sq cm - i.e., 8 A sq cm at 0.5 V) were reported by the USAF/International Fuel Cells in advanced versions of the alkaline system. High power densities (approximately 1 watt/sq cm) in solid polymer electrolyte fuel cells with ten times lower platinum loading in the electrodes (i.e., 0.4 mg/sq cm) were attained. It is now possible to reach a cell potential of 0.620 V at a current density of 2 A/sq cm and at a temperature of 95 C and pressure of 4/5 atm with H2/O2 as reactants. The slope of the linear region of the potential-current density plot for this case is 0.15 ohm-sq cm. With H2/air as reactants and under the same operating conditions, mass transport limitations are encountered at current densities above 1.4 A/sq cm. Thus, the cell potential at 1 A/sq cm with H2/air as reactants is less than that with H2/O2 as reactants by 40 mV, which is the expected value based on electrode kinetics of the oxygen reduction reaction, and at 2 A/sq cm with H2/air as reactant is less than the corresponding value with H2/O2 as reactants by 250 mV, which is due to the considerably greater mass transport limitations in the former case.

  7. High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation.

    PubMed

    Anothumakkool, Bihag; Torris A T, Arun; Veeliyath, Sajna; Vijayakumar, Vidyanand; Badiger, Manohar V; Kurungot, Sreekumar

    2016-01-20

    Here, we report an efficient strategy by which a significantly enhanced electrode-electrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 μm, area = 12 cm(2), and mass loading = 7.3 mg/cm(2)). This prototype device shows a capacitance of 130 F/g at a substantially reduced internal resistance of 0.5 Ω and a high capacitance retention of 84% after 32000 cycles. The present system is found to be clearly outperforming a similar system derived by using the conventional polymer electrolyte (PVA-H3PO4 as the electrolyte), which could display a capacitance of only 95 F/g, and this value falls to nearly 50% in just 5000 cycles. The superior performance in the present case is credited primarily to the excellent interface formation of the in situ generated polymer electrolyte inside the nanopores of the electrode. Further, the interpenetrated nature of the polymer also helps the device to show a low electron spin resonance and power rate and, most importantly, excellent shelf-life in the unsealed flexible conditions. Because the nature of the electrode-electrolyte interface is the major performance-determining factor in the case of many electrochemical energy storage/conversion systems, along with the supercapacitors, the developed process can also find applications in preparing electrodes for the devices such as lithium-ion batteries, metal-air batteries, polymer electrolyte membrane fuel cells, etc. PMID:26697922

  8. Alkaline direct ethanol fuel cell performance using alkali-impregnated polyvinyl alcohol/functionalized carbon nano-tube solid electrolytes

    NASA Astrophysics Data System (ADS)

    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.

  9. Solid polymer electrolytes for lithium ion batteries: Preparation and electrochemical evaluation

    NASA Astrophysics Data System (ADS)

    Zhang, Hanjun

    Three types of composite solid polymer electrolytes based on polyethylene oxide (PEO) have been developed to enhance lithium ion conductivities at ambient temperatures: (i) composites of PEO(600K) and a ceramic filler, silanated silica; and (ii) blends of either PEO(600K) or methylcellulose, and POSS-PEO(n=4) 8. Plain fumed silica was found to be an inert filler in PEO matrix, and did not improve the conductivity at any temperature. Silanated silica, surface modified fumed silica with an oligomeric PEO-silane, was found to be more compatible with the PEO matrix, decreased crystallinity of the matrix, and therefore moderately enhanced the conductivity at ambient temperature. The temperature dependent conductivities of POSS-PEO(n)8, as a function of salt concentration for LiClO4 and LiN(CF 3CF2SO2)2, and the calorimetric properties of the electrolytes have been investigated. Glass transition temperatures, Tg, increased with increasing salt concentration and PEO chain length (n). The effect of anion on conductivity was also evaluated. At high temperatures, the less associative salts had greater conductivities. At low temperatures, the salts with lower Tg had higher conductivities. Solid polymer electrolytes prepared with LiClO4 and blends of POSS-PEO(n=4) 8 and PEO(600K) microphase separated into two amorphous phases (O/Li = 8/1 and 12/1), or a crystalline phase and two amorphous phases (O/Li = 16/1), and showed improved low temperature conductivities compared with PEO(600K). For O/Li = 12/1 and 16/1, improvements in conductivity were due to suppression of crystallization. However, the tendency of PEO(600K) to crystallize limited the amount of POSS-PEO(n=4)8 that could be incorporated into the blends. For O/Li = 8/1, only if the POSS-rich phase was the continuous phase, was there appreciable conductivity improvement. The highest RT conductivity, 8 x 10-6 S/cm, was obtained for a 60% POSS-PEO(n=4)8/40%PEO(600K)/LiClO4 (O/Li = 12/1) blend. POSS-PEO(n=4)8 and methyl

  10. Effect of low energy oxygen ion beam irradiation on ionic conductivity of solid polymer electrolyte

    SciTech Connect

    Manjunatha, H. Kumaraswamy, G. N.; Damle, R.

    2014-04-24

    Over the past three decades, solid polymer electrolytes (SPEs) have drawn significant attention of researchers due to their prospective commercial applications in high energy-density batteries, electrochemical sensors and super-capacitors. The optimum conductivity required for such applications is about 10{sup −2} – 10{sup −4} S/cm, which is hard to achieve in these systems. It is known that the increase in the concentration of salt in the host polymer results in a continuous increase in the ionic conductivity. However, there is a critical concentration of the salt beyond which the conductivity decreases due to formation of ion pairs with no net charge. In the present study, an attempt is made to identify the concentration at which ion pair formation occurs in PEO: RbBr. We have attempted to modify microstructure of the host polymer matrix by low energy ion (Oxygen ion, O{sup +1} with energy 100 keV) irradiation. Ionic conductivity measurements in these systems were carried out using Impedance Spectroscopy before and after irradiation to different fluencies of the oxygen ion. It is observed that the conductivity increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains. The study reveals the importance of ion irradiation as an effective tool to enhance conductivity in SPEs.

  11. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

    2013-11-01

    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 (LiCF3SO3) 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 LiCF3SO3 salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF3SO3.

  12. The dynamic-state effects of sodium ion contamination on the solid polymer electrolyte water electrolysis

    NASA Astrophysics Data System (ADS)

    Zhang, Linsong; Jie, Xiao; Shao, Zhi-Gang; Wang, Xunying; Yi, Baolian

    2013-11-01

    Na+ is a likely intrinsic impurity in water and is a potential cation impurity in the solid polymer electrolyte water electrolysis. In this paper, the dynamic-state effect of low concentration of Na+ is studied by adding Na+ into the deionized water fed in the SPE water electrolyser. The dynamic variation of cell voltage results show that the cell performance degraded more severely in the presence of Na+ impurity by anode poisoning than by cathode poisoning. The severity and poisoning rate of the cell depend on the Na+ concentration, water flow rate and cell temperature. However, the current density does not impact the extent of the cell voltage increase. In the meantime, an external reference electrode is used to measure the anode and cathode potentials. The performance degradation is mainly ascribed to the increase in cathode overpotential by anode poisoning. EIS measurements show that the performance difference primarily comes from the kinetics loss rather than the ohmic loss. The decrease of available protons in the three phase boundaries may lead to the increase in charge transfer resistance. The electron probe microanalysis tests show that Na+ remains in CCM even recovered with deionized water, which results in only partially recovered cell performance.

  13. Chameleonic electrochemical metallization cells: dual-layer solid electrolyte-inducing various switching behaviours.

    PubMed

    Lim, Hyungkwang; Soni, Rohit; Kim, Dohun; Kim, Guhyun; Kornijcuk, Vladimir; Kim, Inho; Park, Jong-Keuk; Hwang, Cheol Seong; Jeong, Doo Seok

    2016-08-25

    We present 'unusual' resistive switching behaviours in electrochemical metallization (ECM) cells utilizing a dual-layer (SiOx/GeSex: SiOx on GeSex) solid electrolyte (SE). The observed switching behaviour markedly varies with the thickness of the upper SiOx layer and compliance current: (i) monostable switching, (ii) counter-eightwise bipolar switching, and (iii) combination of monostable and eightwise bipolar switching behaviours. Focusing on cases (i) and (iii), electrical and chemical analyses on these chameleonic cells were performed in an attempt to gain clues to the understanding of the observed complexity. The chemical analysis indicated the upper SiOx layer as a chemical potential well for Cu ions-Cu ions were largely confined in the well. This non-uniform distribution of Cu across the SE perhaps hints at the mechanism for the complex behaviour; it may be a 'zero-sum game' between SiOx and GeSex layers, in which the two layers fight over the limited number of Cu atoms/ions. PMID:27510607

  14. Does filler surface chemistry impact filler dispersion, polymer dynamics and conductivity in nanofilled solid polymer electrolytes?

    NASA Astrophysics Data System (ADS)

    Ganapatibhotla, Lalitha; Maranas, Janna

    2012-02-01

    We study the impact of nanofiller surface chemistry on filler dispersion, polymer dynamics and ionic conductivity in acidic α-Al2O3 filled PEO+LiClO4 solid polymer electrolytes (SPEs).SPEs are the key to light-weight and high energy density rechargeable Li ion batteries but suffer from low room temperature ionic conductivity. Addition of ceramic nanofillers improves conductivity of SPEs and their surface chemistry influences extent of conductivity enhancement. The ionic conductivity of acidic α-Al2O3 filled SPE is enhanced for salt concentrations at and below eutectic, while neutral γ-Al2O3 filler enhances conductivity only at eutectic composition. Li ion motion is coupled to segmental mobility of polymer and we study how this is affected by addition of α-Al2O3 using quasi-elastic neutron scattering. Aggregation extent of nanoparticles in SPE matrix, a less explored factor in filled SPEs, can affect segmental mobility of polymer. This can vary with surface chemistry of particles and we quantify this using small angle neutron scattering. All measurements are performed as a function of Li concentration, nanoparticle loading and temperature.

  15. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface

    PubMed Central

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-01-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01–1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica. PMID:27416784

  16. Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

    NASA Astrophysics Data System (ADS)

    Praveen, D.; Damle, Ramakrishna

    2016-05-01

    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(ClO4)2, NH4I etc., have already been tried in the past with some success. Also various nanoparticles like Al2O3, TiO2 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. Design and test status for life support applications of SPE oxygen generation systems. [Solid Polymer Electrolyte

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Erickson, A. C.

    1975-01-01

    An advanced six-man rated oxygen generation system has been fabricated and tested as part of a NASA/JSC technology development program for a long lived, manned spacecraft life support system. Details of the design and tests results are presented. The system is based on the Solid Polymer Electrolyte (SPE) water electrolysis technology and its nominal operating conditions are 2760 kN/sq m (400 psia) and 355 K (180 F) with an electrolysis module current density capability up to 350 mA/sq cm (326 ASF). The system is centered on a 13-cell SPE water electrolysis module having a single cell active area of 214 sq cm (33 sq in) and it incorporates instrumentation and controls for single pushbutton automatic startup/shutdown, component fault detection and isolation, and self-contained sensors and controls for automatic safe emergency shutdown. The system has been tested in both the orbital cyclic and continuous mode of operation. Various parametric tests have been completed to define the system capability for potential application in spacecraft environmental systems.

  18. N7-(carboxymethyl)guanine-Lithium Crystalline Complex: A Bioinspired Solid Electrolyte

    NASA Astrophysics Data System (ADS)

    Dutta, Dipak; Nagapradeep, N.; Zhu, Haijin; Forsyth, Maria; Verma, Sandeep; Bhattacharyya, Aninda J.

    2016-04-01

    Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it’s in-built supply of Li+-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10‑7 to 10‑3 Ω‑1 cm‑1) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80–100 °C, from a dual Li+ and H+ (<100 °C) to a pure Li+ conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries.

  19. N7-(carboxymethyl)guanine-Lithium Crystalline Complex: A Bioinspired Solid Electrolyte.

    PubMed

    Dutta, Dipak; Nagapradeep, N; Zhu, Haijin; Forsyth, Maria; Verma, Sandeep; Bhattacharyya, Aninda J

    2016-01-01

    Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it's in-built supply of Li(+)-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10(-7) to 10(-3) Ω(-1) cm(-1)) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80-100 °C, from a dual Li(+) and H(+) (<100 °C) to a pure Li(+) conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries. PMID:27091631

  20. Performance modeling of the Ballard Mark IV solid polymer electrolyte fuel cell. 2: Empirical model development

    SciTech Connect

    Amphlett, J.C.; Baumert, R.M.; Mann, R.F.; Peppley, B.A.; Roberge, P.R. ); Harris, T.J. )

    1995-01-01

    A parametric model predicting the performance of a solid polymer electrolyte, proton exchange membrane (PEM) fuel cell has been developed using a combination of mechanistic and empirical modeling techniques. This paper details the empirical analysis which yielded the parametric coefficients employed in the model. A 28 run experiment covering a range of operating currents (50 to 300 ASF), temperatures (328 to 358 K), oxygen partial pressures (0.6 to 3.1 atm abs.) and hydrogen partial pressures (2.0 to 3.1 atm abs.) was conducted. Parametric equations for the activation overvoltage and the internal resistance of the fuel cell were obtained from linear regression. The factors to be employed in the linear regression had been previously determined through a mechanistic analysis of fuel cell processes. Activation overvoltage was modeled as a function of the operating temperature, the product of operating temperature, and the logarithm of the operating current, and the product of operating temperature and the logarithm of the oxygen concentration at the catalyst reaction sites. The internal resistance of the fuel cell was modeled as a function of the operating temperature and the current. Correlation of the empirical model to experimental data was very good. It is anticipated that the mechanistic validity yielded by the coupling of mechanistic and empirical modeling techniques will also allow for accurate predictive capabilities outside of the experimental range.

