Science.gov

Sample records for solid electrolyte based

  1. 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).

  2. Application of sodium-ion-based solid electrolyte in electrostatic tuning of carrier density in graphene.

    PubMed

    Zhao, Jialin; Wang, Meng; Zhang, Xuefu; Lv, Yue; Wu, Tianru; Qiao, Shan; Song, Shufeng; Gao, Bo

    2017-06-09

    Using a solid electrolyte to tune the carrier density in thin-film materials is an emerging technique that has potential applications in both basic and applied research. Until now, only materials containing small ions, such as protons and lithium ions, have been used to demonstrate the gating effect. Here, we report the study of a lab-synthesised sodium-ion-based solid electrolyte, which shows a much stronger capability to tune the carrier density in graphene than previously reported lithium-ion-based solid electrolyte. Our findings may stimulate the search for solid electrolytes better suited for gating applications, taking benefit of many existing materials developed for battery research.

  3. 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.

  4. Lithium-ion-based solid electrolyte tuning of the carrier density in graphene

    NASA Astrophysics Data System (ADS)

    Zhao, Jialin; Wang, Meng; Li, Hui; Zhang, Xuefu; You, Lixing; Qiao, Shan; Gao, Bo; Xie, Xiaoming; Jiang, Mianheng

    2016-10-01

    We have developed a technique to tune the carrier density in graphene using a lithium-ion-based solid electrolyte. We demonstrate that the solid electrolyte can be used as both a substrate to support graphene and a back gate. It can induce a change in the carrier density as large as 1 × 1014 cm‑2, which is much larger than that induced with oxide-film dielectrics, and it is comparable with that induced by liquid electrolytes. Gate modulation of the carrier density is still visible at 150 K, which is lower than the glass transition temperature of most liquid gating electrolytes.

  5. Lithium-ion-based solid electrolyte tuning of the carrier density in graphene

    PubMed Central

    Zhao, Jialin; Wang, Meng; Li, Hui; Zhang, Xuefu; You, Lixing; Qiao, Shan; Gao, Bo; Xie, Xiaoming; Jiang, Mianheng

    2016-01-01

    We have developed a technique to tune the carrier density in graphene using a lithium-ion-based solid electrolyte. We demonstrate that the solid electrolyte can be used as both a substrate to support graphene and a back gate. It can induce a change in the carrier density as large as 1 × 1014 cm−2, which is much larger than that induced with oxide-film dielectrics, and it is comparable with that induced by liquid electrolytes. Gate modulation of the carrier density is still visible at 150 K, which is lower than the glass transition temperature of most liquid gating electrolytes. PMID:27698413

  6. Superionic solids and solid electrolytes

    SciTech Connect

    Laskar, A. ); Chandra, S. )

    1989-01-01

    Superionic solids and solid electrolytes are a special group of materials showing high ionic conductivity with tremendous technological potential. This book updates the present status of the field. Starting with an overview of recent trends in solid state ionics, the book ends with the assessment of future implications. Different theoretical, experimental (including NMR), and materials aspects have been covered along with applications. Important materials covered include alkali and silver ion conductors, fluorites, Nasicon, heterogeneous solid electrolytes, and glasses. The theoretical topics covered in this volume include phenomenological models, fractal techniques, the pre-exponential problem, and fluctuations.

  7. Fluoride-based, low temperature solid electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Oh, Seajin; Otagawa, T.; Madou, M.

    Lanthanum fluoride electrolytes were tested to determine whether fluoride electrolytes can be used as fuel cell electrolytes at low temperatures. The planar-type fuel cell were operated in oxygen/hydrogen gases with nickel oxide/nickel as the anode and a perovskite structure oxide (La(0.6)Sr(0.4)CoO3) as the cathode. In order to reduce the fuel cell operating temperature while maintaining the highest possible current, various thin and thick film techniques were assessed. They include e-beam evaporation and dc plasma spray methods. Fuel cells incorporating plasma-sprayed LaF3 films yielded a short-circuit current density on the order of 0.4 mA/sq cm at 450 C, and the current density under an overpotential of 0.2V showed no sign of decay over 17 hours. In the co-ionic (fluoride and oxide ion) conduction mode, the lanthanum fluoride electrolyte based fuel cells could sustain current in oxygen/hydrogen gases.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    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.

  9. 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.

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  13. Novel structured gadolinium doped ceria based electrolytes for intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Timurkutluk, Bora; Timurkutluk, Cigdem; Mat, Mahmut D.; Kaplan, Yuksel

    Novel three-layered intermediate temperature solid oxide fuel cell (SOFC) electrolytes based on gadolinium doped ceria (GDC) are developed to suppress the electronic conductivity of GDC, to improve the mechanical properties of the cell and to minimize power loss due to mixed conductive nature of GDC. Three different electrolytes are fabricated by sandwiching thin YSZ, ScSZ and ScCeSZ between two relatively thick GDC layers. An electrolyte composed of pure GDC is also manufactured for comparison. NiO/GDC and LSCF/GDC electrodes are then coated on the electrolytes by a screen printing route. SEM results show that it is possible to obtain dense and crack free thin layers of YSZ, ScSZ and ScCeSZ between two GDC layers without delamination. Performance measurements indicate that interlayered thin electrolytes act as an electronic conduction barrier and improve open circuit voltages (OCVs) of GDC based cells.

  14. The Light Attracting Effect of Pyridine Derivatives Based Quasi-Solid Electrolyte in Dye-Sensitized Solar Cell.

    PubMed

    Cai, Molang; Bell, John; Dai, Songyuan

    2016-06-01

    The pyridine derivatives are added into acetonitrile based electrolyte to establish framework, then form the quasi solid electrolyte. The ion diffusion of cetylpyridinium chloride and cetylpyridinium bromide based electrolytes is enhanced comparing with the ion diffusion of reference acetonitrile electrolyte. The ordered structure of cetylpyridinuium chloride quasi solid electrolyte has been observed by SEM images. Light scattering effect of cetylpyridinuium chloride quasi solid electrolyte is evidenced by the larger resulted by transmitted and scattered spectra. The light harvesting efficiency of device based on C16Cl is much higher than acetonitrile based device. The cell efficiency of C16Cl and C16Br based device are 5.72% and 6.02%, which are 41% and 48% higher than acetonitrile liquid electrolyte based device. The C16l based device produces low cell efficiency 2.06%, which is 49% decrease compare to the blank device due to the limitation of iodide-triodide transportation in the iodide framework.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. All solid-state electric double-layer capacitors based on alkaline polyvinyl alcohol polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Yang, Chun-Chen; Hsu, Sung-Ting; Chien, Wen-Chen

    Solid-state electrochemical double-layer capacitors (ELDCs) based on alkaline polyvinyl alcohol (PVA) solid polymer electrolytes (SPEs) are prepared. Electrochemical capacitance performance of these capacitors is studied by cyclic voltammetry, galvanostatic charge-discharge testing, and ac impedance spectroscopy. For comparison, two types of EDLC cells are constructed and tested. It is found that an EDLC with a PVA polymer electrolyte exhibits much higher capacitance and longer cycle-life than one with the PP/PE separator. The specific capacitance for the EDLC with the PVA-based SPE is in the range of 100-112 F g -1, and depends on the scan rate or the charge-discharge current rates. The results also indicate that the solid-state EDLC shows a relatively stable specific capacitance of 100 F g -1 after 1000 cycles. The findings suggest that the PVA-based SPE is a promising material for use in EDLCs.

  2. Integrated Solid-Electrolyte Construction

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1982-01-01

    Proposed construction method for electrolytic cells would integrate porous surface electrodes into a block of solid electrolyte. Porous electrodes would facilitate unrestricted gas flow thereby improving cell performance. Electrode wire mesh is embedded at surface of solid electrolyte. Construction would assure high electrode conductance and low resistance to gas flow.

  3. Improved properties of LiBOB-based solid polymer electrolyte by additive incorporation

    NASA Astrophysics Data System (ADS)

    Ratri, C.; Sabrina, Q.; Lestariningsih, T.; Wigayati, E.

    2017-04-01

    Solid polymer electrolytes comprising of poly(vinylidene fluoride) (PVdF) and lithium bis (oxalato) borate (LiBOB) have been prepared using solution casting technique. Having an important role in lithium-ion battery system, electrolyte is required to have high ability to transfer lithium ions between electrodes. Safety aspect is the main reason for the development of solid polymer electrolyte as advancement from conventional liquid electrolyte. Nevertheless, solid polymer electrolyte generally has lower conductivities compared to liquid electrolyte. In this research, ceramic additives, as well as plasticiser materials, have been incorporated within the solid polymer electrolyte system to improve its conductivity. Addition of TiO2 filler has proven to increase ionic conductivity by two orders of magnitude. Further improvement was seen in the incorporation of PEG plasticiser, where ionic conductivity was enhanced by three orders of magnitude.

  4. 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.

  5. Photocured PEO-based solid polymer electrolyte and its application to lithium-polymer batteries

    NASA Astrophysics Data System (ADS)

    Kang, Yongku; Kim, Hee Jung; Kim, Eunkyoung; Oh, Bookeun; Cho, Jae Hyun

    A solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) is prepared by photocuring of polyethylene glycol acrylates. The conductivity is greatly enhanced by adding low molecular weight poly(ethylene glycol) dimethylether (PEGDME). The maximum conducticity is 5.1×10 -4 S cm -1 at 30°C. These electrolytes display oxidation stability up to 4.5 V against a lithium reference electrode. Reversible electrochemical plating/stripping of lithium is observed on a stainless steel electrode. Li/SPE/LiMn 2O 4 as well as C(Li)/SPE/LiCoO 2 cells have been fabricated and tested to demonstrate the applicability of the resulting polymer electrolytes in lithium-polymer batteries.

  6. 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)).

  7. Germanium sulfide-based solid electrolytes for non-volatile memory

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Muralikrishnan

    Programmable Metallization Cell (PMC) technology involves the storage of data as reduced metal ions in a solid electrolyte. Earlier work on Selenide-based (Ag-Ge-Se) PMC devices requires relatively low back-end-of-line processing (BEOL) since the electrolyte may undergo undesirable changes at process temperatures in excess of 200°C. This dissertation is focused on Sulfide-based (Ag/Cu-Ge-S) solid electrolytes which have better temperature stability and the PMC technology based on these materials is compatible with most BEOL process in CMOS Integrated Circuits. The devices fabricated using Ag-Ge-S and Cu-Ge-S solid electrolytes were tested after annealing at 300°C and 430°C. Extensive material analysis was performed on both the systems in an effort to understand the behavior of the devices at elevated temperatures. Electrical characterization testing involved standard memory characterization techniques such as quasi-static measurements tests, retention tests, speed tests, elevated temperature operation tests and endurance tests. The Ag-Ge-S PMC devices were made with different compositions to find out the optimum composition which would ensure reliable operation even after the high temperature anneal. The Sulfide-based PMC devices were also tested for reconfigurable logic applications with special test structures that would demonstrate the low resistance connections that can be achieved by programming the PMC elements using higher currents. Optimum composition of the starting glass was found from the material and data analysis, to ensure reliable operation of the Sulfide-based PMC devices with no degradation in the electrical characteristics even after the typical BEOL anneal.

  8. Toward garnet electrolyte-based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface.

    PubMed

    Fu, Kun Kelvin; Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

    2017-04-01

    Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet-type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10(-3) to 10(-4) S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm(2) for the pristine garnet/Li and 75 ohm·cm(2) for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.

  9. 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.

  10. 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.

  11. 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.

  12. 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).

  13. Ionic Conductivity Trends with Molecular Weight in PEO and PEO-Based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Teran, Alexander; Mullin, Scott; Wanakule, Nisita; Panday, Ashoutosh; Balsara, Nitash

    2010-03-01

    Poly(ethylene oxide) based polymer electrolytes with lithium bis(trifluoromethane)sulfonamide (LiTFSI) salt remain one of the most promising class of solid polymer electrolyte for rechargeable lithium metal batteries. Among those, poly(styrene-b-ethyleneoxide) (SEO) doped with LiTFSI has been shown to exhibit acceptable levels of conductivity while possessing a sufficiently high modulus to suppress the growth of dendrites. The purpose of this study is to explore the molecular weight dependence on conductivity for the PEO/LiTFSI system to which previous studies have alluded, but never quantified, and contrast this with the observed molecular weight dependence of SEO reported in previous work. Conductivities were measured using AC impedance spectroscopy over a broad range of temperatures and molecular weights beyond those reported in the literature.

  14. All solid-state comb-like network polymer electrolytes based on poly(methylsiloxane)

    NASA Astrophysics Data System (ADS)

    Jiang, Hui; Fang, Shibi

    All solid-state comb-like network polymer electrolytes (CNPE) based on poly(methylsiloxane) with pendant PEO chains as internal plasticizing chains (IPC) have been designed and synthesized. Ultraviolet (UV) polymerization method was applied for the curing of CNPEs. Effects of the network structure on the conductive properties and mechanical properties were discussed in details. Ionic conductivity of the prepared CNPE is one order of magnitude larger than those without IPCs, which suggests that the expected drop of conductivity caused by crosslinking has been well compensated by the introduction of IPCs. Maximum conductivity of 1.01 × 10 -4 S cm -1 and maximum tensile strength of 0.66 MPa were obtained at 30 °C. Electrochemical stability and electrolyte/electrodes interfacial stability properties were evaluated by cyclic voltammetry and ac impedance, respectively.

  15. Composite solid polymer electrolyte membranes

    DOEpatents

    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.

  16. 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.

  17. 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

  18. All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

    PubMed

    Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

    2012-02-17

    All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

  19. Composite Solid Electrolyte For Lithium Cells

    NASA Technical Reports Server (NTRS)

    Peled, Emmanuel; Nagasubramanian, Ganesan; Halpert, Gerald; Attia, Alan I.

    1994-01-01

    Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

  20. Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes.

    PubMed

    Wang, Chengwei; Gong, Yunhui; Liu, Boyang; Fu, Kun; Yao, Yonggang; Hitz, Emily; Li, Yiju; Dai, Jiaqi; Xu, Shaomao; Luo, Wei; Wachsman, Eric D; Hu, Liangbing

    2017-01-11

    Solid-state electrolytes are known for nonflammability, dendrite blocking, and stability over large potential windows. Garnet-based solid-state electrolytes have attracted much attention for their high ionic conductivities and stability with lithium metal anodes. However, high-interface resistance with lithium anodes hinders their application to lithium metal batteries. Here, we demonstrate an ultrathin, conformal ZnO surface coating by atomic layer deposition for improved wettability of garnet solid-state electrolytes to molten lithium that significantly decreases the interface resistance to as low as ∼20 Ω·cm(2). The ZnO coating demonstrates a high reactivity with lithium metal, which is systematically characterized. As a proof-of-concept, we successfully infiltrated lithium metal into porous garnet electrolyte, which can potentially serve as a self-supported lithium metal composite anode having both high ionic and electrical conductivity for solid-state lithium metal batteries. The facile surface treatment method offers a simple strategy to solve the interface problem in solid-state lithium metal batteries with garnet solid electrolytes.

  1. The Doping Effect on Conductivity and Glass Transition Temperature of Solid Polymeric Electrolyte Based on Polyvinylchloride (pvc)

    NASA Astrophysics Data System (ADS)

    Abd. Rahman, Mohd. Yusri; Mat Salleh, Muhammad; Abu Talib, Ibrahim; Yahaya, Muhamad

    2002-12-01

    Solid electrolyte materials have been widely used in electrochemical devices such as batteries, solar cells and displays. This is because of its advantages over the liquidmaterial.This paper is concerned with the preparation of solid polymeric electrolyte based on polyvinylchloride (PVC) and its conductivity .The effect of percentage by weight of dopant material (LiClO4) on conductivity and glass transition temperature of the electrolyte was studied by using differential scanning calorimeter (DSC) and impedance spectroscopy technique. The electrolyte doped with 4.8%wt LiClO4 exhibits the highest conductivitiy of 7 × 10-6Scm-1 at room temperature but has the lowest glass transition temperature of 36.37°C. The other results are presented in this paper.

  2. 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

  3. Electrolyte for batteries with regenerative solid electrolyte interface

    DOEpatents

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

    2017-08-01

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

  4. 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.

  5. Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks

    NASA Astrophysics Data System (ADS)

    Fu, Guopeng; Dempsey, Janel; Izaki, Kosuke; Adachi, Kaoru; Tsukahara, Yasuhisa; Kyu, Thein

    2017-08-01

    In an effort to fabricate highly conductive, stable solid-state polymer electrolyte membranes (PEM), polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction between polyethylene glycol diamine and ethylene carbonate. Subsequently, dimethacrylate groups were chemically attached to both ends of PEGBC to afford polyethylene glycol-bis-carbamate dimethacrylate (PEGBCDMA) precursor having crosslinking capability. The melt-mixed ternary mixtures consisting of PEGBCDMA, succinonitrile plasticizer, and lithium trifluorosulphonyl imide salt were completely miscible in a wide compositional range. Upon photo-crosslinking, the neat PEGBCDMA network was completely amorphous exhibiting higher tensile strength, modulus, and extensibility relative to polyethylene glycol diacrylate (PEGDA) counterpart. Likewise, the succinonitrile-plasticized PEM network containing PEGBCDMA remained completely amorphous and transparent upon photo-crosslinking, showing superionic conductivity, improved thermal stability, and superior tensile properties with improved capacity retention during charge/discharge cycling as compared to the PEGDA-based PEM.

  6. An Electrically Driven and Readable Molecular Monolayer Switch Based on a Solid Electrolyte.

    PubMed

    Marchante, Elena; Crivillers, Núria; Buhl, Moritz; Veciana, Jaume; Mas-Torrent, Marta

    2016-01-04

    The potential application of molecular switches as active elements in information storage has been demonstrated through numerous works. Importantly, such switching capabilities have also been reported for self-assembled monolayers (SAMs). SAMs of electroactive molecules have recently been exploited as electrochemical switches. Typically, the state of these switches could be read out through their optical and/or magnetic response. These output reading processes are difficult to integrate into devices, and furthermore, there is a need to use liquid environments for switching the redox-active molecular systems. In this work, both of these challenges were overcome by using an ionic gel as the electrolyte medium, which led to an unprecedented solid-state device based on a single molecular layer. Moreover, electrochemical impedance has been successfully exploited as the output of the system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes.

    PubMed

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-24

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li6.4La3Zr1.4Ta0.6O12, LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li2CO3. Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g(-1)carbon at 20 μA cm(-2). Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g(-1)carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g(-1)carbon at 20 μA cm(-2) and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage.

  8. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes

    PubMed Central

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-01

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li6.4La3Zr1.4Ta0.6O12, LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li2CO3. Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g−1carbon at 20 μA cm−2. Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g−1carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g−1carbon at 20 μA cm−2 and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage. PMID:28117359

  9. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-01

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li6.4La3Zr1.4Ta0.6O12, LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li2CO3. Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g-1carbon at 20 μA cm-2. Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g-1carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g-1carbon at 20 μA cm-2 and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage.

  10. 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.

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

    PubMed

    Kammoun, M; Berg, S; Ardebili, H

    2015-11-07

    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.

  12. Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations.

    PubMed

    Sun, Bing; Mindemark, Jonas; Morozov, Evgeny V; Costa, Luciano T; Bergman, Martin; Johansson, Patrik; Fang, Yuan; Furó, István; Brandell, Daniel

    2016-04-14

    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.

  13. Nanocomposite polymer electrolyte based on Poly(ethylene oxide) and solid super acid for lithium polymer battery

    NASA Astrophysics Data System (ADS)

    Xi, Jingyu; Tang, Xiaozhen

    2004-07-01

    This Letter reports a novel PEO-based nanocomposite polymer electrolyte by using solid super acid SO 42-/ZrO 2 as filler. XRD, DSC, and FT-IR results prove the strong Lewis acid-base interactions between SO 42-/ZrO 2 and PEO chains. The addition of SO 42-/ZrO 2 can enhance the ionic conductivity and the lithium ion transference number of the electrolyte. The highest room temperature ionic conductivity of 2.1 × 10 -5 S cm -1 is obtained for the sample PEO 12-LiClO 4-7%SO 42-/ZrO 2. The excellent performances such as good compatibility with lithium electrode, and broad electrochemical stability window suggest that PEO-LiClO 4-SO 42-/ZrO 2 nanocomposite electrolyte can be used as electrolyte materials for lithium polymer batteries.

  14. Antireduction Insulator For Solid-Electrolyte Cell

    NASA Technical Reports Server (NTRS)

    Shlichta, Paul J.

    1990-01-01

    Depletion of oxygen from electrolyte prevented. Proposed to add layer of electrical insulation between solid electrolyte and portion of porous negative electrode under negative metal contact in solid-electrolyte cell. Helps maintain efficiency of cell by preventing "shadow" effect degrading portion of electrolyte under negative contact and sometimes near seals.

  15. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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

  17. 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.

  18. 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.

  19. Iodine-Pseudohalogen Ionic Liquid-Based Electrolytes for Quasi-Solid-State Dye-Sensitized Solar Cells.

    PubMed

    Lennert, Annkatrin; Sternberg, Michelle; Meyer, Karsten; Costa, Rubén D; Guldi, Dirk M

    2017-10-04

    In the current work, novel symmetrically alkyl-substituted imidazolium-based ionic liquids have been synthesized featuring either iodide (I(-)) or selenocyanate (SeCN(-)) as counteranions. Physicochemical assays based on spectroscopy and electrochemistry techniques have been performed to identify the best ionic liquid for application as electrolytes in quasi-solid-state dye-sensitized solar cells (qssDSSC). The latter were mixed with additives such as 4-tert-butylpyridine (4tbpy) and guanidinium thiocyanate (GuSCN) to optimize electrode surface coverage, ionic diffusion, and dye regeneration. In addition, we demonstrate that electrolytes containing a mixture of I2 and (SeCN)2 enhance the open-circuit voltage of the final quasi-solid-state device by up to 70 mV. As such, iodine-pseudohalogen electrolytes reveal in qssDSSCs a good balance between dye regeneration and hole transport and, in turn, enhance the overall solar energy conversion efficiency by 70% with respect to reference qssDSSCs with iodine-based electrolytes. Finally, devices with the iodine-pseudohalogen electrolyte show a 1000 h stable efficiency of 7-8% under outdoor temperature operation conditions and 1 sun illumination.

  20. All solid-state redox supercapacitors based on supramolecular 1,5-diaminoanthraquinone oligomeric electrode and polymeric electrolytes

    NASA Astrophysics Data System (ADS)

    Hashmi, S. A.; Suematsu, Shunzo; Naoi, Katsuhiko

    Supramolecular conducting oligomeric 1,5-diaminoanthraquinone (DAAQ)-based all solid-state redox supercapacitors have been fabricated with the solid polymer electrolyte, poly vinyl alcohol (PVA)-H 3PO 4 blend and polymeric gel electrolyte poly methyl methacrylate (PMMA)-ethylene carbonate (EC)-propylene carbonate (PC)-tetra ethyl ammonium perchlorate (TEAClO 4) system. The films of gel electrolyte of the optimized composition PMMA (35 wt.%)-EC:PC (1:1 v/v)-1 M TEAClO 4 and polymer electrolyte PVA-H 3PO 4 (50:50 w/w) blend exhibited high ionic conductivity (10 -4 to 10 -3 S cm -1 at room temperature) with good mechanical strength, suitable for application in electrochemical supercapacitors. The capacitors have been characterized using a.c. impedance spectroscopy, linear sweep voltammetry and prolonged cyclic test. The maximum capacitance value of 3.7-5.4 mF cm -2 (equivalent to single electrode capacitance 125-184 F g -1 of DAAQ electrode) has been observed for the PMMA-gel electrolyte based capacitor. This corresponds to the energy density 92-135 Wh kg -1. System based on the proton-conducting PVA-H 3PO 4 polymer blend, however has relatively lower capacitance of 1.1-4.0 mF cm -2 (equivalent to single electrode capacitance of 36-136 F g -1).

  1. 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

  2. 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.

  3. Optical and Electrical Characteristics of Silver Ion Conducting Nanocomposite Solid Polymer Electrolytes Based on Chitosan

    NASA Astrophysics Data System (ADS)

    Aziz, Shujahadeen B.; Rasheed, Mariwan A.; Abidin, Zul H. Z.

    2017-10-01

    Optical and electrical properties of nanocomposite solid polymer electrolytes based on chitosan have been investigated. Incorporation of alumina nanoparticles into the chitosan:silver triflate (AgTf) system broadened the surface plasmon resonance peaks of the silver nanoparticles and shifted the absorption edge to lower photon energy. A clear decrease of the optical bandgap in nanocomposite samples containing alumina nanoparticles was observed. The variation of the direct-current (DC) conductivity and dielectric constant followed the same trend with alumina concentration. The DC conductivity increased by two orders of magnitude, which can be attributed to hindrance of silver ion reduction. Transmission electron microscopy was used to interpret the space-charge and blocking effects of alumina nanoparticles on the DC conductivity and dielectric constant. The ion conduction mechanism was interpreted based on the dependences of the electrical and dielectric parameters. The dependence of the DC conductivity on the dielectric constant is explained empirically. Relaxation processes associated with conductivity and viscoelasticity were distinguished based on the incomplete semicircular arcs in plots of the real and imaginary parts of the electric modulus.

  4. Optical and Electrical Characteristics of Silver Ion Conducting Nanocomposite Solid Polymer Electrolytes Based on Chitosan

    NASA Astrophysics Data System (ADS)

    Aziz, Shujahadeen B.; Rasheed, Mariwan A.; Abidin, Zul H. Z.

    2017-06-01

    Optical and electrical properties of nanocomposite solid polymer electrolytes based on chitosan have been investigated. Incorporation of alumina nanoparticles into the chitosan:silver triflate (AgTf) system broadened the surface plasmon resonance peaks of the silver nanoparticles and shifted the absorption edge to lower photon energy. A clear decrease of the optical bandgap in nanocomposite samples containing alumina nanoparticles was observed. The variation of the direct-current (DC) conductivity and dielectric constant followed the same trend with alumina concentration. The DC conductivity increased by two orders of magnitude, which can be attributed to hindrance of silver ion reduction. Transmission electron microscopy was used to interpret the space-charge and blocking effects of alumina nanoparticles on the DC conductivity and dielectric constant. The ion conduction mechanism was interpreted based on the dependences of the electrical and dielectric parameters. The dependence of the DC conductivity on the dielectric constant is explained empirically. Relaxation processes associated with conductivity and viscoelasticity were distinguished based on the incomplete semicircular arcs in plots of the real and imaginary parts of the electric modulus.

  5. Performance/design formulation for a solid polymer based acid electrolyte hydrogen/air fuel cell

    NASA Astrophysics Data System (ADS)

    Sandhu, S. S.; Fellner, J. P.

    Mathematical development of preliminary performance/design equations for a hydrogen/air, solid polymer acid electrolyte based fuel cell is presented. The development is based on the principles of transport phenomena, intrinsic electrochemical kinetics, and classical thermodynamics. The developed formulation is intended to quantitatively describe the mass fraction profiles of the chemical species, hydrogen and oxygen, in the cell anode and cathode diffusion and electrocatalytic reaction layers as a function of the distance in the proton transport direction at an axial distance parallel to the cell anode or cathode channel flow. Given the cell geometry, chemical species and charge transport, and intrinsic electrochemical kinetic parameters, the developed formulation can be employed to compute the species local mass fluxes and predict the cell anode and cathode cell overvoltages for a desired geometric current density. The presented single cell performance predictive formulation has also been linked to the formulation needed to predict the performance of a stack of a number of identical PEMFCs connected in series.

  6. 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}.

  7. A new composite cathode for intermediate temperature solid oxide fuel cells with zirconia-based electrolytes

    NASA Astrophysics Data System (ADS)

    Zhang, Cuijuan; Huang, Kevin

    2017-02-01

    Improving the electrocatalytic activity of electrode materials is vitally important to achieve practically meaningful performance for intermediate temperature solid oxide fuel cells (IT-SOFCs). The present work develops a composite cathode consisting of an electronic conductor Sr-doped LaMnO3 (LSM) and an ionic conductor Y- and Ce- co-doped Bi2O3 (BYC7). BYC7 is an excellent oxide-ion conductor, exhibiting a high and stable ionic conductivity of 0.008 S cm-1 at 500 °C. The polarization resistance of LSM-BYC7 cathode in a symmetrical cell with doped ZrO2 as electrolyte varies from 5.76 at 500 °C to 0.25 Ω cm2 at 650 °C. The surface diffusion and charge transfer at the triple phase boundaries are the rate determining steps based on the dependence of polarization resistance on partial pressure of oxygen. The maximum power density of a ZrO2-based anode-supported cell with LSM-BYC7 composite cathode is 56.4, 154.6, 327.9, and 451.0 mW cm-2 at 500, 550, 600, and 650 °C respectively. AC impedance analysis reveals that the performance of IT-SOFC prepared in this study is actually limited by the anode, not by LSM-BYC7 cathode.

  8. 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.

  9. 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.

  10. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1993-11-01

    We have synthesized a new series of brownmillerite solid electrolyte phases Ba{sub 2}GdIn{sub 1-x}Ga{sub x}O{sub 5} (x = 0,0.2,0.4) with the x = 0.2 phase exhibiting an unusually low E. relative to both the observed ionic conductivity in this phase and to E{sub a}s observed in similar compounds. We attribute measured ionic conductivities to a lack of available charge carriers in Ba{sub 2}GdIn{sub 0.8}Ga{sub 0.2}O{sub 5}. However, the low E{sub a} supports the premise that brownmillerite solid electrolyte structures are suitable for supporting high ionic conductivity. Current work is focusing on enhancing the amount of charge carriers in these materials by systematically introducing disorder into the brownmillerite lattice.

  11. Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

    2016-10-01

    A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

  12. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    NASA Astrophysics Data System (ADS)

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-11-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1-xCaxAlO3-δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400-500 °C. The response current value at -300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

  13. 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.

  14. 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.

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

    PubMed

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

    2017-11-01

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

  16. Effect of Plasticizers on Methyl Cellulose-Based Alkaline Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Rosli, N. H. A.; Harun, N. I.; Taib, M. F. M.; Saaid, S. I. Y.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A.

    2010-07-01

    A preliminary investigation of biopolymer electrolytes based on methyl cellulose (MC), potassium hydroxide (KOH), and various plasticizing additives are described in this presentation. The electrolyte films with the composition of KOH between 5 and 50 wt.% (with respect to MC), were prepared by the solution cast technique. The biopolymer was first dissolved in distilled water with controlled amount of the KOH. The homogenous solutions obtained were evaporated in vacuum oven at constant temperature (40 °C) to form thin films. The room temperature ionic conductivity of the solvent free electrolytes films were characterized using impedance spectroscopy technique. In general, the unplasticized KOH based electrolytes were found to show moderate ionic conductivity up to 5.64×10-6 S/cm. Upon the addition of plasticizers PC and EC the conductivity rises to 6.70×10×6 and up to 3.58×10-3 respectively. However, the addition of propylene carbonate (PC) and ethylene carbonate (EC) as a plasticizing additive lowered the mechanical stability. To control mechanical stability, the addition of such plasticizers is limited the suitability use of the electrolytes.

  17. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations.

    PubMed

    Zhu, Yizhou; He, Xingfeng; Mo, Yifei

    2015-10-28

    First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aid of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.

