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Title: Inorganic-organic composite solid polymer electrolytes

Abstract

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.

Authors:
; ;
Publication Date:
Research Org.:
Covalent Associates, Inc., Woburn, MA (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20075594
DOE Contract Number:
FG02-98ER82555
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the Electrochemical Society; Journal Volume: 147; Journal Issue: 4; Other Information: PBD: Apr 2000
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; SOLID ELECTROLYTES; POLYETHYLENE GLYCOLS; LITHIUM SILICATES; ELECTRIC BATTERIES; BATTERY SEPARATORS

Citation Formats

Abraham, K.M., Koch, V.R., and Blakley, T.J. Inorganic-organic composite solid polymer electrolytes. United States: N. p., 2000. Web. doi:10.1149/1.1393345.
Abraham, K.M., Koch, V.R., & Blakley, T.J. Inorganic-organic composite solid polymer electrolytes. United States. doi:10.1149/1.1393345.
Abraham, K.M., Koch, V.R., and Blakley, T.J. Sat . "Inorganic-organic composite solid polymer electrolytes". United States. doi:10.1149/1.1393345.
@article{osti_20075594,
title = {Inorganic-organic composite solid polymer electrolytes},
author = {Abraham, K.M. and Koch, V.R. and Blakley, T.J.},
abstractNote = {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.},
doi = {10.1149/1.1393345},
journal = {Journal of the Electrochemical Society},
number = 4,
volume = 147,
place = {United States},
year = {Sat Apr 01 00:00:00 EST 2000},
month = {Sat Apr 01 00:00:00 EST 2000}
}
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  • Electrolytes based on 1-ethyl-3-methylimidazolium cation (EMI{sup +}) and either the hexafluorophosphate (EMIPF{sub 6}) or tetrafluorborate (EMIBF{sub 4}) anion in organic alkyl carbonate solvents have been evaluated for use in electrochemical capacitors. The conductivity, capacitance, limiting oxidation and reduction potentials, and thermal stability were assessed. High conductivity and capacitance values were found regardless of whether cyclic (high viscosity/high dielectric constant) or acyclic (low viscosity/low dielectric constant) alkyl carbonates were used. The best correlation with conductivity for the EMIPF{sub 6} salt was found to be the molecular weight and to a lesser degree the viscosity of the solvent. The high specific capacitancemore » (130 F/g) and excellent stability (>3.5 V, >130 C) make these electrolytes well suited for use in electrochemical double-layer capacitors.« less
  • We report experiments that demonstrate methodology for direct measurement of diffusion of molecular or ionic species in solid electrolyte media. The crucial experiments involve anodically stripping Ag from a Ag-coated Pt microelectrode (generator) and electrochemically detecting the resulting Ag{sup +} at nearby (1.4-23.4-{mu}m) Pt electrodes (collectors) by reducing the Ag{sup +} back to Ag.
  • The electrochemical properties of polymer electrolytes based on polyethylene oxide (PEO) and Li[(Cr{sub 3}SO{sub 2}){sub 2}N], with and without the addition of dispersed {gamma}-LiAlO{sub 2} powder, are reported. The results clearly indicate that the use of the {gamma}-LiAlO{sub 2} ceramic filler combined with the Li[(CR{sub 3}SO{sub 2}){sub 2}N] salt greatly reduces the crystallization rate and enhances the lithium/electrolyte interface stability.