  1. Performance modeling of the Ballard Mark IV solid polymer electrolyte fuel cell. 1: Mechanistic model development

    SciTech Connect

    Amphlett, J.C.; Baumert, R.M.; Mann, R.F.; Peppley, B.A.; Roberge, P.R. ); Harris, T.J. )

    1995-01-01

    A parametric model predicting the performance of a solid polymer electrolyte, proton exchange membrane (PEM) fuel cell has been developed using a combination of mechanistic and empirical modeling techniques. This paper details the mechanistic model development. Mass transport properties are considered in the mechanistic development via Stefan-Maxwell equations. Thermodynamic equilibrium potentials are defined using the Nernst equation. Activation overvoltages are defined via a Tafel equation, and internal resistance are defined via the Nernst-Planck equation, leading to a definition of ohmic overvoltage via an Ohm's law equation. The mechanistic model cannot adequately model fuel cell performance, since several simplifying approximations have been used in order to facilitate model development. Additionally, certain properties likely to be observed in operational fuel cells, such as thermal gradients, have not been considered. Nonetheless, the insights gained from the mechanistic assessment of fuel cell processes were found to give the resulting empirical model a firmer theoretical basis than many of the models presently available in the literature. Correlation of the empirical model to actual experimental data was very good.

  2. Studies on the Properties of Plasticizer and Lithium Salt on PMMA-based Solid Polymer Electrolytes

    SciTech Connect

    Chew, K. W.; Tan, C. G.; Osman, Z.

    2010-03-11

    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{sub 3}SO{sub 3} salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF{sub 3}SO{sub 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{sup -10} Scm{sup -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{sub 3}SO{sub 3}) system is 1.36x10{sup -5} Scm{sup -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.

  3. N7-(carboxymethyl)guanine-Lithium Crystalline Complex: A Bioinspired Solid Electrolyte

    PubMed Central

    Dutta, Dipak; Nagapradeep, N.; Zhu, Haijin; Forsyth, Maria; Verma, Sandeep; Bhattacharyya, Aninda J.

    2016-01-01

    Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it’s in-built supply of Li+-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10−7 to 10−3 Ω−1 cm−1) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80–100 °C, from a dual Li+ and H+ (<100 °C) to a pure Li+ conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries. PMID:27091631

  4. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface.

    PubMed

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-01-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01-1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica. PMID:27416784

  5. Lithium battery with solid polymer electrolyte based on comb-like copolymers

    NASA Astrophysics Data System (ADS)

    Daigle, Jean-Christophe; Vijh, Ashok; Hovington, Pierre; Gagnon, Catherine; Hamel-Pâquet, Julie; Verreault, Serge; Turcotte, Nancy; Clément, Daniel; Guerfi, Abdelbast; Zaghib, Karim

    2015-04-01

    In this paper we report on the synthesis of comb-like copolymers as solid polymer electrolytes (SPE). The synthesis involved anionic polymerization of styrene (St) and 4-vinylanisole (VA) as the followed by grafting of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization (ATRP). The comb-like copolymer's structure was analyzed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The membranes were made by solvent casting and the morphologies were analyzed by atomic forces microscopy (AFM) and scanning electron microscopy (SEM). We observed that a nano and micro phase separation occurs which improves ionic conductivity. The ionic conductivities were determined by AC Impedance, which showed that the SPEs have good conductivities (10-5 Scm-1) at room temperature owing to the negligible values (<10 kJ mol-1) of the activation energies for conductivity. The batteries with these polymers exhibit a capacity of 146 mAh g-1 at C/24, and no evidence of degradation after intense cycling was observed. However, poor cycle life was observed at C/6 and C/3, which is a consequence of several factors. We partially explain that behavior by arguing that whereas PEO lightly "solvates" Li+ thus slowing Li-ion mobility, and PEGMA chains "solvate" Li ions too strongly, trapping and inhibiting their mobility.

  6. Synthesis, processing and characterization of calcia-stabilized zirconia solid electrolytes for oxygen sensing applications

    SciTech Connect

    Zhou Minghua . E-mail: mzhou@nrcan.gc.ca; Ahmad, Aftab

    2006-04-13

    Precursor powders of calcia-stabilized zirconia (CSZ) solid electrolytes have been synthesized by a sol-gel method. The phase evolution of the precursor powders after thermal treatments at different temperatures were analysized by X-ray diffraction technique. Disc-shaped sensor elements were fabricated via uniaxial pressing of the calcined powders and subsequently sintered at 1650 deg. C. Scanning electron microscopy (SEM) was used to analyze the microstructure of the sintered pellets. Platinum electrodes were applied to the sintered elements to produce potentiometric/electrochemical gas sensors. The electrical response of the gas sensors to oxygen and the complex impedance of the sensors in air were measured at various temperatures. Impedance analyses indicate that the sensor cell with 15 mol% CaO has much lower resistance (the sum of bulk and grain-boundary resistance) than the sensor cell with 22 mol% CaO. This is also reflected by the EMF responses of both sensor cells to various oxygen concentrations in the testing gas. The EMF deviation from the theoretical value of the CSZ sensor cell with 22 mol% CaO was larger than that of the CSZ sensor cell with 15 mol% CaO. The corrrelations between material compositions, microstructures of the sintered pellets and the electrical properties of the sensors are discussed.

  7. Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices.

    PubMed

    Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

    2016-08-01

    Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices. PMID:27109426

  8. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    SciTech Connect

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

    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}.

  9. A Novel Solid Electrolyte Oxygen Sensor System for In-Situ Measurement and Process Control

    NASA Astrophysics Data System (ADS)

    Hammer, Frank Uwe; Messerschmid, Ernst; Rogg, Markus

    2010-10-01

    In 1993 the oxygen partial pressure was firstly measured inside a plasma wind tunnel using conventional λ-probes. Since then, a considerable amount of knowledge has been gained in using these sensors in ground test facilities and space. However, these commercially available sensors were too large in scale and weight. Consequently, a new development of solid electrolyte sensors called FIPEX more feasible for space was initiated. Due to space driven benefits, interest arose to use FIPEX technique in terrestrial applications e.g. to monitor sputter plants for float glass coating. Therefore, the VacuSen® sensor was developed. The characterization of VacuSen® at nominal sensor temperature TS = 680° C resulted in a sensor current according to IS = bṡpO20ṡ8±0ṡ05 I[μA] in the operation range between ptot = 1ṡ10-3 to 5 Pa. From pulse width modulation (PWM) temperature control, additional information allows to measure ptot according to ptot = aṡRPWM0ṡ107±0ṡ005 thus enlarging the operation range to ptot = 1ṡ10-3 to 1ṡ105Pa. A one point calibration routine with air, ideally at ptot = 5 Pa in order to determine both calibration parameters a and b simultaneously, is proposed.

  10. Strongly enhanced flux pinning in one-step deposition of BaFe2(As0.66P0.33)2 superconductor films with uniformly dispersed BaZrO3 nanoparticles

    PubMed Central

    Miura, Masashi; Maiorov, Boris; Kato, Takeharu; Shimode, Takashi; Wada, Keisuke; Adachi, Seiji; Tanabe, Keiichi

    2013-01-01

    The high upper critical field and low anisotropy of the iron-based superconductor BaFe2As2 make it promising for its use in the construction of superconducting magnets. However, its critical current density in high magnetic fields needs to be improved. Here we demonstrate a simple, one-step and industrially scalable means of achieving just this. We show that introducing controlled amounts of uniformly dispersed BaZrO3 nanoparticles into carrier-doped BaFe2As2 significantly improves its superconducting performance without degrading its structural or superconducting properties. Our BaFe2(As0.66P0.33)2 films also exhibit an increase in both the irreversibility line and critical current density at all magnetic-field orientations. These films exhibit nearly isotropic critical current densities in excess of 1.5 MA cm−2 at 15 K and 1 T—seven times higher than previously reported for BaFe2As2 films. The vortex-pinning force in these films reaches ~59 GN m−3 at 5 K and 3–9 T, substantially higher than that of the conventional Nb3Sn wire. PMID:24051678

  11. Formation mechanism of BaZrO3 nanoparticles in Y1-xSmxBa2Cu3Oy-coated conductors derived from trifluoroacetate metal-organic deposition

    NASA Astrophysics Data System (ADS)

    Miura, M.; Yoshizumi, M.; Izumi, T.; Shiohara, Y.

    2010-01-01

    Grains of BaZrO3 (BZO) in REBa2Cu3Oy (REBCO) films exhibit microstructural differences, depending on whether they were deposited by pulsed-laser deposition (PLD) or metal-organic deposition (MOD). In order to understand the origins of these differences, we examined the formation mechanism of BZO nanoparticles in the MOD process with detailed observations of the quenched films by transmission electron microscopy. The BZO nanoparticle was found to form in the precursor during the temperature ramp prior to the formation of the Y1-xSmxBa2Cu3Oy (YSmBCO) crystals. The YSmBCO grew layer by layer while entrapping the BZO particles, which resulted in random dispersion of the BZO particles in the YSmBCO layer. Consequently, uniformly dispersed BZO nanoparticles were formed in the YSmBCO matrix derived from the TFA-MOD process. These findings indicate that a key factor in achieving fine dispersion of BZO nanoparticles in the superconducting matrix is strongly related to nucleation of the BZO phase crystals in the precursor before growth of the YSmBCO layer, which is unique to the MOD process. In subsequent testing, YSmBCO-coated conductors with uniformly dispersed and densely concentrated BZO nanoparticles showed striking isotropic magnetic-field angular dependence of critical currents.

  12. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    NASA Astrophysics Data System (ADS)

    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.

  13. Advanced solid electrolyte cell for CO2 and H2O electrolysis. [for extended duration manned spaceflights

    NASA Technical Reports Server (NTRS)

    Shumar, J. W.; Berger, T. A.

    1978-01-01

    A solid electrolyte cell with improved sealing characteristics was examined. A tube cell was designed, developed, fabricated, and tested. Design concepts incorporated in the tube cell to improve its sealing capability included minimizing the number of seals per cell and moving seals to lower temperature regions. The advanced tube cell design consists of one high temperature ceramic cement seal, one high temperature gasket seal, and three low temperature silicone elastomer seals. The two high temperature seals in the tube cell design represent a significant improvement over the ten high temperature precious metal seals required by the electrolyzer drum design. For the tube cell design the solid electrolyte was 8 mole percent yttria stabilized zirconium oxide slip cast into the shape of a tube with electrodes applied on the inside and outside surfaces.

  14. Development of bulk-type all-solid-state lithium-sulfur battery using LiBH{sub 4} electrolyte

    SciTech Connect

    Unemoto, Atsushi Ikeshoji, Tamio; Yasaku, Syun; Matsuo, Motoaki; Nogami, Genki; Tazawa, Masaru; Taniguchi, Mitsugu; Orimo, Shin-ichi

    2014-08-25

    Stable battery operation of a bulk-type all-solid-state lithium-sulfur battery was demonstrated by using a LiBH{sub 4} electrolyte. The electrochemical activity of insulating elemental sulfur as the positive electrode was enhanced by the mutual dispersion of elemental sulfur and carbon in the composite powders. Subsequently, a tight interface between the sulfur-carbon composite and the LiBH{sub 4} powders was manifested only by cold-pressing owing to the highly deformable nature of the LiBH{sub 4} electrolyte. The high reducing ability of LiBH{sub 4} allows using the use of a Li negative electrode that enhances the energy density. The results demonstrate the interface modification of insulating sulfur and the architecture of an all-solid-state Li-S battery configuration with high energy density.

  15. Mesoporous silica/ionic liquid quasi-solid-state electrolytes and their application in lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Zhang, Zhengxi; Yin, Kun; Yang, Li; Tachibana, Kazuhiro; Hirano, Shin-ichi

    2015-03-01

    In this work, the ordered mesoporous silica, SBA-15, is chosen as the matrix for the first time to prepare quasi-solid-state electrolytes (QSSEs) with an ionic liquid, LiTFSI salt and PVdF-HFP. The as-obtained QSSEs are evaluated by electrochemical methods. Lithium metal batteries containing these QSSEs exhibit high discharge capacity and good cycle performance at room temperature, indicating successful battery operation.

  16. Detection and classification of gaseous sulfur compounds by solid electrolyte cyclic voltammetry of cermet sensor array.

    PubMed

    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

  17. Organic dopant added polyvinylidene fluoride based solid polymer electrolytes for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Senthil, R. A.; Theerthagiri, J.; Madhavan, J.

    2016-02-01

    The effect of phenothiazine (PTZ) as dopant on PVDF/KI/I2 electrolyte was studied for the fabrication of efficient dye-sensitized solar cell (DSSC). The different weight percentage (wt%) ratios (0, 20, 30, 40 and 50%) of PTZ doped PVDF/KI/I2 electrolyte films were prepared by solution casting method using DMF as a solvent. The following techniques such as Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD) and AC-impedance analysis have been employed to characterize the prepared polymer electrolyte films. The FT-IR studies revealed the complex formation between PVDF/KI/I2 and PTZ. The crystalline and amorphous nature of polymer electrolytes were confirmed by DSC and XRD analysis respectively. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PVDF/KI/I2 electrolyte exhibited the ionic conductivity of 4.68×10-6 S cm-1 and this value was increased to 7.43×10-5 S cm-1 when PTZ was added to PVDF/KI/I2 electrolyte. On comparison with different wt% ratios, the maximum ionic conductivity was observed for 20% PTZ-PVDF/KI/I2 electrolyte. A DSSC assembled with the optimized wt % of PTZ doped PVDF/KI/I2 electrolyte exhibited a power conversion efficiency of 2.92%, than the undoped PVDF/KI/I2 electrolyte (1.41%) at similar conditions. Hence, the 20% PTZ-PVDF/KI/I2 electrolyte was found to be optimal for DSSC applications.