  18. Poly(ethylene oxide)-Based Composite Electrolytes Filled with Periodic Mesoporous Silica for Solid State Ionics

    NASA Astrophysics Data System (ADS)

    Tominaga, Yoichi; Morita, Masahiro; Asai, Shigeo; Sumita, Masao

    Mesoporous silica (MPS) was used for poly(ethylene oxide) (PEO)-based solid polymer electrolytes as novel inorganic filler. For improvement in ionic conductivity in solid state, a room temperature ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate, was introduced into periodic nano-tunnels of MPS, and the modified MPS (IL-MPS) was filled with PEO-LiBF4 electrolyte. Ionic conductivity of neat-MPS-filled composites was approximately 4-fold higher than that of the original electrolyte. On the other hand, the conductivity was more than 11-fold enhanced by addition of IL-MPS, to be more than 10-6 S/cm at 30°C and at least 10 wt% silica contents. The conductivity increased with increasing IL-MPS contents, to be a maximum value of approximately 3×10-6 S/cm at 30°C and at 40 wt%. Dynamic mechanical measurements for neat- and IL-MPS composites revealed that the addition of fillers improves storage modulus of PEO-based electrolytes at room temperature. The addition of IL-MPS was able to realize the improvement in both ionic conductivity and storage modulus.

  19. Investigations on Poly (ethylene oxide) (PEO) - blend based solid polymer electrolytes for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Koduru, H. K.; Iliev, M. T.; Kondamareddy, K. K.; Karashanova, D.; Vlakhov, T.; Zhao, X.-Z.; Scaramuzza, N.

    2016-10-01

    Polymer blend electrolytes based on Polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP), complexed with NaIO4 salt and Graphene oxide (GO) are investigated in the present report. The electrolytes are prepared by a facile solution cast technique. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) are employed to study the influence of ion-polymer interactions on the micro structural properties of blend electrolytes. Measurements of electrical conductivity of the blend polymer complexes have been performed by using complex impedance spectroscopy in the frequency range 1 Hz - 1 MHz and within the temperature range 303 K - 343 K.A study on electrical conductivity properties of GO doped ‘salt complexed electrolyte’ systems is presented.

  20. 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.

  1. In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO2 Lithium Batteries

    PubMed Central

    Chai, Jingchao; Ma, Jun; Wang, Jia; Liu, Xiaochen; Liu, Haisheng; Zhang, Jianjun; Chen, Liquan

    2016-01-01

    Nowadays it is extremely urgent to seek high performance solid polymer electrolyte that possesses both interfacial stability toward lithium/graphitic anodes and high voltage cathodes for high energy density solid state batteries. Inspired by the positive interfacial effect of vinylene carbonate additive on solid electrolyte interface, a novel poly (vinylene carbonate) based solid polymer electrolyte is presented via a facile in situ polymerization process in this paper. It is manifested that poly (vinylene carbonate) based solid polymer electrolyte possess a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 9.82 × 10−5 S cm−1 at 50 °C. Moreover, it is demonstrated that high voltage LiCoO2/Li batteries using this solid polymer electrolyte display stable charge/discharge profiles, considerable rate capability, excellent cycling performance, and decent safety characteristic. It is believed that poly (vinylene carbonate) based electrolyte can be a very promising solid polymer electrolyte candidate for high energy density lithium batteries. PMID:28251055

  2. In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO2 Lithium Batteries.

    PubMed

    Chai, Jingchao; Liu, Zhihong; Ma, Jun; Wang, Jia; Liu, Xiaochen; Liu, Haisheng; Zhang, Jianjun; Cui, Guanglei; Chen, Liquan

    2017-02-01

    Nowadays it is extremely urgent to seek high performance solid polymer electrolyte that possesses both interfacial stability toward lithium/graphitic anodes and high voltage cathodes for high energy density solid state batteries. Inspired by the positive interfacial effect of vinylene carbonate additive on solid electrolyte interface, a novel poly (vinylene carbonate) based solid polymer electrolyte is presented via a facile in situ polymerization process in this paper. It is manifested that poly (vinylene carbonate) based solid polymer electrolyte possess a superior electrochemical stability window up to 4.5 V versus Li/Li(+) and considerable ionic conductivity of 9.82 × 10(-5) S cm(-1) at 50 °C. Moreover, it is demonstrated that high voltage LiCoO2/Li batteries using this solid polymer electrolyte display stable charge/discharge profiles, considerable rate capability, excellent cycling performance, and decent safety characteristic. It is believed that poly (vinylene carbonate) based electrolyte can be a very promising solid polymer electrolyte candidate for high energy density lithium batteries.

  3. Transport Properties Of PbI2 Doped Silver Oxysalt Based Amorphous Solid Electrolytes

    NASA Astrophysics Data System (ADS)

    Shrisanjaykumar Jayswal, Manishkumar

    Solid electrolytes are a class of materials that conduct electricity by means of motion of ions like Ag+, Na+, Li +, Cu+, H+, F-, O -2 etc. in solid phase. The host materials include crystalline, polycrystalline, glasses, polymers and composites. Ion conducting glasses are one of the most sought after solid electrolytes that are useful in various electrochemical applications like solid state batteries, gas sensors, supercapacitors, electrochromic devices, to name a few. Since the discovery of fast silver ion transport in silver oxyhalide glasses at the end of the 1960s, many glasses showing large ionic conductivity up to 10-4 10-2 S/cm at room temperature have been developed, chiefly silver and copper ion conductors. The silver ion conducting glasses owe their high ionic conductivity mainly to stabilized alpha-AgI. AgI, as we know, undergoes a structural phase transition from wurtzite (beta phase) at room temperature to body centered cubic (alpha phase) structure at temperatures higher than 146 °C. The alpha-AgI possesses approximately six order of higher ionic conductivity than beta-AgI. The high ionic conductivity of alpha-AgI is attributed to its molten sublattice type of structure, which facilitates easy Ag+ ion migration, like a liquid. And hence, several attempts have been made to stabilize it at room temperature in crystalline as well as non-crystalline hosts like oxide and non-oxide glasses. Recently, in order to stabilize AgI in glasses, instead of directly doping it, indirect routes have also been explored. Where, a metal iodide salt along with silver oxide or silver phosphate is taken and an exchange reaction permitted by Hard and Soft, Acid and Base (HSAB) principle occurs between the two and AgI and metal oxide form in the glass forming melt. Work done in the present thesis has been organized in seven chapters as follows: Chapter 1: A review and background information of different solid electrolyte materials and their development is presented. Along

  4. Lithium battery chemistries enabled by solid-state electrolytes

    NASA Astrophysics Data System (ADS)

    Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei

    2017-02-01

    Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.

  5. High-performance flexible all-solid-state microbatteries based on solid electrolyte of lithium boron oxynitride

    NASA Astrophysics Data System (ADS)

    Song, Seung-Wan; Lee, Ki-Chang; Park, Ho-Young

    2016-10-01

    Rapidly growing interest and demand for wearable electronics require the development of flexible and lightweight all-solid-state batteries as power sources that guarantee high performance and safety with the absence of the risk of fire or explosion that can occur with traditional liquid electrolyte systems. Herein, we successfully fabricate new flexible all-solid-state microbatteries integrating a solid electrolyte film of lithium boron oxynitride (LiBON) on a flexible substrate using sophisticated thin-film fabrication technology. The new microbattery of Li/LiBON/LiCoO2 exhibits excellent mechanical integrity even under severe bending and twisting test conditions, enabling the realization of flexible microbatteries. The microbatteries demonstrate superior electrochemical cycling stability relative to conventional batteries, delivering an outstanding capacity retention of 90% on the 1000th cycle. Furthermore, operation at various temperatures from -10 °C to +60 °C and fast charging within 3-6 min are achieved. With various types of flexible substrates, the microbatteries can provide diverse opportunities for flexible and wearable electronics.

  6. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    PubMed Central

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-01-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1−xCaxAlO3−δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400–500 °C. The response current value at −300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles. PMID:27886278

  7. 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.

  8. All-solid state supercapacitors operating at 3.5 V by using ionic liquid based polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Ayalneh Tiruye, Girum; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2015-04-01

    All-solid state supercapacitors (SCs) using Ionic Liquid based Polymer Electrolyte (IL-b-PE) and activated carbon were assembled and characterized electrochemically. IL-b-PE consisted of a binary blend of a polymeric ionic liquid (PIL), poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (pDADMATFSI), and their corresponding ionic liquid (IL), N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR14TFSI) in a ratio of 40:60,w/w respectively. Assembling of supercapacitors simply consists of facing two impregnated electrodes without the need of additional separator. Several all-solid state SCs with impregnation ratios (IL-b-PE mass/active material mass) ranging from 5 to 18 were characterized. An all-solid state SC with impregnation ratio of 7 showed the best performance with specific capacitance (Cam) and real energy (Ereal) of 100 F g-1 and 32 Wh kg-1, respectively. After increasing temperatures to 60 °C, the performance of SCs further improved exhibiting Ereal values of 42 Wh kg-1 at 1 mA cm-2. These figures of merit are only slightly lower than those obtained for convectional SCs using pure PYR14TFS and much higher as compared with other solid SCs based on conventional polymer electrolytes. This is mainly due to the high electrochemical stability of this IL-b-PE that allows these solid SCs to operate at maximum voltages as high as 3.5 V for the first time.

  9. Semiconductor/Solid Electrolyte Junctions for Optical Information Storage. Electrochromic Effects on Heptylviologen Incorporated within a Solid Polymer Electrolyte Cell.

    DTIC Science & Technology

    1986-05-15

    cathode5 . Electrochromic devices based upon these electrochemically reversible viologen redox couples would greatly benefit by their incorporation...electrolyte analogs. Here we wish to discuss some recent work from our laboratory on solid- state electrochromic cells in which heptyl viologen (HV2+) was...OPTICAL INFORMATION STORAGE. ELECTROCHROMIC EFFECTS QN HEPTYLVIOLOGEN INCORPORATED WITHIN A SOLID POLYMER ELECTROLYTE CELL By Anthony F. Sammells and

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Phase-field based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li 3 PS 4

    DOE PAGES

    Hu, Jia-Mian; Wang, Bo; Ji, Yanzhou; ...

    2017-09-07

    Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. But, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. In using nanoporous β-Li3PS4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functional theory (DFT)more » calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14×10-3 S/cm) and experimentally measured bulk Li-ion conductivity (8.93×10-7 S/cm) of β-Li3PS4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. Furthemore, when porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74×10-4 S/cm) that is in good agreement with experimental data (1.64×10-4 S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.« less

  16. Phase-Field Based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li3PS4.

    PubMed

    Hu, Jia-Mian; Wang, Bo; Ji, Yanzhou; Yang, Tiannan; Cheng, Xiaoxing; Wang, Yi; Chen, Long-Qing

    2017-09-27

    Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. However, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. Using nanoporous β-Li3PS4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functional theory (DFT) calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14 × 10(-3) S/cm) and experimentally measured bulk Li-ion conductivity (8.93 × 10(-7) S/cm) of β-Li3PS4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. When porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74 × 10(-4) S/cm) that is in good agreement with experimental data (1.64 × 10(-4) S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.

  17. 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

    2016-03-02

    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.

  18. Compositional effect investigation by addition PEG, PEO plasticiser of LiBOB based solid polymer electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sabrina, Qolby; Ratri, Christin Rina

    2017-08-01

    Development polymer electrolyte with high ionic conductivity is main of object in solid state electrolyte will be potential application as electrolyte batteries. Casting method have been used to prepared solid polymer electrolyte. Adding polyethylene(glycol) PEG and Poly(ethylene oxide) PEO as polymer matrix be made of poly(vinylidene fluoride) (PVdF) and lithium bis(oxalato) borate (LiBOB) to improve structure morphology and impedance characterization of solid electrolyte. The ratio of PEG and PEO is varied to study effect on the conductivity. Electro impedance spectroscopy (EIS) studies are carried out on the prepared samples. The impedance measurement show that the conductivity with composition PVdF- PEG- LiBOB 10% better than the other varieties to applied as solid electrolyte batteries. SEM morphology PVdF- PEG- LiBOB 10% sample showed the low crystallinity was caused by interaction between lithium salt and polymer. With their properties the solid polymer electrolyte are considered as promising candidates of applications for lithium ion batteries.

  19. Effect of Al2O3 nanoparticles in plasticized PMMA-LiClO4 based solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Pal, P.; Ghosh, A.

    2017-05-01

    We have studied the broadband complex conductivity spectra covering a 0.01 Hz-3 GHz frequency range for plasticized PMMA-LiClO4 based solid polymer electrolyte embedded with Al2O3 nanoparticle. We have analyzed the conductivity spectra using the random free-energy barrier model (RBM) coupled with electrode polarization contribution in the low frequency region and at high temperatures. The temperature dependence of the ionic conductivity obtained from the analysis has been analyzed using Vogel-Tammann-Fulcher equation. The maximum ionic conductivity ˜ 1.93×10-4 S/cm has been obtained for 1 wt% Al2O3 nanoparticle.

  20. 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

  1. Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

    PubMed Central

    Fu, Kun (Kelvin); Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D.; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

    2017-01-01

    Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10−3 to 10−4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries. PMID:28435874

  2. Composite Solid Electrolyte for Li Battery Applications

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Attia, A. I.; Halpert, G.; Peled, E.

    1993-01-01

    The electrochemical, bulk and interfacial properties of the polyethylene oxide (PEO) based composite solid electrolyte (CSE) comprising LiI, PEO, and Al2O3 have been evaluated for Li battery applications. The bulk interfacial and transport properties of the CSEs seem to strongly depend on the alumina particle size. For the CSE films with 0.05 micron alumina while the bulk conductivity is around 10(exp -4) (mho/cm) at 103 C, the Li ion transport number seems to be close to unity at the same temperature. Compared to the PEO electrolyte this polymer composite electrolyte seems to exhibit robust mechanical and interfacial properties. We have studied three different films with three different alumina sizes in the range 0.01-0.3 micron. Effects of Al2O3 particle size on the electrochemical performance of polymer composite electrolyte is discussed. With TiS2 as cathode a 10 mAh small capacity cell was charged and discharged at C/40 and C/20 rates respectively.

  3. Composite Solid Electrolyte for Li Battery Applications

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Attia, A. I.; Halpert, G.; Peled, E.

    1993-01-01

    The electrochemical, bulk and interfacial properties of the polyethylene oxide (PEO) based composite solid electrolyte (CSE) comprising LiI, PEO, and Al2O3 have been evaluated for Li battery applications. The bulk interfacial and transport properties of the CSEs seem to strongly depend on the alumina particle size. For the CSE films with 0.05 micron alumina while the bulk conductivity is around 10(exp -4) (mho/cm) at 103 C, the Li ion transport number seems to be close to unity at the same temperature. Compared to the PEO electrolyte this polymer composite electrolyte seems to exhibit robust mechanical and interfacial properties. We have studied three different films with three different alumina sizes in the range 0.01-0.3 micron. Effects of Al2O3 particle size on the electrochemical performance of polymer composite electrolyte is discussed. With TiS2 as cathode a 10 mAh small capacity cell was charged and discharged at C/40 and C/20 rates respectively.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

    PubMed

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

    2017-09-05

    Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li1.5 Al0.5 Ti1.5 (PO4 )3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g(-1) at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Fundamental Aspects of Ion Transport in Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Narayanan, S. R.

    1994-01-01

    Solid electrolytes (also termed as superionic solids or fast ion conductors) are characterized by high electrical conductivity, comparable to concentrated liquid electrolytes or even molten salt electrolytes, made possible by rapid transport of ions in the crystalline lattice.

  10. 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.

  11. CP actuator based on chemically-deposited polypyrrole and PU based solid polymer electrolyte working in air

    NASA Astrophysics Data System (ADS)

    Choi, Hwa Jeong; Lim, Hyun-Ok; Chung, Ildoo; Ryu, Kwang-Sun; Jo, Nam-Ju

    2007-07-01

    Conducting polymers (CPs), such as polypyrrole, polythiophene and polyaniline, are unique in that they have switchable properties due to their two or more mechanically stable oxidation state. Thus, their films or coatings can be easily switched by the application of small voltage and current to change volume during their electrochemical redox process. In particular, polypyrrole (PPy) has been studied most extensively because of its high electrical conductivity and good environmental stability under ambient condition. In this work, we have studied a new CP actuator, fully polymeric, assembled with two PPy film electrodes and a solid polymer electrolyte (SPE), polyurethane/Mg(ClO 4) II. Polyurethanes (PUs) were synthesized from 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (1,4-BD) and three types of polyols, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and PPG-block-PEG-block-PPG (PPG-co-PEG). The chemical polymerization of PPy by immersion in Py monomer aqueous solution and oxidant aqueous solution is an adequate method to prepare PU/PPy composite film as actuator. To find the proper thickness of PPy coating layer for actuation, we measured the displacement of actuators according to the thickness of PPy coating layer. And, the displacement of all actuators was discussed in connection with the properties of SPE and PPy. All the results obtained in this work show the feasibility of electrochemomechanical devices based on PPy and SPE film able to work in air.

  12. Conducting polymer actuator based on chemically deposited polypyrrole and polyurethane-based solid polymer electrolyte working in air

    NASA Astrophysics Data System (ADS)

    Choi, Hwa-Jeong; Song, Young-Min; Chung, Ildoo; Ryu, Kwang-Sun; Jo, Nam-Ju

    2009-02-01

    Conducting polymers (CPs), such as polypyrrole, polythiophene, and polyaniline, are unique in that they have switchable properties due to their two or more mechanically stable oxidation states. Thus, their films or coatings can be easily switched by the application of a small voltage and current to change their volume during electrochemical redox processes. In particular, polypyrrole (PPy) has been studied most extensively because of its high electrical conductivity and good environmental stability under ambient conditions. In this work, we have studied a new CP actuator, fully polymeric, assembled with two PPy film electrodes and a solid polymer electrolyte (SPE), polyurethane/Mg(ClO4)2. Polyurethanes (PUs) were synthesized from 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (1,4-BD) and three types of polyol: poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and PPG-block-PEG-block-PPG (PPG-co-PEG). The chemical polymerization of PPy by immersion in Py monomer aqueous solution and oxidant aqueous solution is an adequate method to prepare PU/PPy composite film as an actuator. To find the proper thickness of the PPy coating layer for actuation, we measured the displacements of the actuators according to the thickness of the PPy coating layer. The displacement of all actuators is discussed in connection with the properties of the SPE and PPy. All the results obtained in this work show the feasibility of electrochemomechanical devices based on PPy and SPE film being able to work in air.

  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

    2016-06-08

    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.

  14. 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

  15. Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

    PubMed

    Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

    2015-03-28

    Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

  16. 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

  17. Thin films of solid electrolytes and studies of their surface

    NASA Astrophysics Data System (ADS)

    Pan, Xiaoren; Gu, Zhi X.

    1991-11-01

    Much research work has been done on the materials of solid electrolytes and their applications. Solid electrolytes or fast ionic conductors are generally used in solid state batteries and solid state ionic devices. In the utilization of solid electrolytes, thin film forms have practical advantages. They will make the devices and batteries miniaturization which is particularly important for certain applications such as microelectronic devices, space programs, and integrated circuits of self-contained power. So preparation of thin films of solid electrolytes and studies of their surfaces are significant. There has been interest in the properties of amorphous ionic conductors, as glasses have acknowledged advantages over crystalline electrolytes, including physical isotropy, the absence of grain boundaries, and continuously-variable composition. Furthermore, many glasses based on silver halides have conductivities as high as 10 Scm-1 at room temperature. So we have chosen the quaternary system AgI-Ag2O-P2O5-B2O3 as the basic materials, prepared thin films, studied their properties, and constructed thin film electrolytic batteries.

  18. High-temperature solid-state dye-sensitized solar cells based on organic ionic plastic crystal electrolytes.

    PubMed

    Li, Qing; Zhao, Jie; Sun, Baoquan; Lin, Bencai; Qiu, Lihua; Zhang, Yueguang; Chen, Xiaojian; Lu, Jianmei; Yan, Feng

    2012-02-14

    Organic ionic plastic crystal, 1-ethyl-1-methyl pyrrolidinium iodide (P(12) I), is employed as the solid-state electrolytes for dye-sensitized solar cells. The fabricated solid-state devices show an overall power conversion efficiency of ~5.8% under AM 1.5 radiation (50 mW/cm(2) ) and excellent long-term stability at 80 °C.

  19. 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.

  20. 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

    2016-05-26

    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.

  1. 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

  2. Water-resistant, solid-state, dye-sensitized solar cells based on hydrophobic organic ionic plastic crystal electrolytes.

    PubMed

    Li, Shichao; Qiu, Lihua; Shi, Chengzhen; Chen, Xiaojian; Yan, Feng

    2014-02-26

    Water-resistant, solid-state, dye-sensitized solar cells with excellent long-term stability at 100% relative humidity and at 50 °C are fabricated on the basis of a novel hydrophobic organic ionic plastic crystal electrolyte and hybrid redox couple. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The Effects of Lithium Triflate (LiCF3SO3) on the PMMA-based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Chew, K. W.; Chen, S. S.; Pang, W. L.; Tan, C. G.; Osman, Z.

    2010-03-01

    The effects of Lithium triflate salt (LiCF3SO3), on the poly (methyl methacrylate) (PMMA)-based solid polymer electrolytes plasticized with propylene carbonate (PC) solvated in Tetrahydrofuran (THF) have been studied through a.c impedance spectroscopy and infrared spectroscopy. Lithium triflate was incorporated into the predetermined PMMA/PC system that has the highest value of ionic conductivity. In current investigations, four combination systems: Pure PMMA, (PMMA+PC) systems, (PMMA+LiCF3SO3) and (PMMA+PC+LiCF3SO3) systems were prepared using the solution cast method. Solutions were stirred for numerous hours to obtain a homogenous solution before it is poured into the petri dishes under ambient temperature to form the solid electrolyte thin film. The films were then removed from petri discs and transferred into the dessicator for further drying prior to the different tests. From the characterization done through the a.c impedance spectroscopy, the highest room temperature ionic conductivity in the pure PMMA sample, (PMMA+PC) system and (PMMA+LiCF3SO3) system is 2.83×10-12 Scm-1, 4.39×10-11 Scm-1 and 3.93×10-6 Scm-1 respectively. The conductivity for (PMMA+PC+LiCF3SO3) system was obtained with the 30 wt% of lithium triflate, which is 2.48×10-5 Scm-1. Infrared spectroscopy shows that complexation occurred between the polymer and the plasticizer, and the polymer and plasticizer and salt. The interactions have been studied in the C=O band, C-O-C band and the O-CH3 band.

  4. Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

    2016-12-01

    We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

  5. Secondary calcium solid electrolyte high temperature battery

    NASA Astrophysics Data System (ADS)

    Sammells, A. F.; Schumacher, B.

    1986-01-01

    The application of polycrystalline Ca(2+) conducting beta-double prime alumina solid electrolytes to a new type of high temperature battery is investigated, experimentally. The negative electrode in the battery consisted of a calcium-silicon alloy whose redox electrochemistry was mediated by the solid electrolyte via molten salt eutectic CaCl2 (51.4 m/o), and CaI2 (mp 550 C). The molten salt and the calcium alloy material were separated from the positive active material via the Ca2 Ca(2+) conducting polycrystalline electrolyte. The positive electrode consisted of a solid-state matrix having related crystallographic structure. The electrochemical reversibility of the cells was measured at 580 C. The charge-discharge characteristics of the cells are plotted vs. time in a graph.

  6. Highly efficient solid-state dye-sensitized solar cells based on hexylimidazolium iodide ionic polymer electrolyte prepared by in situ low-temperature polymerization

    NASA Astrophysics Data System (ADS)

    Wang, Guiqiang; Yan, Chao; Zhang, Juan; Hou, Shuo; Zhang, Wei

    2017-03-01

    Solid-state dye-sensitized solar cells (DSCs) are fabricated using a novel ionic polymer electrolyte containing hexylimidazolium iodide (HII) ionic polymer prepared by in situ polymerization of N,N‧-bis(imidazolyl) hexane and 1,6-diiodohexane without an initiator at low temperature (40 °C). The as-prepared HII ionic polymer has a similar structure to alkylimidazolium iodide ionic liquid, and the imidazolium cations are contained in the polymer main chain; so, it can act simultaneously as the redox mediator in the electrolyte. By incorporating an appropriate amount of 1,3-dimethylimidazolium iodide (DMII) in HII ionic polymer (DMII/HII ionic polymer = 0.7:1, weight ratio), the conductivity of the ionic polymer electrolyte is greatly improved due to the formation of Grotthuss bond exchange. In addition, in situ synthesis of ionic polymer electrolyte guarantees a good pore-filling of the electrolyte in the TiO2 photoanode. As a result, the solid-state DSC based on the ionic polymer electrolyte containing HII ionic polymer and DMII without iodine achieves a conversion efficiency of 6.55% under the illumination of 100 mW cm-2 (AM 1.5), which also exhibits a good at-rest stability at room temperature.

  7. Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

    NASA Astrophysics Data System (ADS)

    Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

    2017-01-01

    A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm‑1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

  8. Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

    PubMed Central

    Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

    2017-01-01

    A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm−1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications. PMID:28067301

  9. Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts.

    PubMed

    Bitner-Michalska, Anna; Nolis, Gene M; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

    2017-01-09

    A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, "liquid-like" high conductivities (>1 mS cm(-1)) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

  10. Nanoscale electrochemical characterization of a solid-state electrolyte using a manganese-based thin-film probe.

    PubMed

    Liu, Yi-Hung; Liao, Sin-Syu; Haochih Liu, Bernard

    2016-12-08

    A Li-Mn-O thin-film electrode probe has been developed via a facile synthesis process, which enables nanoscale electrochemical investigation of the solid-state electrolyte LiPON. Detailed information of ion transport can be obtained by the thin-film probe, rather than the macroscale electrochemical impedance analysis. It is clarified from the nanoscale analysis that the charge transfer resistance at the Li-Mn-O/LiPON interface dominates the localized impedance, while it can be significantly reduced rather than the electrolyte resistance by applying a DC bias.

  11. A supramolecular gel electrolyte formed from amide based co-gelator for quasi-solid-state dye-sensitized solar cell with boosted electron kinetic processes

    NASA Astrophysics Data System (ADS)

    Huo, Zhipeng; Wang, Lu; Tao, Li; Ding, Yong; Yi, Jinxin; Alsaedi, Ahmed; Hayat, Tasawar; Dai, Songyuan

    2017-08-01

    A supramolecular gel electrolyte (Tgel > 100 °C) is formed from N,N‧-1,8-octanediylbis-dodecanamide and iodoacetamide as two-component co-gelator, and introduced into the quasi-solid-state dye-sensitized solar cells (QS-DSSCs). The different morphologies of microscopic network between two-component and single-component gel electrolytes have influence on the diffusion of redox couple in gel electrolytes and further affect the electron kinetic processes in QS-DSSCs. Compared with the single-component gel electrolyte, the two-component gel electrolyte has less compact gel network and weaker steric hindrance effect, which provides more effective charge transport channel for the diffusion of I3/I- redox couple. Meanwhile, the sbnd NH2 groups of iodoacetamide molecules interact with Li+ and I3-, which also accelerate the transport of I3-/I- and decrease in the I3- concentration in the TiO2/electrolyte interface. As a result, nearly a 12% improvement in short-circuit photocurrent density (Jsc) and much higher open circuit potential (Voc) are found in the two-component gel electrolyte based QS-DSSC. Consequently, the QS-DSSC based on the supramolecular gel electrolyte obtains a 17% enhancement in the photoelectric conversion efficiency (7.32%) in comparison with the QS-DSSC based on the single-component gel electrolyte (6.24%). Furthermore, the degradations of these QS-DSSCs are negligible after one sun light soaking with UV cutoff filter at 50 °C for 1000 h.

  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. Improved Preparation Of Solid-Electrolyte Films

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan; Attia, Alan

    1995-01-01

    Modified process ensures compatability among components. Improved chemical-blending procedure produces composite material for thin, large-area solid-electrolyte films for lithium batteries. Films have uniform compositions and dimensionally stable. Transport number of their lithium cations is high, close to unity. Batteries made with these films expected to have energy and power densities up to about 100 W h/kg and 100 W/kg, respectively. Previous version of composite material described in "Composite Solid Electrolyte for Lithium Cells" (NPO-18694).

  14. Structure and properties of solid polymer electrolyte based on chitosan and ZrO2 nanoparticle for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Sudaryanto, Yulianti, Evi; Patimatuzzohrah

    2016-02-01

    In order to develop all solid lithium ion battery, study on the structure and properties of solid polymer electrolytes (SPE) based on chitosan has been done. The SPE were prepared by adding Zirconia (ZrO2) nanoparticle and LiClO4 as lithium salt into the chitosan solution followed by casting method. Effect of the ZrO2 and salt concentration to the structure and properties of SPE were elaborated using several methods. The structure of the SPE cast film, were characterized mainly by using X-ray diffractometer (XRD). While the electrical properties of SPE were studied by electrochemical impedance spectrometer (EIS) and ion transference number measurement. XRD profiles show that the addition of ZrO2 and LiClO4 disrupts the crystality of chitosan. The decrease in sample crytalinity with the nanoparticle and salt addition may increase the molecular mobility result in the increasing sample conductivity and cathionic transference number as determined by EIS and ion transference number measurement, respectively. The highest ionic conductivity (3.58×10-4 S cm-1) was obtained when 4 wt% of ZrO2 nanoparticle and 40 wt% of LiClO4 salt were added to the chitosan. The ion transference number with that composition was 0.55. It is high enough to be used as SPE for lithium ion battery.

  15. Influence of nano-sized LSCF cathode and its firing temperature on electrochemical performance in oxygen-excess-type solid electrolyte (OESE)-based fuel cells

    NASA Astrophysics Data System (ADS)

    Mieda, Hiroyuki; Mineshige, Atsushi; Saito, Atsushi; Yazawa, Tetsuo; Yoshioka, Hideki; Mori, Ryohei

    2014-12-01

    Dense films of an oxygen-excess-type solid electrolyte (OESE) based on Mg-doped lanthanum silicate (MDLS) were fabricated and applied to electrolyte materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). To obtain dense MDLS films on NiO-MDLS porous substrates, a conventional spin-coating technique using the MDLS printable paste, obtained by mixing nano-sized MDLS particles and a dispersant, was employed. The Ni-MDLS anode supported single cells were then fabricated by printing porous cathode layer onto the electrolyte film surface. By optimizing fabrication conditions of an MDLS film and cathode, the highly active cathode/OESE interface (ASR = 0.23 Ω cm2 at 873 K) were successfully obtained, which resulted in high power density of 0.166 W cm-2 at 873 K in the fuel cell test when operated with argon-diluted hydrogen and pure oxygen as the fuel and the cathode gas, respectively.

  16. 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.

  17. 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.

  18. 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.

  19. Solid-polymer-electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    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 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.

  20. Structural, Vibrational, Thermal And Electrical Characterization Of Gamma Radiation-Crosslinked Poly (Vinyl Alcohol)-Based Solid Polymer Electrolytes Blended With LiOHṡH2O Salt

    NASA Astrophysics Data System (ADS)

    Khafagy, Rasha M.; Madani, M.; Badr, Y. A.

    2008-09-01

    Solid polymer electrolytes based on poly(vinyl alcohol) (PVA) blended with different concentrations of LiOHṡH2O salt were prepared using casting and γ-irradiation techniques. The structure and blending of the poly-electrolytes were studied by X-ray diffraction (XRD) and Fourier transform Raman spectroscopy. The thermal properties of these solid polymer electrolytes were examined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The XRD spectra for the electrolytes indicated that the crystalline ratio of PVA decreases with the concentration of Lithium salt. Crystallinity, isotacticity and syndiotacticity percentages were also determined from Raman spectra at different salt concentrations revealing that the crystallinity and the Isotactic regularity of PVA molecule is reduced with salt addition, while the syndiotacticity increases linearly. DSC thermograms showed good accordance with these facts by detecting two melting temperatures corresponding to the two regularities, and these melting points change with the salt content. All characterizing techniques revealed the blend formation between LiOHṡH2O salt and the polymer matrix. To account for the performance of the prepared solid polymer electrolytes, thermally stimulated depolarization current (TSDC) studies of the prepared blends were done. Short circuit TSDC at a polarizing temperature 353 K with a polarizing field of 3 kV cm-1 have been analyzed in the temperature range 300-410 K. Two peaks are evident from the global TSDC measurements on the pure PVA homopolymer. Meanwhile, in all blended samples; there is only one broad peak with a shoulder on the high temperature side due to the relaxation of the poly-blend system. The prepared solid polymer electrolytes showed good charge storage capacity, and moderate current density values near the ambient.

  1. 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.

  2. Solid state double layer capacitor based on a polyether polymer electrolyte blend and nanostructured carbon black electrode composites

    NASA Astrophysics Data System (ADS)

    Lavall, Rodrigo L.; Borges, Raquel S.; Calado, Hállen D. R.; Welter, Cezar; Trigueiro, João P. C.; Rieumont, Jacques; Neves, Bernardo R. A.; Silva, Glaura G.

    An all solid double layer capacitor was assembled by using poly(ethylene oxide)/poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol)-bis(2-aminopropyl ether) blend (PEO-NPPP) and LiClO 4 as polymer electrolyte layer and PEO-NPPP-carbon black (CB) as electrode film. High molecular weight PEO and the block copolymer NPPP with molecular mass of 2000 Da were employed, which means that the design is safe from the point of view of solvent or plasticizer leakage and thus, a separator is not necessary. Highly conductive with large surface area nanostructured carbon black was dispersed in the polymer blend to produce the electrode composite. The electrolyte and electrode multilayers prepared by spray were studied by differential scanning calorimetry, atomic force microscopy (AFM) and impedance spectroscopy. The ionic conductivity as a function of temperature was fitted with the Williams-Landel-Ferry equation, which indicates a conductivity mechanism typical of solid polymer electrolyte. AFM images of the nanocomposite electrode showed carbon black particles of approximately 60 nm in size well distributed in a semicrystalline and porous polymer blend coating. The solid double layer capacitor with 10 wt.% CB was designed with final thickness of approximately 130 μm and delivered a capacitance of 17 F g -1 with a cyclability of more than 1000 cycles. These characteristics make possible the construction of a miniature device in complete solid state which will avoid electrolyte leakage and present a performance superior to other similar electric double layer capacitors (EDLCs) presented in literature, as assessed in specific capacitance by total carbon mass.

  3. Lithium-ion batteries having conformal solid electrolyte layers

    DOEpatents

    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.

  4. 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.

  5. A highly stable sodium solid-state electrolyte based on a dodeca/deca-borate equimolar mixture.

    PubMed

    Duchêne, L; Kühnel, R-S; Rentsch, D; Remhof, A; Hagemann, H; Battaglia, C

    2017-04-11

    Na2(B12H12)0.5(B10H10)0.5, a new solid-state sodium electrolyte is shown to offer high Na(+) conductivity of 0.9 mS cm(-1) at 20 °C, excellent thermal stability up to 300 °C, and a large electrochemical stability window of 3 V including stability towards sodium metal anodes, all essential prerequisites for a stable room-temperature 3 V all-solid-state sodium-ion battery.

  6. Solid electrolyte interphases at Li-ion battery graphitic anodes in propylene carbonate (PC)-based electrolytes containing FEC, LiBOB, and LiDFOB as additives

    NASA Astrophysics Data System (ADS)

    Bhatt, Mahesh Datt; O'Dwyer, Colm

    2015-01-01

    Density functional theory is used to investigate the reactivity, reduction and effect of electrolyte additives such as fluoroethylene carbonate (FEC), lithium bis(oxalate) borate (LiBOB) and lithium difluoro(oxalato) borate (LiDFOB) in propylene carbonate (PC)-based Li-ion battery electrolytes. The structural, thermodynamical and calculated infra-red vibrational analyses indicate that FEC additives reduce prior to PC, providing stable SEI film formation near the graphite anode. The reduction and reaction mechanisms of LiBOB and LiDFOB influence the SEI film composition at the graphite surface. These additives contribute to stable SEI film formation without degradation of the anode structure by PC co-intercalation.

  7. 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.

  8. 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.

  9. 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.

  10. Structural and Ionic Transport Properties of Protonic Conducting Solid Biopolymer Electrolytes Based on Carboxymethyl Cellulose Doped with Ammonium Fluoride.

    PubMed

    Ramlli, M A; Isa, M I N

    2016-11-10

    Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and transference number measurement (TNM) techniques were applied to investigate the complexation, structural, and ionic transport properties of and the dominant charge-carrier species in a solid biopolymer electrolyte (SBE) system based on carboxymethyl cellulose (CMC) doped with ammonium fluoride (NH4F), which was prepared via a solution casting technique. The SBEs were partially opaque in appearance, with no phase separation. The presence of interactions between the host polymer (CMC) and the ionic dopant (NH4F) was proven by FT-IR analysis at the C-O band. XRD spectra analyzed using Origin 8 software disclose that the degree of crystallinity (χc%) of the SBEs decreased with the addition of NH4F, indicating an increase in the amorphous nature of the SBEs. Analysis of the ionic transport properties reveals that the ionic conductivity of the SBEs is dependent on the ionic mobility (μ) and diffusion of ions (D). TNM analysis confirms that the SBEs are proton conductors.

  11. In situ observation of nickel as an oxidizable electrode material for the solid-electrolyte-based resistive random access memory

    SciTech Connect

    Sun, Jun; Wu, Xing; Xu, Feng; Xu, Tao; Sun, Litao; Liu, Qi; Xie, Hongwei; Long, Shibing; Lv, Hangbing; Li, Yingtao; Liu, Ming

    2013-02-04

    In this letter, we dynamically investigate the resistive switching characteristics and physical mechanism of the Ni/ZrO{sub 2}/Pt device. The device shows stable bipolar resistive switching behaviors after forming process, which is similar to the Ag/ZrO{sub 2}/Pt and Cu/ZrO{sub 2}/Pt devices. Using in situ transmission electron microscopy, we observe in real time that several conductive filaments are formed across the ZrO{sub 2} layer between Ni and Pt electrodes after forming. Energy-dispersive X-ray spectroscopy results confirm that Ni is the main composition of the conductive filaments. The ON-state resistance increases with increasing temperature, exhibiting the feature of metallic conduction. In addition, the calculated resistance temperature coefficient is equal to that of the 10-30 nm diameter Ni nanowire, further indicating that the nanoscale Ni conductive bridge is the physical origin of the observed conductive filaments. The resistive switching characteristics and the conductive filament's component of Ni/ZrO{sub 2}/Pt device are consistent with the characteristics of the typical solid-electrolyte-based resistive random access memory. Therefore, aside from Cu and Ag, Ni can also be used as an oxidizable electrode material for resistive random access memory applications.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  13. 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.

  14. 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

  15. 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.

  16. 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.

  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. 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.

  19. 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.

  20. 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.

  1. Synthesis and characterization of substituted garnet and perovskite-based lithium-ion conducting solid electrolytes

    DOE PAGES

    Abreu-Sepúlveda, Maria; Huq, Ashfia; Dhital, Chetan; ...

    2015-09-30

    In this study, titanium, tantalum-substituted Li7La3Zr2-xAxO12 (LLZO, A = Ta, Ti) garnets, and chromium-substituted La(2/3)-xLi3xTi1-yCryO3 (LLTO) perovskites were prepared by a conventional solid-state reaction and the Pechini processes. The desired crystal phases were obtained by varying the calcination temperature and time, as well as the substitution concentration. All samples indicated decomposition of the precursors when heated above 750 °C and formation of the desired phase after heat treatment at higher temperatures. Neutron diffraction data shows the formation of a predominant cubic phase in the case of Ta-LLZO, and monoclinic phase with minor impurity phases for Cr-LLTO. Ionic conductivity for Ti-LLZOmore » (Li7La3Zr1.4Ti0.6O12), Ta-LLZO (Li6.03La3Zr1.533Ta0.46O12), and Cr-LLTO (La(2/3)-xLi3xTi0.9Cr0.1O3) at room temperature were found to be 5.21 × 10–6, 1.01 ×10–6, and 1.2 × 10–4 S cm–1, respectively. The activation energies of the compounds were determined from the Arrhenius plot and were 0.44 eV (Ti0.6-LLZO), 0.54 eV (Ta0.5-LLZO), and 0.20 eV (Cr0.1-LLTO).« less

  2. Anti-perovskite solid electrolyte compositions

    DOEpatents

    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.

  3. 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.

  4. 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.

  5. 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.

  6. Toward electrochromic device using solid electrolyte with polar polymer host.

    PubMed

    Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

    2009-06-11

    Polymer electrolyte is an important component in many multilayer devices such as batteries, fuel cells, and electrochromic devices. The effects of polymer electrolyte solidification on the ionic movement and device performance are presented based on near-infrared (IR) (860-2500 nm) electrochromic (EC) devices using the conducting polymer polyaniline. EC devices using electrolyte with polar polymer host of P(VDF-TrFE) show stable and reversible light modulation up to 65% in gel state and 30% in solid state. This is significantly improved when compared to devices with solidified nonpolar polymer host which retains less than 10% light modulation. Electrochemical impedance combined with in situ light modulation measurement identifies various key characteristics exerted by the electrolyte states on device performance. Gel-state devices are affected by the amount of dissociated ions while ionic movement in the electrolyte bulk and through the electrolyte/EC material interface dictates the light modulation in semisolid devices. For solid-state devices, electronic leakage, ionic dissociation, and interaction with electrochrome molecules have been found to limit the operation.

  7. Synthesis and characterization of substituted garnet and perovskite-based lithium-ion conducting solid electrolytes

    SciTech Connect

    Abreu-Sepúlveda, Maria; Huq, Ashfia; Dhital, Chetan; Dominique E. Williams; Li, Yunchao; Paranthaman, M. Parans; Zaghib, Karim; Manivannan, A.

    2015-09-30

    In this study, titanium, tantalum-substituted Li7La3Zr2-xAxO12 (LLZO, A = Ta, Ti) garnets, and chromium-substituted La(2/3)-xLi3xTi1-yCryO3 (LLTO) perovskites were prepared by a conventional solid-state reaction and the Pechini processes. The desired crystal phases were obtained by varying the calcination temperature and time, as well as the substitution concentration. All samples indicated decomposition of the precursors when heated above 750 °C and formation of the desired phase after heat treatment at higher temperatures. Neutron diffraction data shows the formation of a predominant cubic phase in the case of Ta-LLZO, and monoclinic phase with minor impurity phases for Cr-LLTO. Ionic conductivity for Ti-LLZO (Li7La3Zr1.4Ti0.6O12), Ta-LLZO (Li6.03La3Zr1.533Ta0.46O12), and Cr-LLTO (La(2/3)-xLi3xTi0.9Cr0.1O3) at room temperature were found to be 5.21 × 10–6, 1.01 ×10–6, and 1.2 × 10–4 S cm–1, respectively. The activation energies of the compounds were determined from the Arrhenius plot and were 0.44 eV (Ti0.6-LLZO), 0.54 eV (Ta0.5-LLZO), and 0.20 eV (Cr0.1-LLTO).

  8. Performance of intermediate temperature (600-800 °C) solid oxide fuel cell based on Sr and Mg doped lanthanum-gallate electrolyte

    NASA Astrophysics Data System (ADS)

    Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

    The solid electrolyte chosen for this investigation was La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSGM). To select appropriate electrode materials from a group of possible candidate materials, AC complex impedance spectroscopy studies were conducted between 600 and 800 °C on symmetrical cells that employed the LSGM electrolyte. Based on the results of the investigation, LSGM electrolyte supported solid oxide fuel cells (SOFCs) were fabricated with La 0.6Sr 0.4Co 0.8Fe 0.2O 3-La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSCF-LSGM) composite cathode and nickel-Ce 0.6La 0.4O 2 (Ni-LDC) composite anode having a barrier layer of Ce 0.6La 0.4O 2 (LDC) between the LSGM electrolyte and the Ni-LDC anode. Electrical performances of these cells were determined and the electrode polarization behavior as a function of cell current was modeled between 600 and 800 °C.

  9. Vibrational studies of flexible solid polymer electrolyte based on PCL-EC incorporated with proton conducting NH4SCN

    NASA Astrophysics Data System (ADS)

    Woo, H. J.; Arof, A. K.

    2016-05-01

    A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50 wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94 × 10- 7 Scm- 1 to 3.82 × 10- 5 Scm- 1. Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN- stretching mode (2030-2090 cm- 1). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4+ complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.

  10. Vibrational studies of flexible solid polymer electrolyte based on PCL-EC incorporated with proton conducting NH4SCN.

    PubMed

    Woo, H J; Arof, A K

    2016-05-15

    A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50 wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94 × 10(-7) Scm(-1) to 3.82 × 10(-5) Scm(-1). Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN(-) stretching mode (2030-2090 cm(-1)). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4(+) complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.

  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. An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes.

    PubMed

    Fattah, N F A; Ng, H M; Mahipal, Y K; Numan, Arshid; Ramesh, S; Ramesh, K

    2016-06-06

    Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge-discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g(-1), which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

  14. An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes

    PubMed Central

    Fattah, N. F. A.; Ng, H. M.; Mahipal, Y. K.; Numan, Arshid; Ramesh, S.; Ramesh, K.

    2016-01-01

    Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge–discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g−1, which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application. PMID:28773573

  15. Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

    SciTech Connect

    Black, Hayden T.; Harrison, Katharine Lee

    2016-10-01

    The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Li+ ions, and that the mobility of polymer associated Li+ was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li+ within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.

  16. 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.

  17. 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

  18. 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

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

    PubMed

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

    2013-08-12

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (< 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.

  20. Development of complex hydride-based all-solid-state lithium ion battery applying low melting point electrolyte

    NASA Astrophysics Data System (ADS)

    Suzuki, Shohei; Kawaji, Jun; Yoshida, Koji; Unemoto, Atsushi; Orimo, Shin-ichi

    2017-08-01

    A thermally durable all-solid-state lithium ion battery composed of a complex hydride, oxide electrolytes, and LiNi1/3Mn1/3Co1/3O2 active material is developed. This battery exhibits a discharge capacity of 56 mAh g-1, and the tenth capacity retention ratio is 29% at 150 °C owing to the large contact resistance between the electrolyte layer and the composite positive electrode layer. This large contact resistance is reduced by introducing an adhesive layer comprised of a mixture of LiBH4 and LiNH2 that is easily melted by thermal treatment and fills the voids and pores at the interface between the two layers. As a result, repeated charge-discharge cycles are successfully demonstrated at 150 °C with a high discharge capacity and discharge capacity retention ratio. The first discharge capacity is enhanced to 114 mAh g-1 and the capacity retention ratio at the tenth cycle is improved to 71%. These results demonstrate that using an adhesive layer is an effective measure to reduce the contact resistance and thereby enhance the performance of the battery.

  1. Nanostructured all-solid-state supercapacitor based on Li2S-P2S5 glass-ceramic electrolyte

    NASA Astrophysics Data System (ADS)

    Francisco, Brian E.; Jones, Christina M.; Lee, Se-Hee; Stoldt, Conrad R.

    2012-03-01

    While today's lithium-ion batteries offer acceptable energy storage capability, they lack the ability to be cycled repeatedly more than a couple thousand times. Electrochemical capacitors, i.e., supercapacitors, are being developed whose lifetimes exceed 1 × 106 cycles and power densities surpass those of batteries by several times. Here, we present an all-solid-state supercapacitor using a Li2S-P2S5 glass-ceramic electrolyte as both separator and ion conductor. Three device architectures are examined including two with nanostructured electrodes which incorporate multi-walled carbon nanotubes (MWCNTs). Cyclic voltammograms and electrochemical impedance measurements demonstrate that these devices develop reversible double layer capacitance, and a maximum of 7.75 F/g is achieved in the device constructed by mechanically mixing the nanostructured electrodes. Electrochemical impedance spectroscopy explains non-idealities observed when MWCNTs are incorporated in the electrode layers.

  2. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

    PubMed Central

    Chai, M. N.; Isa, M. I. N.

    2016-01-01

    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. PMID:27265642

  3. 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.

  4. Electrochromic window based on poly(aniline-N-butylsulfonate)s with a radiation-cured solid polymer electrolyte film

    SciTech Connect

    Kim, E.; Lee, K.; Rhee, S.B.

    1997-01-01

    Electrochromic properties of poly(aniline N-butylsulfonate)s (PANBUS) coatings on indium-tin oxide (ITO) glasses exposed to an ion conducting polymer films were investigated. The ion conducting polymer films were prepared via photocross-linking reactions of methoxy polyethylene glycol-mono methacrylate with tri(propylene glycol) diacrylate in the presence of a photoinitiator and LiClO{sub 4}. Mechanical properties of the electrolyte film were enhanced by introducing styrene or butylmethacrylate into the polymer network. Color contrast and optical response of the PANBUS-based window were improved by adding Nafion into the electrolyte. The electrochromic (EC) window assembled with PANBUS, Nafion containing polymer electrolyte film, and tungsten trioxide coated ITO glass (type 2) required less energy for operation ({+-}1.5 V) compared to the EC window without tungsten trioxide film (type 1, {+-}2.0 V). By applying {+-}1.5 V, optical density of the type 2 window changed from zero to maximum of 1.2, corresponding transmission change of higher than 95%. Lifetime tests show that the type 2 window could support more than 2.3 {times} 10{sup 3} cycles, of 60 s duration.

  5. 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.

  6. 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.

  7. 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

  8. 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

    2015-03-09

    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.

  9. 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.

  10. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

    NASA Astrophysics Data System (ADS)

    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.

  11. 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

  12. 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

  13. Lithium stoichiometry of solid electrolytes based on tetragonal Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}

    SciTech Connect

    Il’ina, E.A.; Raskovalov, A.A.; Shevelin, P.Y.; Voronin, V.I.; Berger, I.F.; Zhyravlev, N.A.

    2014-05-01

    Graphical abstract: - Highlights: • We prepared Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 6, 7, 8, 9, 10) by the citrate–nitrate method. • We studied phase composition and conductivity of Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x}. • We proposed a simple method to determine the carbonate impurity content in the solid electrolytes. • The synthesized solid electrolytes Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 7–9) have 1.32–3.49 wt.% Li{sub 2}CO{sub 3}. • The composition with x = 9 has high total conductivity, 7.5 × 10{sup −6} S cm{sup −1}, at room temperature. - Abstract: Samples of Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 6, 7, 8, 9, 10) were synthesized with the citrate–nitrate method. Neutron diffraction studies have shown the presence of lithium carbonate impurities in the synthesized compounds. We propose a simple and effective method to determine the carbonate impurity content in the solid electrolytes. The technique is based on the measurement of the carbon dioxide volume produced from the interaction of the investigated material with acid. Determined in this way, the content of Li{sub 2}CO{sub 3} in the synthesized electrolytes Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}, Li{sub 8}La{sub 3}Zr{sub 2}O{sub 12.5} and Li{sub 9}La{sub 3}Zr{sub 2}O{sub 13} are 1.32 ± 0.04, 1.95 ± 0.06 and 3.49 ± 0.10 wt.%, respectively. From the obtained data, the actual lithium content per formula unit of complex oxide was calculated for the synthesized compounds. The composition with x = 9 had the highest total conductivity, σ = 7.5 × 10{sup −6} S cm{sup −1}, at room temperature. All the investigated electrolytes have an activation energy of approximately 50 kJ mol{sup −1}.

  14. 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.

  15. 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.

  16. 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.

  17. Electric accumulator with a solid electrolyte

    SciTech Connect

    Voinov, M.

    1980-07-29

    An electric accumulator is described that is comprised of an anode compartment containing an anode formed from at least one metal selected from the group consisting of metals belonging to groups IA, IIA, IIB, and IIIB of the periodic table of elements; a cathode compartment containing a cathode formed at least partly from a conducting member comprising a substance capable of accepting electrons, to form anions by cathodic reduction, and an electrolyte consisting of a substance capable of dissolving the product or products generated during discharge of the accumulator, said electrolyte being maintained in a molten state; the anode compartment and cathode compartment being separated from each other by a wall impervious to fluids and formed from a solid mineral electrolyte capable of allowing selective migration of the anode metal in the form of cations; wherein the anode compartment contains a porous matrix adjacent to the anode and at least one salt of the anode metal capable of allowing migration of this metal in the form of cations, said salt being maintained in a molten state and permeating said porous matrix, with said salt and said matrix being interposed between the anode and said separation wall, and wherein said anode metal salt is selected from the group consisting of compounds of the two general formulas: Me(Br/sub 4/)N and Me(AlR/sub 4/)N (in which Me represents a metal selected from the group consisting of metals belonging to groups IA, IIA, IIB, and IIIB of the periodic table of elements, R represents an alkyl or aryl group, and N is 1, 2 or 3, according to the valency of the metal Me) and mixtures of at least two of these compounds.

  18. Ion Engine With Solid-Electrolyte Ion Generator

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1984-01-01

    Working fluid utilized efficiently. Working fluid positive ions conducted through solid electrolyte to outside, then accelerated in external electric field. While in solid-electrolyte material, ions do not recombine with electrons: transported to surface with high ionization efficiency. Provides new way to generate beam of ions for implantation in semiconductors or other applications.

  19. Ion Engine With Solid-Electrolyte Ion Generator

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1984-01-01

    Working fluid utilized efficiently. Working fluid positive ions conducted through solid electrolyte to outside, then accelerated in external electric field. While in solid-electrolyte material, ions do not recombine with electrons: transported to surface with high ionization efficiency. Provides new way to generate beam of ions for implantation in semiconductors or other applications.

  20. Garnet Solid Electrolyte Protected Li-Metal Batteries.

    PubMed

    Liu, Boyang; Gong, Yunhui; Fu, Kun; Han, Xiaogang; Yao, Yonggang; Pastel, Glenn; Yang, Chunpeng; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

    2017-06-07

    Garnet-type solid state electrolyte (SSE) is a promising candidate for high performance lithium (Li)-metal batteries due to its good stability and high ionic conductivity. One of the main challenges for garnet solid state batteries is the poor solid-solid contact between the garnet and electrodes, which results in high interfacial resistance, large polarizations, and low efficiencies in batteries. To address this challenge, in this work gel electrolyte is used as an interlayer between solid electrolyte and solid electrodes to improve their contact and reduce their interfacial resistance. The gel electrolyte has a soft structure, high ionic conductivity, and good wettability. Through construction of the garnet/gel interlayer/electrode structure, the interfacial resistance of the garnet significantly decreased from 6.5 × 10(4) to 248 Ω cm(2) for the cathode and from 1.4 × 10(3) to 214 Ω cm(2) for the Li-metal anode, successfully demonstrating a full cell with high capacity (140 mAh/g for LiFePO4 cathode) over 70 stable cycles in room temperature. This work provides a binary electrolyte consisting of gel electrolyte and solid electrolyte to address the interfacial challenge of solid electrolyte and electrodes and the demonstrated hybrid battery presents a promising future for battery development with high energy and good safety.

  1. Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

    NASA Astrophysics Data System (ADS)

    Obeidat, Amr M.

    Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also

  2. A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte

    NASA Astrophysics Data System (ADS)

    Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

    2016-06-01

    A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating

  3. 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.

  4. Nano scale electrochemistry: Application to solid electrolytes

    NASA Astrophysics Data System (ADS)

    Lee, Minhwan

    Electrochemistry underlies a variety of useful applications such as batteries, fuel cells, and ionic sensors. However, these applications are currently facing numerous problems and challenges such as low power/energy density, short running time, low efficiency, vulnerability to contamination and costliness. The rate of improvement has recently decreased because the fundamental scientific understanding for each electrochemical phenomenon is limited. For the fundamental understanding of physics behind the observed bulk phenomena, direct nano-scale observation should be of great help. In the last few decades, a variety of scanning probe based nano-scale electrical/electrochemical measurement schemes has been developed. The first part of this thesis presents a newly proposed method to obtain AC impedance maps and its application to a few solid electrolytes. The Kelvin Probe Microscopy (KPM) and electrostatic force microscopy (EFM) were considered as alternative methods to investigate ionic systems. A series of surface potential maps could reveal the local distribution and movement of ionic species. However, the geometric convolution between the tip and the surface causes significant artifacts in surface potential measurement. A novel method for suppressing this artifact is presented in this thesis. For the KPM or EFM, due to the long range property of electrostatic interaction and the finite size of probe, the detected electric signal is obscured and subject to complicated interaction. For that reason, the modeling and analysis of these techniques is crucial to obtain accurate information. Numerical calculations using the boundary element method help to link the observed electrostatic signal with quantitative physical parameters. In addition, this simulation shows the impact of the feature size and the tip geometry on the experimental resolution and accuracy. Besides the "probing" or "characterizing" capability, a sharp tip enables highly accurate and nano

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

    DOEpatents

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

    2011-01-11

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

  6. MultiLayer solid electrolyte for lithium thin film batteries

    DOEpatents

    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.

  7. 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.

  8. Study of Solid State Protonic Battery with Composite Solid Electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, K.; Ambekar, P.; Bhoga, S. S.; Tiwari, R. U.

    2002-12-01

    The performance of all solid-state battery fabricated using a protonic solid electrolyte in conjunction with different cathodes namely MnO2, PbO2 and V6O13 is studied systematically. Composite proton conducting solid electrolyte NaH2PO4:Na2HPO4 is prepared following chemical route. The proton transport number determined following both the coulometric and the emf technique are found approximately equal to unity. Particularly, the cells are tested under constant load and constant current drain conditions. Open circuit voltage of cell with MnO2, PbO2 and V6O13 cathodes is found 1.5, 1.8 and 2.22V, respectively. The short-circuit-current 1, 0.5, and 0.3mA, respectively is obtained. The complex impedance analyses of the cell before during and after the discharge are carried. The maximum current drain of the order of 200 μA is achieved.

  9. 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).

  10. Improved performance of Li hybrid solid polymer electrolyte cells

    NASA Astrophysics Data System (ADS)

    Nagasubramanian, G.; Bronstein, Lyudmila; Carini, John

    The seminal research by Wright et al. on polyethylene oxide (PEO) solid polymer electrolyte (SPE) generated intense interest in all solid-state rechargeable lithium batteries. Following this a number of researchers have studied the physical, electrical and transport properties of thin film PEO electrolyte containing Li salt. These studies have clearly identified the limitations of the PEO electrolyte. Chief among the limitations are a low cation transport number (t +), high crystallinity and segmental motion of the polymer chain, which carries the cation through the bulk electrolyte. While low t + leads to cell polarization and increase in cell resistance high T g reduces conductivity at and around room temperatures. For example, the conductivity of PEO electrolyte containing lithium salt is <10 -7 S cm -1 at room temperature. Although modified PEO electrolytes with lower T g exhibited higher conductivity (∼10 -5 S cm -1 at RT) the t + is still very low ∼0.25 for lithium ion. Numerous other attempts to improving t + have met with limited success. The latest approach involves integrating nano domains of inorganic moieties, such as silcate, alumosilicate, etc. within the polymer component. This approach yields an inorganic-organic component (OIC) based polymer electrolyte with higher conductivity and t + for Li + . This paper describes the improved electrical and electrochemical properties of OIC-based polymer electrolyte and cells containing Li anode with either a TiS 2 cathode or Mag-10 carbon electrode. Several solid polymer electrolytes derived from silicate OIC and salt-in-polymer constituent based on Li triflate (LiTf) and PEO are studied. A typical composition of the SPE investigated in this work consists of 600 kDa PEO, lithium triflate (LiTf, LiSO 3CF 3) and 55% of silicate based on (3-glycidoxypropyl)trimethoxysilane and tetramethoxysilane at molar ratio 4:1 and 0.65 mol% of aluminum(tri- sec-butoxide) (GTMOS-Al1-900k-55%). Several pouch cells

  11. Self‐Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery

    PubMed Central

    Wu, Feng; Chen, Nan; Zhu, Qizhen; Tan, Guoqiang; Li, Li

    2016-01-01

    The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator‐based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable “nanogelator” that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid‐like apparent ionic conductivity of 2.93 × 10−3 S cm−1 at room temperature. The results show that the nanogelator, which possess self‐regulating ability, is able to immobilize imidazolium‐, pyrrolidinium‐, or piperidinium‐based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti‐nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes. PMID:27774385

  12. Self-Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery.

    PubMed

    Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li

    2016-01-01

    The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator-based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable "nanogelator" that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid-like apparent ionic conductivity of 2.93 × 10(-3) S cm(-1) at room temperature. The results show that the nanogelator, which possess self-regulating ability, is able to immobilize imidazolium-, pyrrolidinium-, or piperidinium-based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti-nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes.

  13. Controllable growth of nanoscale conductive filaments in solid-electrolyte-based ReRAM by using a metal nanocrystal covered bottom electrode.

    PubMed

    Liu, Qi; Long, Shibing; Lv, Hangbing; Wang, Wei; Niu, Jiebin; Huo, Zongliang; Chen, Junning; Liu, Ming

    2010-10-26

    Resistive memory (ReRAM) based on a solid-electrolyte insulator is a promising nanoscale device and has great potentials in nonvolatile memory, analog circuits, and neuromorphic applications. The underlying resistive switching (RS) mechanism of ReRAM is suggested to be the formation and rupture of nanoscale conductive filament (CF) inside the solid-electrolyte layer. However, the random nature of the nucleation and growth of the CF makes their formation difficult to control, which is a major obstacle for ReRAM performance improvement. Here, we report a novel approach to resolve this challenge by adopting a metal nanocrystal (NC) covered bottom electrode (BE) to replace the conventional ReRAM BE. As a demonstration vehicle, a Ag/ZrO(2)/Cu NC/Pt structure is prepared and the Cu NC covered Pt BE can control CF nucleation and growth to provide superior uniformity of RS properties. The controllable growth of nanoscale CF bridges between Cu NC and Ag top electrode has been vividly observed by transmission electron microscopy (TEM). On the basis of energy-dispersive X-ray spectroscopy (EDS) and elemental mapping analyses, we further confirm that the chemical contents of the CF are mainly Ag atoms. These testing/metrology results are consistent with the simulation results of electric-field distribution, showing that the electric field will enhance and concentrate on the NC sites and control location and orientation of Ag CFs.

  14. 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.

  15. Effect of aqueous pH and electrolyte concentration on structure, stability and flow behavior of non-ionic surfactant based solid lipid nanoparticles.