  18. Oxygen vacancy diffusion across cathode/electrolyte interface in solid oxide fuel cells: An electrochemical phase-field model

    NASA Astrophysics Data System (ADS)

    Hong, Liang; Hu, Jia-Mian; Gerdes, Kirk; Chen, Long-Qing

    2015-08-01

    An electrochemical phase-field model is developed to study electronic and ionic transport across the cathode/electrolyte interface in solid oxide fuel cells. The influences of local current density and interfacial electrochemical reactions on the transport behaviors are incorporated. This model reproduces two electrochemical features. Nernst equation is satisfied through the thermodynamic equilibriums of the electron and oxygen vacancy. The distributions of charged species around the interface induce charge double layer. Moreover, we verify the nonlinear current/overpotential relationship. This model facilitates the exploration of problems in solid oxide fuel cells, which are associated with transport of species and electrochemical reactions at high operating temperature.

  19. Method for producing electricity from a fuel cell having solid-oxide ionic electrolyte

    DOEpatents

    Mason, David M.

    1984-01-01

    Stabilized quadrivalent cation oxide electrolytes are employed in fuel cells at elevated temperatures with a carbon and/or hydrogen containing fuel anode and an oxygen cathode. The fuel cell is operated at elevated temperatures with conductive metallic coatings as electrodes and desirably having the electrolyte surface blackened. Of particular interest as the quadrivalent oxide is zirconia.

  20. A new solid polymer electrolyte incorporating Li10GeP2S12 into a polyethylene oxide matrix for all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Yanran; Wu, Chuan; Peng, Gang; Chen, Xiaotian; Yao, Xiayin; Bai, Ying; Wu, Feng; Chen, Shaojie; Xu, Xiaoxiong

    2016-01-01

    Li10GeP2S12 (LGPS) is incorporated into polyethylene oxide (PEO) matrix to fabricate composite solid polymer electrolyte (SPE) membranes. The lithium ion conductivities of as-prepared composite membranes are evaluated, and the optimal composite membrane exhibits a maximum ionic conductivity of 1.21 × 10-3 S cm-1 at 80 °C and an electrochemical window of 0-5.7 V. The phase transition behaviors for electrolytes are characterized by DSC, and the possible reasons for their enhanced ionic conductivities are discussed. The LGPS microparticles, acting as active fillers incorporation into the PEO matrix, have a positive effect on the ionic conductivity, lithium ion transference number and electrochemical stabilities. In addition, two kinds of all-solid-state lithium batteries (LiFeO4/SPE/Li and LiCoO2/SPE/Li) are fabricated to demonstrate the good compatibility between this new SPE membrane and different electrodes. And the LiFePO4/Li battery exhibits fascinating electrochemical performance with high capacity retention (92.5% after 50 cycles at 60 °C) and attractive capacities of 158, 148, 138 and 99 mAh g-1 at current rates of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C, respectively. It is demonstrated that this new composite SPE should be a promising electrolyte applied in solid state batteries based on lithium metal electrode.

  1. Systematic Investigation of Binders for Silicon Anodes: Interactions of Binder with Silicon Particles and Electrolytes and Effects of Binders on Solid Electrolyte Interphase Formation.

    PubMed

    Nguyen, Cao Cuong; Yoon, Taeho; Seo, Daniel M; Guduru, Pradeep; Lucht, Brett L

    2016-05-18

    The effects of different binders, polyvinylidene difluoride (PVdF), poly(acrylic acid) (PAA), sodium carboxymethyl cellulose (CMC), and cross-linked PAA-CMC (c-PAA-CMC), on the cycling performance and solid electrolyte interphase (SEI) formation on silicon nanoparticle electrodes have been investigated. Electrodes composed of Si-PAA, Si-CMC, and Si-PAA-CMC exhibit a specific capacity ≥3000 mAh/g after 20 cycles while Si-PVdF electrodes have a rapid capacity fade to 1000 mAh/g after just 10 cycles. Infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) reveal that PAA and CMC react with the surface of the Si nanoparticles during electrode fabrication. The fresh Si-CMC electrode has a thicker surface coating of SiOx than Si-PAA and Si-PAA-CMC electrodes, due to the formation of thicker SiOx during electrode preparation, which leads to lower cyclability. The carboxylic acid functional groups of the PAA binder are reactive toward the electrolyte, causing the decomposition of LiPF6 and dissolution of SiOx during the electrode wetting process. The PAA and CMC binder surface films are then electrochemically reduced during the first cycle to form a protective layer on Si. This layer effectively suppresses the decomposition of carbonate solvents during cycling resulting in a thin SEI. On the contrary, the Si-PVDF electrode has poor cycling performance and continuous reduction of carbonate solvents is observed resulting in the generation of a thicker SEI. Interestingly, the Lewis basic -CO2Na of CMC was found to scavenge HF in electrolyte. PMID:27135935

  2. A New Miniaturized Inkjet Printed Solid State Electrolyte Sensor for Applications in Life Support Systems - First Results

    NASA Astrophysics Data System (ADS)

    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

  3. Measurement of atomic oxygen in the middle atmosphere using solid electrolyte sensors and catalytic probes

    NASA Astrophysics Data System (ADS)

    Eberhart, M.; Löhle, S.; Steinbeck, A.; Binder, T.; Fasoulas, S.

    2015-09-01

    The middle- and upper-atmospheric energy budget is largely dominated by reactions involving atomic oxygen (O). Modeling of these processes requires detailed knowledge about the distribution of this oxygen species. Understanding the mutual contributions of atomic oxygen and wave motions to the atmospheric heating is the main goal of the rocket project WADIS (WAve propagation and DISsipation in the middle atmosphere). It includes, amongst others, our instruments for the measurement of atomic oxygen that have both been developed with the aim of resolving density variations on small vertical scales along the trajectory. In this paper the instrument based on catalytic effects (PHLUX: Pyrometric Heat Flux Experiment) is introduced briefly. The experiment employing solid electrolyte sensors (FIPEX: Flux φ(Phi) Probe Experiment) is presented in detail. These sensors were laboratory calibrated using a microwave plasma as a source of atomic oxygen in combination with mass spectrometer reference measurements. The spectrometer was in turn calibrated for O with a method based on methane. In order to get insight into the horizontal variability, the rocket payload had instrument decks at both ends. Each housed several sensor heads measuring during both the up- and downleg of the trajectory. The WADIS project comprises two rocket flights during different geophysical conditions. Results from WADIS-1 are presented, which was successfully launched in June 2013 from the Andøya Space Center, Norway. FIPEX data were sampled at 100 Hz and yield atomic oxygen density profiles with a vertical resolution better than 9 m. This allows density variations to be studied on very small spatial scales. Numerical simulations of the flow field around the rocket were done at several points of the trajectory to assess the influence of aerodynamic effects on the measurement results. Density profiles peak at 3 × 1010 cm-3 at altitudes of 93.6 and 96 km for the up- and downleg, respectively.

  4. A Novel Solid Electrolyte Oxygen Sensor System for In-Situ Measurement and Process Control

    SciTech Connect

    Hammer, Frank Uwe; Messerschmid, Ernst; Rogg, Markus

    2010-10-13

    In 1993 the oxygen partial pressure was firstly measured inside a plasma wind tunnel using conventional {lambda}-probes. Since then, a considerable amount of knowledge has been gained in using these sensors in ground test facilities and space. However, these commercially available sensors were too large in scale and weight. Consequently, a new development of solid electrolyte sensors called FIPEX more feasible for space was initiated. Due to space driven benefits, interest arose to use FIPEX technique in terrestrial applications e.g. to monitor sputter plants for float glass coating. Therefore, the VacuSen registered sensor was developed. The characterization of VacuSen registered at nominal sensor temperature T{sub S} = 680 deg. C resulted in a sensor current according to I{sub S} = b{center_dot}p{sub O2}{sup 0{center_dot}8{+-}0{center_dot}05} I[{mu}A] in the operation range between p{sub tot} = 1{center_dot}10{sup -3} to 5 Pa. From pulse width modulation (PWM) temperature control, additional information allows to measure ptot according to p{sub tot} = a{center_dot}RPWM{sup 0{center_dot}107{+-}0{center_dot}005} thus enlarging the operation range to p{sub tot} = 1{center_dot}10{sup -3} to 1{center_dot}10{sup 5} Pa. A one point calibration routine with air, ideally at p{sub tot} = 5 Pa in order to determine both calibration parameters a and b simultaneously, is proposed.

  5. Measurement of atomic oxygen in the middle atmosphere using solid electrolyte sensors and catalytic probes

    NASA Astrophysics Data System (ADS)

    Eberhart, M.; Löhle, S.; Steinbeck, A.; Binder, T.; Fasoulas, S.

    2015-03-01

    The atmospheric energy budget is largely dominated by reactions involving atomic oxygen (O). Modeling of these processes requires detailed knowledge about the distribution of this oxygen species. Understanding the mutual contributions of atomic oxygen and wave motions to the atmospheric heating is the main goal of the rocket campaign WADIS. It includes, amongst others, two of our instruments for the measurement of atomic oxygen that have both been developed with the aim of resolving density variations on small vertical scales along the trajectory. In this paper the instrument based on catalytic effects (PHLUX) is introduced briefly. The experiment employing solid electrolyte sensors (FIPEX) is presented in detail. These sensors were laboratory calibrated using a microwave plasma as a source for atomic oxygen in combination with mass spectrometer reference measurements. The spectrometer was in turn calibrated for O with a method based on methane. In order to get insight into the horizontal variability the rocket payload had instrument decks at both ends. Each housed several sensor heads measuring during both the up- and downleg of the trajectory. The WADIS campaign comprises two rocket flights during different geophysical conditions. Results from WADIS-1 are presented which was successfully launched in June 2013 from Andøya Rocket Range, Norway. FIPEX data was sampled with 100 Hz and yield atomic oxygen density profiles with a vertical resolution better than 10 m. Numerical simulations of the flow field around the rocket were done at several points of the trajectory to assess the influence of aerodynamic effects on the measurement results. Density profiles peak at 3 × 1010 cm-3 at altitudes of 93.6 and 96 km for up- and downleg respectively.

  6. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    DOE PAGESBeta

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; Meng, Ying Shirley; Stevenson, Keith J.; Alvarado, Judith

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition bymore » X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.« less

  7. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    SciTech Connect

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; Meng, Ying Shirley; Stevenson, Keith J.; Alvarado, Judith

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.

  8. Boosting properties of 3D binder-free manganese oxide anodes by preformation of a solid electrolyte interphase.

    PubMed

    Zhou, Haitao; Wang, Xuehang; Sheridan, Edel; Chen, De

    2015-04-24

    Huge irreversible capacity loss prevents the successful use of metal oxide anodes in Li-ion full cells. Here, we focus on the critical prelithiation step and demonstrate the challenge of electrolyte decomposition on a pristine anode in a full cell. Both an electrochemical activation process (54 h) with Li metal and a new electrolytic process (75 min) without Li metal were used to preform complete solid electrolyte interphase (SEI) layers on 3 D binder-free MnOy -based anodes. The preformed SEI layers mitigated the electrolyte decomposition effectively and widened the working voltage for the MnOy /LiMn2 O4 full cell, which resulted in a big boost of the specific energy to 300 and 200 W h kgcathode (-1) , largely improved cycling stability, and much higher specific power (4200 W h kgtotal (-1) ) compared to conventional Li-ion batteries. Detailed characterization, such as cyclic voltammetry, scanning transmission electron microscopy, and FTIR spectroscopy, gives mechanistic insight into SEI preformation. This work provides guidance for the design of anode SEI layers and enables the application of oxides for Li-ion battery full cells. PMID:25760685

  9. Inhibition of solid electrolyte interface formation on cathode particles for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Wentao; Lucht, Brett L.

    Thermal reactions between cathode particles (LiNi 0.8Co 0.2O 2, LiCoO 2, LiMn 2O 4 and LiFePO 4) and ternary electrolyte (1.0 M LiPF 6 in 1:1:1 diethyl carbonate/dimethyl carbonate/ethylene carbonate) with or without the thermal stabilizing additive dimethyl acetamide (DMAc) have been investigated. Ternary electrolyte reacts with the surface of lithiated metal oxides (LiNi 0.8Co 0.2O 2, LiCoO 2 and LiMn 2O 4) upon storage to corrode the surface and generate a complex mixture of organic and inorganic surface species, but the bulk ternary electrolyte does not decompose. There is little evidence for reaction between the surface of carbon coated LiFePO 4 and ternary electrolyte upon storage at elevated temperature (>60 °C), but the bulk ternary electrolyte decomposes. Addition of DMAc to ternary electrolyte reduces the surface corrosion of the lithiated metal oxides and stabilizes the electrolyte in the presence of LiFePO 4.

  10. Novel solid polymer electrolytes based on poly(trimethylene carbonate) and lithium hexafluoroantimonate

    NASA Astrophysics Data System (ADS)

    Manuela Silva, Maria; Barbosa, Paula; Evans, Alan; Smith, Michael John

    2006-11-01

    The results of the characterization of a polymer electrolyte system based on the poly(trimethylene carbonate) host matrix, with lithium hexafluoroantimonate as guest salt, are described in this study. Electrolytes with lithium salt compositions with values of n between 5 and 100 (where n represents the total number of monomeric cation-coordinating units sbnd (O dbnd COCH 2CH 2CH 2O) sbnd per lithium ion) were prepared by co-dissolution and deposition from acetonitrile. The solvent-casting technique was used to prepare flexible, transparent and self-supporting films of electrolytes which were characterized by measurements of conductivity, cyclic voltammetry, differential scanning calorimetry and thermogravimetry.

  11. All-solid-state electrochemical capacitors using MnO2 electrode/SiO2-Nafion electrolyte composite prepared by the sol-gel process

    NASA Astrophysics Data System (ADS)

    Shimamoto, Kazushi; Tadanaga, Kiyoharu; Tatsumisago, Masahiro

    2014-02-01

    Electrode-electrolyte composites of MnO2 active material, acetylene black (AB), and SiO2-Nafion solid electrolyte were prepared using the sol-gel process to form good solid-solid interfaces. The composites were obtained by the addition of MnO2 and AB into a sol of hydrolyzed tetraethoxysilane with Nafion, and successive solidification of the precursor sol. Scanning electron microscope and energy dispersive X-ray spectroscopy measurements show that good solid-solid interface is formed between electrodes and solid electrolytes in the composites. All-solid-state hybrid capacitors were fabricated using the composites or the hand-grinding mixture of MnO2, AB and SiO2-Nafion powder as positive electrodes, activated carbon powder as a negative electrode, and phosphosilicate gel as a solid electrolyte. The all-solid-state hybrid capacitors using the composites exhibit larger capacitances and better rate performance than the capacitors using the electrode prepared by hand-mixing of powders. Specific discharge capacitances of the capacitor with the composite are 85 F g-1 for the one with the composite electrode and 48 F g-1 for the one with the hand-mixed electrode, at 1 mA cm-2. Moreover, the all-solid-state capacitors using the composite electrode can be operated at temperatures between -30 °C and 60 °C.

  12. Patternable gel electrolyte infiltrated into all-solid porous Li-ion electrodes

    NASA Astrophysics Data System (ADS)

    Sun, Ke; Dillon, Shen J.

    2014-06-01

    Gel electrolyte based on 1M LiPF6 in ethylene carbonate:dimethyl carbonate, polyethyleneglycol diacrylate oligomer, and 2,2'-azobis(2-methylpropionitrile) is infiltrated into porous sintered LiCoO2 electrodes and cured in situ. The associated batteries function well, which is consistent with microscopy observations indicating that the gel electrolyte penetrates the electrode well and wets to the electrode particles. Trimethyl silyl acrylate is used to functionalize glass substrates and will cross link with polyethyleneglycol diacrylate during curing to promote bonding between the substrate and the gel electrolyte. The functionalization can localize adhesion allowing the electrolyte to easily release from unfunctionalized glass, which can be used as a mold.

  13. Cellulose acetate-lithium bis(trifluoromethanesulfonyl)imide solid polymer electrolyte: ATR-FTIR and ionic conductivity behavior

    NASA Astrophysics Data System (ADS)

    Mohd Razalli, Siti Masyitah; Sheikh Mohd Saaid, Siti Irma Yuana; Marwan Ali, Ab Malik; Hassan, Oskar Hasdinor; Yahya, Muhd Zu Azhan

    2015-05-01

    Solid polymer electrolytes (SPEs) based on cellulose acetate (CA) doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt are prepared by solution cast technique. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy of the polymer salt complexes are recorded in the frequency range between 400 cm-1 and 4000 cm-1. The shifting of carbonyl band (C=O) at 1737 cm-1 to a lower wavenumber confirms the occurrence of complexation between the polymer and the salt. The electrochemical impedance spectroscopy (EIS) analysis discovered that the film with 25 wt.% of salt shows the highest ionic conductivity at room temperature. The change in real dielectric permittivity (ɛr) as a function of frequency at different salt concentrations which exhibits a dispersive behavior at low frequencies and decays at higher frequencies, shows the electrode polarization and space charge effect. The real modulus formalism (Mr) analysis shows that the polymer electrolytes in this work are ionic conductors.

  14. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    DOE PAGESBeta

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquidmore » cell.« less

  15. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Fritz B.; Lee, Wonyoung

    2015-11-01

    We report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte-electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  16. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    SciTech Connect

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-07-10

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  17. Critical current density of YBa2Cu3O7-x films with BaZrO3 inclusions on SrTiO3 and Al2O3 substrates

    NASA Astrophysics Data System (ADS)

    Augieri, A.; Galluzzi, V.; Celentano, G.; Fabbri, F.; Mancini, A.; Rufoloni, A.; Vannozzi, A.; Gambardella, U.; Padeletti, G.; Cusmà, A.; Petrisor, T.; Ciontea, L.

    2008-02-01

    Recently, many efforts have been dedicated to the development of a reliable technology for the introduction of artificial pinning sites in YBa2Cu3O7-x (YBCO) films with the aim of improving the in-field Jc performances. One of the most effective technique resulted to be the inclusion of BaZrO3 (BZO) second phase embedded in the YBCO films. In this contribution we present Jc measurements on BZO-added YBCO films deposited on SrTiO3 (STO) and CeO2-buffered-Al2O3 (ALO) substrates. Samples were deposited by pulsed laser ablation technique using a composite YBCO + 5mol.% BZO target at the optimum conditions for fully oxygenated c-axis oriented YBCO films. Despite of a slight Tc reduction, BZO addition in YBCO-STO films resulted in an improvement of in-field performances with the appearance of a Jc plateau in the low field region which extends up to about 2.5 Tesla irrespective of the temperature at least in the investigated range (down to 65K). On the other hand, samples deposited on ALO did not exhibit any remarkable difference neither in the Jc value nor in the magnetic field dependences as compared with pure YBCO. The presence of 0° (magnetic field parallel to the c-axis) peaks in the Jc. angular behaviour revealed a c-axis correlated character of the pinning forces in BZO added YBCO films grown on both STO and ALO substrates. X-ray diffraction measurements and AFM investigations were carried out in order to determine the influence of BZO addition on films crystalline quality and microstructure.

  18. Electrolyte supported solid oxide fuel cells with the super large size and thin ytterbia stabilized zirconia substrate

    NASA Astrophysics Data System (ADS)

    Xue, Ye Jian; Miao, He; He, Chang Rong; Wang, Jian Xin; Liu, Man; Sun, Shan Shan; Wang, Qin; Wang, Wei Guo

    2015-04-01

    In this work, the (ZrO2)0.95(Yb2O3)0.05(5YbSZ) electrolyte supported SOFCs with the large area of 10 cm × 10 cm and thin substrate of about 70 μm are prepared, and the microstructures, electrochemical and anti-redox properties of the single cells are investigated systematically. The powders of 5YbSZ with the tetragonal and cubic mixed phase are synthesized by the so-called "solid-liquid composite method" at a somewhat low temperature of 1100 °C. The 5YbSZ electrolyte substrates which are prepared by the tape-casting, multilayer-lamination and sintering method showed the optimal comprehensive performances with the sintering temperature being 1500 °C. By using these electrolyte substrates, the NiO+GDC/5YbSZ/LSM+5YbSZ single cells are obtained at the co-sinter temperature of 1100 °C. The power densities of these cells can reach 0.56 W cm-2 at the output voltage of 0.7 V, and the degradation rate can attain 1.45% kh-1 under a constant current density of 0.2 A cm-2 at the temperature of 830 °C. After 11 redox cycles, no crack through the 5YbSZ electrolyte can be found in the single cells, and the electrochemical properties of the 5YbSZ electrolyte supported single cells show an acceptable degradation.

  19. Multiprobe Study of the Solid Electrolyte Interphase on Silicon-Based Electrodes in Full-Cell Configuration

    PubMed Central

    Moreau, P.; De Vito, E.; Quazuguel, L.; Boniface, M.; Bordes, A.; Rudisch, C.; Bayle-Guillemaud, P.; Guyomard, D.

    2016-01-01

    The failure mechanism of silicon-based electrodes has been studied only in a half-cell configuration so far. Here, a combination of 7Li, 19F MAS NMR, XPS, TOF-SIMS, and STEM-EELS, provides an in-depth characterization of the solid electrolyte interphase (SEI) formation on the surface of silicon and its evolution upon aging and cycling with LiNi1/3Mn1/3Co1/3O2 as the positive electrode in a full Li-ion cell configuration. This multiprobe approach indicates that the electrolyte degradation process observed in the case of full Li-ion cells exhibits many similarities to what has been observed in the case of half-cells in previous works, in particular during the early stages of the cycling. Like in the case of Si/Li half-cells, the development of the inorganic part of the SEI mostly occurs during the early stage of cycling while an incessant degradation of the organic solvents of the electrolyte occurs upon cycling. However, for extended cycling, all the lithium available for cycling is consumed because of parasitic reactions and is either trapped in an intermediate part of the SEI or in the electrolyte. This nevertheless does not prevent the further degradation of the organic electrolyte solvents, leading to the formation of lithium-free organic degradation products at the extreme surface of the SEI. At this point, without any available lithium left, the cell cannot function properly anymore. Cycled positive and negative electrodes do not show any sign of particles disconnection or clogging of their porosity by electrolyte degradation products and can still function in half-cell configuration. The failure mechanism for full Li-ion cells appears then very different from that known for half-cells and is clearly due to a lack of cyclable lithium because of parasitic reactions occurring before the accumulation of electrolyte degradation products clogs the porosity of the composite electrode or disconnects the active material particles. PMID:27212791

  20. Sensor-actuator coupled device for active tracheal tube using solid polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    Ihara, Tadashi; Nakamura, Taro; Mukai, Toshiharu; Asaka, Kinji

    2007-04-01

    A sensor-actuator coupled device was developed using solid polymer electrolyte membrane (SPM) as an active tracheal tube for ventilator. Active tracheal tube is a novel type of tube for ventilator that removes patient's phlegm automatically upon sensing the narrowing of trachea by phlegm. This type of active tube is extremely useful in clinical settings as currently the sole measure to remove phlegm from patient's tube is to do it manually by a nurse every few hours. As SPM works both as a sensor and an actuator, an effective compact device was developed. SPM based sensor-actuator coupled device was fabricated with modified gold plating method. Prepared SPM was fixed as an array on a plastic pipe of diameter 22 mm and was connected to a ventilator circuit and driven by a ventilator with a volume control ventilation (VCV) mode. SPM was connected both to a sensing unit and an actuation unit. Generated voltage developed by the membrane with the setting of the maximum pressure from 5 cmH IIO to 20 cmH IIO was in order of several hundred μV. SPM sensor demonstrated a biphasic response to the ventilator flow. The sensor data showed nearly linearly proportional voltage development to the intra-tracheal pressure. The sensed signal was filtered and digitized with an A/D converting unit on a PC board. A real time operating program was used to detect the sensed signal that indicates the narrowing of trachea. The program then activated a driving signal to control the actuation of the membrane. The signal was sent to a D/A converting unit. The output of the D/A unit was sent to an amplifier and the galvanostat unit which drives the membrane with constant current regardless of the change in the load. It was demonstrated that the sensor-actuator unit detects the narrowing of trachea within several hundreds milli-seconds and responds by actuating the same membrane with the driving voltage of 3-4 V and driving current of several hundred milli-ampere for each membrane. SPM array

  1. A new silver ion conducting SbI3-Ag4P2O7 nanocomposite solid electrolyte

    NASA Astrophysics Data System (ADS)

    Suthanthiraraj, S. Austin; Sarumathi, R.

    2013-12-01

    This paper presents an investigation on a new series of silver ion conducting nanocomposite materials of silver pyrophosphate-based solid electrolytes with various amounts of antimony iodide. The detailed electrical conductivity studies carried out by impedance spectroscopic analysis in the frequency range from 20 Hz to 1 MHz have shown that silver ionic conductivity attains a maximum value of 4.1 × 10-4 S cm-1 at room temperature for the typical composition having 60 mol% of SbI3. Powder samples characterized by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetric analysis and silver ionic transport studies were identified to indicate the existence of AgI, in addition to certain new phases in all the different compositions of the system. The conduction channel for Ag+ ions across phosphate network was found to get expanded by the presence of iodide ion. The formation of P-O-M (M=Sb3+) within the crystal structure is also favoured, where Sb3+ ions may serve as ionic cross-links between non-bridging oxygen of different phosphate groups. The field emission scanning electron microscopic investigations of their microstructures have suggested the presence of nanocomposites, leading to the observed electrical conductivity data coupled with many interesting features closely related to the particle size and practical application as solid electrolyte for the fabrication of solid-state battery at ambient conditions.

  2. Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells

    PubMed Central

    Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

    2015-01-01

    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). PMID:26218470

  3. POSS-Based Electrolyte for Efficient Solid-State Dye-Sensitized Solar Cells at Sub-Zero Temperatures.

    PubMed

    Lv, Kai; Zhang, Wei; Zhang, Lu; Wang, Zhong-Sheng

    2016-03-01

    To expand the application of solid-state dye-sensitized solar cells (ssDSSCs) to low temperatures, it is necessary to develop new solid electrolytes with low glass transition temperature (Tg). The Tg is regulated by varying the length of alkyl chain that is connected with the nitrogen atom in the imidazolium ring linked to the polyhedral oligomeric silsesquioxane (POSS). The Tg as low as -8.8 °C is achieved with the POSS grafted with methyl-substituted imidazolium. The effect of alkyl group on the conductivity, Tg, and photovoltaic performance has also been investigated. The conductivity and power conversion efficiency increase with the alkyl length, while the Tg first increases and then decreases with the alkyl length. Among the synthesized POSS-based ionic conductors, the POSS grafted with the methyl-substituted imidazolium yields the highest power conversion efficiency of 6.98% at RT due to its highest conductivity, and the efficiency (6.52%) is still good at -4 °C, as its Tg (-8.8 °C) is lower than the working temperature (-4 °C). This finding suggests that the POSS-based solid electrolyte is promising for subzero-temperature applications of ssDSSCs. PMID:26860035

  4. Molten salt electrolyte separator

    DOEpatents

    Kaun, Thomas D.