    PubMed

    Choi, Kyeong-Ok; Aditya, N P; Ko, Sanghoon

    2014-03-15

    The effects of pH and electrolyte concentration on the structure evolution, polymorphism, flow behavior and stability of solid lipid nanoparticles (SLNs), stabilized by the food-grade non-ionic surfactant Tween 80, were investigated. Development of a lipid crystal was governed by thermodynamically stable β- and β'-subunits and relative crystallinity decreased with increasing pH and electrolyte concentration. Aqueous stability and dispersibility increased with increasing pH and decreased with increasing electrolyte concentration. Flow behavior of the SLNs suspension was affected by the electrolyte concentration. However, the pH of the aqueous surfactant medium has not shown any effect on the flow behavior. From the results, it is clear that the pH and electrolyte concentration are among the potential factors which determines the stability and release properties of entrapped materials from SLNs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Solid oxide reversible cells (SORCs) using LaGaO3-based oxide electrolyte and oxide fuel electrode

    NASA Astrophysics Data System (ADS)

    Ishihara, Tatsumi

    2017-09-01

    Activity of La0.8Sr0.2FeO3 (LSF) to the fuel electrode reaction in Solid Oxide Reversible Cells (SORCs) was investigated by using La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) and Ba0.6La0.4CoO3 (BLC) as electrolyte and air electrode, respectively. In electrolysis mode (SOEC), LSF electrode exhibited small overpotential under the atmosphere without H2 co-feeding; the current densities reached -1.42, -0.92, -0.36 A/cm2 at 1.4 V at 900, 800, 700 °C, respectively and H2 formation rate is well agreed with that estimated by Faraday's law. On the other hand, in the SOEC-SOFC reversible mode with the gas composition of 20% steam /20%H2/60%Ar, the maximum power densities of 0.42, 0.28, 0.11 W/cm2 were achieved at 900, 800 and 700 °C, respectively. In addition, the cyclic reversible operation was also investigated at 800 °C, and it was found that the cell showed high stability over 30 cycles. DC polarization measurement suggests that the exchange current density of LSF is 14 mA/cm2 at 700 °C, which is almost the same with that of Ni-YSZ reported. XRD measurement and SEM observation after the reversible measurement suggest that LSF is highly stable under SOEC-SOFC cyclic operation condition. Therefore, LSF is promising as the fuel electrode for SORCs, although the conductivity is not sufficiently high as electrode.

  17. Effect of organic acids and nano-sized ceramic doping on PEO-based solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Park, Jae Won; Jeong, Euh Duck; Won, Mi-Sook; Shim, Yoon-Bo

    Composite solid polymer electrolytes (CSPEs) consisting of polyethyleneoxide (PEO), LiClO 4, organic acids (malonic, maleic, and carboxylic acids), and/or Al 2O 3 were prepared in acetonitrile. CSPEs were characterized by Brewster Angle Microscopy (BAM), thermal analysis, ac impedance, cyclic voltammetry, and tested for charge-discharge capacity with the Li or LiNi 0.5Co 0.5O 2 electrodes coated on stainless steel (SS). The morphologies of the CSPE films were homogeneous and porous. The differential scanning calorimetric (DSC) results suggested that performance of the CSPE film was highly enhanced by the acid and inorganic additives. The composite membrane doped with organic acids and ceramic showed good conductivity and thermal stability. The ac impedance data, processed by non-linear least square (NLLS) fitting, showed good conducting properties of the composite films. The ionic conductivity of the film consisting of (PEO) 8LiClO 4:citric acid (99.95:0.05, w/w%) was 3.25 × 10 -4 S cm -1 and 1.81 × 10 -4 S cm -1 at 30 °C. The conductivity has further improved to 3.81 × 10 -4 S cm -1 at 20 °C by adding 20 w/w% Al 2O 3 filler to the (PEO) 8LiClO 4 + 0.05% carboxylic acid composite. The experimental data for the full cell showed an upper limit voltage window of 4.7 V versus Li/Li + for CSPE at room temperature.

  18. Lithium ion transport of solid electrolytes based on PEO/CF 3SO 3Li and aluminum carboxylate

    NASA Astrophysics Data System (ADS)

    Zygadło-Monikowska, E.; Florjańczyk, Z.; Rogalska-Jońska, E.; Werbanowska, A.; Tomaszewska, A.; Langwald, N.; Golodnitsky, D.; Peled, E.; Kovarsky, R.; Chung, S. H.; Greenbaum, S. G.

    A homogeneous, composite polymer electrolyte (PE) containing poly(ethylene oxide) (PEO), CF 3SO 3Li and 33 wt.% of aluminum carboxylate [RC(O)OAlEt 2] 2 with an oligooxyethylene group R = CH 2CH 2C(O)O(CH 2CH 2O) nCH 3 (n = 7) (AlCarb7), characterized by low glass transition temperature T g = -51.4 °C was prepared. The interaction of aluminum carboxylate with various lithium salts was characterized on the basis of 27Al NMR spectroscopy in CDCl 3 solutions. The bulk conductivity of solid PE with AlCarb7 is of the order of 10 -5 S cm -1 at 60 °C and 10 -4 S cm -1 at 90 °C. Electrochemical tests of Li|PE|Li cells showed a decrease in the R SEI with temperature, stabilizing at about 10 Ω cm -2. The lithium ion transference numbers determined by ac-dc polarization experiments range from 0.7 to 0.9. 7Li, 19F and 1H NMR spectra, the relaxation time and diffusion data were obtained. The calculated lithium transference number t + at 50 °C is equal to 0.995, which suggests practically complete immobilization of the triflate salt anions. In the range of high temperatures (130-180 °C) t + is equal 0.35-0.39. The dependence of t + on temperature should probably be connected with the partial dissociation of the aluminum carboxylate and lithium salt complex.

  19. Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium Ion Batteries.

    PubMed

    Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

    2017-10-06

    Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO4/Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

  20. In situ gelation of Al(III)-4-tert-butylpyridine based metal-organic gel electrolyte for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Dong, Yu-Jie; Rao, Hua-Shang; Cao, Yang; Chen, Hong-Yan; Kuang, Dai-Bin; Su, Cheng-Yong

    2017-03-01

    A novel Al(III)-4-tert-butylpyridine (TBP) gel electrolyte is successfully achieved by a simple and facile in situ gelation method and applied as quasi-solid-state electrolyte for dye-sensitized solar cells (DSSCs). Through directly adding Al3+ into the TBP solution, the induced hydrolysis of Al3+ and the coordination interaction between Al3+ and TBP facilitates the formation of metal-organic gels(MOGs), in which such bi-functional TBP molecules will act as both gelators and active additives to tailor the performance of electrolytes. In addition, the gel electrolytes can largely preserve the properties of liquid electrolyte and penetrate well into the TiO2 photoanode film. Both Al3+ and TBP in the gel electrolytes affect the performance of cells. The Jsc of gel electrolytes decrease with the increasing concentration of gelators due to the enhanced strength and viscosity of the gel electrolytes, while the competition between Al3+ and TBP causes conduction band edge shift and electron recombination, leading to a variation of Voc. Herein, by tuning the molar ratio of Al3+/TBP, an impressive conversion efficiency of 8.25% is obtained, indicating a promising protocol of preparing MOGs not only to achieve high performance in solar cells, but also opens up extended scopes in other energy-related fields such as catalysis.

  1. 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.

  2. 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.

  3. Solid Polymer Electrolytes with Excellent High-Temperature Properties Based on Brush Block Copolymers Having Rigid Side Chains.

    PubMed

    Ping, Jing; Pan, Hongbing; Hou, Ping Ping; Zhang, Meng-Yao; Wang, Xing; Wang, Chao; Chen, Jitao; Wu, Decheng; Shen, Zhihao; Fan, Xing-He

    2017-02-22

    A series of brush block copolymers (BBCPs) with polynorbornene backbones containing poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS, which is a rigid chain) and poly(ethylene oxide) (PEO) side chains were synthesized by tandem ring-opening metathesis polymerizations. The weight fractions of PEO in BBCPs are similar, and the degrees of polymerization (DPs) of PEO side chains are the same while the DPs of PMPCS are different. The bulk self-assembling behaviors were studied by small-angle X-ray scattering (SAXS). The neat BBCPs cannot form ordered nanostructures. However, after the doping of lithium salt, the BBCPs self-assemble into lamellar (LAM) structures. When the DPs of the PEO and PMPCS side chains are similar, the LAM structure is more ordered, which is attributed to the more flat interface between PMPCS and PEO phases. The ionic conductivity (σ) values of the BBCP/lithium salt complex with the most ordered LAM structure at different temperatures were measured. The σ value increases with increasing temperature in the range of 40-200 °C, and the relationship between σ and T fits the Vogel-Tamman-Fulcher (VTF) equation. The σ value at 200 °C is 1.58 × 10(-3) S/cm, which is one of the highest values for PEO-based polymer electrolytes. These materials with high σ values at high temperatures may be used in high-temperature lithium ion batteries.

  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. 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.

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

    NASA Astrophysics Data System (ADS)

    Wang, Weimin

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

  7. Sulfide solid electrolyte with favorable mechanical property for all-solid-state lithium battery.

    PubMed

    Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2013-01-01

    All-solid-state secondary batteries that employ inorganic solid electrolytes are desirable because they are potentially safer than conventional batteries. The ionic conductivities of solid electrolytes are currently attracting great attention. In addition to the conductivity, the mechanical properties of solid electrolytes are important for improving the energy density and cycle performance. However, the mechanical properties of sulfide electrolytes have not been clarified in detail. Here, we demonstrate the unique mechanical properties of sulfide electrolytes. Sulfide electrolytes show room temperature pressure sintering. Ionic materials with low bond energies and a highly covalent character, which is promising for achieving a high ionic conductivity, tend to be suitable for room-temperature processing. The Young's moduli of sulfide electrolytes were measured to be about 20 GPa, which is an intermediate value between those of typical oxides and organic polymers.

  8. Sulfide Solid Electrolyte with Favorable Mechanical Property for All-Solid-State Lithium Battery

    PubMed Central

    Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2013-01-01

    All-solid-state secondary batteries that employ inorganic solid electrolytes are desirable because they are potentially safer than conventional batteries. The ionic conductivities of solid electrolytes are currently attracting great attention. In addition to the conductivity, the mechanical properties of solid electrolytes are important for improving the energy density and cycle performance. However, the mechanical properties of sulfide electrolytes have not been clarified in detail. Here, we demonstrate the unique mechanical properties of sulfide electrolytes. Sulfide electrolytes show room temperature pressure sintering. Ionic materials with low bond energies and a highly covalent character, which is promising for achieving a high ionic conductivity, tend to be suitable for room-temperature processing. The Young's moduli of sulfide electrolytes were measured to be about 20 GPa, which is an intermediate value between those of typical oxides and organic polymers. PMID:23877241

  9. Detailed electrical measurements on sago starch biopolymer solid electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Rahul; Baghel, Jaya; Shukla, S.; Bhattacharya, B.; Rhee, Hee-Woo; Singh, Pramod K.

    2014-12-01

    The biopolymer solid electrolyte has been synthesized and characterized. Potassium iodide (KI) has been added in polymer matrix to develop solid polymer electrolyte. Relationships between electrical, ionic transport parameter and mechanism have been studied in detail. Impedance spectroscopy reveals the detailed electrical studies and ion transport mechanism. The ion dissociation factor is compared with a measured dielectric constant at a fixed frequency. The dielectric data are calculated which support the ionic conductivity data.

  10. 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

  11. The Effects of Lithium Triflate (LiCF{sub 3}SO{sub 3}) on the PMMA-based Solid Polymer Electrolytes

    SciTech Connect

    Chew, K. W.; Chen, S. S.; Pang, W. L.; Tan, C. G.; Osman, Z.

    2010-03-11

    The effects of Lithium triflate salt (LiCF{sub 3}SO{sub 3}), on the poly (methyl methacrylate)(PMMA)-based solid polymer electrolytes plasticized with propylene carbonate (PC) solvated in Tetrahydrofuran (THF) have been studied through a.c impedance spectroscopy and infrared spectroscopy. Lithium triflate was incorporated into the predetermined PMMA/PC system that has the highest value of ionic conductivity. In current investigations, four combination systems: Pure PMMA, (PMMA+PC) systems, (PMMA+LiCF{sub 3}SO{sub 3}) and (PMMA+PC+LiCF{sub 3}SO{sub 3}) systems were prepared using the solution cast method. Solutions were stirred for numerous hours to obtain a homogenous solution before it is poured into the petri dishes under ambient temperature to form the solid electrolyte thin film. The films were then removed from petri discs and transferred into the dessicator for further drying prior to the different tests. From the characterization done through the a.c impedance spectroscopy, the highest room temperature ionic conductivity in the pure PMMA sample, (PMMA+PC) system and (PMMA+LiCF{sub 3}SO{sub 3}) system is 2.83x10{sup -12} Scm{sup -1}, 4.39x10{sup -11} Scm{sup -1} and 3.93x10{sup -6} Scm{sup -1} respectively. The conductivity for (PMMA+PC+LiCF{sub 3}SO{sub 3}) system was obtained with the 30 wt% of lithium triflate, which is 2.48x10{sup -5} Scm{sup -1}. Infrared spectroscopy shows that complexation occurred between the polymer and the plasticizer, and the polymer and plasticizer and salt. The interactions have been studied in the C=O band, C-O-C band and the O-CH{sub 3} band.

  12. Polyethylene glycol as a solid polymer electrolyte

    SciTech Connect

    Cha, D.K.; Park, S.M.

    1997-12-01

    Polymer electrolytes were prepared from polyethylene glycol (PEG)-lithium perchlorate complexes and characterized at a stainless steel electrode using a variety of electrochemical techniques. The charge transfer process was affected by the oxide film on the stainless steel electrode surface in the early stages of redox processes. The polymer electrolytes showed a transference number of 0.2 for Li{sup +}. The conductivity of the PEG-10000 electrolyte has been determined to be 4.7 {times} 10{sup {minus}5} S/cm. This rather high value is attributed to the anionic end groups increasing the polarity of the matrix.

  13. 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.

  14. Solid lithium ion conducting electrolytes and methods of preparation

    DOEpatents

    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.

  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. Structure and properties of solid polymer electrolyte based on chitosan and ZrO{sub 2} nanoparticle for lithium ion battery

    SciTech Connect

    Sudaryanto, Yulianti, Evi; Patimatuzzohrah

    2016-02-08

    In order to develop all solid lithium ion battery, study on the structure and properties of solid polymer electrolytes (SPE) based on chitosan has been done. The SPE were prepared by adding Zirconia (ZrO{sub 2}) nanoparticle and LiClO{sub 4} as lithium salt into the chitosan solution followed by casting method. Effect of the ZrO{sub 2} and salt concentration to the structure and properties of SPE were elaborated using several methods. The structure of the SPE cast film, were characterized mainly by using X-ray diffractometer (XRD). While the electrical properties of SPE were studied by electrochemical impedance spectrometer (EIS) and ion transference number measurement. XRD profiles show that the addition of ZrO{sub 2} and LiClO{sub 4} disrupts the crystality of chitosan. The decrease in sample crytalinity with the nanoparticle and salt addition may increase the molecular mobility result in the increasing sample conductivity and cathionic transference number as determined by EIS and ion transference number measurement, respectively. The highest ionic conductivity (3.58×10{sup −4} S cm{sup −1}) was obtained when 4 wt% of ZrO{sub 2} nanoparticle and 40 wt% of LiClO{sub 4} salt were added to the chitosan. The ion transference number with that composition was 0.55. It is high enough to be used as SPE for lithium ion battery.

  17. 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+%.

  18. Semiconductor/solid electrolyte junctions for optical information storage

    NASA Astrophysics Data System (ADS)

    Sammells, Anthony F.

    1986-09-01

    The program was directed towards characterization of electrode and photoelectrode solid-state junctions with solid polymer electrolytes (SPEs) possessing incorporated electrochromic materials. Excellent electrochemical reversibility and corresponding electrochromic phenomena were found for cells utilizing lutecium diphthalocyanine and heptyl viologen as incorporated electrochromic materials.

  19. 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.

  20. Solid polymeric electrolytes obtained from modified natural polymers

    NASA Astrophysics Data System (ADS)

    Pawlicka, Agnieszka; Machado, G. O.; Guimaraes, K. V.; Dragunski, Douglas C.

    2003-10-01

    Polysaccharides like starch and cellulose derivatives, hydroxyethylcellulose (HEC) or hydroxypropylcellulose (HPC) were modified to obtain solid polymeric electrolytes. The chemical modifications were performed by the grafting of polymers with poly(ethylene oxide) mono and diisocyanates or JEFFAMINE (Shiff base). The physical modifications were made by the plasticization process of starch and cellulose derivatives with glycerol and ethylene glycol. All the samples obtained from polysaccharides were characterized by X-ray, thermal analysis (DSC) and impedance spectroscopy. The plasticized samples showed low glass transition temperatures (Tg); for HEC the value was about -60°C and for starch it was about -30°C. Tg values for grafted samples were of about -58°C for starch and -7°C for HPC. The low Tg values obtained are important to ensure good ionic conductivity that reached the values of about 10-5 Scm-1 for plasticized samples and 10-6 Scm-1 for grafted ones at room temperature. The good film forming and ionic conductivity properties of the samples of HEC, HPC and starch are very interesting candidates to be used as solid polymer electrolytes.

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

    DOE PAGES

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; ...

    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

  2. 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.

  3. An open circuit voltage equation enabling separation of cathode and anode polarization resistances of ceria electrolyte based solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Yanxiang; Chen, Yu; Yan, Mufu

    2017-07-01

    The open circuit voltage (OCV) of solid oxide fuel cells is generally overestimated by the Nernst equation and the Wagner equation, due to the polarization losses at electrodes. Considering both the electronic conduction of electrolyte and the electrode polarization losses, we express the OCV as an implicit function of the characteristic oxygen pressure of electrolyte (p* [atm], at which the electronic and ionic conductivities are the same), and the relative polarization resistance of electrodes (rc = Rc/Ri and ra = Ra/Ri, where Ri/c/a [Ωcm2] denotes the ionic resistance of electrolyte, and the polarization resistances of cathode and anode, respectively). This equation approaches to the Wagner equation when the electrodes are highly active (rc and ra → 0), and approaches to the Nernst equation when the electrolyte is a purely ionic conductor (p* → 0). For the fuel cells whose OCV is well below the prediction of the Wagner equation, for example with thin doped ceria electrolyte, it is demonstrated that the combination of OCV and impedance spectroscopy measurements allows the determination of p*, Rc and Ra. This equation can serve as a simple yet powerful tool to study the internal losses in the cell under open circuit condition.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Structural, Vibrational, Thermal And Electrical Characterization Of Gamma Radiation-Crosslinked Poly (Vinyl Alcohol)-Based Solid Polymer Electrolytes Blended With LiOH{center_dot}H{sub 2}O Salt

    SciTech Connect

    Khafagy, Rasha M.; Madani, M.; Badr, Y. A.

    2008-09-23

    Solid polymer electrolytes based on poly(vinyl alcohol)(PVA) blended with different concentrations of LiOH{center_dot}H{sub 2}O salt were prepared using casting and {gamma}-irradiation techniques. The structure and blending of the poly-electrolytes were studied by X-ray diffraction (XRD) and Fourier transform Raman spectroscopy. The thermal properties of these solid polymer electrolytes were examined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The XRD spectra for the electrolytes indicated that the crystalline ratio of PVA decreases with the concentration of Lithium salt. Crystallinity, isotacticity and syndiotacticity percentages were also determined from Raman spectra at different salt concentrations revealing that the crystallinity and the Isotactic regularity of PVA molecule is reduced with salt addition, while the syndiotacticity increases linearly. DSC thermograms showed good accordance with these facts by detecting two melting temperatures corresponding to the two regularities, and these melting points change with the salt content. All characterizing techniques revealed the blend formation between LiOH{center_dot}H{sub 2}O salt and the polymer matrix. To account for the performance of the prepared solid polymer electrolytes, thermally stimulated depolarization current (TSDC) studies of the prepared blends were done. Short circuit TSDC at a polarizing temperature 353 K with a polarizing field of 3 kV cm{sup -1} have been analyzed in the temperature range 300-410 K. Two peaks are evident from the global TSDC measurements on the pure PVA homopolymer. Meanwhile, in all blended samples; there is only one broad peak with a shoulder on the high temperature side due to the relaxation of the poly-blend system. The prepared solid polymer electrolytes showed good charge storage capacity, and moderate current density values near the ambient.

  9. In situ observation of electrolyte-concentration-dependent solid electrolyte interphase on graphite in dimethyl sulfoxide.

    PubMed

    Liu, Xing-Rui; Wang, Lin; Wan, Li-Jun; Wang, Dong

    2015-05-13

    High lithium salt concentration strategy has been recently reported to be an effective method to enable various organic solvents as electrolyte of Li-ion batteries. Here, we utilize in situ atomic force microscopy (AFM) to investigate the interfacial morphology on the graphite electrode in dimethyl sulfoxide (DMSO)-based electrolyte of various concentrations. The significant differences in interfacial features of the graphite in electrolytes of different concentrations are revealed. In the concentrated electrolyte, stable films form primarily at the step edges and defects on the graphite surface after initial electrochemical cycling. On the other hand, in the dilute electrolyte, DMSO-solvated lithium ions constantly intercalate into graphite layers, and serious decomposition of solvent accompanied by structural deterioration of the graphite surface is observed. The in situ AFM results provide direct evidence for the concentration-dependent interface reactions between graphite electrode and DMSO-based electrolyte.

  10. 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.

  11. Highly Conductive Solid-State Hybrid Electrolytes Operating at Subzero Temperatures.

    PubMed

    Kwon, Taeyoung; Choi, Ilyoung; Park, Moon Jeong

    2017-07-19

    We report a unique, highly conductive, dendrite-inhibited, solid-state polymer electrolyte platform that demonstrates excellent battery performance at subzero temperatures. A design based on functionalized inorganic nanoparticles with interconnected mesopores that contain surface nitrile groups is the key to this development. Solid-state hybrid polymer electrolytes based on succinonitrile (SN) electrolytes and porous nanoparticles were fabricated via a simple UV-curing process. SN electrolytes were effectively confined within the mesopores. This stimulated favorable interactions with lithium ions, reduced leakage of SN electrolytes over time, and improved mechanical strength of membranes. Inhibition of lithium dendrite growth and improved electrochemical stability up to 5.2 V were also demonstrated. The hybrid electrolytes exhibited high ionic conductivities of 2 × 10(-3) S cm(-1) at room temperature and >10(-4) S cm(-1) at subzero temperatures, leading to stable and improved battery performance at subzero temperatures. Li cells made with lithium titanate anodes exhibited stable discharge capacities of 151 mAh g(-1) at temperatures below -10 °C. This corresponds to 92% of the capacity achieved at room temperature (164 mAh g(-1)). Our work represents a significant advance in solid-state polymer electrolyte technology and far exceeds the performance available with conventional polymeric battery separators.

  12. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    PubMed

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries.

  13. High discharge capacity solid composite polymer electrolyte lithium battery

    NASA Astrophysics Data System (ADS)

    Chen, Y. T.; Chuang, Y. C.; Su, J. H.; Yu, H. C.; Chen-Yang, Y. W.

    2011-03-01

    In this study, a series of nanocomposite polymer electrolytes (CPEs), PAN/LiClO4/SAP, with high conductivity are prepared based on polyacrylonitrile (PAN), LiClO4 and low content of the silica aerogel powder (SAP) prepared by the sol-gel method with ionic liquid (IL) as the template. The effect of addition of SAP on the properties of the CPEs is investigated by FTIR, AC impedance, linear sweep voltagrams and cyclic voltammetry measurements as well as the charge-discharge performance. It is found that the ionic conductivity of the CPE is significantly improved by addition of SAP. The maximum ambient ionic conductivity of CPEs is about 12.5 times higher than that without addition of SAP. The results of the voltammetry measurements of CPE-3, which contained 3 wt% of SAP, show that the anodic and cathodic peaks are well maintained after 100 cycles, showing excellent electrochemical stability and cyclability over the potential range between 0 V and 4 V vs. Li/Li+. Besides, the room temperature discharge capacity measured at 0.5C for the coin cell based on CPE-3 is 120 mAh g-1 and the capacity is retained after 20 cycles discharge, indicating the potential for practical use. This is perhaps the first report of the room temperature charge-discharge performance on the solid composite polymer electrolyte to the best of our knowledge.

  14. 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

  15. 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).

  16. 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.

  17. Yttria-stabilized zirconia solid oxide electrolyte fuel cells--- monolithic solid oxide fuel cells

    SciTech Connect

    Not Available

    1990-10-01

    The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H{sub 2} or simulated coal gas and air or oxygen. 68 figs., 29 tabs.

  18. 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.

  19. Ferroelectric Dispersed Composite Solid Electrolyte for CO2 Gas Sensor

    NASA Astrophysics Data System (ADS)

    Singh, K.; Ambekar, P.; Bhoga, S. S.

    2002-12-01

    The Li2CO3:LiNbO3 composite system was investigated for the application in electrochemical gas sensor. The conductivity maximum is observed for 50Li2CO3+50LiNbO3. An enhancement in conductivity is understood to be due to the percolation threshold. The composite is also seen less sensitive to moisture. Potentiometric sensors are obtained using optimized composition. At the reference electrode, the activity of Li+ is fixed by using open reference electrode material. Good reversibility of cell emf was observed for PCO2 ranging from 200 ppm to 20% at 400°C. The cell response was Nernstian, following nearly two-electron reaction. The sensor showed negligible cross-sensitivity to moisture. Developed solid electrolyte not only exhibit shorter response time but also improves over all performance relative to the sensor based on pure carbonate.

  20. Simulation Protocol for Prediction of a Solid-Electrolyte Interphase on the Silicon-based Anodes of a Lithium-Ion Battery: ReaxFF Reactive Force Field.

    PubMed

    Yun, Kang-Seop; Pai, Sung Jin; Yeo, Byung Chul; Lee, Kwang-Ryeol; Kim, Sun-Jae; Han, Sang Soo

    2017-07-06

    We propose the ReaxFF reactive force field as a simulation protocol for predicting the evolution of solid-electrolyte interphase (SEI) components such as gases (C2H4, CO, CO2, CH4, and C2H6), and inorganic (Li2CO3, Li2O, and LiF) and organic (ROLi and ROCO2Li: R = -CH3 or -C2H5) products that are generated by the chemical reactions between the anodes and liquid electrolytes. ReaxFF was developed from ab initio results, and a molecular dynamics simulation with ReaxFF realized the prediction of SEI formation under real experimental conditions and with a reasonable computational cost. We report the effects on SEI formation of different kinds of Si anodes (pristine Si and SiOx), of the different types and compositions of various carbonate electrolytes, and of the additives. From the results, we expect that ReaxFF will be very useful for the development of novel electrolytes or additives and for further advances in Li-ion battery technology.

  1. Nonlinear ion transport in liquid and solid electrolytes

    NASA Astrophysics Data System (ADS)

    Roling, B.; Patro, L. N.; Burghaus, O.; Gräf, M.

    2017-08-01

    This paper describes nonlinear ion transport properties of liquid and solid electrolytes. Typically, the relation between ionic current density and electric field becomes nonlinear at electric fields above 50-100 kV/cm. We review the 1st and 2nd Wien effect found in classical strong and weak electrolyte solutions as well as the strong nonlinear ion transport effects observed for inorganic glasses and for polymer electrolytes. Furthermore, we give an overview over models describing nonlinear ion transport in electrolyte solutions, in glasses and in polymers. Recent results are presented for the nonlinear ionic conductivity of supercooled ionic liquids. We show that supercooled ionic liquids exhibit anomalous Wien effects, which are clearly distinct from the classical Wien effects. We also discuss the frequency dependence of higher-order conductivity and permittivity spectra of these liquids.

  2. Double layer capacitance of anode/solid-electrolyte interfaces.

    PubMed

    Ge, Xiaoming; Fu, Changjing; Chan, Siew Hwa

    2011-09-07

    The double layer of electrode/electrolyte interfaces plays a fundamental role in determining the performance of solid state electrochemical cells. The double layer capacitance is one of the most-studied descriptors of the double layer. This work examines a case study on lanthanum strontium vanadate (LSV)/yttria-stabilized zirconia (YSZ) interfaces exposed in solid oxide fuel cell anode environment. The apparent double layer capacitance is obtained from impedance spectroscopy. The intrinsic double layer capacitance is evaluated based on Stern's method in conjunction with the Volta potential analysis across LSV/YSZ interfaces. Both the apparent and the intrinsic double layer capacitances exhibit right-skewed volcano patterns, when the interfaces are subjected to anodic biases from 0 to 150 mV. The apparent double layer capacitance is about one order of magnitude larger than the intrinsic double layer capacitance. This discrepancy roots in the inconsistent surface areas that are involved. This analysis of capacitance would provide a more realistic TPB estimate of a working solid-state electrochemical device. This journal is © the Owner Societies 2011

  3. 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.

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

    DOE PAGES

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; ...

    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

  5. Modeling mechanical degradation in lithium ion batteries during cycling: Solid electrolyte interphase fracture

    NASA Astrophysics Data System (ADS)

    Laresgoiti, Izaro; Käbitz, Stefan; Ecker, Madeleine; Sauer, Dirk Uwe

    2015-12-01

    During cycling, mechanical stresses can occur in the composite electrode, inside the active material, but also in the solid electrolyte interphase layer. A mechanical model is proposed based on a system made of a spherical graphite particle surrounded by the solid electrolyte interphase layer. During lithium intercalation or de-intercalation, stresses in the graphite are produced, governed by the diffusion induced stress phenomena and in the solid electrolyte interphase, driven by the graphite expansion. The stresses in both materials were simulated and a sensitivity analysis was performed to clarify the influence of principal parameters on both processes. Finally, assuming that the solid electrolyte interphase is the weakest material and therefore more prone to fracture than graphite, the experimental capacity fade during cycling was modeled based on its break and repair effect rather than on the fracture of the active material. The mechanical model of the solid electrolyte interphase was implemented in a single particle lithium ion battery model in order to reproduce capacity fade during battery lifetime. The model results were compared against cycle life aging experimental data, reproducing accurately the influence of the depth of discharge as well as the average state of charge on the capacity fade.

  6. Status and applicability of solid polymer electrolyte technology to electrolytic hydrogen and oxygen production

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.

    1973-01-01

    The solid polymer electrolyte (SPE) water electrolysis technology is presented as a potential energy conversion method for wind driven generator systems. Electrolysis life and performance data are presented from laboratory sized single cells (7.2 sq in active area) with high cell current density selected (1000 ASF) for normal operation.

  7. Construction of All-Solid-State Batteries based on a Sulfur-Graphene Composite and Li9.54 Si1.74 P1.44 S11.7 Cl0.3 Solid Electrolyte.

    PubMed

    Xu, Ruochen; Wu, Zhang; Zhang, Shenzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Huang, Xiaohua; Tu, Jiangping

    2017-10-09

    Herein an effective way for construction of all-solid-state lithium-sulfur batteries (LSBs) with sulfur/reduced graphene oxide (rGO) and Li9.54 Si1.74 P1.44 S11.7 Cl0.3 solid electrolyte is reported. In the composite cathode, the Li9.54 Si1.74 P1.44 S11.7 Cl0.3 powder is homogeneously mixed with the S/rGO composite to enhance the ionic conductivity. Coupled with a metallic Li anode and solid electrolyte, the designed S/rGO-Li9.54 Si1.74 P1.44 S11.7 Cl0.3 composite cathode exhibits a high specific capacity and good cycling stability. A high initial discharge capacity of 969 mAh g(-1) is achieved at a current density of 80 mA g(-1) at room temperature and the cell retains a reversible capacity of over 827 mAh g(-1) after 60 cycles. The enhanced performance is attributed to the intimate contact between the S/rGO and Li9.54 Si1.74 P1.44 S11.7 Cl0.3 electrolyte, and high electrical conductivity of rGO and high ionic conductivity of the solid electrolyte. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Norbornene-Based Polymer Electrolytes for Lithium Cells

    NASA Technical Reports Server (NTRS)

    Cheung, Iris; Smart, Marshall; Prakash, Surya; Miyazawa, Akira; Hu, Jinbo

    2007-01-01

    Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements.