    1996-01-01

    A molten salt electrolyte/separator for battery and related electrochemical systems including a molten electrolyte composition and an electrically insulating solid salt dispersed therein, to provide improved performance at higher current densities and alternate designs through ease of fabrication.

  5. Structure of spontaneously formed solid-electrolyte interphase on lithiated graphite determined using small-angle neutron scattering

    DOE PAGESBeta

    Sacci, Robert L.; Banuelos, Jose Leobardo; Veith, Gabriel M.; Littrell, Ken C.; Cheng, Yongqiang Q.; Wildgruber, Christoph U.; Jones, Lacy L.; Ramirez-Cuesta, Anibal J.; Rother, Gernot; Dudney, Nancy J.

    2015-03-25

    We report the first small-angle neutron scattering of a chemically formed solid-electrolyte interphase from LixC6 reacting with ethylene carbonate/dimethyl carbon solvent. This provides a different and perhaps simpler view of SEI formation than the usual electrochemically-driven reaction. We show that an organic layer coats the graphite particles filling in micro-pores and is polymeric in nature being 1-3 nm thick. We used inelastic neutron scattering to probe the chemistry, and we found that the SEI showed similar inelastic scattering to polyethylene oxide.

  6. An Integrated Approach for Structural Characterization of Complex Solid State Electrolytes: The Case of Lithium Lanthanum Titanate

    SciTech Connect

    Cheng, Yongqiang; Bi,; Huq, Ashfia; Feygenson, Mikhail; Bridges, Craig A; Paranthaman, Mariappan Parans; Sumpter, Bobby G

    2014-01-01

    Neutron scattering and first principles simulation are integrated to reveal the atomic-level to nanoscale structure of lithium lanthanum titanate (LLTO), a representative solid electrolyte material with applications in Li-ion batteries. The integrated approach solves the hierarchical local structure of LLTO in detail, including the coupled chemical order and topological distortion, as well as their correlation length scale and the spatial modulation with coherent boundaries. Ab initio molecular dynamics simulations are used to map out the distribution of the mobile ions and identify the migration pathway. Overall, this integrated approach provides a powerful means for detailed study of materials with complex local chemical and topological environment.

  7. Extracting local surface charges and charge regulation behavior from atomic force microscopy measurements at heterogeneous solid-electrolyte interfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Cunlu; Ebeling, Daniel; Siretanu, Igor; van den Ende, Dirk; Mugele, Frieder

    2015-10-01

    We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces.

  8. Self-Assembled in-Plane-Gate Thin-Film Transistors Gated by WOx Solid-State Electrolytes

    NASA Astrophysics Data System (ADS)

    Zhu, De-Ming; Men, Chuan-Ling; Wan, Xiang; Deng, Chuang; Li, Zhen-Peng

    2013-08-01

    Low-voltage WOx gated indium-zinc-oxide thin-film transistors (TFTs) with in-plane-gate structures are fabricated by using an extremely simplified one-shadow mask method at room temperature. The proton conductive WOx solid-state electrolyte is demonstrated to form an electric-double-layer (EDL) effect associated with a huge capacitance of 0.51 μF/cm2. The special EDL capacitance of the WOx electrolyte is also extended to novel in-plane-gate structure TFTs as the gate dielectric, reducing the operating voltage to 1.8 V. Such TFTs operate at n-type depletion mode with a threshold voltage of -0.5 V, saturation electron mobility of 13.2 cm2/V·s, ON/OFF ratio of 1.7 × 106, subthreshold swing of 110 mV/dec, and low leakage current less than 7 nA. The hysteresis window of the transfer curves is also explained by an unique reaction within the WOx electrolyte.

  9. Reduced-temperature firing of solid oxide fuel cells with zirconia/ceria bi-layer electrolytes

    NASA Astrophysics Data System (ADS)

    Gao, Zhan; Kennouche, David; Barnett, Scott A.

    2014-08-01

    Solid oxide fuel cells (SOFCs) with bi-layer Zirconia/Ceria electrolytes have been studied extensively because of their great potential for producing high power density at reduced operating temperature, important for reducing cost and thereby allowing broader SOFC commercialization. The bi-layer electrolytes are designed to take advantage of the high oxygen ion conductivity of Ceria, the low electronic conductivity of Zirconia, and the low reactivity of Ceria with high-performance cathodes. However, zirconia/ceria processing has proven problematic due to interdiffusion during high temperature co-firing, or ceria layer porosity after two-step firing. Here we first show a new method for bi-layer co-firing at a reduced temperature of 1250 °C, ∼150 °C lower than the usual sintering temperature, achieved using Fe2O3 as a sintering aid. This novel process enables high power density SOFCs by producing: (1) low-resistance Y0.16Zr0.92O2-δ (YSZ)/Gd0.1Ce0.9O1.95 (GDC) electrolytes that also yield high open-circuit voltage, (2) dense GDC layers that prevent reactions between highly-active La0.6Sr0.4Fe0.8Co0.2O3 (LSFC) cathode materials and YSZ, and (3) Ni-YSZ anodes with high electrochemical activity due to fine-scale microstructure with high TPB densities.

  10. Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

    SciTech Connect

    Das, S.; Ghosh, A.

    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.

  11. Micro-solid oxide fuel cells using free-standing 3 mol.% yttria-stabilised-tetragonal-zirconia-polycrystal electrolyte foils

    NASA Astrophysics Data System (ADS)

    Evans, Anna; Bieberle-Hütter, Anja; Bonderer, Lorenz J.; Stuckenholz, Stefanie; Gauckler, Ludwig J.

    Ultrathin 3 mol.% yttria-stabilised-tetragonal-zirconia-polycrystal (Y-TZP) foils with thicknesses of 1-10 μm are fabricated by a new wet-chemical processing route. The foils are free-standing, semi-transparent and flexible. The in-plane electrical conductivity of the Y-TZP foil is 0.03 S m -1 at 500 °C. Cross-plane impedance measurements with sputtered Pt electrodes yield two arcs, of which the high-frequency arc is attributed to the ohmic resistance of the electrolyte and the low-frequency arc to the electrode-electrolyte interface. A symmetrical micro-solid oxide fuel cell (SOFC) is designed using this ultrathin free-standing Y-TZP foil as the electrolyte and sputtered Pt electrodes. An open-circuit voltage of 0.98 V and a maximum power density of 12 mW cm -2 are measured at 500 °C. These results prove the feasibility of this approach to the fabrication of miniaturised planar SOFCs without the need for microfabrication.

  12. Extracting local surface charges and charge regulation behavior from atomic force microscopy measurements at heterogeneous solid-electrolyte interfaces.

    PubMed

    Zhao, Cunlu; Ebeling, Daniel; Siretanu, Igor; van den Ende, Dirk; Mugele, Frieder

    2015-10-21

    We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces. PMID:26377347

  13. Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

    NASA Technical Reports Server (NTRS)

    Isenberg, Arnold O.; Cusick, Robert J.

    1988-01-01

    The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

  14. Study, selection, and preparation of solid cationic conductors. [characteristics of solid electrolytes for rechargeable high energy and high power density batteries

    NASA Technical Reports Server (NTRS)

    Roth, W. L.; Muller, O.

    1974-01-01

    Crystal chemical principles and transport theory have been used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. Structures with 1-, 2-, and 3-dimensional channels were synthesized and screened by nuclear magnetic resonance, dielectric loss, and conductivity. There is significant conductivity at room temperature in some of the materials but none attain a level that is comparable to beta-alumina. Microwave and fast pulse methods were developed to measure conductivity in powders and in small crystals.

  15. Conduction mechanisms in concentrated LiI-polyethylene oxide-Al{sub 2}O{sub 3}-based solid electrolytes

    SciTech Connect

    Golodnitsky, D.; Ardel, G.; Strauss, E.; Peled, E.; Lareah, Y.; Rosenberg, Y.

    1997-10-01

    The ionic conductivity of concentrated LiI-polyethylene oxide P(EO){sub n} high surface area oxide composite polymer electrolytes has been investigated. Two different Arrhenius dependences for concentrated composite polymer electrolytes (CPEs) have been identified. The first one is characterized by an inflection point at about 80 C, and the second, by a conductivity jump. The authors have suggested that in CPEs, where 3solid phase is major contributor to the overall ionic conductivity at temperatures above, but close to the melting point of the eutectic (T{sub m}solid electrolytes (CSEs, n{le}3), is about 40% of that for CPEs. The authors believe that the preferred conduction path in even more concentrated CPEs, which are defined as CSEs, is interfacial conduction. Differential scanning calorimetry, scanning electron microscopy, and X-ray data, presented here, are evidence supporting the view. The effects of several parameters including type and content of oxide matrix, Li salt to ethylene oxide ratio, copolymers, and solvents on polymer electrolyte conductivity (especially at T >T{sub k}orT{sub jump}) and on Ea have been studied (T{sub jump}=temperature of the conductivity jump). The addition of small quantities of ethylene carbonate, poly(methyl methacrylate), and polyacrylonitrile were found to be beneficial while poly(methyl acrylate), poly(butyl acrylate), and poly(vinylidene fluoride) additions made the polymer electrolyte stiffer and less conductive. MgO, Al{sub 2}O{sub 3}, and potassium aluminosilicate muscovite mica based CSEs have similar conductivity. Results clearly demonstrated the depression of CPE crystallinity by addition of fine Al{sub 2}O{sub 3} powder, ethylene carbonate, and poly(ethylene glycol) dimethyl ether, in agreement with the conductivity enhancement of the CPE.

  16. The Characteristics Improvement of Ozone Water Production by Multi-layer Electrodes at Water Electrolysis Cell by Solid Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Ohba, Takahiro; Kusunoki, Hironobu; Sunakawa, Daisuke; Araki, Takuto; Onda, Kazuo

    Ozone is recently used for many purposes as an environmental friendly oxidant, so the ozone production device with high ozone concentration and low production energy is desired. One of the candidates for such device is the ozone water production by water electrolysis cell using the solid polymer electrolyte with PbO2 anode catalyst, which has merits to be compact and to produce high-concentration ozone water directly by the deionized water electrolysis. In this study, we have tested ozone water production by changing electrodes and electrolytes constitution in order to improve the ozone production performance. Tested two electrolytes are Nafion117 and a membrane-electrode assembly (MEA) with Pt catalyst on cathode side of Nafion117. Tested two electrodes are mono-layer of Ti expanded metal and four different mesh layers of Ti expanded metal. Ozone water production tests are performed under long-term operations changing temperature and flow rate to optimize experimental conditions. The voltage-current characteristic for electrolysis cell have been improved significantly, when the electrode is four layers of Ti metal and the electrolyte is the MEA with Pt catalyst. The stable ozone water concentration has been obtained by operating the cell for about 8 hours. The optimum temperature and water flow rate for ozone water production are 25˜30° and 33L/h, respectively. Furthermore, the optimum overpotential was measured by a reference electrode at the cathode-side MEA, and the anode catalyst suitable for ozone water production was identified to be βPbO2 by the X ray diffraction pattern.

  17. Crystalline Li(sub 3)PO(sub 4)/SiO(sub 4) solid solutions as an electrolyte for film batteries using sputtered cathode layers

    NASA Technical Reports Server (NTRS)

    Whitacre, J. F.; West, W. C.

    2003-01-01

    Crystalline solid solutions of 1:1 Li3PO4/SiO4 were synthesized and tested electrochemically using thin film, physical vapor deposited electrodes. After cathode deposition, the electrolyte/cathode structures were annealed at 700 degrees Celsius for 2 hours, a process that resulted in cathode crystallization without encouraging deleterious interfacial reactions. Results indicate that the electrolyte functioned well in this configuration.

  18. Estimation of energy density of Li-S batteries with liquid and solid electrolytes

    NASA Astrophysics Data System (ADS)

    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.

  19. Effect of Poly(Ether Urethane) Introduction on the Performance of Polymer Electrolyte for All-Solid-State Dye-Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Zhou, Yan-Fang; Xiang, Wan-Chun; Fang, Shi-Bi; Chen, Shen; Zhou, Xiao-Wen; Zhang, Jing-Bo; Lin, Yuan

    2009-12-01

    The introduction of poly(ether urethane) (PEUR) into polymer electrolyte based on poly(ethylene oxide), LiI and I2, has significantly increased the ionic conductivity by nearly two orders of magnitudes. An increment of I-3 diffusion coefficient is also observed. All-solid-state dye-sensitized solar cells are constructed using the polymer electrolytes. It was found that PEUR incorporation has a beneficial effect on the enhancement of open circuit voltage Voc by shifting the band edge of TiO2 to a negative value. Scanning electron microscope images indicate the perfect interfacial contact between the TiO2 electrode and the blend electrolyte.