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

    PubMed

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

    2017-03-08

    Li-ion batteries (LIB) have been successfully commercialized after the identification of ethylene-carbonate (EC)-containing electrolyte that can form a stable solid electrolyte interphase (SEI) on carbon anode surface to passivate further side reactions but still enable the transportation of the Li(+) cation. These electrolytes are still utilized, with only minor changes, after three decades. However, the long-term cycling of LIB leads to continuous consumption of electrolyte and growth of SEI layer on the electrode surface, which limits the battery's life and performance. Herein, a new anode protection mechanism is reported in which, upon changing of the cell potential, the electrolyte components at the electrode-electrolyte interface reorganize reversibly to form a transient protective surface layers on the anode. This layer will disappear after the applied potential is removed so that no permanent SEI layer is required to protect the carbon anode. This phenomenon minimizes the need for a permanent SEI layer and prevents its continuous growth and therefore may lead to largely improved performance for LIBs.

  14. A Novel Lithiated Silicon-Sulfur Battery Exploiting an Optimized Solid-Like Electrolyte to Enhance Safety and Cycle Life.

    PubMed

    Zhou, Dong; Liu, Ming; Yun, Qinbai; Wang, Xia; He, Yan-Bing; Li, Baohua; Yang, Quan-Hong; Cai, Qiang; Kang, Feiyu

    2017-01-01

    Anovel lithiated Si-S battery exploiting an optimized solid-like electrolyte is presented. This electrolyte is fabricated by integrating ether-based liquid electrolyte with SiO2 hollow nanosphere layer to suppress the shuttle effect and fluoroethylene carbonate additive to optimize the anodic solid electrolyte interface. The prepared lithiated Si-S batteries exhibit enhanced cycle life, low flammability, and strong recovery ability against short-circuit. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Electrode-Electrolyte Interfaces in Solid Polymer Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Hu, Qichao

    This thesis studies the performance of solid polymer lithium batteries from room temperature to elevated temperatures using mainly electrochemical techniques, with emphasis on the bulk properties of the polymer electrolyte and the electrode-electrolyte interfaces. Its contributions include: 1) Demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence, and improved the conductivity of the graft copolymer electrolyte (GCE) by almost an order of magnitude by changing the ion-conducting block from poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). 2) Identified the rate-limiting step in the battery occurs at the cathode-electrolyte interface using both full cell and symmetric cell electrochemical impedance spectroscopy (EIS), improved the battery rate capability by using the GCE as both the electrolyte and the cathode binder to reduce the resistance at the cathode-electrolyte interface, and used TEM and SEM to visualize the polymer-particle interface (full cells with LiFePO4 as the cathode active material and lithium metal as the anode were assembled and tested). 3) Applied the solid polymer battery to oil and gas drilling application, performed high temperature (up to 210 °C) cycling (both isothermal and thermal cycling), and demonstrated for the first time, current exchange between a solid polymer electrolyte and a liquid lithium metal. Both the cell open-circuit-voltage (OCV) and the overall GCE mass remained stable up to 200 °C, suggesting that the GCE is electrochemically and gravimetrically stable at high temperatures. Used full cell EIS to study the behavior of the various battery parameters as a function of cycling and temperature. 4) Identified the thermal instability of the cell was due to the reactivity of lithium metal and its passivation film at high temperatures, and used Li/GCE/Li symmetric cell

  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. Novel Solid Electrolytes for Li-Ion Batteries: A Perspective from Electron Microscopy Studies

    SciTech Connect

    Ma, Cheng; Chi, Miaofang

    2016-06-08

    Solid electrolytes can simultaneously overcome two of the most formidable challenges of Li-ion batteries: the severe safety issues and insufficient energy densities. However, before they can be implemented in actual batteries, the ionic conductivity needs to be improved and the interface with electrodes must be optimized. The prerequisite for addressing these issues is a thorough understanding of the material’s behavior at the microscopic and/or the atomic level. (Scanning) transmission electron microscopy is a powerful tool for this purpose, as it can reach an ultrahigh spatial resolution. Here, we review recent electron microscopy investigations on the ion transport behavior in solid electrolytes and their interfaces. Specifically, three aspects will be highlighted: the influence of grain interior atomic configuration on ionic conductivity, the contribution of grain boundaries, and the behavior of solid electrolyte/electrode interfaces. In conclusion, based on this, the perspectives for future research will be discussed.

  18. Conductivity studies on ceramic Li 1.3Al 0.3Ti 1.7(PO 4) 3-filled PEO-based solid composite polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Wang, Yan-Jie; Pan, Yi; Kim, Dukjoon

    With the promise of its high conductivity, the ceramic Li 1.3Al 0.3Ti 1.7(PO 4) 3 (x = 0.85) of Li 3 - 2 x(Al 1 - xTi x) 2(PO 4) 3 (x = 0.55 to 1.0), as a lithium fast ionic conductor, is produced by a conventional solid-state reaction and introduced into the poly(ethylene oxide) (PEO)-based composite polymer electrolyte films (CPE) to improve their ionic conductivity. The CPE films are prepared by a solution-cast technique and their characteristics are investigated by several experimental techniques including X-ray diffraction (XRD), infrared (IR) spectra, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). As measured by electrochemical impedance spectrum (EIS) measurement, the temperature-dependent ionic conductivity of PEO-Li 1.3Al 0.3Ti 1.7(PO 4) 3 film with EO/Li = 16 is maximized at 2.631 × 10 -6 S cm -1 at room temperature and at 1.185 × 10 -4 S cm -1 at 343 K, while the ionic conductivity of the PEO-LiClO 4-Li 1.3Al 0.3Ti 1.7(PO 4) 3 film with EO/Li = 8 is maximized at 7.985 × 10 -6 S cm -1 at room temperature and at 1.161 × 10 -3 S cm -1 at 373 K when Li 1.3Al 0.3Ti 1.7(PO 4) 3 content is 15 wt.%.

  19. Reference electrodes for solid polymer electrolytes

    SciTech Connect

    Johnson, C.S.; Dees, D.W.

    1993-12-31

    Electrochemical experiments were conducted on a binary metallic lithium-tin alloy that may be suitable as a reference electrode of the first kind in studies of lithium-polymer batteries. Two types of tin electrodes were tested: bulk tin foil and tin thin films deposited on a stainless steel substrate. Electrochemical test cells were fabricated, with tin, metallic lithium, poly(ethylene oxide), and lithium trifluoromethanesulfonate as electrodes and polymer electrolyte material. To form the alloy, the tin electrodes were galvanostatically loaded in situ with lithium. Each cell reached one or more steady-state voltage plateaus during the electrochemical reduction of lithium cations at the tin electrode surface. The lithiated tin foil electrode (1 C/cm{sup 2} of charge passed; area {approx} 5 cm{sup 2}; thickness = 1.0 mm) demonstrated good voltage stability over months under open-circuit conditions. This electrode maintained an average open circuit voltage of 0.7336 V with only {plus_minus}0.17 mV variance. Composition of phases in the thin film electrodes (x in Li{sub x}Sn) was coulometrically varied via reversible lithium loading and unloading reactions. Results show that three different, two-phase compositions may be formed that maintain flat voltage regions at approximately 0.53, 0.63, and 0.73 V vs lithium metal.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  6. 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.

  7. Electrolytes

    MedlinePlus

    ... Chloride Magnesium Phosphorus Potassium Sodium Electrolytes can be acids, bases, or salts. They can be measured by different ... Saunders; 2013:464-467. DuBose TD. Disorders of acid-base balance. In: Taal MW, Chertow GM, Marsden PA, ...

  8. TOPICAL REVIEW: Solid polymer electrolytes: materials designing and all-solid-state battery applications: an overview

    NASA Astrophysics Data System (ADS)

    Agrawal, R. C.; Pandey, G. P.

    2008-11-01

    Polymer electrolytes are promising materials for electrochemical device applications, namely, high energy density rechargeable batteries, fuel cells, supercapacitors, electrochromic displays, etc. The area of polymer electrolytes has gone through various developmental stages, i.e. from dry solid polymer electrolyte (SPE) systems to plasticized, gels, rubbery to micro/nano-composite polymer electrolytes. The polymer gel electrolytes, incorporating organic solvents, exhibit room temperature conductivity as high as ~10-3 S cm-1, while dry SPEs still suffer from poor ionic conductivity lower than 10-5 S cm-1. Several approaches have been adopted to enhance the room temperature conductivity in the vicinity of 10-4 S cm-1 as well as to improve the mechanical stability and interfacial activity of SPEs. In this review, the criteria of an ideal polymer electrolyte for electrochemical device applications have been discussed in brief along with presenting an overall glimpse of the progress made in polymer electrolyte materials designing, their broad classification and the recent advancements made in this branch of materials science. The characteristic advantages of employing polymer electrolyte membranes in all-solid-state battery applications have also been discussed.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Rubbery solid electrolytes with dominant cationic transport and high ambient conductivity

    NASA Astrophysics Data System (ADS)

    Angell, C. A.; Liu, C.; Sanchez, E.

    1993-03-01

    EFFORTS to develop a high-voltage, lightweight rechargeable battery for electrically powered vehicles have focused on batteries based on solid electrolytes, which offer good mechanical strength, easy packaging and high energy densities. An important objective is to identify an electrolyte with the desired combination of mechanical properties, electrical conductivity and stability against powerfully oxidizing and reducing electrodes (lithium is preferred for the anode). Among the most promising materials are rubbery 'salt-in-polymer' electrolytes and highly conducting but brittle superionic glass electrolytes. In the latter category are salts with good lithium-ion conductivity, which are compatible with lithium-anode systems. Here we describe new ionic conductors - 'polymer-in-salt' materials - in which lithium salts are mixed with small quantities of the polymers polypropylene oxide and polyethylene oxide. These materials have glass transitions low enough to remain rubbery at room temperature while preserving good lithium-ion conductivities and high electrochemical stability.

  18. Superior ion-conducting hybrid solid electrolyte for all-solid-state batteries.

    PubMed

    Kim, Jae-Kwang; Scheers, Johan; Park, Tae Joo; Kim, Youngsik

    2015-02-01

    Herein, we developed a high-performance lithium ion conducting hybrid solid electrolyte, consisted of LiTFSI salt, Py14 TFSI ionic liquid, and TiO2 nanoparticles. The hybrid solid electrolyte prepared by a facile method had high room temperature ionic conductivity, excellent thermal stability and low interface resistance with good contact. In addition, the lithium transference number was highly increased by the scavenger effect of TiO2 nanoparticles. With the hybrid solid electrolyte, the pouch-type solid-state battery exhibited high initial discharge capacity of 150 mA h g(-1) at room temperature, and even at 1 C, the reversible capacity was as high as 106 mA h g(-1) .

  19. Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

    PubMed

    Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

    2012-04-07

    Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

  20. Depth profiling the solid electrolyte interphase on lithium titanate (Li4Ti5O12) using synchrotron-based photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nordh, Tim; Younesi, Reza; Brandell, Daniel; Edström, Kristina

    2015-10-01

    The presence of a surface layer on lithium titanate (Li4Ti5O12, LTO) anodes, which has been a topic of debate in scientific literature, is here investigated with tunable high surface sensitive synchrotron-based photoelectron spectroscopy (PES) to obtain a reliable depth profile of the interphase. Li||LTO cells with electrolytes consisting of 1 M lithium hexafluorophosphate dissolved in ethylene carbonate:diethyl carbonate (LiPF6 in EC:DEC) were cycled in two different voltage windows of 1.0-2.0 V and 1.4-2.0 V. LTO electrodes were characterized after 5 and 100 cycles. Also the pristine electrode as such, and an electrode soaked in the electrolyte were analyzed by varying the photon energies enabling depth profiling of the outermost surface layer. The main components of the surface layer were found to be ethers, P-O containing compounds, and lithium fluoride.

  1. 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.

  2. Confined Solid Electrolyte Interphase Growth Space with Solid Polymer Electrolyte in Hollow Structured Silicon Anode for Li-Ion Batteries.

    PubMed

    Ma, Tianyi; Yu, Xiangnan; Cheng, Xiaolu; Li, Huiyu; Zhu, Wentao; Qiu, Xinping

    2017-04-19

    Silicon anodes for lithium-ion batteries are of much interest owing to their extremely high specific capacity but still face some challenges, especially the tremendous volume change which occurs in cycling and further leads to the disintegration of electrode structure and excessive growth of solid electrolyte interphase (SEI). Here, we designed a novel approach to confine the inward growth of SEI by filling solid polymer electrolyte (SPE) into pores of hollow silicon spheres. The as-prepared composite delivers a high specific capacity of more than 2100 mAh g(-1) and a long-term cycle stability with a reversible capacity of 1350 mAh g(-1) over 500 cycles. The growing behavior of SEI was investigated by electrochemical impedance spectroscopy and differential scanning calorimetry, and the results revealed that SPE occupies the major space of SEI growth and thus confines its excessive growth, which significantly improves cycle performance and Coulombic efficiency of cells embracing hollow silicon spheres.

  3. Quasi-solid electrolyte: a thixotropic gel of imogolite and an ionic liquid.

    PubMed

    Shikinaka, K; Taki, N; Kaneda, K; Tominaga, Y

    2017-01-03

    We report a quasi-solid electrolyte comprising a transparent thixotropic gel swelled by an ionic liquid that is formed by a framework of single-walled aluminosilicate cylindrical inorganic "imogolite" nanotubes. The quasi-solid electrolyte shows moldability, thermal stability, and high ionic conductivity, and has potential applications in free-moldable conductive and anti-icing coatings, or electrolytes for batteries.

  4. Novel Solid Electrolytes for Li-Ion Batteries: A Perspective from Electron Microscopy Studies

    DOE PAGES

    Ma, Cheng; Chi, Miaofang

    2016-06-08

    Solid electrolytes can simultaneously overcome two of the most formidable challenges of Li-ion batteries: the severe safety issues and insufficient energy densities. However, before they can be implemented in actual batteries, the ionic conductivity needs to be improved and the interface with electrodes must be optimized. The prerequisite for addressing these issues is a thorough understanding of the material’s behavior at the microscopic and/or the atomic level. (Scanning) transmission electron microscopy is a powerful tool for this purpose, as it can reach an ultrahigh spatial resolution. Here, we review recent electron microscopy investigations on the ion transport behavior in solidmore » electrolytes and their interfaces. Specifically, three aspects will be highlighted: the influence of grain interior atomic configuration on ionic conductivity, the contribution of grain boundaries, and the behavior of solid electrolyte/electrode interfaces. In conclusion, based on this, the perspectives for future research will be discussed.« less

  5. A Flexible Solid Composite Electrolyte with Vertically Aligned and Connected Ion-Conducting Nanoparticles for Lithium Batteries.

    PubMed

    Zhai, Haowei; Xu, Pengyu; Ning, Mingqiang; Cheng, Qian; Mandal, Jyotirmoy; Yang, Yuan

    2017-04-14

    Replacing flammable organic liquid electrolytes with solid Li-ion conductors is a promising approach to realize safe rechargeable batteries with high energy density. Composite solid electrolytes, which are comprised of a polymer matrix with ceramic Li-ion conductors dispersed inside, are attractive, since they combine the flexibility of polymer electrolytes and high ionic conductivities of ceramic electrolytes. However, the high conductivity of ceramic fillers is largely compromised by the low conductivity of the matrix, especially when nanoparticles (NPs) are used. Therefore, optimizations of the geometry of ceramic fillers are critical to further enhance the conductivity of composite electrolytes. Here we report the vertically aligned and connected Li1+xAlxTi2-x(PO4)3 (LATP) NPs in the polyethylene oxide (PEO) matrix to maximize the ionic conduction, while maintaining the flexibility of the composite. This vertically aligned structure can be fabricated by an ice-templating-based method, and its conductivity reaches 0.52 × 10^-4 S/cm, which is 3.6 times that of the composite electrolyte with randomly dispersed LATP NPs. The composite electrolyte also shows enhanced thermal and electrochemical stability compared to the pure PEO electrolyte. This method opens a new approach to optimize ion conduction in composite solid electrolytes for next-generation rechargeable batteries.

  6. Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

    NASA Astrophysics Data System (ADS)

    Isenberg, Arnold O.

    1989-06-01

    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.

  7. 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.

  8. Effect of zwitterion on the lithium solid electrolyte interphase in ionic liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Byrne, N.; Howlett, P. C.; MacFarlane, D. R.; Smith, M. E.; Howes, A.; Hollenkamp, A. F.; Bastow, T.; Hale, P.; Forsyth, M.

    An understanding of the solid electrolyte interphase (SEI) that forms on the lithium-metal surface is essential to the further development of rechargeable lithium-metal batteries. Currently, the formation of dendrites during cycling, which can lead to catastrophic failure of the cell, has mostly halted research on these power sources. The discovery of ionic liquids as electrolytes has rekindled the possibility of safe, rechargeable, lithium-metal batteries. The current limitation of ionic liquid electrolytes, however, is that when compared with conventional non-aqueous electrolytes the device rate capability is limited. Recently, we have shown that the addition of a zwitterion such as N-methyl- N-(butyl sulfonate) pyrrolidinium resulted in enhancement of the achievable current densities by 100%. It was also found that the resistance of the SEI layer in the presence of a zwitterion is 50% lower. In this study, a detailed chemical and electrochemical analysis of the SEI that forms in both the presence and absence of a zwitterion has been conducted. Clear differences in the chemical nature and also the thickness of the SEI are observed and these may account for the enhancement of operating current densities.

  9. Polymeric electrolytes based on hydrosilyation reactions

    DOEpatents

    Kerr, John Borland; Wang, Shanger; Hou, Jun; Sloop, Steven Edward; Han, Yong Bong; Liu, Gao

    2006-09-05

    New polymer electrolytes were prepared by in situ cross-linking of allyl functional polymers based on hydrosilation reaction using a multifunctional silane cross-linker and an organoplatinum catalyst. The new cross-linked electrolytes are insoluble in organic solvent and show much better mechanical strength. In addition, the processability of the polymer electrolyte is maintained since the casting is finished well before the gel formation.

  10. Fabrication and characterization of anode-supported micro-tubular solid oxide fuel cell based on BaZr 0.1Ce 0.7Y 0.1Yb 0.1O 3- δ electrolyte

    NASA Astrophysics Data System (ADS)

    Zhao, Fei; Jin, Chao; Yang, Chenghao; Wang, Siwei; Chen, Fanglin

    Anode-supported micro-tubular solid oxide fuel cells (SOFCs) based on a proton and oxide ion mixed conductor electrolyte, BaZr 0.1Ce 0.7Y 0.1Yb 0.1O 3- δ (BZCYYb), have been fabricated using phase inversion and dip-coating techniques with a co-firing process. The single cell is composed of NiO-BZCYYb anode, BZCYYb electrolyte and La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ (LSCF)-BZCYYb cathode. Maximum power densities of 0.08, 0.15, and 0.26 W cm -2 have been obtained at 500, 550 and 600 °C, respectively, using H 2 as fuel and ambient air as oxidant.

  11. 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.

  12. An investigation of lithium solid electrolyte materials with first principles calculations

    NASA Astrophysics Data System (ADS)

    Lepley, Nicholas

    Inorganic solid electrolyte materials have recently become the focus of considerable interest due to the discovery of novel compounds with high ionic conductivities (> 1e-4 S/cm ). Sulfur based solid electrolytes are particularly notable in this regard, as well as for their compatibility for Li-S electrode systems. This work applies compu- tational methods based on density functional theory to the problem of identifying and characterizing novel electrolyte materials, with an emphasis on the Li2S-P2S5 system. In addition to a broad overview of likely materials, two compounds are studied in depth, Li7P3S11 and Li3PS4 . For Li7P3 S11 the results show excellent agreement with respect to migration energetics, and good agreement with the experimentally described structure and observed stability. For Li3PS4 , in addition to structure, stability, and migration energetics, the properties of the interface between the electrolyte and vacuum and the electrolyte and lithium metal are considered.

  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. Novel reversible and switchable electrolytes based on magneto-rheology

    PubMed Central

    Ding, Jie; Peng, Gangrou; Shu, Kewei; Wang, Caiyun; Tian, Tongfei; Yang, Wenrong; Zhang, Yuanchao; Wallace, Gordon G.; Li, Weihua

    2015-01-01

    Replacing organic liquid electrolytes with solid electrolytes has led to a new perspective on batteries, enabling high-energy battery chemistry with intrinsically safe cell designs. However, most solid/gel electrolytes are easily deformed; under extreme deformation, leakage and/or short-circuiting can occur. Here, we report a novel magneto-rheological electrolyte (MR electrolyte) that responds to changes in an external magnetic field; the electrolyte exhibits low viscosity in the absence of a magnetic field and increased viscosity or a solid-like phase in the presence of a magnetic field. This change from a liquid to solid does not significantly change the conductivity of the MR electrolyte. This work introduces a new class of magnetically sensitive solid electrolytes that can enhance impact resistance and prevent leakage from electronic devices through reversible active switching of their mechanical properties. PMID:26493967

  15. Novel reversible and switchable electrolytes based on magneto-rheology.

    PubMed

    Ding, Jie; Peng, Gangrou; Shu, Kewei; Wang, Caiyun; Tian, Tongfei; Yang, Wenrong; Zhang, Yuanchao; Wallace, Gordon G; Li, Weihua

    2015-10-23

    Replacing organic liquid electrolytes with solid electrolytes has led to a new perspective on batteries, enabling high-energy battery chemistry with intrinsically safe cell designs. However, most solid/gel electrolytes are easily deformed; under extreme deformation, leakage and/or short-circuiting can occur. Here, we report a novel magneto-rheological electrolyte (MR electrolyte) that responds to changes in an external magnetic field; the electrolyte exhibits low viscosity in the absence of a magnetic field and increased viscosity or a solid-like phase in the presence of a magnetic field. This change from a liquid to solid does not significantly change the conductivity of the MR electrolyte. This work introduces a new class of magnetically sensitive solid electrolytes that can enhance impact resistance and prevent leakage from electronic devices through reversible active switching of their mechanical properties.

  16. Novel reversible and switchable electrolytes based on magneto-rheology

    NASA Astrophysics Data System (ADS)

    Ding, Jie; Peng, Gangrou; Shu, Kewei; Wang, Caiyun; Tian, Tongfei; Yang, Wenrong; Zhang, Yuanchao; Wallace, Gordon G.; Li, Weihua

    2015-10-01

    Replacing organic liquid electrolytes with solid electrolytes has led to a new perspective on batteries, enabling high-energy battery chemistry with intrinsically safe cell designs. However, most solid/gel electrolytes are easily deformed; under extreme deformation, leakage and/or short-circuiting can occur. Here, we report a novel magneto-rheological electrolyte (MR electrolyte) that responds to changes in an external magnetic field; the electrolyte exhibits low viscosity in the absence of a magnetic field and increased viscosity or a solid-like phase in the presence of a magnetic field. This change from a liquid to solid does not significantly change the conductivity of the MR electrolyte. This work introduces a new class of magnetically sensitive solid electrolytes that can enhance impact resistance and prevent leakage from electronic devices through reversible active switching of their mechanical properties.

  17. High temperature lithium cells with solid polymer electrolytes

    DOEpatents

    Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

    2017-03-07

    Electrochemical cells that use electrolytes made from new polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers. Such electrochemical cells can operate safely at higher temperatures than have been possible before, especially in lithium cells. The ionic conductivity of the electrolytes increases with increasing temperature.

  18. Polymer-Rich Composite Electrolytes for All-Solid-State Li-S Cells.

    PubMed

    Judez, Xabier; Zhang, Heng; Li, Chunmei; Eshetu, Gebrekidan Gebresilassie; Zhang, Yan; González-Marcos, José A; Armand, Michel; Rodriguez-Martinez, Lide M

    2017-08-03

    Polymer-rich composite electrolytes with lithium bis(fluorosulfonyl)imide/poly(ethylene oxide) (LiFSI/PEO) containing either Li-ion conducting glass ceramic (LICGC) or inorganic Al2O3 fillers are investigated in all-solid-state Li-S cells. In the presence of the fillers, the ionic conductivity of the composite polymer electrolytes (CPEs) does not increase compared to the plain LiFSI/PEO electrolyte at various tested temperatures. The CPE with Al2O3 fillers improves the stability of the Li/electrolyte interface, while the Li-S cell with a LICGC-based CPE delivers high sulfur utilization of 1111 mAh g(-1) and areal capacity of 1.14 mAh cm(-2). In particular, the cell performance gets further enhanced when combining these two CPEs (Li | Al2O3-CPE/LICGC-CPE | S), reaching a capacity of 518 mAh g(-1) and 0.53 mAh cm(-2) with Coulombic efficiency higher than 99% at the end of 50 cycles at 70 °C. This study shows that the CPEs can be promising electrolyte candidates to develop safe and high-performance all-solid-state Li-S batteries.

  19. Artificial solid electrolyte interphase for aqueous lithium energy storage systems.

    PubMed

    Zhi, Jian; Yazdi, Alireza Zehtab; Valappil, Gayathri; Haime, Jessica; Chen, Pu

    2017-09-01

    Aqueous lithium energy storage systems address environmental sustainability and safety issues. However, significant capacity fading after repeated cycles of charge-discharge and during float charge limit their practical application compared to their nonaqueous counterparts. We introduce an artificial solid electrolyte interphase (SEI) to the aqueous systems and report the use of graphene films as an artificial SEI (G-SEI) that substantially enhance the overall performance of an aqueous lithium battery and a supercapacitor. The thickness (1 to 50 nm) and the surface area (1 cm(2) to 1 m(2)) of the G-SEI are precisely controlled on the LiMn2O4-based cathode using the Langmuir trough-based techniques. The aqueous battery with a 10-nm-thick G-SEI exhibits a discharge capacity as high as 104 mA·hour g(-1) after 600 cycles and a float charge current density as low as 1.03 mA g(-1) after 1 day, 26% higher (74 mA·hour g(-1)) and 54% lower (1.88 mA g(-1)) than the battery without the G-SEI, respectively. We propose that the G-SEI on the cathode surface simultaneously suppress the structural distortion of the LiMn2O4 (the Jahn-Teller distortion) and the oxidation of conductive carbon through controlled diffusion of Li(+) and restricted permeation of gases (O2 and CO x ), respectively. The G-SEI on both small (~1 cm(2) in 1.15 mA·hour cell) and large (~9 cm(2) in 7 mA·hour cell) cathodes exhibit similar property enhancement, demonstrating excellent potential for scale-up and manufacturing.

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

    PubMed

    Soto, Fernando A; Yan, Pengfei; Engelhard, Mark H; Marzouk, Asma; Wang, Chongmin; Xu, Guiliang; Chen, Zonghai; Amine, Khalil; Liu, Jun; Sprenkle, Vincent L; El-Mellouhi, Fedwa; Balbuena, Perla B; Li, Xiaolin

    2017-03-07

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

  1. Forming solid electrolyte interphase in situ in an ionic conducting Li1.5Al0.5Ge1.5(PO4)3-polypropylene (PP) based separator for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Jiao-Yang, Wu; Shi-Gang, Ling; Qi, Yang; Hong, Li; Xiao-Xiong, Xu; Li-Quan, Chen

    2016-07-01

    A new concept of forming solid electrolyte interphases (SEI) in situ in an ionic conducting Li1.5Al0.5Ge1.5(PO4)3-polypropylene (LAGP-PP) based separator during charging and discharging is proposed and demonstrated. This unique structure shows a high ionic conductivity, low interface resistance with electrode, and can suppress the growth of lithium dendrite. The features of forming the SEI in situ are investigated by scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). The results confirm that SEI films mainly consist of lithium fluoride and carbonates with various alkyl contents. The cell assembled by using the LAGP-coated separator demonstrates a good cycling performance even at high charging rates, and the lithium dendrites were not observed on the lithium metal electrode. Therefore, the SEI-LAGP-PP separator can be used as a promising flexible solid electrolyte for solid state lithium batteries. Project supported by the Beijing Science and Technology Project, China (Grant No. Z13111000340000), the National Basic Research Program of China (Grant No. 2012CB932900), and the National Natural Science Foundation of China (Grant Nos. 51325206 and 51421002).

  2. High Capacity, Superior Cyclic Performances in All-Solid-State Lithium-Ion Batteries Based on 78Li2S-22P2S5 Glass-Ceramic Electrolytes Prepared via Simple Heat Treatment.

    PubMed

    Zhang, Yibo; Chen, Rujun; Liu, Ting; Shen, Yang; Lin, Yuanhua; Nan, Ce-Wen

    2017-08-30

    Highly Li-ion conductive 78Li2S-22P2S5 glass-ceramic electrolytes were prepared by simple heat treatment of the glass phase obtained via mechanical ball milling. A high ionic conductivity of ∼1.78 × 10(-3) S cm(-1) is achieved at room temperature and is attributed to the formation of a crystalline phase of high lithium-ion conduction. All-solid-state lithium-ion batteries based on these glass-ceramic electrolytes are assembled by using Li2S nanoparticles or low-cost commercially available FeS2 as active cathode materials and Li-In alloys as anode. A high discharge capacity of 535 mAh g(-1) is achieved after at least 50 cycles for the all-solid-state cells with Li2S as cathode materials, suggesting a rather high capacity retention of 97.4%. Even for the cells using low-cost FeS2 as cathode materials, same high discharge capacity of 560 mAh g(-1) is also achieved after at least 50 cycles. Moreover, the Coulombic efficiency remain at ∼99% for these all-solid-state cells during the charge-discharge cycles.

  3. Ozone electrosynthesis in an electrolyzer with solid polymer electrolyte

    SciTech Connect

    Babak, A.A.; Fateev, V.N.; Amadelli, R.; Potapova, G.F.

    1994-06-01

    Environmental problems have provided a focus of growing attention within the past few years. Of particular interest are preparation techniques for ozone, which is known to be an environmentally clean oxidant applicable to conditioning of potable water, sewage treatment, and disinfection of various domestic media. It also can be employed in chemical synthesis and a number of other applications. An electrolyzer with PbO{sub 2}-covered anode pressed against a membrane of a solid polymer electrolyte of sulfocationite type is shown to exhibit high operational qualities in electrochemical production of ozone.