  20. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman; Keith L. Duncan

    2002-09-30

    A bilayer electrolyte consisting of acceptor-doped ceria (on the fuel/reducing side) and cubic-stabilized bismuth oxide (on the oxidizing side) was developed. The bilayer electrolyte that was developed showed significant improvement in open-circuit potential versus a typical ceria based SOFC. Moreover, the OCP of the bilayer cells increased as the thickness of the bismuth oxide layer increased relative to the ceria layer. Thereby, verifying the bilayer concept. Although, because of the absence of a suitable cathode (a problem we are still working assiduously to solve), we were unable to obtain power density curves, our modeling work predicts a reduction in electrolyte area specific resistance of two orders of magnitude over cubic-stabilized zirconia and projects a maximum power density of 9 W/m{sup 2} at 800 C and 0.09 W/m{sup 2} at 500 C. Towards the development of the bilayer electrolyte other significant strides were made. Among these were, first, the development of a, bismuth oxide based, oxide ion conductor with the highest conductivity (0.56 S/cm at 800 C and 0.043 S/cm at 500 C) known to date. Second, a physical model of the defect transport mechanisms and the driving forces for the ordering phenomena in bismuth oxide and other fluorite systems was developed. Third, a model for point defect transport in oxide mixed ionic-electronic conductors was developed, without the typical assumption of a uniform distribution of ions and including the effect of variable loads on the transport properties of an SOFC (with either a single or bilayer electrolyte).

  1. A High Temperature Electrochemical Energy Storage System Based on Sodium Beta-Alumina Solid Electrolyte (Base)

    SciTech Connect

    Anil Virkar

    2008-03-31

    This report summarizes the work done during the period September 1, 2005 and March 31, 2008. Work was conducted in the following areas: (1) Fabrication of sodium beta{double_prime} alumina solid electrolyte (BASE) using a vapor phase process. (2) Mechanistic studies on the conversion of {alpha}-alumina + zirconia into beta{double_prime}-alumina + zirconia by the vapor phase process. (3) Characterization of BASE by X-ray diffraction, SEM, and conductivity measurements. (4) Design, construction and electrochemical testing of a symmetric cell containing BASE as the electrolyte and NaCl + ZnCl{sub 2} as the electrodes. (5) Design, construction, and electrochemical evaluation of Na/BASE/ZnCl{sub 2} electrochemical cells. (6) Stability studies in ZnCl{sub 2}, SnCl{sub 2}, and SnI{sub 4} (7) Design, assembly and testing of planar stacks. (8) Investigation of the effect of porous surface layers on BASE on cell resistance. The conventional process for the fabrication of sodium ion conducting beta{double_prime}-alumina involves calcination of {alpha}-alumina + Na{sub 2}CO{sub 3} + LiNO{sub 3} at 1250 C, followed by sintering powder compacts in sealed containers (platinum or MgO) at {approx}1600 C. The novel vapor phase process involves first sintering a mixture of {alpha}-alumina + yttria-stabilized zirconia (YSZ) into a dense ceramic followed by exposure to soda vapor at {approx}1450 C to convert {alpha}-alumina into beta{double_prime}-alumina. The vapor phase process leads to a high strength BASE, which is also resistant to moisture attack, unlike BASE made by the conventional process. The PI is the lead inventor of the process. Discs and tubes of BASE were fabricated in the present work. In the conventional process, sintering of BASE is accomplished by a transient liquid phase mechanism wherein the liquid phase contains NaAlO{sub 2}. Some NaAlO{sub 2} continues to remain at grain boundaries; and is the root cause of its water sensitivity. In the vapor phase process, Na

  2. Solid Electrolyte Lithium Phosphous Oxynitride as a Protective Nanocladding Layer for 3D High-Capacity Conversion Electrodes.

    PubMed

    Lin, Chuan-Fu; Noked, Malachi; Kozen, Alexander C; Liu, Chanyuan; Zhao, Oliver; Gregorczyk, Keith; Hu, Liangbing; Lee, Sang Bok; Rubloff, Gary W

    2016-02-23

    Materials that undergo conversion reactions to form different materials upon lithiation typically offer high specific capacity for energy storage applications such as Li ion batteries. However, since the reaction products often involve complex mixtures of electrically insulating and conducting particles and significant changes in volume and phase, the reversibility of conversion reactions is poor, preventing their use in rechargeable (secondary) batteries. In this paper, we fabricate and protect 3D conversion electrodes by first coating multiwalled carbon nanotubes (MWCNT) with a model conversion material, RuO2, and subsequently protecting them with conformal thin-film lithium phosphous oxynitride (LiPON), a well-known solid-state electrolyte. Atomic layer deposition is used to deposit the RuO2 and the LiPON, thus forming core double-shell MWCNT@RuO2@LiPON electrodes as a model system. We find that the LiPON protection layer enhances cyclability of the conversion electrode, which we attribute to two factors. (1) The LiPON layer provides high Li ion conductivity at the interface between the electrolyte and the electrode. (2) By constraining the electrode materials mechanically, the LiPON protection layer ensures electronic connectivity and thus conductivity during lithiation/delithiation cycles. These two mechanisms are striking in their ability to preserve capacity despite the profound changes in structure and composition intrinsic to conversion electrode materials. This LiPON-protected structure exhibits superior cycling stability and reversibility as well as decreased overpotentials compared to the unprotected core-shell structure. Furthermore, even at very low lithiation potential (0.05 V), the LiPON-protected electrode largely reduces the formation of a solid electrolyte interphase. PMID:26820038

  3. Ion transport in a polymer-plastic solid soft matter electrolyte in the light of solvent dynamics and ion association.

    PubMed

    Patel, Monalisa; Menezes, Pramod V; Bhattacharyya, Aninda J

    2010-04-29

    Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state, compliable mechanical strength (approximately 1 MPa), and wide electrochemical voltage stability (> or = 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO(4))-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO(4)-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polymer concentration shows an effective increase in trans conformer concentration along with free Li(+) ion concentration. This strongly supports the view that enhancement in LiClO(4)-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO(4)-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO(4)-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance (1)H and (7)Li line width measurements. PMID:20373767

  4. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li(+) /H(+) exchange in aqueous solutions.

    PubMed

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren L; Chi, Miaofang

    2015-01-01

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7 La3 Zr2 O12 garnet as a Li-stable solid electrolyte. The material underwent a Li(+) /H(+) exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6 %. When treated with a 2 M LiOH solution, the Li(+) /H(+) exchange was reversed without any structural change. These observations suggest that cubic Li7 La3 Zr2 O12 is a promising candidate for the separator in aqueous lithium batteries. PMID:25331968

  5. Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

    NASA Astrophysics Data System (ADS)

    Harun, Fatin; Chan, Chin Han; Sim, Lai Har; Winie, Tan; Zainal, Nurul Fatahah Asyqin

    2015-08-01

    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 (LiClO4) salt and titanium dioxide (TiO2) 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 LiClO4 causes a greater increase in glass transition temperature (Tg) and ionic conductivity of ENR50 as compared to ENR25. Upon addition of TiO2 in ENR/LiClO4 system, a remarkable Tg 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 TiO2 loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.

  6. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    DOE PAGESBeta

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren Leslie; Chi, Miaofang

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchangedmore » even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.« less

  7. Nanocomposite semi-solid redox ionic liquid electrolytes with enhanced charge-transport capabilities for dye-sensitized solar cells.

    PubMed

    Rutkowska, Iwona A; Marszalek, Magdalena; Orlowska, Justyna; Ozimek, Weronika; Zakeeruddin, Shaik M; Kulesza, Pawel J; Grätzel, Michael

    2015-08-10

    The ability of Pt nanostructures to induce the splitting of the II bond in iodine (triiodide) molecules is explored here to enhance electron transfer in the iodine/iodide redox couple. Following the dispersal of Pt nanoparticles at 2 % (weight) level, charge transport was accelerated in triiodide/iodide-containing 1,3-dialkylimidazolium room-temperature ionic liquid. If both Pt nanoparticles and multi-walled carbon nanotubes were introduced into the ionic-liquid-based system, a solid-type (nonfluid) electrolyte was obtained. By using solid-state voltammetric (both sandwich-type and microelectrode-based) methodology, the apparent diffusion coefficients for charge transport increased to approximately 1×10(-6)  cm(2)  s(-1) upon the incorporation of the carbon-nanotube-supported iodine-modified Pt nanostructures. A dye-sensitized solar cell comprising TiO2 covered with a heteroleptic Ru(II) -type sensitizer (dye) and the semisolid triiodide/iodide ionic liquid electrolyte admixed with carbon-nanotube-supported Pt nanostructures yielded somewhat higher power conversion efficiencies (up to 7.9 % under standard reporting conditions) than those of the analogous Pt-free system. PMID:26119519

  8. Effect of ionic conductivity of zirconia electrolytes on the polarization behavior of various cathodes in solid oxide fuel cells

    SciTech Connect

    Uchida, Hiroyuki; Yoshida, Manabu; Watanabe, Masahiro

    1999-01-01

    The polarization behaviors of porous platinum and La(Sr)MnO{sub 3} (LSM) cathodes coupled with zirconia electrolytes with various ionic conductivities ({sigma}{sub ion}) were investigated. The exchange current density, j{sub 0}, on Pt cathode was not influenced by the {sigma}{sub ion} at 900 and 1,000 C, whereas j{sub 0} increased proportionally to {sigma}{sub ion} at a lower temperature of 800 C. However, the j{sub 0} on LSM cathodes increased in proportion to the {sigma}{sub ion} in the temperature region between 800 and 1,000 C. The dispersion of nanometer-sized Pt catalysts on LSM particles greatly enhanced the performance, the magnitude of which depended on the temperature, the {sigma}{sub ion}, and the microstructure of LSM. The observations are well explained kinetically, i.e., the cathode performance is controlled by the transport rate of O{sup 2{minus}} at the interface when the surface reaction rate is sufficiently high. Consequently, the use of high-performance electrodes in combination with the solid electrolyte having high {sigma}{sub ion} is very important for achieving the high performance of solid oxide fuel cells.

  9. Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

    SciTech Connect

    Harun, Fatin; Chan, Chin Han; Winie, Tan; Sim, Lai Har; Zainal, Nurul Fatahah Asyqin

    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.

  10. Development of bipolar all-solid-state lithium battery based on quasi-solid-state electrolyte containing tetraglyme-LiTFSA equimolar complex.

    PubMed

    Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

    2015-01-01

    The development of high energy-density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V. PMID:25746860

  11. Development of Bipolar All-solid-state Lithium Battery Based on Quasi-solid-state Electrolyte Containing Tetraglyme-LiTFSA Equimolar Complex

    PubMed Central

    Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

    2015-01-01

    The development of high energy–density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V. PMID:25746860

  12. Upward shift of the vortex solid phase in high-temperature-superconducting wires through high density nanoparticle addition

    NASA Astrophysics Data System (ADS)

    Miura, Masashi; Maiorov, Boris; Balakirev, Fedor F.; Kato, Takeharu; Sato, Michio; Takagi, Yuji; Izumi, Teruo; Civale, Leonardo

    2016-02-01

    We show a simple and effective way to improve the vortex irreversibility line up to very high magnetic fields (60T) by increasing the density of second phase BaZrO3 nanoparticles. (Y0.77,Gd0.23)Ba2Cu3Oy films were grown on metal substrates with different concentration of BaZrO3 nanoparticles by the metal organic deposition method. We find that upon increase of the BaZrO3 concentration, the nanoparticle size remains constant but the twin-boundary density increases. Up to the highest nanoparticle concentration (n ~ 1.3 × 1022/m3), the irreversibility field (Hirr) continues to increase with no sign of saturation up to 60 T, although the vortices vastly outnumber pinning centers. We find extremely high Hirr, namely Hirr = 30 T (H||45°) and 24 T (H||c) at 65 K and 58 T (H||45°) and 45 T (H||c) at 50K. The difference in pinning landscape shifts the vortex solid-liquid transition upwards, increasing the vortex region useful for power applications, while keeping the upper critical field, critical temperature and electronic mass anisotropy unchanged.

  13. Upward shift of the vortex solid phase in high-temperature-superconducting wires through high density nanoparticle addition.