  4. Electrolytic Enrichment of Tritium with Solid Polymer Electrolyte for Application to Environmental Measurements

    SciTech Connect

    Momoshima, Noriyuki; Nagao, Yusaku; Toyoshima, Takahiro

    2005-07-15

    We evaluated electrolytic separation factors of hydrogen isotopes by SPE (Solid Polymer Electrolyte) for application to environmental tritium analysis. The apparent separation factors {alpha}{sub a} for deuterium and {beta}{sub a} for tritium were determined as 3.5 {+-} 0.1 and 6.2 {+-} 0.5, respectively. The tritium enrichment of 8.4 times was achieved, when a 1000 ml of sample water was electrolyzed to about 60 ml. The chemical composition changes before and after the electrolysis were examined, showing an increase in H{sup +} and Na{sup +} concentrations and a decrease in Mg{sup 2+} and Ca{sup 2+}concentrations. F{sup -}, which was not contained in the sample water, was detected after electrolysis accompanying with a reduction of SO{sub 4}{sup 2-}, Cl{sup -} and NO{sub 3}{sup -}. The memory of tritium and ions in the electrolysis cell after electrolysis was possible to be eliminated by washings with de-ionized water. Tritium concentrations of rain at Kumamoto, Japan were determined with a combination of the present electrolytic enrichment system and liquid scintillation counting.

  5. A Review of Solid Electrolyte Interphases on Lithium Metal Anode

    PubMed Central

    Cheng, Xin‐Bing; Zhang, Rui; Zhao, Chen‐Zi; Wei, Fei; Zhang, Ji‐Guang

    2015-01-01

    Lithium metal batteries (LMBs) are among the most promising candidates of high‐energy‐density devices for advanced energy storage. However, the growth of dendrites greatly hinders the practical applications of LMBs in portable electronics and electric vehicles. Constructing stable and efficient solid electrolyte interphase (SEI) is among the most effective strategies to inhibit the dendrite growth and thus to achieve a superior cycling performance. In this review, the mechanisms of SEI formation and models of SEI structure are briefly summarized. The analysis methods to probe the surface chemistry, surface morphology, electrochemical property, dynamic characteristics of SEI layer are emphasized. The critical factors affecting the SEI formation, such as electrolyte component, temperature, current density, are comprehensively debated. The efficient methods to modify SEI layer with the introduction of new electrolyte system and additives, ex‐situ‐formed protective layer, as well as electrode design, are summarized. Although these works afford new insights into SEI research, robust and precise routes for SEI modification with well‐designed structure, as well as understanding of the connection between structure and electrochemical performance, is still inadequate. A multidisciplinary approach is highly required to enable the formation of robust SEI for highly efficient energy storage systems. PMID:27774393

  6. A Review of Solid Electrolyte Interphases on Lithium Metal Anode.

    PubMed

    Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi; Wei, Fei; Zhang, Ji-Guang; Zhang, Qiang

    2016-03-01

    Lithium metal batteries (LMBs) are among the most promising candidates of high-energy-density devices for advanced energy storage. However, the growth of dendrites greatly hinders the practical applications of LMBs in portable electronics and electric vehicles. Constructing stable and efficient solid electrolyte interphase (SEI) is among the most effective strategies to inhibit the dendrite growth and thus to achieve a superior cycling performance. In this review, the mechanisms of SEI formation and models of SEI structure are briefly summarized. The analysis methods to probe the surface chemistry, surface morphology, electrochemical property, dynamic characteristics of SEI layer are emphasized. The critical factors affecting the SEI formation, such as electrolyte component, temperature, current density, are comprehensively debated. The efficient methods to modify SEI layer with the introduction of new electrolyte system and additives, ex-situ-formed protective layer, as well as electrode design, are summarized. Although these works afford new insights into SEI research, robust and precise routes for SEI modification with well-designed structure, as well as understanding of the connection between structure and electrochemical performance, is still inadequate. A multidisciplinary approach is highly required to enable the formation of robust SEI for highly efficient energy storage systems.

  7. 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).

  8. 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.

  9. 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

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

    SciTech Connect

    Kartini, Evvy; Manawan, Maykel

    2016-02-08

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

  11. Effects of some rare earth and carbonate-based co-dopants on structural and electrical properties of samarium doped ceria (SDC) electrolytes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Anwar, Mustafa; Khan, Zuhair S.; Mustafa, Kamal; Rana, Akmal

    2015-09-01

    In the present study, samarium doped ceria (SDC) and SDC-based composite with the addition of K2CO3 were prepared by co-precipitation route and effects of pH of the solution and calcination temperature on microstructure of SDC and SDC-K2CO3, respectively, were investigated. Furthermore, experimentation was performed to investigate into the ionic conductivity of pure SDC by co-doping with yttrium i.e., YSDC, XRD and SEM studies show that the crystallite size and particle size of SDC increases with the increase in pH. The SEM images of all the samples of SDC synthesized at different pH values showed the irregular shaped and dispersed particles. SDC-K2CO3 was calcined at 600∘C, 700∘C and 800∘C for 4 h and XRD results showed that crystallite size increases while lattice strain, decreases with the increase in calcination temperature and no peaks were detected for K2CO3 as it is present in an amorphous form. The ionic conductivity of the electrolytes increases with the increase in temperature and SDC-K2CO3 shows the highest value of ionic conductivity as compared to SDC and YSDC. Chemical compatibility tests were performed between the co-doped electrolyte and lithiated NiO cathode at high temperature. It revealed that the couple could be used up to the temperature of 700∘C.

  12. Ni-based anode-supported Al2O3-doped-Y2O3-stabilized ZrO2 thin electrolyte solid oxide fuel cells with Y2O3-stabilized ZrO2 buffer layer

    NASA Astrophysics Data System (ADS)

    Lei, Libin; Bai, Yaohui; Liu, Jiang

    2014-02-01

    In order to reduce the sintering temperature of Ni-based anode-supported thin 8 mol% yttria-stabilized zirconia (YSZ) elsectrolyte solid oxide fuel cells (SOFCs), alumina, with a weight percent of 1, 3, 5, and 7, is respectively doped into YSZ as sintering aid. A pure YSZ buffer layer is introduced between the Al2O3-doped-YSZ electrolyte and Ni-YSZ anode, to prevent Al2O3 and NiO from forming non-conductive spinel NiAl2O4. The experimental results show that doping proper amount of Al2O3 doping can reduce the sintering temperature of YSZ, e.g., 1 wt.% doping decreases the temperature from 1673 K to 1573 K. Anode-supported SOFCs are prepared with Al2O3-doped-YSZ electrolytes sintered at different temperatures. Electrochemical characterization of the SOFCs shows that the single cell with 1 wt.% alumina-doped YSZ electrolyte sintered at 1573 K gives the highest output. The effect of alumina doping on sintering behavior and electrical performance of YSZ is discussed in detail.

  13. 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.

  14. Geometrical implication of ion transporters employing an ellipsoidal hollow structure in pseudo-solid electrolytes.

    PubMed

    Kim, Youngjin; Park, Jong Hyuk; Jung, Jihoon; Lee, Sang-Soo

    2015-02-14

    We demonstrate facilitated ion transport in oligomer electrolytes by introducing TiO2 hollow particles of ellipsoidal and spherical shapes. It was found that the TiO2 hollow particles of ellipsoidal shape are much more effective in constructing ionic diffusion paths for the Grotthuss mechanism, resulting in highly enhanced diffusion coefficients of ions such as I(-) and I3(-) in oligomer electrolytes. Compared to the hollow spheres of the TiO2 component, the ellipsoidal hollow particles of the TiO2 component provide 11% larger ionic diffusion coefficients, because of their geometry with a relatively small diffusion resistance. Since the facilitated ion transport can render fast redox reactions at both photo and counter electrodes, the solid state dye-sensitized solar cells employing oligomer electrolytes based on the TiO2 hollow ellipsoids exhibit highly improved photovoltaic performances including highly improved energy-conversion efficiency without destabilizing the cell.

  15. Electrolyte Volume Effects on Electrochemical Performance and Solid Electrolyte Interphase in Si-Graphite/NMC Lithium-Ion Pouch Cells

    DOE PAGES

    An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

    2017-05-15

    This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF6 in ethylene carbonate:ethylmethyl carbonate with 10 wt % fluoroethylene carbonate. Single layer pouch cells (100 mA h) were constructed with 15 wt % Si-graphite/LiNi0.5Mn0.3CO0.2O2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times to the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendrites aremore » observed when the electrolyte volume factor is low. As a result, the resistances from the anodes become significant as the cells are discharged. Solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is nonuniform after cycling.« less

  16. Electrolyte Volume Effects on Electrochemical Performance and Solid Electrolyte Interphase in Si-Graphite/NMC Lithium-Ion Pouch Cells.

    PubMed

    An, Seong Jin; Li, Jianlin; Daniel, Claus; Meyer, Harry M; Trask, Stephen E; Polzin, Bryant J; Wood, David L

    2017-06-07

    This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF6 in ethylene carbonate:ethylmethyl carbonate with 10 wt % fluoroethylene carbonate. Single layer pouch cells (100 mA h) were constructed with 15 wt % Si-graphite/LiNi0.5Mn0.3CO0.2O2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times to the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendrites are observed when the electrolyte volume factor is low. The resistances from the anodes become significant as the cells are discharged. Solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is nonuniform after cycling.

  17. Stability of the Solid Electrolyte Interface on the Li Electrode in Li–S Batteries

    DOE PAGES

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

    2016-04-05

    In this study, 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.

  18. Stability of the Solid Electrolyte Interface on the Li Electrode in Li–S Batteries

    SciTech Connect

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

    2016-04-05

    In this study, 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.

  19. 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

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

    PubMed

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

    2016-01-21

    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.

  2. Ionic conductor with high conductivity as single-component electrolyte for efficient solid-state dye-sensitized solar cells.

    PubMed

    Wang, Hong; Li, Juan; Gong, Feng; Zhou, Gang; Wang, Zhong-Sheng

    2013-08-28

    Imidazolium iodide is an often used component in iodine-based dye-sensitized solar cells (DSSCs), but it cannot operate an efficient DSSC in the absence of iodine due to its low conductivity. For this study, lamellar solid iodide salts of imidazolium or piperidinium with an N-substituted propargyl group have been prepared and applied in solid-state DSSCs. Owing to the high conductivity arising from the lamellar structure, these solid-state ionic conductors can be used as single-component solid electrolytes to operate solid-state DSSCs efficiently without any additives in the electrolyte and post-treatments on the dye-loaded TiO2 films. With a propargyl group attached to the imidazolium ring, the conductivity is enhanced by about 4 × 10(4)-fold as compared to the alkyl-substituted imidazolium iodide. Solid-state DSSC with the 1-propargyl-3-methylimidazolium iodide as the single-component solid-state electrolyte has achieved a light-to-electricity power conversion efficiency of 6.3% under illumination of simulated AM1.5G solar light (100 mW cm(-2)), which also exhibits good long-term stability under continuous 1 sun soaking for 1500 h. This finding paves the way for development of high-conductivity single-component solid electrolytes for use in efficient solid-state DSSCs.

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

    DOE PAGES

    Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

    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.

  4. 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.

  5. 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

  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

    DOEpatents

    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. A durable polyvinyl butyral-CsH2PO4 composite electrolyte for solid acid fuel cells

    NASA Astrophysics Data System (ADS)

    Dang, Dai; Zhao, Bote; Chen, Dongchang; Yoo, Seonyoung; Lai, Samson Y.; Doyle, Brian; Dai, Shuge; Chen, Yu; Qu, Chong; Zhang, Lei; Liao, Shijun; Liu, Meilin

    2017-08-01

    A composite electrolyte membrane composed of polyvinyl butyral (PVB) and CsH2PO4 has been prepared via a facile and cost-effective method for solid acid fuel cells. The effect of PVB content on conductivity, mechanical integrity, and fuel cell performance is investigated. A minimum amount of 3 wt% PVB in the CsH2PO4-based composite electrolyte not only offers the required mechanical integrity but also allows high conductivity (∼28 mS cm-1 at 260 °C). Single cells based on the composite electrolytes demonstrate a peak power density of 108 mW cm-2 at 260 °C. Almost no degradation in electrochemical performance could be observed during the stability test for 10 h and three thermal-cycling test in H2/O2 fuel cell, indicating the promising application of the composite electrolyte in solid acid fuel cells.

  8. Hierarchically oriented macroporous anode-supported solid oxide fuel cell with thin ceria electrolyte film.

    PubMed

    Chen, Yu; Zhang, Yanxiang; Baker, Jeffrey; Majumdar, Prasun; Yang, Zhibin; Han, Minfang; Chen, Fanglin

    2014-04-09

    Application of anode-supported solid oxide fuel cell (SOFC) with ceria based electrolyte has often been limited by high cost of electrolyte film fabrication and high electrode polarization. In this study, dense Gd0.1Ce0.9O2 (GDC) thin film electrolytes have been fabricated on hierarchically oriented macroporous NiO-GDC anodes by a combination of freeze-drying tape-casting of the NiO-GDC anode, drop-coating GDC slurry on NiO-GDC anode, and co-firing the electrolyte/anode bilayers. Using 3D X-ray microscopy and subsequent analysis, it has been determined that the NiO-GDC anode substrates have a porosity of around 42% and channel size from around 10 μm at the electrolyte side to around 20 μm at the other side of the NiO-GDC (away from the electrolyte), indicating a hierarchically oriented macroporous NiO-GDC microstructure. Such NiO-GDC microstructure shows a tortuosity factor of ∼1.3 along the thickness direction, expecting to facilitate gas diffusion in the anode during fuel cell operation. SOFCs with such Ni-GDC anode, GDC film (30 μm) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3-GDC (LSCF-GDC) cathode show significantly enhanced cell power output of 1.021 W cm(-2) at 600 °C using H2 as fuel and ambient air as oxidant. Electrochemical Impedance Spectroscopy (EIS) analysis indicates a decrease in both activation and concentration polarizations. This study has demonstrated that freeze-drying tape-casting is a very promising approach to fabricate hierarchically oriented porous substrate for SOFC and other applications.

  9. 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

  10. Handheld Microneedle-Based Electrolyte Sensing Platform.

    SciTech Connect

    Miller, Philip R.; Rivas, Rhiana; Johnson, David; Edwards, Thayne L.; Koskelo, Markku; Shawa, Luay; Brener, Igal; Chavez, Victor H.; Polsky, Ronen

    2015-11-01

    Sandia National Laboratories will provide technical assistance, within time and budget, to Requester on testing and analyzing a microneedle-based electrolyte sensing platform. Hollow microneedles will be fabricated at Sandia and integrated with a fluidic chip using plastic laminate prototyping technology available at Sandia. In connection with commercial ion selective electrodes the sensing platform will be tested for detection of electrolytes (sodium and/or potassium) within physiological relevant concent ration ranges.

  11. Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

    PubMed

    Ai, Na; Li, Na; Rickard, William D A; Cheng, Yi; Chen, Kongfa; Jiang, San Ping

    2017-03-09

    Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y2 O3 -ZrO2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO3-δ (LC) and Sm0.95 CoO3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm(-2) and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm0.95 Co0.95 Pd0.05 O3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm(-2) at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A Limiting Current Oxygen Sensor Based on LSGM as a Solid Electrolyte and LSGMN ( N = Fe, Co) as a Dense Diffusion Barrier

    NASA Astrophysics Data System (ADS)

    Liu, Tao; Gao, Xiang; He, Bei-Gang; Yu, Jing-Kun

    2016-07-01

    The La0.8Sr0.2(Ga1- x Co x )0.8Mg0.2O3- δ (LSGMC x = 0.05, 0.1, 0.15, 0.2, 0.25) and La0.8Sr0.2(Ga1- x Fe x )0.8Mg0.2O3- δ (LSGMF x = 0.1, 0.2, 0.3) samples were prepared by solid-state reaction. The structure, conductivity, thermal expansion behavior, and chemical compatibility were studied by XRD, dilatometry, and four-terminal method. A limiting current oxygen sensor was prepared with La0.8Sr0.2Ga0.83Mg0.17O2.815 as a solid electrolyte and La0.8Sr0.2(Ga0.75Co0.25)0.8Mg0.2O3- δ as a dense diffusion barrier. The oxygen-sensitive characteristic was measured at different oxygen concentrations. The results show that the phase structure of samples is cubic, except La0.8Sr0.2(Ga0.75Co0.25)0.8Mg0.2O3- δ , which has a hexagonal structure. The change in activation energy for electrical conductivity and the increase in thermal expansion coefficient are confirmed to correlate with an increasing concentration of oxygen vacancies. The limiting current oxygen sensor exhibits a good limiting current platform and the limiting current depends linearly on the oxygen concentration: I L(mA) = 12.8519 + 2.2667 x_{{{O}_{{2}} }} (mol%, 0 < x_{{{{O}}_{ 2} }} < 3.31) at 750 °C, I L(mA) = 14.3222 + 3.5180 x_{{{O}_{{2}} }} (mol%, 0 < x_{{{{O}}_{ 2} }} < 4.16) at 800 °C, and I L(mA) = 15.2872 + 5.0269x_{{{O}_{{2}} }}(mol%, 0 < x_{{{{O}}_{ 2} }} < 4.12) at 850 °C. The sensor has the best sensitivity at 850 °C. As the oxygen concentration increases, the interface resistance of the sensor decreases at 850 °C.

  13. 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.

  14. A Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium Batteries.

    PubMed

    Gao, Hongcai; Xue, Leigang; Xin, Sen; Park, Kyusung; Goodenough, John B

    2017-05-08

    The development of all-solid-state rechargeable batteries is plagued by a large interfacial resistance between a solid cathode and a solid electrolyte that increases with each charge-discharge cycle. The introduction of a plastic-crystal electrolyte interphase between a solid electrolyte and solid cathode particles reduces the interfacial resistance, increases the cycle life, and allows a high rate performance. Comparison of solid-state sodium cells with 1) solid electrolyte Na3 Zr2 (Si2 PO4 ) particles versus 2) plastic-crystal electrolyte in the cathode composites shows that the former suffers from a huge irreversible capacity loss on cycling whereas the latter exhibits a dramatically improved electrochemical performance with retention of capacity for over 100 cycles and cycling at 5 C rate. The application of a plastic-crystal electrolyte interphase between a solid electrolyte and a solid cathode may be extended to other all-solid-state battery cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Estimating the thickness of diffusive solid electrolyte interface

    NASA Astrophysics Data System (ADS)

    Wang, XiaoHe; Shen, WenHao; Huang, XianFu; Zang, JinLiang; Zhao, YaPu

    2017-06-01

    The solid electrolyte interface (SEI) is a hierarchical structure formed in the transition zone between the electrode and the electrolyte. The properties of lithium-ion (Li-ion) battery, such as cycle life, irreversible capacity loss, self-discharge rate, electrode corrosion and safety are usually ascribed to the quality of the SEI, which are highly dependent on the thickness. Thus, understanding the formation mechanism and the SEI thickness is of prime interest. First, we apply dimensional analysis to obtain an explicit relation between the thickness and the number density in this study. Then the SEI thickness in the initial charge-discharge cycle is analyzed and estimated for the first time using the Cahn-Hilliard phase-field model. In addition, the SEI thickness by molecular dynamics simulation validates the theoretical results. It has been shown that the established model and the simulation in this paper estimate the SEI thickness concisely within order-of-magnitude of nanometers. Our results may help in evaluating the performance of SEI and assist the future design of Li-ion battery.

  16. Enhanced ionic conductivity and optical studies of plasticized (PEO-KCl) solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Chapi, Sharanappa; H, Devendrappa

    2015-06-01

    Solid polymer electrolytes (SPEs) based on Polyethylene oxide (PEO) doped with potassium chloride (KCl) were prepared by the solution cast technique. The conductivity increases from 10-10 to 10-6 Scm-1 at 303K with dopant. Optical absorption study shows that the direct & indirect optical band gaps were found decreased from 5.45-4.46eV and 4.96-3.86eV respectively with increasing the KCl. The XRD patterns reveal increasing the amorphous with increasing the dopent. The obtained results suggest that, these polymer systems are suitable candidates for solid state battery, electro chromic devices & optoelectronics display etc.

  17. Structure, morphology and ionic conductivity of solid polymer electrolyte

    SciTech Connect

    Dey, Arup; Karan, S.; Dey, Ashis; De, S.K.

    2011-11-15

    Graphical abstract: Two-dimensional atomic force image of pure polyethylene oxide presents a crystallized network of regular spherulites developing spirals and branches of well distributed surface contours. Highlights: {yields} The incorporation of ceria significantly modifies the morphology of polyethylene oxide (PEO)-KI complex. {yields} The ionic conductivity increases by about two orders of magnitude by the addition of ceria nanoparticles. {yields} Ionic conductivity as a function of ceria concentration reveals two maxima. {yields} Grain boundary effect of nanofiller, strong Lewis acid-base interaction between PEO and nanosized ceria, change of conformation of PEO molecule and epitaxial effect of ceria nanoparticles control the ionic conductivity of composite polymer electrolyte. -- Abstract: Polyethylene oxide (PEO) complexed with potassium iodide (KI) is synthesized to investigate the ionic conductivity of alkaline based polymer electrolytes. The structural and morphological characterizations of the nanocomposite polymer electrolytes are performed by X-ray diffractometry (XRD), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) measurements. The ionic conductivity increases with the increase of KI concentration up to about 20 wt.%. The effect of nanosized ceria (CeO{sub 2} {approx} 10 nm) fillers on ionic conductivity in PEO-KI polymer electrolyte is also carried out, keeping PEO to KI wt.% ratio 80:20 and 85:15. The result reveals that the addition of ceria nanoparticles enhances the conductivity by two orders of magnitude. The presence of ceria at the highest concentration induces the same molecular environment within PEO chain as that of undoped PEO. Temperature dependence of ionic conductivity follows Arrhenius mechanism.

  18. Bendable and thin sulfide solid electrolyte film: a new electrolyte opportunity for free-standing and stackable high-energy all-solid-state lithium-ion batteries.

    PubMed

    Nam, Young Jin; Cho, Sung-Ju; Oh, Dae Yang; Lim, Jun-Muk; Kim, Sung Youb; Song, Jun Ho; Lee, Young-Gi; Lee, Sang-Young; Jung, Yoon Seok

    2015-05-13

    Bulk-type all-solid-state lithium batteries (ASLBs) are considered a promising candidate to outperform the conventional lithium-ion batteries. Unfortunately, the current technology level of ASLBs is in a stage of infancy in terms of cell-based (not electrode-material-based) energy densities and scalable fabrication. Here, we report on the first ever bendable and thin sulfide solid electrolyte films reinforced with a mechanically compliant poly(paraphenylene terephthalamide) nonwoven (NW) scaffold, which enables the fabrication of free-standing and stackable ASLBs with high energy density and high rate capabilities. The ASLB, using a thin (∼70 μm) NW-reinforced SE film, exhibits a 3-fold increase of the cell-energy-density compared to that of a conventional cell without the NW scaffold.

  19. Electrolyte volume effects on electrochemical performance and solid electrolyte interphase in Si-graphite/NMC lithium-ion pouch cells

    DOE PAGES

    An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

    2017-05-15

    This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF6 in ethylene carbonate:ethylmethyl carbonate with 10 wt.% fluoroethylene carbonate. Single layer pouch cells (100 mAh) were constructed with 15 wt.% Si-graphite/LiNi0.5Mn0.3CO0.2O2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendrites are observed when the electrolytemore » volume factor is low. The resistances from the anodes become significant as the cells are discharged. As a result, solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is non-uniform after cycling.« less

  20. 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.

  1. 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.

  2. Nanoscale electrochemistry using dielectric thin films as solid electrolytes

    NASA Astrophysics Data System (ADS)

    Valov, Ilia; Lu, Wei D.

    2016-07-01

    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.

  3. 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.

  4. Tritium Separation by Electrolysis Using Solid Polymer Electrolyte

    SciTech Connect

    Ogata, Y.; Sakuma, Y.; Ohtani, N.; Kotaka, M.

    2005-07-15

    Hydrogen isotope separation effect by electrolysis of water was theoretically investigated and was compared with experimental results. The separation mechanism was analyzed as the hydrogen isotope exchange reaction between water and diatomic hydride that consists of hydrogen and cathode material. The equilibrium constants of the isotope exchange reaction were calculated from reduced partition function ratio. Using the constants, the separation factor (SF) of the isotopes was calculated according to the two-phase distribution theory for isotopes. Experimentally, light or heavy water spiked with tritiated water was electrolyzed by a device with a solid polymer electrolyte, which equipped with SUS, Ni, or carbon cathode. Thus, the SFs were experimentally obtained. Calculated SFs were well agreed with the experimentally values for SUS and Ni cathodes, and that for carbon cathode was somewhat small then the experimental value.

  5. Divalent beta aluminas: High conductivity solid electrolytes for divalent cations

    NASA Astrophysics Data System (ADS)

    Farrington, G. C.; Dunn, B.

    1982-10-01

    The Na(+) content of beta alumina can be replaced by a variety of divalent cations in simple ion exchange reactions. The resulting divalent beta' aluminas are the first family of high conductivity solid electrolytes for divalent cations. Divalent beta' aluminas which have been prepared so far include conductors of Ca(2+), Sr(2+), Ba(2+), Zn(2+), Cd(2+), Pb(2+), Hg(2+), and Mn(2+). Most have conductivities of about 0.1/(ohm-cm) at 300-400 C. However, the conductivity of Pb(++) beta alumina is 0.0046/(ohm-cm) at 40 C, nearly equal to that of Na(+) beta alumina. Preliminary structure studies indicate that order-disorder reactions among the divalent cations and vacancies in the conduction region of beta alumina critically influence conductivity in the structure.

  6. Achieving high capacity in bulk-type solid-state lithium ion battery based on Li6.75La3Zr1.75Ta0.25O12 electrolyte: Interfacial resistance

    NASA Astrophysics Data System (ADS)

    Liu, Ting; Ren, Yaoyu; Shen, Yang; Zhao, Shi-Xi; Lin, Yuanhua; Nan, Ce-Wen

    2016-08-01

    A bulk-type all-solid-state lithium ion battery based on Ta-doped Li6.75La3Zr1.75Ta0.25O12 (LLZ-Ta) is prepared by a simple solid state process with high capacity of 279.0 μAh cm-2 at 80 °C. However, severe polarization is discovered during charging/discharging cycles at room temperature (RT) for battery with a higher active cathode loading. Large interfacial resistance due to the poor contact at the interfaces between cathode and LLZ-Ta solid electrolyte and at the interfaces within the composite cathode layer is proven to be the main reason for the poor electrochemical performance of the battery at RT. The polarization could be suppressed at elevated temperature, which is attributed to the decreased interfacial resistance as indicated by the results of impedance measurements and gives rise to much enhanced performance of the all-solid-state battery.

  7. Battery electrolytes. Citations from the NTIS data base

    NASA Astrophysics Data System (ADS)

    Young, C. G.

    1980-05-01

    Many types of solid, liquid and gaseous battery electrolytes are described and analyzed in the cited abstracts. Battery design, construction, and use, employing the listed electrolytes, are discussed. Battery design, construction, and use, employing the listed electrolytes, are discussed. Battery life, efficiency, and maintenance characteristics are also delineated. Included are 196 citations.

  8. 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.

  9. Aluminum oxyhydroxide based separator/electrolyte and battery system, and a method of making the same

    SciTech Connect

    Gerald, II; Rex E.; Klingler, Robert J.; Rathke, Jerome W.

    2011-02-15

    The instant invention relates a solid-state electrochemical cell and a novel separator/electrolyte incorporated therein. The invented electrochemical cell generally comprising: a unique metal oxyhydroxide based (i.e. AlOOH) separator/electrolyte membrane sandwiched between a first electrode and a second electrode. The novel separator/electrolyte comprises a nanoparticulate metal oxyhydroxide, preferably AlOOH and a salt which are mixed and then pressed together to form a monolithic metal oxyhydroxide-salt membrane.

  10. Studies on Gel Electrolyte Based on Nitrile-Butadiene Copolymers

    DTIC Science & Technology

    1993-06-01

    preparation of a hybrid electrolyte, suitable for solid-polymer batteries. Based on the study of ionic conductivity in the presence of LiBF4 of a...lithium salts in different plasticizers showed the highest conductivity for LiBF4 . Conductivity of LiBF4 in different plasticizers decreases in the order...GLASS TRANSITION 53 TEMPERATURE OF VARIOUS NBR COPOLYMERS WITH AND WITHOUT LiBF4 APPENDIX B: ANOMALY IN THE IONIC 63 CONDUCTIVITY-TEMPERATURE STUDIES

  11. Novel Li[(CF3SO2)(n-C4F9SO2)N]-Based Polymer Electrolytes for Solid-State Lithium Batteries with Superior Electrochemical Performance.

    PubMed

    Ma, Qiang; Qi, Xingguo; Tong, Bo; Zheng, Yuheng; Feng, Wenfang; Nie, Jin; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan; Zhou, Zhibin

    2016-11-02

    Solid polymer electrolytes (SPEs) would be promising candidates for application in high-energy rechargeable lithium (Li) batteries to replace the conventional organic liquid electrolytes, in terms of the enhanced safety and excellent design flexibility. Herein, we first report novel perfluorinated sulfonimide salt-based SPEs, composed of lithium (trifluoromethanesulfonyl)(n-nonafluorobutanesulfonyl)imide (Li[(CF3SO2)(n-C4F9SO2)N], LiTNFSI) and poly(ethylene oxide) (PEO), which exhibit relatively efficient ionic conductivity (e.g., 1.04 × 10(-4) S cm(-1) at 60 °C and 3.69 × 10(-4) S cm(-1) at 90 °C) and enough thermal stability (>350 °C), for rechargeable Li batteries. More importantly, the LiTNFSI-based SPEs could not only deliver the excellent interfacial compatibility with electrodes (e.g., Li-metal anode, LiFePO4 and sulfur composite cathodes), but also afford good cycling performances for the Li|LiFePO4 (>300 cycles at 1C) and Li-S cells (>500 cycles at 0.5C), in comparison with the conventional LiTFSI (Li[(CF3SO2)2N])-based SPEs. The interfacial impedance and morphology of the cycled Li-metal electrodes are also comparatively analyzed by electrochemical impedance spectra and scanning electron microscopy, respectively. These indicate that the LiTNFSI-based SPEs would be potential alternatives for application in high-energy solid-state Li batteries.

  12. 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.

  13. 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.

  14. 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

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

    PubMed

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

    2014-12-19

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  17. Low temperature processing of sulfide and oxide lithium solid electrolytes to bridge ionically resistive boundaries

    NASA Astrophysics Data System (ADS)

    Berbano, Seth Sevidal

    Solid electrolytes are enabling materials for solid-state batteries. The theme of the contributions in this thesis center around low temperature processing of solid electrolytes and their resulting microstructures and ionic conductivities. Solid electrolytes are of interest for safer and more reliable replacements to liquid electrolytes at a wide range of operating temperatures. Using pressure-temperature-assisted densification (200 °C and 190 MPa), ionically resistive pores were minimized and ionic conductivity was maximized in x Li2S + (1-x) P2S5 (x = 0.70, 0.75, 0.80) solid electrolytes. For 0.70 Li2S + 0.30 P2S 5, the powder-in-a-tube method was demonstrated as a method to fabricate 120 mum thin electrolytes with 10-3 S/cm ionic conductivities at 25 °C for large area format batteries. Using cold sintering, the solid electrolyte Li1+xAlx Ge2-x(PO4)3 (x = 0.50) was densified to around 80% theoretical density in minutes at 120 °C and 400 MPa. In order to bridge ionically resistive grain boundaries, a 5 minute post-processing at 650 °C was required. High volume fractions of ceramic electrolyte could be co-sintered with polymer. Up to 95 vol. % Li1.5Al0.5Ge 1.5(PO4)3 + 5 vol. % Poly(vinylidene fluoride hexafluoropropylene) composite electrolytes were cold sintered at 120 °C to densities exceeding 85 %. After soaking in 1 M LiPF6 ethylene carbonate-dimethyl carbonate (50:50 vol. %), composite electrolyte ionic conductivities at 25 °C reached 10-4 S/cm. Using cold sintering, processing and integration of solid electrolytes and other important technical ceramics may now be possible at polymer processing temperatures.