    PubMed

    Miura, Masashi; Maiorov, Boris; Balakirev, Fedor F; Kato, Takeharu; Sato, Michio; Takagi, Yuji; Izumi, Teruo; Civale, Leonardo

    2016-01-01

    We show a simple and effective way to improve the vortex irreversibility line up to very high magnetic fields (60T) by increasing the density of second phase BaZrO3 nanoparticles. (Y0.77,Gd0.23)Ba2Cu3Oy films were grown on metal substrates with different concentration of BaZrO3 nanoparticles by the metal organic deposition method. We find that upon increase of the BaZrO3 concentration, the nanoparticle size remains constant but the twin-boundary density increases. Up to the highest nanoparticle concentration (n ~ 1.3 × 10(22)/m(3)), the irreversibility field (Hirr) continues to increase with no sign of saturation up to 60 T, although the vortices vastly outnumber pinning centers. We find extremely high Hirr, namely Hirr = 30 T (H||45°) and 24 T (H||c) at 65 K and 58 T (H||45°) and 45 T (H||c) at 50K. The difference in pinning landscape shifts the vortex solid-liquid transition upwards, increasing the vortex region useful for power applications, while keeping the upper critical field, critical temperature and electronic mass anisotropy unchanged. PMID:26853703

  14. Upward shift of the vortex solid phase in high-temperature-superconducting wires through high density nanoparticle addition

    PubMed Central

    Miura, Masashi; Maiorov, Boris; Balakirev, Fedor F.; Kato, Takeharu; Sato, Michio; Takagi, Yuji; Izumi, Teruo; Civale, Leonardo

    2016-01-01

    We show a simple and effective way to improve the vortex irreversibility line up to very high magnetic fields (60T) by increasing the density of second phase BaZrO3 nanoparticles. (Y0.77,Gd0.23)Ba2Cu3Oy films were grown on metal substrates with different concentration of BaZrO3 nanoparticles by the metal organic deposition method. We find that upon increase of the BaZrO3 concentration, the nanoparticle size remains constant but the twin-boundary density increases. Up to the highest nanoparticle concentration (n ~ 1.3 × 1022/m3), the irreversibility field (Hirr) continues to increase with no sign of saturation up to 60 T, although the vortices vastly outnumber pinning centers. We find extremely high Hirr, namely Hirr = 30 T (H||45°) and 24 T (H||c) at 65 K and 58 T (H||45°) and 45 T (H||c) at 50K. The difference in pinning landscape shifts the vortex solid-liquid transition upwards, increasing the vortex region useful for power applications, while keeping the upper critical field, critical temperature and electronic mass anisotropy unchanged. PMID:26853703

  15. Upward shift of the vortex solid phase in high-temperature-superconducting wires through high density nanoparticle addition

    DOE PAGESBeta

    Miura, Masashi; Maiorov, Boris; Balakirev, Fedor F.; Kato, Takeharu; Sato, Michio; Takagi, Yuji; Izumi, Teruo; Civale, Leonardo

    2016-02-08

    Here, we show a simple and effective way to improve the vortex irreversibility line up to very high magnetic fields (60T) by increasing the density of second phase BaZrO3 nanoparticles. (Y0.77,Gd0.23)Ba2Cu3Oy films were grown on metal substrates with different concentration of BaZrO3 nanoparticles by the metal organic deposition method. We find that upon increase of the BaZrO3 concentration, the nanoparticle size remains constant but the twin-boundary density increases. Up to the highest nanoparticle concentration (n ~ 1.3 × 1022/m3), the irreversibility field (Hirr) continues to increase with no sign of saturation up to 60 T, although the vortices vastly outnumbermore » pinning centers. We find extremely high Hirr, namely Hirr = 30 T (H||45°) and 24 T (H||c) at 65 K and 58 T (H||45°) and 45 T (H||c) at 50K. The difference in pinning landscape shifts the vortex solid-liquid transition upwards, increasing the vortex region useful for power applications, while keeping the upper critical field, critical temperature and electronic mass anisotropy unchanged.« less

  16. Chemical compatibility study of melilite-type gallate solid electrolyte with different cathode materials

    NASA Astrophysics Data System (ADS)

    Mancini, Alessandro; Felice, Valeria; Natali Sora, Isabella; Malavasi, Lorenzo; Tealdi, Cristina

    2014-05-01

    Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La1.50Sr0.50Ga3O7.25 has been extensively investigated by X-ray powder diffraction in a wide temperature range (up to 1573 K). Perovskite-type La0.8Sr0.2MnO3-d and La0.8Sr0.2Fe0.8Cu0.2O3-d and K2NiF4-type La2NiO4+d were selected as cathode materials. The results of this study allow identifying the most suitable electrode material to be used in combination with the melilite-type gallate electrolyte and set the basis for future work on this novel system.

  17. Dynamics of Ion-Gating 2D Crystals Using a Solid Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Li, Hua-Min; Bourdon, Buchanan; Lin, Yu-Chuan; Robinson, Joshua; Seabaugh, Alan; Fullerton, Susan; CenterLow Energy Systems Technology (Least) Team

    2015-03-01

    Ion-gating can significantly increase the static carrier density of graphene due to the formation of an electric double layer (EDL); however, the dynamics of ion-gating have not been extensively reported. A comprehensive understanding of ion dynamics is important because it establishes the timescales required to achieve EDL equilibrium, and directly affects the operating speed of devices and circuits employing electrolytic gates. Here, ion dynamics are measured on epitaxial graphene Hall-bar devices that are electrolytically gated with polyethylene oxide and lithium perchlorate. The time constants for EDL formation and dissipation are measured as a function of temperature. The measured formation time is slower than the dissipation time, because ion diffusion resulting from a concentration gradient must be opposed during EDL formation. These results quantitatively agree with COMSOL multiphysics simulations. EDL dissipation follows a stretched exponential decay described by the Kohlrausch-Williams-Watts (KWW) equation. The temperature-dependent relaxation times extracted from the KWW fit follow the Vogel-Fulcher-Tammann (VFT) temperature dependence. At temperatures approaching the glass transition temperature of the electrolyte, the relaxation times exceed several hours, demonstrating the long timescales over which the EDL can persist in the absence of a gate bias.

  18. Solid state cell with alkali metal halo-alkali thiocyanate electrolyte

    SciTech Connect

    Rao, B. M.; Silbernagel, B. G.

    1980-02-26

    A novel electrochemical cell is disclosed utilizing: (A) an anode which contains an alkali metal as an anode-active material; (B) a cathode and (C) an electrolyte comprising an electrolytically effective amount of one or more compounds having the formula: (Ax)ma'scn wherein a is an alkali metal, X is a halogen, a' is an alkali metal and 0.1 < or = N < or = 10. Preferred systems include lithium-containing anodes, lithium-containing electrolytes and cathodes which contain cathode-active material selected from the group consisting of cathode-active sulfurs, halogens, halides, chromates, phosphates, oxides and chalcogenides, especially those chalcogenides of the empirical formula mzm wherein M is one or more metals selected from the group consisting of iron, titanium, zirconium, hafnium, niobium, tantalum and vanadium, Z is one or more chalcogens selected from the group consisting of oxygen, sulfur, selenium and tellurium, and M is a numerical value between about 1.8 and about 3.2.

  19. Preparation and characterization of solid electrolytes for solid oxide fuel cells. Quarterly report, July 1--September 30, 1996

    SciTech Connect

    1996-12-31

    During this quarter, the authors have analyzed EXAFS spectra of rare earth doped ceria and identified Gd and Sm doped ceria electrolytes for further investigations in this project. Although electrical properties of the material have been examined in detail, very little work has considered the microstructural/property relationships, particularly in relationship to atomic and geometric structures of these ceria based oxides. The authors have observed an ionic conductivity of 8.3 {times} 10{sup {minus}2} S/Cm in the (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2} at 800 C which is approximately four times that of Y{sub 2}O{sub 3} doped ZrO{sub 3} doped ZrO{sub 2} at the same temperature. The fraction of Ce{sup +4} ions reduced to Ce{sup +3} as a function of temperature and oxygen partial pressure. The partial reduction of cerium oxide generates mobile electrons and causes electronic conductivity in the electrolyte at temperatures above 500 C. In this quarter, the authors have attempted to measure the microstructural properties using SEM, TEM and HVC STM techniques. Other parts of this investigation are also discussed.

  20. Anhydrous state proton and lithium ion conducting solid polymer electrolytes based on sulfonated bisphenol-A-poly(arylene ethers)

    NASA Astrophysics Data System (ADS)

    Guha Thakurta, Soma

    Sulfonated polymer based solid polymer electrolytes (SPEs) have received considerable interest in recent years because of their wide variety of applications particularly in fuel cells, batteries, supercapacitors, and electrochromic devices. The present research was focused on three interrelated subtopics. First, two different bisphenol-A-poly(arylene ethers), polyetherimide (PEI) and polysulfone (PSU) were sulfonated by a post sulfonation method to various degrees of sulfonation, and their thermal and mechanical properties were examined. The effects of poly(arylene ether) chemical structure, reaction time, concentration, and types of sulfonating agents on sulfonation reaction were investigated. It was found that deactivation of bisphenol A unit caused by the electron withdrawing imide, retarded the sulfonation of PEI compared to PSU. Sulfonation conducted with a high concentration of sulfonating agent and/or prolonged reaction time exhibited evidence of degradation at the isopropylidene unit. The degradation occurred through the same mechanistic pathway with the two different sulfonating agents, chlorosulfonic acid (CSA) and trimethylsilyl chlorosulfonate (TMSCS). The degradation was faster with CSA than its silyl ester, TMSCS, and was evident even at low acid concentration. Second, novel anhydrous proton conducting solid polymer electrolytes (SPEs) were prepared by the incorporation of 1H-1,2,4-triazole (Taz) as a proton solvent in sulfonated polyetherimide (SPEI) matrix. The size, shape, and state of dispersion (crystal morphology) of triazole crystals in SPEI were examined as a function of degree of sulfonation and triazole concentration. Increasing sulfonic acid content caused reduction of triazole crystallite size, hence the depression of melting temperature and their uniform distribution throughout the sulfonated polymer matrix. The increased rate of structure diffusion within the smaller size crystals due to the improved molecular mobility contributed

  1. Simultaneous improvement in ionic conductivity and flexibility of solid polymer electrolytes for thin film lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Ji, Jianying

    Solid polymer electrolytes (SPEs) provide advantages over liquid electrolytes in terms of safety, reliability, less temperature sensitive, and simplicity of design. With the use of a SPE in lithium batteries, high specific energy and specific power, safe operation, flexibility in packaging, and low cost of fabrication can be expected. However, after 30 years, SPEs have rarely found commercial success due to the low ionic conductivity and/or insufficient mechanical properties, both of which are related to the movement of the polymer chains. Many physical/chemical methods have been exploited to simultaneously create enhancement in ionic conductivity and mechanical properties, and some suggested ways have shown promise. However, the complex strategies have always introduced other challenge issues and incurred extra costs for manufacturing. In such a context, the development of dry solid state electrolytes is the central challenge to be faced worldwide. This thesis deals with the approaches to improving ionic conductivity and mechanical properties simultaneously. The method is to apply two kinds of controllable organic fillers: copolymer and protein. Our work revealed that the commercial available copolymer, poly (ethylene oxide)- block-polyethylene (PEO-b-PE), possesses a capability for enhancing the multiple performances of poly(ethylene oxide)(PEO)-based polymer electrolyte. And the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs were examined. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties, while increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity. A rubber-like, soy protein-based SPE (s-SPE)was obtained by employing soy protein isolate (SPI), a soy product usually used as rigid fillers for enhancing mechanical properties of

  2. A Novel Small-Molecule Compound of Lithium Iodine and 3-Hydroxypropionitride as a Solid-State Electrolyte for Lithium-Air Batteries.

    PubMed

    Liu, Fang-Chao; Shadike, Zulipiya; Wang, Xiao-Fang; Shi, Si-Qi; Zhou, Yong-Ning; Chen, Guo-Ying; Yang, Xiao-Qing; Weng, Lin-Hong; Zhao, Jing-Tai; Fu, Zheng-Wen

    2016-07-01

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I(-)-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium-air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g(-1) with a cyclic performance over 10 cycles. Our findings provide a new way to design solid-state electrolytes toward high-performance lithium-air batteries. PMID:27308962

  3. Lithium ion conducting electrolytes

    SciTech Connect

    Angell, C.A.; Liu, C.; Xu, K.; Skotheim, T.A.

    1999-10-05

    The present invention relates generally to highly conductive alkali-metal ion non-crystalline electrolyte systems, and more particularly to novel and unique molten (liquid), rubbery, and solid electrolyte systems which are especially well suited for use with high current density electrolytic cells such as primary and secondary batteries.

  4. Lithium ion conducting electrolytes

    DOEpatents

    Angell, Charles Austen; Liu, Changle; Xu, Kang; Skotheim, Terje A.

    1999-01-01

    The present invention relates generally to highly conductive alkali-metal ion non-crystalline electrolyte systems, and more particularly to novel and unique molten (liquid), rubbery, and solid electrolyte systems which are especially well suited for use with high current density electrolytic cells such as primary and secondary batteries.

  5. Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life.

    PubMed

    Tan, Guoqiang; Wu, Feng; Zhan, Chun; Wang, Jing; Mu, Daobin; Lu, Jun; Amine, Khalil

    2016-03-01

    The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li(+)-conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices. PMID:26862941

  6. Ionic conductivity measurement in magnesium aluminate spinel and solid state galvanic cell with magnesium aluminate electrolyte

    NASA Astrophysics Data System (ADS)

    Lee, Myongjai

    This thesis work is about the experimental measurement of electronic and ionic conductivities in the MgAl2O4 spinel at 500˜600°C range and exploring the fundamental origin of solid-state galvanic cell behavior in the cell of Al|MgAl2O4|Mg, Al|MgAl2O 4|C, and Mg|MgAl2O4|C, in which at least one metal electrode in common with the composition of the electrolyte. For the electronic conductivity measurement, we have used the ion-blocking Gold and Carbon electrodes which are inert with both Mg and Al ions to suppress the ionic conduction from the total conduction. DC polarization method was used to measure the conduction through Au|MgAl2O4|Au and C|MgAl2O4|C specimens. The measured electrical conductivity using Au|MgAl2O4|Au and C|MgAl2O4|C specimens showed 10-9.3 ˜ 10-8.4 (O·cm) -1 at 600˜720°C range following the Arrhenius-type relation. These conductivity data are in agreement with reported data obtained from Pt and Ag ion-blocking electrodes deposited on MgAl2O4 specimens. For the ionic conductivity measurement, we have used the non-blocking Al and Mg electrodes for Al and Mg ionic conductivities, respectively. Ionic conductivity measurement of Al and Mg in separate manner has not been reported yet. In both Al|MgAl2O4|Al and Mg|MgAl2O 4|Mg specimens, gradual increase of conduction was observed once at the initial period before it reaches the steady state conduction. By DC method on the range of 580˜650°C, steady state Al ionic conductivity was measured from Al|MgAl2O4|Al specimen showing 10 -7.7 ˜ 10-6.8 (O·cm)-1 with the activation energy of 1.9eV in sigma = sigma0 exp-QRT formula. There was no difference in the conductivity by the change of the atmosphere from 5%H2 + 95%N2 mixed gas to pure Ar gas. So it was confirmed that the oxygen defect chemistry did not play a role. For Mg ionic conductivity Mg|MgAl2O4|Mg specimen was used and the measured conductivity shows 10-6.7 ˜ 10-4.4 (O·cm)-1 at 400˜550°C with the activation energy of 1.44eV at Ar gas

  7. Plasma-enhanced atomic layer deposition of nanoscale yttria-stabilized zirconia electrolyte for solid oxide fuel cells with porous substrate.