  18. Composite Electrolyte for All-Solid-State Lithium Batteries: Low-Temperature Fabrication and Conductivity Enhancement.

    PubMed

    Lee, Sang-Don; Jung, Kyu-Nam; Kim, Hyeongil; Shin, Hyun-Seop; Song, Seung-Wan; Park, Min-Sik; Lee, Jong-Won

    2017-03-20

    All-solid-state lithium batteries offer notable advantages over conventional Li-ion batteries with liquid electrolytes in terms of energy density, stability, and safety. To realize this technology, it is critical to develop highly reliable solid-state inorganic electrolytes with high ionic conductivities and adequate processability. Li1+x Alx Ti2-x (PO4 )3 (LATP) with a NASICON (Na superionic conductor)-like structure is regarded as a potential solid electrolyte, owing to its high "bulk" conductivity (ca. 10(-3)  S cm(-1) ) and excellent stability against air and moisture. However, the solid LATP electrolyte still suffers from a low "total" conductivity, mainly owing to the blocking effect of grain boundaries to Li(+) conduction. In this study, an LATP-Bi2 O3 composite solid electrolyte shows very high total conductivity (9.4×10(-4)  S cm(-1) ) at room temperature. Bi2 O3 acts as a microstructural modifier to effectively reduce the fabrication temperature of the electrolyte and to enhance its ionic conductivity. Bi2 O3 promotes the densification of the LATP electrolyte, thereby improving its structural integrity, and at the same time, it facilitates Li(+) conduction, leading to reduced grain-boundary resistance. The feasibility of the LATP-Bi2 O3 composite electrolyte in all-solid-state Li batteries is also examined in this study.

  19. 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.

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

    SciTech Connect

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

    2016-07-06

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

  1. Analysis of the solid electrolyte interphase formed with an ionic liquid electrolyte for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Xiong, Shizhao; Xie, Kai; Blomberg, Erik; Jacobsson, Per; Matic, Aleksandar

    2014-04-01

    We have investigated the formation of the solid electrolyte interphase (SEI) on lithium electrodes in the presence of an ionic liquid electrolyte with a particular focus on the influence of polysulfides present in the electrolyte on the SEI. The electrochemical performance of symmetric cells with lithium electrodes and electrolytes composed of N-Methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14-TFSI) and LiTFSI, with and without the addition of polysulfides, were analyzed as well as the chemical composition of the SEI, before and after cycling. The cycling behavior of the symmetrical cells shows that the SEI films are relatively stable in the ionic liquid electrolyte, also in the presence of polysulfides. However, the presence of polysulfides results in a higher SEI layer resistance (RSEI) and a higher activation energy. From X-ray photoelectron spectroscopy spectra (XPS), with argon-ion sputtering for depth profiling, we find that the SEI is formed by decomposition products from both cations and anions of the electrolyte. The XPS spectra show that the presence of polysulfides alters the decomposition process of the electrolyte, resulting in a SEI film with different chemical composition and structure, in line with the results from the electrochemical performance.

  2. Chemical stability of γ-butyrolactone-based electrolytes for aluminum electrolytic capacitors

    NASA Astrophysics Data System (ADS)

    Ue, Makoto; Takeda, Masayuki; Suzuki, Yoko; Mori, Shoichiro

    γ-Butyrolactone-based electrolytes have been used as the operating electrolytes for aluminum electrolytic capacitors. The chemical stability of these electrolytes at elevated temperatures has been examined by monitoring the decrease in their electrolytic conductivities. The deteriorated electrolytes were analyzed by gas and liquid chromatography and the conductivity decrease was directly correlated with the loss of acid components. In quaternary ammonium hydrogen maleate/γ-butyrolactone electrolytes, the maleate anion decomposed by decarboxylation resulting in a complex polymer containing polyester and polyacrylate structures. Quaternary ammonium benzoate/γ-butyrolactoneelectrolytes decomposed by SN2 reactions giving alkyi benzoates and trialkylamines. The deterioration of the carboxylate salt/γ-butyrolactone electrolytes was accelerated by electrolysis.

  3. Silica nanoparticle doped organic ionic plastic crystal electrolytes for highly efficient solid-state dye-sensitized solar cells.

    PubMed

    Shi, Chengzhen; Qiu, Lihua; Chen, Xiaojian; Zhang, Haigang; Wang, Lei; Yan, Feng

    2013-02-01

    Organic ionic plastic crystal, 1-propyl-1-methylpyrrolidinium iodide (P₁₃I), which possesses a broad plastic phase from -36 to 135 °C, was doped with silica nanoparticles (SiO₂ NPs) and 1-ethyl-3-methylimidazolium iodide (EMII), for the preparation of SiO₂/EMII/P₁₃I solid-state electrolytes for dye-sensitized solar cells (DSSCs). The thermal properties of all the electrolytes, including solid-solid phase transitions and melting temperatures, were investigated by differential scanning calorimetry (DSC). The effect of silica particles on the ionic conductivity, diffusion of I⁻/I₃⁻ redox couple in electrolytes, and photovoltaic performance for solid-state DSSCs were investigated. The fabricated solid-state DSSCs yielded a high power conversion efficiency of 5.25% under simulated air mass 1.5 solar spectrum illuminations at 50 mW cm⁻². Furthermore, the DSSCs based on SiO₂/EMII/P₁₃I solid-state electrolytes show good stability after an accelerating aging test, demonstrating potential practical applications.

  4. Solidified inorganic-organic hybrid electrolyte for all solid state flexible lithium battery

    NASA Astrophysics Data System (ADS)

    Baek, Seung-Wook; Honma, Itaru; Kim, Jedeok; Rangappa, Dinesh

    2017-03-01

    Solidified lithium conducting hybrid electrolyte is designed and processed to realize the large scale and flexible solid state Li battery satisfying energy capability and safety issue. This paper presents a solidified inorganic-organic hybrid electrolyte to obtain commercially-acceptable ionic conductivity and a stable electrochemical window to prevent electrolyte decomposition in Li ion batteries. Li3PO4 coated with solidified [Li][EMI][TFSI] ionic liquid is developed as hybrid electrolyte material. The material has high electrochemical stability on a high-voltage cathode and metallic anode, and the solid electrolyte has high ionic conductivity. This Li3PO4-[Li][EMI][TFSI] hybrid electrolyte has the advantages of long-term operation, safety and flexibility, so it may be suitable for use in high-voltage cathodes and Li anode.

  5. Preparation of YSZ-TZP solid electrolytes by gel-casting technology.

    PubMed

    Li, Guojun; Ren, Ruiming

    2011-06-01

    8 mol% yttria stabilized zirconia, TZP: 3 mol% yttria stabilized tetragonal zirconia polycrystal) solid electrolytes were prepared by gel-casting technology. The densification, microstructure, mechanical and electrical properties were characterized and discussed. The densification of YSZ-TZP solid electrolytes increased with increasing TZP content. The strength and fracture toughness showed a maximum value when TZP was 20 vol.%. However, addition of TZP decreased the conductivities of solid electrolyte. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  6. 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.

  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. Influence of carbon nanotubes on the optical properties of plasticized solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Ibrahim, Suriani; Yasin, Siti Mariah Mohd; Johan, Mohd Rafie

    2013-07-01

    Polyethylene oxide (PEO) based solid polymer electrolyte films complexed with lithium hexafluorophosphate (LiPF6), ethylene carbonate (EC) and carbon nanotubes (CNTs) are prepared by solution-casting technique. The complexation of doping materials with polymer is confirmed by X-ray diffraction and infrared studies. The incorporation of LiPF6, EC and CNTs into the host polymer shows a significant increase in conductivity of 10-10 and 10-3 S cm-1. The optical properties such as direct and indirect band gaps are investigated for pure and doped polymer films within a wavelength range of 200-400 nm. It is found that the energy gaps and band edge values shift towards lower energies upon doping. It is shown that LiPF6, EC and CNTs are responsible for the formation of defects in polymer electrolytes, which increases the degree of disorder in the films.

  9. Safety-Reinforced Succinonitrile-Based Electrolyte with Interfacial Stability for High-Performance Lithium Batteries.

    PubMed

    Zhang, Qingqing; Liu, Kai; Ding, Fei; Li, Wei; Liu, Xingjiang; Zhang, Jinli

    2017-09-06

    Different contents of fluoroethylene carbonate (FEC) as cosolvent is added into succinonitrile (SN) solution to form a novel electrolyte for lithium batteries. The SN-based electrolyte with 20 wt % FEC exhibits the most favorable properties involving the good thermal stability, wide electrochemical window and high ionic conductivity. Comparing with the commercial electrolyte, the 20% FEC-SN electrolyte demonstrates the advantage of high safety and excellent interfacial compatibility with lithium due to the form of compact and smooth solid electrolyte interphase layer on the anode. LiCoO2/Li cells using the SN-based electrolyte behave a high reversible discharge capacity of 122.4 mAh g(-1) and keep an outstanding capacity retention of 91% (122.1 mAh g(-1)) at 0.5 C after 100 cycles at 25 °C, 50 °C, respectively. More importantly, the soft-package cells with the SN-based electrolyte can withstand harsh surroundings at 120 °C for 30 min without gas emitted, and can still keep the capacity retention of 77% compared to that before heat treatment, significantly higher than traditional commercial electrolyte (0%). All above results indicate the novel SN-based electrolyte can be an excellent alternative electrolyte in a practical lithium battery.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    PubMed

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

    2014-08-01

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

  12. 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.

  13. Non-aqueous gel polymer electrolyte with phosphoric acid ester and its application for quasi solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Łatoszyńska, Anna A.; Żukowska, Grażyna Zofia; Rutkowska, Iwona A.; Taberna, Pierre-Louis; Simon, Patrice; Kulesza, Pawel J.; Wieczorek, Władysław

    2015-01-01

    A mechanically-stable non-aqueous proton-conducting gel polymer electrolyte that is based on methacrylate monomers, is considered here for application in solid-state type supercapacitors. An electrochemical cell using activated carbon as active materials and the new gel polymer electrolyte has been characterized at room temperature using cyclic voltammetry, galvanostatic charge-discharge cycle tests as well as impedance spectroscopy. The use of phosphoric acid ester (instead of phosphoric acid) as a proton donor has led to an increase of both the operation voltage window (up to 1.3 V) and the electrolyte ionic conductivity (on the level of an order of magnitude). The resulting double layer capacitance of the microporous activated carbon was found to be as high as 120 F g-1; even more important, the supercapacitor utilizing non-aqueous proton-conducting gel polymer electrolyte is well-behaved in the wide temperature range (namely, from -40 to 80 °C).

  14. 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.

  15. Safety of solid-state Li metal battery: Solid polymer versus liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Perea, Alexis; Dontigny, Martin; Zaghib, Karim

    2017-08-01

    In this article we present the difference in thermal stability of Li/LiFePO4| half cells with liquid and solid polymer electrolytes. After two initial cycles, the cells were charged to two different state of charge (SOC) of 50 and 100%. The thermal stability of the half cells is assessed with an accelerating rate calorimeter, and the thermal runaway parameters are discussed for each experiment: dependence of self-heating rate on temperature, temperature of a first-detected exothermic reaction, and maximum cell temperature. The dependence of those parameters with respect to the SOC is also presented.

  16. Ultrahigh Mobility in Solution-Processed Solid-State Electrolyte-Gated Transistors.

    PubMed

    Nketia-Yawson, Benjamin; Kang, Seok-Ju; Tabi, Grace Dansoa; Perinot, Andrea; Caironi, Mario; Facchetti, Antonio; Noh, Yong-Young

    2017-04-01

    A new concept of a high-capacitance polymeric dielectric based on high-k polymer and ion gel blends is reported. This solid-state electrolyte gate insulator enables remarkable field-effect mobilities exceeding 10 cm(2) V(-1) s(-1) for common polymer and other semiconductor families at VG ≤ 2 V owing to high areal capacitance (>4 µF cm(-2) ) from combined polarization of CF interface dipoles and electrical-double-layer formation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. Stable dye-sensitized solar cells based on a gel electrolyte with ethyl cellulose as the gelator

    NASA Astrophysics Data System (ADS)

    Vasei, Maryam; Tajabadi, Fariba; Jabbari, Ali; Taghavinia, Nima

    2015-09-01

    A simple gelating process is developed for the conventional acetonitrile-based electrolyte of dye solar cells, based on ethyl cellulose as the gelator. The electrolyte becomes quasi-solid-state upon addition of an ethanolic solution of ethyl cellulose to the conventional acetonitrile-based liquid electrolyte. The photovoltaic conversion efficiency with the new gel electrolyte is only slightly lower than with the liquid electrolyte, e.g., 6.5 % for liquid electrolyte versus 5.9 % for gel electrolyte with 5.8 wt% added ethyl cellulose. Electrolyte gelation has small effect on the ionic diffusion coefficient of iodide, and the devices are remarkably stable for at least 550 h under irradiation at 55 °C.

  19. Gassing behavior of lithium titanate based lithium ion batteries with different types of electrolytes

    NASA Astrophysics Data System (ADS)

    Liu, Jiali; Bian, Peiwen; Li, Jia; Ji, Wenjiao; Hao, Hao; Yu, Aishui

    2015-07-01

    Gassing behavior of LiMn2O4/Li4Ti5O12 full cell with different electrolytes that stored at elevated temperature of 70 °C is investigated. Scanning electron microscope (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) are used to study the solid electrolyte interphase (SEI) layer formed in battery formation and storage processes. The results suggest that the SEI film is formed as a consequence of intrinsic reaction between Li4Ti5O12 electrode and electrolyte solvents. A smooth SEI layer is formed on Li4Ti5O12 electrode with full coverage in propylene carbonate (PC) based electrolyte during lithium intercalation process while gradually dissolved with lithium extraction. Moreover, the gas specificities generated in the different electrolyte solvents are also determined by gas chromatography-mass spectrometer (GC-MS) analysis and the reaction mechanisms of LTO electrode with electrolyte solvents are proposed.

  20. Magnetic field processed solid-state dye-sensitized solar cells with nickel oxide modified agarose electrolyte

    NASA Astrophysics Data System (ADS)

    Yang, Ying; Yi, Pengfei; Zhou, Conghua; Cui, Jiarui; Zheng, Xiaolu; Xiao, Si; Guo, Xueyi; Wang, Wenyong

    2013-12-01

    In this work we investigate novel, agarose-based polymer electrolyte that is modified by magnetic NiO nanoparticles for solid-state dye-sensitized solar cells (DSSCs) applications. After proper treatment under an external magnetic field, the agarose electrolyte exhibits increased ionic conductivity and better penetration into the mesoporous TiO2 photoanode film, which improves the power conversion efficiency of the DSSCs. Electrochemical impedance spectroscopy measurement is also performed to analyze the magnetic field effect on cell performance. After applying proper magnetic filed intensity, the recombination resistance and redox transport resistance in the devices are improved. This method can be possibly applied to other solid-state electrolyte materials to improve their performance and can lead to more efficient DSSCs.

  1. All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

    PubMed

    Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

    2014-11-26

    The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

  2. 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.

  3. 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.

  4. Improved Electrodes and Electrolytes for Dye-Based Solar Cells

    SciTech Connect

    Harry R. Allcock; Thomas E. Mallouk; Mark W. Horn

    2011-10-26

    The most important factor in limiting the stability of dye-sensitized solar cells is the use of volatile liquid solvents in the electrolytes, which causes leakage during extended operation especially at elevated temperatures. This, together with the necessary complex sealing of the cells, seriously hampers the industrial-scale manufacturing and commercialization feasibilities of DSSCs. The objective of this program was to bring about a significant improvement in the performance and longevity of dye-based solar cells leading to commercialization. This had been studied in two ways first through development of low volatility solid, gel or liquid electrolytes, second through design and fabrication of TiO2 sculptured thin film electrodes.

  5. Anion Solvation in Carbonate-Based Electrolytes

    DOE PAGES

    von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg; ...

    2015-11-16

    The correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. Now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. Moreover, as a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate,more » PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.« less

  6. Anion Solvation in Carbonate-Based Electrolytes

    SciTech Connect

    von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg; Peng, Jing; Russell, Selena M.; Wikner, Emily; Fu, Adele; Hu, Libo; Lee, Hung-Sui; Zhang, Zhengcheng; Yang, Xiao-Qing; Greenbaum, Steven; Amine, Khalil; Xu, Kang

    2015-11-16

    The correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. Now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. Moreover, as a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  7. 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. © Wiley Periodicals, Inc.

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

    DOE PAGES

    Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; ...

    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

  9. 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.

  10. A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

    SciTech Connect

    Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; Shi, Jinan; Chu, Yong S.; Yu, Xiqian; Xu, Kaiqi; Ge, Mingyuan; Yan, Hanfei; Li, Wenjun; Gu, Lin; Hu, Yong -Sheng; Li, Hong; Chen, Liquan; Huang, Xuejie

    2016-10-31

    Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na+ ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm–1 at 25°C and 14 ms cm–1 at 80°C.

  11. A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

    DOE PAGES

    Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; ...

    2016-10-31

    Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na+ ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm–1 at 25°C and 14 ms cm–1 at 80°C.

  12. The thermal stability of sodium beta''-Alumina solid electrolyte ceramic in AMTEC cells

    NASA Astrophysics Data System (ADS)

    Williams, Roger M.; Ryan, Margaret A.; Homer, Margie L.; Lara, Liana; Manatt, Ken; Shields, Virgil; Cortez, Roger H.; Kulleck, James

    1999-01-01

    A critical component of alkali metal thermal-to electric converter (AMTEC) devices for long duration space missions is the beta''-alumina solid electrolyte ceramic (BASE), for which there exists no substitute. The temperature and environmental conditions under which BASE remains stable control operational parameters of AMTEC devices. We have used mass loss experiments in vacuum to 1573K to characterize the kinetics of BASE decomposition, and conductivity and exchange current measurements in sodium vapor filled exposure cells to 1223K to investigate changes in the BASE which affect its ionic conductivity. There is no clear evidence of direct thermal decomposition of BASE below 1273K, although limited soda loss may occur. Reactive metals such as Mn or Cr can react with BASE at temperatures at least as low as 1223K.

  13. Lithium Bis(fluorosulfonyl)imide/Poly(ethylene oxide) Polymer Electrolyte for All Solid-State Li-S Cell.

    PubMed

    Judez, Xabier; Zhang, Heng; Li, Chunmei; González-Marcos, José Antonio; Zhou, Zhi-Bin; Armand, Michel; Rodriguez-Martinez, Lide Mercedes

    2017-04-13

    Solid polymer electrolytes (SPEs) comprising lithium bis(fluorosulfonyl)imide (Li[N(SO2F)2], LiFSI) and poly(ethylene oxide) (PEO) have been studied as electrolyte material and binder for the Li-S polymer cell. The LiFSI-based Li-S all solid polymer cell can deliver high specific discharge capacity of 800 mAh gsulfur-1 (i.e., 320 mAh gcathode-1), high areal capacity of 0.5 mAh cm-2 and relatively good rate capability. The cycling performances of Li-S polymer cell with LiFSI are significantly improved compared to with those with conventional LiTFSI (Li[N(SO2CF3)2]) salt in the polymer membrane, due to the improved stability of the Li anode/electrolyte interphases formed in the LiFSI-based SPEs. These results suggest that the LiFSI-based SPEs are attractive electrolyte materials for solid-state Li-S batteries.

  14. Towards safer sodium-ion batteries via organic solvent/ionic liquid based hybrid electrolytes

    NASA Astrophysics Data System (ADS)

    Monti, Damien; Ponrouch, Alexandre; Palacín, M. Rosa; Johansson, Patrik

    2016-08-01

    Hybrid electrolytes aimed at application in sodium-ion batteries (SIB) consisting of an organic solvent mixture (EC:PC) and different ionic liquids (ILs); EMImTFSI, BMImTFSI, and Pyr13TFSI, and with the NaTFSI salt providing the Na+ charge carriers have here been extensively studied. The physico-chemical and electrochemical characterisation includes ionic conductivity, viscosity, density, cation coordination and solvation, various safety measures, and electrochemical stability window (ESW). Hybrid electrolytes with 10-50% of IL content were found to have ionic conductivities on par with comparable organic solvent based electrolytes, but with highly enhanced safety properties. A systematic Raman spectroscopy study of the cation coordination and solvation before and after electrolyte safety tests by ignition suggest that IL cations and TFSI remain stable when ignited while organic solvents are consumed. Finally, the solid electrolyte interphase (SEI) formed when using hybrid electrolytes has both better mechanical and electrochemical stability than the SEI derived from pure IL based electrolytes. For a half-cell with a hard carbon (HC) electrode and a hybrid electrolyte with a composition of 0.8 m NaTFSI in EC0.45:PC0.45:Pyr13TFSI0.10 encouraging results were obtained for IL based electrolytes - ca. 182 mAhg-1 at C/10 over 40 cycles.

  15. Poly(arylene)-based anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Bae, Chulsung

    2015-06-09

    Poly(arylene) electrolytes including copolymers lacking ether groups in the polymer may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  16. On the interfacial charge transfer between solid and liquid Li(+) electrolytes.

    PubMed

    Schleutker, Marco; Bahner, Jochen; Tsai, Chih-Long; Stolten, Detlef; Korte, Carsten

    2017-10-11

    The Li(+) ion transfer between a solid and a liquid Li(+) electrolyte has been investigated by DC polarisation techniques. The current density i is measured as a function of the electrochemical potential drop Δ[small mu, Greek, tilde]Li(+) at the interface, using a liquid electrolyte with different Li(+) concentrations. The subject of this experimental study is the interface between the solid electrolyte Ta-substituted lithium lanthanum zirconate (Li6.6La3Zr1.6Ta0.4O12) and a liquid electrolyte consisting of LiPF6 dissolved in ethylene carbonate/dimethyl carbonate (1 : 1). The functional course of i vs. Δ[small mu, Greek, tilde]Li(+) can be described by a serial connection between a constant ohmic resistance Rslei and a current dependent thermally activated ion transfer process. For the present solid-liquid electrolyte interface the areal resistance Rslei of the surface layer is independent of the Li(+) concentration in the liquid electrolyte. At room temperature a value of about 300 Ω cm(2) is found. The constant ohmic resistance Rslei can be attributed to a surface layer on the solid electrolyte with a (relatively) low conductivity (solid-liquid electrolyte interphase). The low conducting surface layer is formed by degradation reactions with the liquid electrolyte. Rslei is considerably increased if a small amount (ppm) of water is added to the liquid electrolyte. The thermally activated ionic transfer process obeys a Butler-Volmer like behaviour, resulting in an exchange current density i0 depending on the Li(+) concentration in the liquid electrolyte by a power-law. At a Li(+) concentration of 1 mol l(-1) a value of 53.1 μA cm(-2) is found. A charge transfer coefficient α of ∼0.44 is measured. The finding of a superposed constant ohmic resistance due to a solid-liquid electrolyte interphase and a current dependent thermally activated ion transfer process is confirmed by the results of two former experimental studies from the literature, performing AC

  17. Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer.

    PubMed

    Li, Yunsong; Leung, Kevin; Qi, Yue

    2016-10-18

    A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have "selective" transport properties: blocking electrons from attacking the electrolytes, while allowing Li(+) ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li(+) + e → Li(0), occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. This passivation layer is called "solid electrolyte interphase (SEI)" and is considered as "the most important but the least understood in rechargeable Li-ion batteries," partly due to the lack of understanding of its structure-property relationship. Predictive modeling, starting from the ab initio level, becomes an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li(+) ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li(+) and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li(+) transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure-property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li2CO3, LiF, Li2O, and their mixtures. After sorting out the Li(+) ion diffusion carriers and their diffusion

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

    PubMed

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

    2014-07-09

    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.

  19. 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.

  20. 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.

  1. Single lithium-ion conducting solid polymer electrolytes: advances and perspectives.

    PubMed

    Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M; Armand, Michel; Zhou, Zhibin

    2017-02-06

    Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid

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

    PubMed

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

    2015-08-05

    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.

  4. Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte.

    PubMed

    Luo, Wei; Gong, Yunhui; Zhu, Yizhou; Fu, Kun Kelvin; Dai, Jiaqi; Lacey, Steven D; Wang, Chengwei; Liu, Boyang; Han, Xiaogang; Mo, Yifei; Wachsman, Eric D; Hu, Liangbing

    2016-09-21

    All-solid-state Li-batteries using solid-state electrolytes (SSEs) offer enhanced safety over conventional Li-ion batteries with organic liquid electrolytes due to the nonflammable nature of SSEs. The superior mechanical strength of SSEs can also protect against Li dendrite penetration, which enables the use of the highest specific capacity (3861 mAh/g) and lowest redox potential (-3.04 V vs standard hydrogen electrode) anode: Li metal. However, contact between the Li metal and SSEs presents a major challenge, where a large polarization occurs at the Li metal/SSE interface. Here, the chemical properties of a promising oxide-based SSE (garnet) changed from "super-lithiophobicity" to "super-lithiophilicity" through an ultrathin coating of amorphous Si deposited by plasma-enhanced chemical vapor deposition (PECVD). The wettability transition is due to the reaction between Li and Si and the in situ formation of lithiated Si. As a result, symmetric cells composed of a Si-coated garnet-structured SSE and Li metal electrodes exhibited much smaller impedance and excellent stability upon plating/stripping cycles compared to cells using bare garnet SSE. Specifically, the interfacial resistance between Li and garnet dramatically decreased from 925 to 127 Ω cm(2) when lithiated Si was formed on the garnet. Our discovery of switchable lithiophobic-lithiophilic surfaces to improve the Li metal/SSE interface opens opportunities for improving many other SSEs.

  5. 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.

  6. Solid polymer MEMS-based fuel cells

    DOEpatents

    Jankowski, Alan F.; Morse, Jeffrey D.

    2008-04-22

    A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

  7. Solid oxide MEMS-based fuel cells

    DOEpatents

    Jankowksi, Alan F.; Morse, Jeffrey D.

    2007-03-13

    A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

  8. An all-solid-state lithium-sulfur battery using two solid electrolytes having different functions

    NASA Astrophysics Data System (ADS)

    Nagata, Hiroshi; Chikusa, Yasuo

    2016-10-01

    All-solid-state lithium-sulfur batteries are expected to be valuable next generation batteries. To improve the performance of all-solid-state lithium-sulfur batteries, it is essential to raise both the reactivity of sulfur and the ionic conductivity of the positive composite electrode. For achieving this, we investigate a positive composite electrode prepared using P2S5 and a solid electrolyte with a high ionic conductivity. As a result, we have found that the lithium-sulfur cell exhibits a relatively low activation energy together with high ionic conductivity. The positive composite electrode exhibits an extremely high capacity of 1550 mA h g-1 (sulfur) at 1.3 mA cm-2 and 25 °C. Moreover, when using the positive electrode, the energy densities at the cell level (18650) are 540 W h kg-1 and 990 W h L-1, estimated from the equivalent structure of a current lithium-ion battery.

  9. One-pot preparation of new copolymer electrolytes with tunable network structure for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Chen, Bo; Xu, Qiang; Huang, Zhen; Zhao, Yanran; Chen, Shaojie; Xu, Xiaoxiong

    2016-11-01

    A new class of copolymer electrolytes with tunable network structure is successfully designed and prepared via a facile one-pot reaction. The trimethylolpropane triglycidyl ether (TMPEG) is cross-linked with poly (ethylene glycol) diamine (NPEG) to create well-defined solid network polymer electrolyte (SNPE). The network structure could be tuned by changing the molar ratio of TMPEG and NPEG or the molecular weight of NPEG. The effects of molecular weight of NPEG and molar ratio of EO/Li+ on the ionic conductivity are systematically investigated. The optimal electrolyte TMPEG-NPEG4K[2:1]-16:1 presents a maximum conductivity of 1.10 × 10-4 S cm-1 under 30 °C, and an 18-fold ionic conductivity enhancement in that of PEO-based electrolyte. Furthermore, it also exhibits wide electrochemical window (0-5.4 V), excellent compatibility with metallic Li, and superior mechanical properties. The all-solid-state lithium batteries LiFePO4/Li are assembled with TMPEG-NPEG4K[2:1]-16:1 electrolyte, and present good cycling and rate performance under 60 °C. The initial discharge specific capacities of the batteries are 161.7 mAh g-1 at 0.2 C and 132.7 mAh g-1 at 1 C, and the capacity retention ratio can be retained at 90.6% and 90.5% after 100 cycles. This new copolymer electrolyte may become a promising candidate for applications in all-solid-state lithium battery.

  10. 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.

  11. High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

    PubMed

    Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

    2011-08-07

    Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

  12. All-solid-state lithium secondary batteries using NiS-carbon fiber composite electrodes coated with Li₂S-P₂S₅ solid electrolytes by pulsed laser deposition.

    PubMed

    Aso, Keigo; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2013-02-01

    Composite materials including NiS active materials, sulfide-based solid electrolytes (SE), and conductive additives (VGCF: vapor grown carbon fiber) were prepared by coating a highly conductive Li(2)S-P(2)S(5) solid electrolyte onto NiS-VGCF composite using pulsed laser deposition (PLD). From scanning electron microscopy, NiS nanoparticles were on VGCF surface after coating of solid electrolytes using PLD. All-solid-state cells using the SE-coated NiS-VGCF composite and the uncoated NiS-VGCF composite were fabricated, and then the coating effects on the electrochemical performance by forming the SE thin film onto the NiS-VGCF composite were investigated. At a high current density of 3.8 mA cm(-2) (corresponding to ca. 1 C), an all-solid-state cell fabricated using the SE-coated NiS-VGCF composite as a working electrode showed the initial discharge capacity of 300 mA h g(-1), and exhibited better cycle performance than the cell using the uncoated NiS-VGCF composite.

  13. Thermal stability of beta''-alumina solid electrolyte under AMTEC operating conditions

    NASA Astrophysics Data System (ADS)

    Williams, Roger M.; Homer, Margie L.; Kulleck, James; Lara, Liana; Kisor, Adam K.; Cortez, Roger H.; Shields, Virgil B.; Ryan, Margaret A.

    2000-01-01

    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. The major phase in this ceramic, sodium beta''-alumina shows no evidence of thermal decomposition in AMTEC environments including clean liquid sodium and low pressure sodium gas, at temperatures below 1173K, or in vacuum below 1273K. This paper presents additional results of ionic conductivity and exchange current studies in sodium exposure test cells (SETCs) to characterize the changes occurring in BASE below 1273K in low pressure sodium vapor. Also presented are additional annealing studies to characterize the kinetics of processes occurring in the BASE ceramic in the AMTEC operating regime. .

  14. 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.

  15. 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

  16. Aluminum oxyhydroxide based separator/electrolyte and battery system, and a method making the same

    SciTech Connect

    Gerald, II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.

    2011-03-08

    The instant invention relates a solid-state electrochemical cell and a novel separator/electrolyte incorporated therein. A preferred embodiment of the invented electrochemical cell generally comprises a unique metal oxyhydroxide based (i.e. AlOOH) separator/electrolyte membrane sandwiched between a first electrode and a second electrode. A preferred novel separator/electrolyte comprises a nanoparticulate metal oxyhydroxide, preferably AlOOH and a salt which are mixed and then pressed together to form a monolithic metal oxyhydroxide-salt membrane.