    PubMed

    Ji, Sanghoon; Cho, Gu Young; Yu, Wonjong; Su, Pei-Chen; Lee, Min Hwan; Cha, Suk Won

    2015-02-11

    Nanoscale yttria-stabilized zirconia (YSZ) electrolyte film was deposited by plasma-enhanced atomic layer deposition (PEALD) on a porous anodic aluminum oxide supporting substrate for solid oxide fuel cells. The minimum thickness of PEALD-YSZ electrolyte required for a consistently high open circuit voltage of 1.17 V at 500 °C is 70 nm, which is much thinner than the reported thickness of 180 nm using nonplasmatic ALD and is also the thinnest attainable value reported in the literatures on a porous supporting substrate. By further reducing the electrolyte thickness, the grain size reduction resulted in high surface grain boundary density at the cathode/electrolyte interface. PMID:25625537

  8. Role of surface oxides in the formation of solid-electrolyte interphases at silicon electrodes for lithium-ion batteries.

    PubMed

    Schroder, Kjell W; Dylla, Anthony G; Harris, Stephen J; Webb, Lauren J; Stevenson, Keith J

    2014-12-10

    Nonaqueous solvents in modern battery technologies undergo electroreduction at negative electrodes, leading to the formation of a solid-electrolyte interphase (SEI). The mechanisms and reactions leading to a stable SEI on silicon electrodes in lithium-ion batteries are still poorly understood. This lack of understanding inhibits the rational design of electrolyte additives, active material coatings, and the prediction of Li-ion battery life in general. We prepared SEI with a common nonaqueous solvent (LiPF6 in PC and in EC/DEC 1:1 by wt %) on silicon oxide and etched silicon (001) surfaces in various states of lithiation to understand the role of surface chemistry on the SEI formation mechanism and SEI structure. Anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films, allowing for more accurate characterization of SEI chemical stratification and composition by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling. Additionally, multivariate statistical methods were used to better understand TOF-SIMS depth profiling studies. We conclude that the absence of native-oxide layer on silicon has a significant impact on the formation, composition, structure, and thickness of the SEI. PMID:25402271

  9. TG-MS analysis of solid electrolyte interphase (SEI) on graphite negative-electrode in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Liwei; Watanabe, Izumi; Doi, Takayuki; Okada, Shigeto; Yamaki, Jun-ichi

    The thermal stability and chemical structure of solid electrolyte interphase (SEI) formed on a natural-graphite negative-electrode in ethylene carbonate (EC) and dimethyl carbonate (DMC)-based electrolyte was investigated by thermogravimetry-differential thermal analysis combined with mass spectrometry (TG-DTA/MS) and X-ray photoemission spectroscopy (XPS). Due to the decomposition of SEI, two CO 2 evolution peaks at around 330 and 430 °C were detected in TG-MS studies with continuous CO 2 background. The continuous CO 2 background was attributed to the gradual decomposition of oxygen-containing polymeric species of SEI. Another two dominant components of SEI, lithium alkyl carbonate and lithium oxalate, were found to contribute to the CO 2 peaks at 330 and 430 °C separately. The effects of charging-depth, current density and cycle number on the CO 2 distribution and XPS spectra were studied. It was found that lithium oxalate was reduction product of lithium alkyl carbonate during the intercalation of lithium ions. The reduction reaction could be accelerated by elevated temperature. The transformation of SEI chemical structure showed direct effect on the thermal stability of SEI. At the same time, lithium carbonate was also found in SEI on the graphite electrode after long cycles, while it was negligible in the electrode subjected to short cycles.

  10. First principles simulations of structural phase transformations in the solid electrolyte LiBH4 with chemical substitutions

    NASA Astrophysics Data System (ADS)

    Bernstein, Noam; Hoang, Khang; Johannes, Michelle

    2014-03-01

    The proposed hydrogen storage material LiBH4 has been shown to have possible applications as a Li-ion battery solid electrolyte, due to its high Li-ion conductivity over 10-3 S/cm-1 [1], comparable to polymer gel electrolytes. The high conductivity is only observed above a phase transition temperature that is outside of the useful operating range, but doping the material with various substitutions for the Li or BH4 units can bring the phase transition below room temperature. Both smaller and larger substituting species can stabilize the high T structure, indicating that it is not a simple volume effect. We show that variable-cell-shape molecular-dynamics simulations using density functional theory forces and stresses reproduce the structural phase transition. Using umbrella integration to compute the free energy differences between the two structures, we calculate the phase transition temperature and its dependence on substitutional I, Cl, and Na concentrations, and show that they are in very good agreement with experiment. We calculate the effect of K substitution, and predict that it will be even more effective at stabilizing the high T structure. Decomposing the free energy difference changes into enthalpy and entropy contributions shows that the mechanis

  11. Isothermal microcalorimetry as a tool to study solid-electrolyte interphase formation in lithium-ion cells.

    PubMed

    Hall, David S; Glazier, Stephen L; Dahn, J R

    2016-04-28

    Isothermal microcalorimetry can be used in conjunction with electrochemical measurements to study solid-electrolyte interphase (SEI) formation reactions as they occur in a Li-ion cell. The heat flow was measured in wound cells that contained no electrolyte additives and in cells prepared with four additives that are known to produce an SEI at the negative electrode surface: vinylene carbonate (VC), fluoroethylene carbonate (FEC), pyridine boron trifluoride (PBF), and prop-1-ene-1,3-sultone (PES). For VC, two distinct features in the differential capacity (dQ/dV vs. Q) plot that align with overlapping peaks in the heat flow plot do not agree with a simple one-electron reduction followed by anionic polymerization. For FEC, three distinct differential capacity and calorimetric peaks are observed. Heat flow measurements at multiple PBF concentrations show that PBF reduction does not significantly affect the reduction of EC at higher cell voltage. The total heat flow during SEI formation in PBF- and PES-containing cells match the calculated energies in recently published reaction pathways. It is concluded that IMC may be used to study the underlying chemistry of SEI formation, especially when paired with computational studies. PMID:27056253

  12. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    DOE PAGESBeta

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-07-10

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

  13. 3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

    PubMed

    Kang, Yu Jin; Yoo, Yongju; Kim, Woong

    2016-06-01

    State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics. PMID:27167760

  14. Highly conductive quasi-coaxial electrospun quaternized polyvinyl alcohol nanofibers and composite as high-performance solid electrolytes

    NASA Astrophysics Data System (ADS)

    Liao, Guan-Ming; Li, Pin-Chieh; Lin, Jia-Shiun; Ma, Wei-Ting; Yu, Bor-Chern; Li, Hsieh-Yu; Liu, Ying-Ling; Yang, Chun-Chen; Shih, Chao-Ming; Lue, Shingjiang Jessie

    2016-02-01

    Electrospun quaternized polyvinyl alcohol (Q-PVA) nanofibers are prepared, and a potassium hydroxide (KOH)-doped nanofiber mat demonstrates enhanced ionic conductivity compared with a dense Q-PVA film with KOH doping. The Q-PVA composite containing 5.98% electrospun Q-PVA nanofibers exhibits suppressed methanol permeability. Both the high conductivity and suppressed methanol permeability are attributed to the quasi-coaxial structure of the electrospun nanofibers. The core of the fibers exhibits a more amorphous region that forms highly conductive paths, while the outer shell of the nanofibers contains more polymer crystals that serve as a hard sheath surrounding the soft core. This shell induces mass transfer resistance and creates a tortuous fuel pathway that suppresses methanol permeation. Such a Q-PVA composite is an effective solid electrolyte that makes the use of alkaline fuel cells viable. In a direct methanol alkaline fuel cell operated at 60 °C, a peak power density of 54 mW cm-2 is obtained using the electrospun Q-PVA composite, a 36.4% increase compared with a cell employing a pristine Q-PVA film. These results demonstrate that highly conductive coaxial electrospun nanofibers can be prepared through a single-opening spinneret and provide a possible approach for high-performance electrolyte fabrication.

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

    SciTech Connect

    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.

  16. Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries.

    PubMed

    Porcarelli, Luca; Shaplov, Alexander S; Salsamendi, Maitane; Nair, Jijeesh R; Vygodskii, Yakov S; Mecerreyes, David; Gerbaldi, Claudio

    2016-04-27

    Polymer electrolytes have been proposed as replacement for conventional liquid electrolytes in lithium-ion batteries (LIBs) due to their intrinsic enhanced safety. Nevertheless, the power delivery of these materials is limited by the concentration gradient of the lithium salt. Single-ion conducting polyelectrolytes represent the ideal solution since their nature prevents polarization phenomena. Herein, the preparation of a new family of single-ion conducting block copolymer polyelectrolytes via reversible addition-fragmentation chain transfer polymerization technique is reported. These copolymers comprise poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) and poly(ethylene glycol) methyl ether methacrylate blocks. The obtained polyelectrolytes show low Tg values in the range of -61 to 0.6 °C, comparatively high ionic conductivity (up to 2.3 × 10(-6) and 1.2 × 10(-5) S cm(-1) at 25 and 55 °C, respectively), wide electrochemical stability (up to 4.5 V versus Li(+)/Li), and a lithium-ion transference number close to unity (0.83). Owing to the combination of all mentioned properties, the prepared polymer materials were used as solid polyelectrolytes and as binders in the elaboration of lithium-metal battery prototypes with high charge/discharge efficiency and excellent specific capacity (up to 130 mAh g(-1)) at C/15 rate. PMID:27043201

  17. In-Situ Observation of Solid Electrolyte Interphase Formation in Ordered Mesoporous Hard Carbon by Small-Angle Neutron Scattering

    SciTech Connect

    Bridges, Craig A; Paranthaman, Mariappan Parans; Sun, Xiao-Guang; Zhao, Jinkui; Dai, Sheng

    2012-01-01

    The aim of this work was to better understand the electrochemical processes occurring during the cycling of a lithium-ion half-cell containing ordered mesoporous hard carbon using time-resolved in situ small-angle neutron scattering (SANS). Utilizing electrolytes containing mixtures of deuterated (2H) and non-deuterated (1H) carbonates, we have addressed the challenging task of monitoring the formation and evolution of the solid-electrolyte interphase (SEI) layer. An evolution occurs in the SEI layer during discharge from a composition dominated by a higher scattering length density (SLD) lithium salt, to a lower SLD lithium salt for the ethylene carbonate/dimethyl carbonate (EC/DMC) mixture employed. By comparing half-cells containing different solvent deuteration levels, we show that it is possible to observe both SEI formation and lithium intercalation occurring concurrently at the low voltage region in which lithium intercalates into the hard carbon. These results demonstrate that SANS can be employed to monitor complicated electrochemical processes occurring in rechargeable batteries, in a manner that simultaneously provides information on the composition and microstructure of the electrode.

  18. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

    NASA Astrophysics Data System (ADS)

    Chai, M. N.; Isa, M. I. N.

    2016-06-01

    The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10‑4 S cm‑1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.

  19. Intermediate-temperature operation of solid oxide fuel cells (IT-SOFCs) with thin film proton conductive electrolyte

    NASA Astrophysics Data System (ADS)

    Kariya, T.; Uchiyama, K.; Tanaka, H.; Hirono, T.; Kuse, T.; Yanagimoto, K.; Henmi, M.; Hirose, M.; Kimura, I.; Suu, K.; Funakubo, H.

    2015-12-01

    A novel solid oxide fuel cell (SOFC) structure, which is fabricated on a Pd-plated porous stainless steel substrate, was proposed for low-temperature SOFC operation. The surface of the substrate was covered with Pd layer without any pores, which reduces the difficulty of depositing thin film electrolyte on the porous substrate. A 1.2-μm thick proton conductive Sr(Zr0.8Y0.2)O3-δ (SZYO) layer and the cathode of a 100-nm thick (La0.6Sr0.4)(Co0.2Fe0.8)O3-δ (LSCF) layer were deposited on the Pd-plated substrates by the pulsed laser deposition (PLD) method. The low temperature operations at 400 and 450 °C were demonstrated with proposed SOFC cells.

  20. Density functional and molecular dynamics studies of solid electrolyte Li7La3Zr2O12

    NASA Astrophysics Data System (ADS)

    Johannes, Michelle; Hoang, Khang; Bernstein, Noam

    2012-02-01

    Garnet-type structured Li7La3Zr2O12(LLZO) is considered as a promising candidate for Li-ion battery solid electrolytes because of its high ionic conductivity and electrochemical and chemical stability. We use first-principles density-functional theory calculations and molecular dynamics simulations to reveal the underlying mechanism that drives a tetragonal to cubic transition at elevated temperatures, and also to explain why the cubic phase can be stabilized with the incorporation of a certain amount of impurities such as Al. We show that the relationship between the observance of a cubic phase and the measurement of a substantially higher ionic conductivity is a secondary effect not directly attributable to the presence of Al in the crystal structure. Suggestions for enhancing the ionic conductivity in LLZO will also be discussed.