  17. Electrochemical intercalation of lithium into carbons using a solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Choquette, Y.; Guerfi, A.; Simoneau, M.; Bélanger, A.; Gauthier, M.

    A study of the electrochemical performance of carbon materials from different types was carried out on true solid polymer-based poly(ethylene oxide) (PEO) with LiTFSI for application as the negative electrode in lithium ion solid-state batteries (LISSBs) at 60 °C. The reversible and irreversible capacity depend strongly on the crystallinity, the form of carbon and the impurities. A comparison of particle versus fiber was done when we investigated the charge/discharge characteristics with different current densities. The galvanostatic curves show high reversibility of the lithium—carbon in solid polymer electrolyte. The kinetics of electrochemical intercalation of lithium into carbon was studied by impedance spectroscopy especially for evaluating the diffusion coefficient in different origins of carbon. The degree of ionization of lithium was investigated by using solid-state 7Li nuclear magnetic resonance spectroscopy when the electrode is fully intercalated or doped down to 0 V. The chemical shift of 7Li NMR in lithium intercalation or doping in the carbons was classified in two ranges, 42 ppm and 9 ppm. 7Li NMR suggests the carbon with a 42 ppm range is the best choice for LISSBs.

  18. Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

    PubMed

    Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

    2015-12-15

    The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Multiphysics modeling of lithium ion battery capacity fading process with solid-electrolyte interphase growth by elementary reaction kinetics

    NASA Astrophysics Data System (ADS)

    Xie, Yuanyuan; Li, Jianyang; Yuan, Chris

    2014-02-01

    A pseudo two-dimensional mathematical model is developed for a lithium ion battery, integrating the elementary reaction based solid-electrolyte interphase (SEI) growth model with multiple transport processes. The model is validated using the experimental data. Simulation results indicate that the operating temperature has great effect on the SEI layer generation and growth. Under different charging-discharging rates, it is found that high charging-discharging rate can intensify the battery capacity fading process. Different cooling conditions are then applied and show that enhanced surface convective cooling condition can effectively slow down the battery capacity fading. After that, the effect of electrolyte salt concentration and exchange current density are studied. It is found that raising the electrolyte salt concentration can improve the diffusion property of lithium ions, and stabilize the battery performance under lithium ion consumption induced resistance rising. It also suggests that improving exchange current density could greatly decrease the lithium ion battery capacity fading.

  20. High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

    PubMed

    Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

    2013-06-21

    Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

  1. Solid-State Electrolyte-Gated Graphene in Optical Modulators.

    PubMed

    Rodriguez, Francisco J; Aznakayeva, Diana E; Marshall, Owen P; Kravets, Vasyl G; Grigorenko, Alexander N

    2017-05-01

    The gate-tunable wide-band absorption of graphene makes it suitable for light modulation from terahertz to visible light. The realization of graphene-based modulators, however, faces challenges connected with graphene's low absorption and the high electric fields necessary to change graphene's optical conductivity. Here, a solid-state supercapacitor effect with the high-k dielectric hafnium oxide is demonstrated that allows modulation from the near-infrared to shorter wavelengths close to the visible spectrum with remarkably low voltages (≈3 V). The electroabsorption modulators are based on a Fabry-Perot-resonator geometry that allows modulation depths over 30% for free-space beams. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed

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

    2014-09-24

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

  3. Enhancement of ionic conductivity of PEO based polymer electrolyte by the addition of nanosize ceramic powders.

    PubMed

    Wang, G X; Yang, L; Wang, J Z; Liu, H K; Dou, S X

    2005-07-01

    The ionic conductivity of polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) has been improved by the addition of nanosize ceramic powders (TiO2 and AL2O3). The PEO based solid polymer electrolytes were prepared by the solution-casting method. Electrochemical measurement shows that the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte has the best ionic conductivity (about 10(-4) S cm(-1) at 40-60 degrees C). The lithium transference number of the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte was measured to be 0.47, which is much higher than that of bare PEO polymer electrolyte. Ac impedance testing shows that the interface resistance of ceramic-added PEO polymer electrolyte is stable. Linear sweep voltammetry measurement shows that the PEO polymer electrolytes are electrochemically stable in the voltage range of 2.0-5.0 V versus a Li/Li+ reference electrode.

  4. Preparation of Li2S-P2S5 solid electrolyte from N-methylformamide solution and application for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Teragawa, Shingo; Aso, Keigo; Tadanaga, Kiyoharu; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2014-02-01

    Electrode-solid electrolyte composite materials for all-solid-state lithium batteries were prepared by coating of the Li2S-P2S5 solid electrolyte onto LiCoO2 particles using a N-methylformamide (NMF) solution of 80Li2S·20P2S5 (mol%) solid electrolyte. SEM and EDX analysis showed that the Li2S-P2S5 solid electrolyte was uniformly coated on LiCoO2 particles. The all-solid-state cell using the LiCoO2 particles coated with the solid electrolyte showed higher charge-discharge capacity than the cells using uncoated LiCoO2 particles.

  5. Structural and electrical properties of NASICON type solid electrolyte nanoscaled glass-ceramic powder by mechanical milling for thin film batteries.

    PubMed

    Patil, Vaishali; Patil, Arun; Yoon, Seok-Jin; Choi, Ji-Won

    2013-05-01

    During last two decades, lithium-based glasses have been studied extensively as electrolytes for solid-state secondary batteries. For practical use, solid electrolyte must have high ionic conductivity as well as chemical, thermal and electrochemical stability. Recent progresses have focused on glass electrolytes due to advantages over crystalline solid. Glass electrolytes are generally classified into two types oxide glass and sulfide glass. Oxide glasses do not react with electrode materials and this chemical inertness is advantageous for cycle performances of battery. In this study, major effort has been focused on the improvement of the ion conductivity of nanosized LiAlTi(PO4)3 oxide electrolyte prepared by mechanical milling (MM) method. After heating at 1000 degrees C the material shows good crystallinity and ionic conductivity with low electronic conductivity. In LiTi2(PO4)3, Ti4+ ions are partially substituted by Al3+ ions by heat-treatment of Li20-Al2O3-TiO2-P2O5 glasses at 1000 degrees C for 10 h. The conductivity of this material is 1.09 x 10(-3) S/cm at room temp. The glass-ceramics show fast ion conduction and low E(a) value. It is suggested that high conductivity, easy fabrication and low cost make this glass-ceramics promising to be used as inorganic solid electrolyte for all-solid-state Li rechargeable batteries.

  6. 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.

  7. 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.

  8. Atomic Layer Deposited Lithium Silicates as Solid-State Electrolytes for All-Solid-State Batteries.

    PubMed

    Wang, Biqiong; Liu, Jian; Norouzi Banis, Mohammad; Sun, Qian; Zhao, Yang; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

    2017-09-20

    Development of solid-state electrolyte (SSE) thin films is a key toward the fabrication of all-solid-state batteries (ASSBs). However, it is challenging for conventional deposition techniques to deposit uniform and conformal SSE thin films in a well-controlled fashion. In this study, atomic layer deposition (ALD) was used to fabricate lithium silicate thin films as a potential SSE for ASSBs. Lithium silicates thin films were deposited by combining ALD Li2O and SiO2 subcycles using lithium tert-butoxide, tetraethylorthosilane, and H2O as precursors. Uniform and self-limiting growth was achieved at temperatures between 225 and 300 °C. X-ray absorption spectroscopy analysis disclosed that the as-deposited lithium silicates were composed of SiO4 tetrahedron structure and lithium oxide as the network modifier. X-ray photoelectron spectroscopy confirmed the chemical states of Li in the thin films were the same with that in standard lithium silicate. With one to one subcycle of Li2O and SiO2 the thin films had a composition close to Li4SiO4 whereas one more subcycle of Li2O delivered a higher lithium content. The lithium silicate thin film prepared at 250 °C exhibited an ionic conductivity of 1.45× 10(-6) S cm(-1) at 373 K. The high ionic conductivity of lithium silicate was due to the higher lithium concentration and lower activation energy.

  9. 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.

  10. 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.

  11. 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.

  12. In situ micro-FTIR study of the solid-solid interface between lithium electrode and polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Cheng, H.; Zhu, C. B.; Lu, M.; Yang, Y.

    In situ micro-FTIR spectroscopy was explored to characterize the solid-solid interface between lithium electrode and polymer electrolytes. The cyclic voltammetric (CV) results indicated that the reduction reactions of oxygen and water as well as the formation of underpotential deposition (UPD) Li occur in the Li/PEO 20-LiN(CF 3SO 2) 2 electrolyte interface in the different potential region. The infrared spectral changes observed during the CV process revealed that there is a direct correlation between the CV peaks and the magnitude of the infrared peaks. It is shown that the infrared reflectivity from the solid-solid interface is very sensitive to the formation of the passive layer on the lithium electrodes. The results obtained from optical micrographs also displayed directly the formation of the passive layer along with lithium deposition and dissolution process. It is correlated well with in situ FTIR and electrochemical experiments.

  13. A solid dielectric gated graphene nanosensor in electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Zhu, Yibo; Wang, Cheng; Petrone, Nicholas; Yu, Jaeeun; Nuckolls, Colin; Hone, James; Lin, Qiao

    2015-03-01

    This letter presents a graphene field effect transistor (GFET) nanosensor that, with a solid gate provided by a high-κ dielectric, allows analyte detection in liquid media at low gate voltages. The gate is embedded within the sensor and thus is isolated from a sample solution, offering a high level of integration and miniaturization and eliminating errors caused by the liquid disturbance, desirable for both in vitro and in vivo applications. We demonstrate that the GFET nanosensor can be used to measure pH changes in a range of 5.3-9.3. Based on the experimental observations and quantitative analysis, the charging of an electrical double layer capacitor is found to be the major mechanism of pH sensing.

  14. A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

    PubMed

    Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

    2017-05-23

    A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo2O4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo2O4) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g(-1) at a scan rate of 5 mV s(-1) in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe3O4 nanoparticles and SiCF (SiCF/Fe3O4) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g(-1) at a scan rate of 5 mV s(-1). Therefore, by pairing the SiCF/MgCo2O4 positive electrode and the SiCF/Fe3O4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g(-1) at a scan rate of 5 mV s(-1)) and energy density (maximum energy density of 72.79 Wh kg(-1) at a power density of 727.96 W kg(-1)).

  15. 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.

  16. Solvent activities of the fluorinated solid polymer electrolyte/water system in fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Tae Hwan; Bae, Young Chan

    We modified the lattice fluid equation-of-state by the introducing Debye-Hückel equation. A thermodynamic model taking into account the specific interaction and ionic strength between the polymer and the solvent is proposed. The proposed model successfully predicts the vapor/liquid equilibria (VLE) of solvents and the solid polymer electrolyte (SPE). A generalized lattice fluid model is modified to describe the change of water activity in solid polymer electrolyte (SPE)/water systems. The calculated activity curves using the proposed model agree remarkably well with the experimental data.

  17. 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.

  18. 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.

  19. 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.

  20. Bubble-solid interactions in water and electrolyte solutions.

    PubMed

    Pushkarova, Rada A; Horn, Roger G

    2008-08-19

    Surface forces between an air bubble and a flat mica surface immersed in aqueous electrolyte solutions have been investigated using a modified surface force apparatus. An analysis of the deformation of the air bubble with respect to the mutual position of the bubble and the mica surface, the capillary pressure, and the disjoining pressure allows the air-liquid surface electrical potential to be determined. The experiments show that a long-range, double-layer repulsion acts between the mica (which is negatively charged) and an air bubble in water and in various electrolyte solutions at low concentration, thereby indicating that the air bubble surface is negatively charged. However, there is clear evidence that charge regulation occurs at the air-water interface to maintain a constant surface potential, and as a result of this, the charge at this interface changes from negative to positive as the bubble approaches the mica surface. Because of the attraction that arises as a result of the charge reversal, a finite force is required to separate the bubble from the mica, though the mica remains wetted by the aqueous phase. At the low concentrations investigated, the potential on the gas-liquid interface is independent of the electrolyte type within experimental uncertainty.

  1. An imidazolium based ionic liquid electrolyte for lithium batteries

    NASA Astrophysics Data System (ADS)

    Kim, Jae-Kwang; Matic, Aleksandar; Ahn, Jou-Hyeon; Jacobsson, Per

    An electrolyte for lithium batteries based on the ionic liquid 3-methy-1-propylimidazolium bis(trifluoromethysulfony)imide (PMIMTFSI) complexed with lithium bis(trifluoromethysulfony)imide (LiTFSI) at a molar ratio of 1:1 has been investigated. The electrolyte shows a high ionic conductivity (∼1.2 × 10 -3 S cm -1) at room temperature. Over the whole investigated temperature range the ionic conductivity is more than one order of magnitude higher than for an analogue electrolyte based on N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py 14TFSI) complexed with LiTFSI and used here as a benchmark. Raman results indicate furthermore that the degree of lithium coordinated TFSI is slightly lower in the electrolyte based on PMIMTFSI and thus that the Li + charge carriers should be higher than in electrolytes based on Py 14TFSI. An ionic liquid gel electrolyte membrane was obtained by soaking a fibrous fully interconnected membrane, made of electrospun P(VdF-HFP), in the electrolyte. The gel electrolyte was cycled in Li/ionic liquid polymer electrolyte/Li cells over 15 days and in Li/LiFePO 4 cells demonstrating good interfacial stability and highly stable discharge capacities with a retention of >96% after 50 cycles (∼146 mAh g -1).

  2. Performance of composite electrolyte SOFCs

    SciTech Connect

    Khandkar, A.C.; Elangovan, S.; Milliken, C.; Guruswamy, S.

    1994-12-31

    In an effort to minimize the ohmic losses in solid oxide fuel cells (SOFC), especially at lower operating temperatures around 800 C, an alternate electrolyte material such as ceria is often adopted. However, ceria based electrolytes develop mixed conduction, which lowers faradaic efficiency. To alleviate this effect, ceria electrolytes were coated with a thin layer zirconia using high temperature magnetron sputter deposition. This paper discusses the characterization of electrolytes and performance of single cells fabricated from these composite electrolytes.

  3. Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

    NASA Astrophysics Data System (ADS)

    Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

    2016-06-01

    Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

  4. Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

    SciTech Connect

    Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

    2016-06-15

    Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

  5. Flexible all-solid-state supercapacitors based on graphene/carbon black nanoparticle film electrodes and cross-linked poly(vinyl alcohol)-H2SO4 porous gel electrolytes

    NASA Astrophysics Data System (ADS)

    Fei, Haojie; Yang, Chongyang; Bao, Hua; Wang, Gengchao

    2014-11-01

    Flexible all-solid-state supercapacitors (SCs) are fabricated using graphene/carbon black nanoparticle (GCB) film electrodes and cross-linked poly(vinyl alcohol)-H2SO4 porous gel electrolytes (gPVAP-H2SO4). The GCB composite films, with carbon black (CB) nanoparticles uniformly distributed in the graphene nanosheets, greatly improve the active surface areas and ion transportation of pristine graphene film. The porous structure of as-prepared gPVAP-H2SO4 membrane improves the equilibrium swelling ratio in electrolyte and provides interconnected ion transport channels. The chemical crosslinking solves the fluidity problem of PVA-H2SO4 gel electrolyte at high temperature. As-fabricated GCB//gPVAP(20)-H2SO4//GCB flexible SC displays an increased specific capacitance (144.5 F g-1 at 0.5 A g-1) and a higher specific capacitance retention (67.9% from 0.2 to 4 A g-1). More importantly, the flexible SC possesses good electrochemical performance at high temperature (capacitance retention of 78.3% after 1000 cycles at 70 °C).

  6. Multinuclear NMR Study of the Solid Electrolyte Interface Formed in Lithium Metal Batteries.

    PubMed

    Wan, Chuan; Xu, Suochang; Hu, Mary Y; Cao, Ruiguo; Qian, Jiangfeng; Qin, Zhaohai; Liu, Jun; Mueller, Karl T; Zhang, Ji-Guang; Hu, Jian Zhi

    2017-04-04

    The composition of the solid electrolyte interphase (SEI) layers formed in Cu|Li cells using lithium bis(fluorosulfonyi)imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-dimethoxyethane (DME) electrolytes is determined by a multinuclear solid-state MAS NMR study at high magnetic field. It is found that the "dead" metallic Li is largely reduced in the SEI layers formed in a 4 M LiFSI-DME electrolyte system compared with those formed in a 1 M LiFSI-DME electrolyte system. This finding relates directly to the safety of Li metal batteries, as one of the main safety concerns for these batteries is associated with the "dead" metallic Li formed after long term cycling. It is also found that a large amount of LiF, which exhibits superior mechanical strength and good Li(+) ionic conductivity, is observed in the SEI layer formed in the concentrated 4 M LiFSI-DME and 3 M LiTFSI-DME systems, but not in the diluted 1 M LiFSI-DME system. Quantitative (6)Li MAS NMR results indicate that the SEI associated with the 4 M LiFSI-DME electrolyte is denser than those formed in the 1 M LiFSI-DME and 3 M LiTFSI-DME systems. These studies reveal the fundamental mechanisms behind the excellent electrochemical performance associated with higher concentration LiFSI-DME electrolyte systems.

  7. Molecular Dynamics Simulation Study of PEO-Based Nanocomposite Polymer Electrolytes el

    NASA Astrophysics Data System (ADS)

    Borodin, Oleg; Bandyopadhyaya, Rajdip; Smith, Grant D.

    2002-03-01

    Solid polymer electrolytes exhibit good chemical, electrochemical and photochemical stability in combination with good mechanical properties, ease of processing and adequate conductivity at elevated temperatures. Addition of solid nanoparticle fillers such as TiO2 and SiO2 to lithium solid polymer electrolytes is known to improve mechanical properties, interfacial stability, conductivity and transfer numbers, particularly for poly(ethylene oxide) (PEO) based polymer electrolytes. We have performed molecular dynamics simulations of PEO/LiBF4 and PEO/LiBF4/TiO2 systems in order to study changes of the structure and mechanism of ion conduction in PEO/LiBF4 near TiO2 surfaces compared to the bulk PEO/LiBF4.

  8. Mobility enhancement of SnO2 nanowire transistors gated with a nanogranular SiO2 solid electrolyte.

    PubMed

    Sun, Jia; Huang, Wenlong; Qian, Chuan; Yang, Junliang; Gao, Yongli

    2014-01-21

    Field-effect transistors (FETs) based on semiconducting nanowires are the most fundamental electronic elements for exploring charge transport as well as possible applications in functional nanoelectronics. Here, we report the effect of different gate dielectrics on the electrical performance of SnO2 nanowire FETs. By using solid-electrolytes with large electric-double-layer (EDL) capacitance as gate dielectrics, both low-voltage operation and high gating efficiency can be obtained. Electrical transport measurements indicate that the nanowire FETs gated by solid-electrolytes show improved electrical performances in terms of on-current, sub-threshold swing, and mobility, in comparison to those gated by traditional thermally grown dielectrics. The observed performance improvement is possibly due to the reduction of the contact-resistance and the Schottky barrier at the semiconductor/metal junctions.

  9. Performance and modelling of a direct methanol solid polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Scott, K.; Taama, W.; Cruickshank, J.

    The performance and modelling of a direct methanol fuel cell based on a solid polymer electrolyte membrane (SPE) is reported. Two sizes of cell are used: a small cell with an area of 9 cm 2 and a large single cell with an area of 250 cm 2. The fuel cell utilises a vapourised methanol fuel at a porous carbon/Pt-Ru catalyst electrode. The performance of the fuel cell is affected by the cross-over of methanol from the anode to the cathode through the polymer membrane and this behaviour is modelled. To evaluate cell performance, mathematical models are constructed which describe mass transport in the porous electrode structures and the potential and concentration distributions in the electrode regions. These models are used to predict the cell voltage and current density response of the fuel cell.

  10. 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.

  11. 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.

  12. 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.

  13. Effect of matrix crystallinity on the ionic conductivity in microstructured block copolymer solid electrolytes

    NASA Astrophysics Data System (ADS)

    Young, Nicholas; Balsara, Nitash

    2012-02-01

    Polyethylene oxide (PEO)-based block copolymers have been studied extensively for use as solid electrolytes for rechargeable lithium metal batteries. Previous work has concentrated on block copolymers containing an amorphous second block, such as polystyrene, for which the modulus is sufficiently high to resist growth of dendrites that would lead to short circuiting. In this work, we instead focus on using semicrystalline polyethylene as the mechanically robust component. Polyethylene-polyethylene oxide (EEO) block copolymers doped with lithium bis(trifluoromethanesulfone) imide (LiTFSI) were characterized using AC impedance spectroscopy over a range of temperature, molecular weight, and composition values in order to determine the effect of crystallinity in the structural microphase on the conductivity of this material.

  14. DNA Based Electrolyte/Separator for Lithium Battery Application (Postprint)

    DTIC Science & Technology

    2015-10-07

    electronics to hybrid and electric vehicles . Two general categories of secondary batteries are mainly explored: the first are liquid electrolyte metal-ion...AFRL-RX-WP-JA-2016-0302 DNA BASED ELECTROLYTE/SEPARATOR FOR LITHIUM BATTERY APPLICATION (POSTPRINT) Jitendra Kumar1, Fahima...BASED ELECTROLYTE/SEPARATOR FOR LITHIUM BATTERY APPLICATION (POSTPRINT) 5a. CONTRACT NUMBER FA8650-15-D-5405-0001 5b. GRANT NUMBER 5c. PROGRAM

  15. 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.

  16. 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.

  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. Structure and mobility of PEO/LiClO4 solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Fullerton, Susan; Maranas, Janna

    2009-03-01

    Solid polymer electrolytes [SPEs] for use in rechargeable lithium-ion batteries offer many advantages over traditional liquid electrolytes, including mechanical flexibility and environmental friendliness. The practical limitation is that room temperature conductivity remains insufficient to power a portable device. While it is well-established that ion mobility is driven by polymer dynamics, high conductivity values have also been reported through fully crystalline SPEs. PEO-based SPEs have a rich phase behavior, and can form several crystalline complexes depending on the lithium concentration, temperature, and recrystallization time. We investigate the structure, mobility, conductivity, and thermal properties of both semi-crystalline and amorphous PEO/LiClO4 SPEs. Structure is measured with small-angle neutron scattering, and PEO mobility with quasi-elastic neutron scattering. We observe a decoupling of ionic conductivity and PEO mobility in a semi-crystalline sample. We also determine that PEO hydrogen atoms undergo restricted rotation on a circle. The radius of the circle is consistent with a cylindrical, crystalline structure that persists to some extent in the amorphous phase. The results suggest that directed ion transport via ordered structures is perhaps equally important as polymer mobility for increasing conductivity, provided that the structures percolate over large spatial scales.

  19. Solid Electrolyte NOx Gas Sensor Using Perovskite-Type Oxide Electrodes

    NASA Astrophysics Data System (ADS)

    Yoon, Jong-Won; Grilli, Maria Luisa; di Bartolomeo, Elisabetta; Traversa, Enrico

    2000-12-01

    Electrochemical devices based on coupling an oxygen ionic conductor (Y2O3-stabilized ZrO2 : YSZ) with a perovskite-type oxide (LaFeO3) were found to exhibit promising performance for the sensing of NO2 at 400 and 450°C. EMF values of the (Pt)LaFeO3/YSZ/Pt sensor increased in NO2 atmosphere with a quick response time. The increase in EMF value has been attributed to an increase in LaFeO3 conductivity in the presence of oxidizing gas. The polarization curves showed a nonlinear behavior in NO2 gas. The nonlinear behaviour could be explained to be due to the potential drop at the electrode interfaces. The electrochemical impedance spectroscopy (EIS) analysis of the devices showed that the resistance and reactance at the electrolyte/electrode interfaces decreased with introduction of NO2 gas. This would induce the lowering of electrode overvoltage and a current increase through the solid electrolyte.

  20. Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

    PubMed

    Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

    2012-06-01

    Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

  1. Measurement of oxygen chemical potential in thin electrolyte film, anode-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Lim, Hyung-Tae; Virkar, Anil V.

    Thin (∼30-45 μm) gadolinia-doped ceria (GDC) electrolyte, Ni + yttria-stabilized zirconia (YSZ) anode-supported cells were fabricated with platinum reference electrodes (probes) embedded within the electrolyte layer. The exposed parts of the probes were sealed off from the atmosphere using an oxygen impermeable glass. Thus, no oxygen exchange could occur and voltage measurements at the probes correspond to the reduced negative electrochemical potential of electrons (φ = - μ˜e / e , where μ˜e is the electrochemical potential of electrons and e is the electronic charge). The φ was measured at 650 °C under open circuit conditions with air circulated past the cathode and hydrogen circulated past the anode. The open circuit voltage was ∼0.84 V. The voltages between the anode and reference electrodes were very small-less than 30 mV. This was attributed to significant electronic conduction throughout the electrolyte from anode/electrolyte interface to cathode/electrolyte interface. Thus, voltage drop mainly occurs across the cathode/electrolyte interface. The variation of chemical potential of oxygen, μO2 , within the GDC electrolyte was estimated, which showed a large drop in μO2 across the cathode/electrolyte interface. The oxygen partial pressure in GDC just inside the cathode was estimated to be ∼10 -22 atm. Thus, in GDC-based anode-supported cells the effective electrolyte thickness is very small.

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

    SciTech Connect

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

    2016-05-06

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10{sup −1} – 10{sup −3} Scm{sup −1}, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEO{sub x}NaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O{sup +1} ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  3. 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.

  4. Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries.

    PubMed

    Ruzmetov, Dmitry; Oleshko, Vladimir P; Haney, Paul M; Lezec, Henri J; Karki, Khim; Baloch, Kamal H; Agrawal, Amit K; Davydov, Albert V; Krylyuk, Sergiy; Liu, Yang; Huang, Jiany; Tanase, Mihaela; Cumings, John; Talin, A Alec

    2012-01-11

    Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.

  5. Perioperative Acid-Base and Electrolyte Disturbances.

    PubMed

    Beer, Kari Santoro; Waddell, Lori S

    2015-09-01

    Obtaining and interpreting blood gas and electrolyte levels is essential in the management of perioperative veterinary patients. Metabolic and electrolyte alterations are common in critically ill surgical patients, and can lead to alterations in cardiovascular function, neurologic status, respiratory function, and even response to various drug therapies. Several common perioperative conditions are discussed in this article, including metabolic disturbances, electrolyte abnormalities (hyponatremia and hypernatremia, hyperkalemia), and respiratory abnormalities.

  6. Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

    SciTech Connect

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

    2016-06-30

    A fluorine-doped antiperovskite Li-ion conducto Li2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li+/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li2OHCl. As a result, an all-solid-state Li/LiFePO4 with F-dope Li2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

  7. Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

    DOE PAGES

    Li, Yutao; Zhou, Weidong; Xin, Sen; ...

    2016-06-30

    A fluorine-doped antiperovskite Li-ion conducto Li2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li+/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li2OHCl. As a result, an all-solid-state Li/LiFePO4 with F-dope Li2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

  8. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

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

    SciTech Connect

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

    2016-05-07

    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.

  11. [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.

  12. 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.

  13. Thermodynamic study of solid solutions in the SnTe-AgSbTe2 system by means of EMF with solid electrolyte Ag4RbI5

    NASA Astrophysics Data System (ADS)

    Mashadieva, L. F.; Yusibov, Yu. A.; Kevser, Dzh.; Babanly, M. B.

    2017-09-01

    The results from studying the SnTe-AgSbTe2 system by means of EMF with the solid electrolyte Ag4RbI5 in the temperature range of 300-430 K are presented. The formation of a wide (≥80 mol % of AgSbTe2) region of solid solutions based on SnTe is confirmed. Partial thermodynamic functions Δ G̅, Δ H̅, and Δ S̅ of silver in alloys are calculated from the equations for the EMF temperature dependences. Based on the literature data regarding solid-phase equilibria in the Ag2Te-SnTe-Sb2Te3-Te system, potential-determining reactions are identified that allow us to calculate the standard thermodynamic formation functions and standard entropies of solid solutions (2SnTe) x (AgSbTe2)1- x ( x = 0.2, 0.4, 0.6, 0.8, and 0.9).

  14. High-performance solid oxide fuel cells based on a thin La0.8Sr0.2Ga0.8Mg0.2O3-δ electrolyte membrane supported by a nickel-based anode of unique architecture

    NASA Astrophysics Data System (ADS)

    Sun, Haibin; Chen, Yu; Chen, Fanglin; Zhang, Yujun; Liu, Meilin

    2016-01-01

    Solid oxide fuel cells (SOFCs) based on a thin La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) electrolyte membrane supported by a nickel-based anode often suffers from undesirable reaction/diffusion between the Ni anode and the LSGM during high-temperature co-firing. In this study, a high performance intermediate-temperature SOFC is fabricated by depositing thin LSGM electrolyte membranes on a LSGM backbone of unique architecture coated with nano-sized Ni and Gd0.1Ce0.9O2-δ (GDC) particles via a combination of freeze-drying tape-casting, slurry drop-coating, and solution infiltration. The thickness of the dense LSGM electrolyte membranes is ∼30 μm while the undesirable reaction/diffusion between Ni and LSGM are effectively hindered because of the relatively low firing temperature, as confirmed by XRD analysis. Single cells show peak power densities of 1.61 W cm-2 at 700 °C and 0.52 W cm-2 at 600 °C using 3 vol% humidified H2 as fuel and ambient air as oxidant. The cell performance is very stable for 115 h at a constant current density of 0.303 A cm-2 at 600 °C.

  15. 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.

  16. LSO apatite-YSZ composite as a solid electrolyte for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Noviyanti, Atiek Rostika; Hastiawan, Iwan; Yuliyati, Yati. B.; Rahayu, Iman; Rosyani, Desy; Syarif, Dani Gustaman

    2017-05-01

    LSO (Lanthanun Silicate Oxide) Apatite-YSZ (Yttria-stabilized zirconia) composite has been synthesized by combining the LSO apatite with commercial YSZ with different composition ratio (LSO Apatite:YSZ = 60:40wt.% and 50:50 wt. %). Structure, morphology, and conductivity of sintered pellets composite (sintered at 1330oC for 3 hours) were characterized by XRD, SEM, and impedance spectroscopy, respectively. The sintered density of the composite materials with 50:50 wt. % and 60:40 wt. % (apatite: YSZ) ratios were 3.785 g.cm-3 and 3.770 g.cm-3, respectively. The typical peak of LSO and YSZ were observed in the X-ray pattern of the composite materials. The conductivity of the LSO apatite : YSZ composite 50:50wt. % and 60:40 wt. % ratios showed high level of ionic conductivities with values of 1.26 × 10-3 S/cm and 1.60 × 10-4 S/cm, respectively,with very low level of activation energy (0.95-1.02 eV) at 700 °C. These results indicate that the LSO-YSZ composite materials are good conductors that can be used as solid electrolyte in SOFC applications.

  17. Nano-Sponge Ionic Liquid-Polymer Composite Electrolytes for Solid-State Lithium Power Sources

    DTIC Science & Technology

    2010-01-01

    images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these... thin film batteries, 150 charge–discharge cycles are run for LixCoO2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects...9702;C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate

  18. 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.

  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

    2014-11-07

    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.

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

    DOE PAGES

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; ...

    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