GB2119162A - Solid state electrochemical cell - Google Patents

Solid state electrochemical cell Download PDF

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Publication number
GB2119162A
GB2119162A GB8309139A GB8309139A GB2119162A GB 2119162 A GB2119162 A GB 2119162A GB 8309139 A GB8309139 A GB 8309139A GB 8309139 A GB8309139 A GB 8309139A GB 2119162 A GB2119162 A GB 2119162A
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United Kingdom
Prior art keywords
electrochemical cell
solid state
poly
anion
state electrochemical
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GB8309139A
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GB2119162B (en
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Dennis James Bannister
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UK Atomic Energy Authority
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UK Atomic Energy Authority
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Primary Cells (AREA)

Abstract

A solid state electrochemical cell comprises an anode having at least one alkali metal as its active material, a cathode and an electrolyte comprising an anion and a cation comprising at least one electrolytically active alkali metal ion. The anion is at least partially immobilised by it constituting part of a polymer chain, e.g. as in the poly (methacryloyl-oxy-benzoate) or poly (2-(4-carboxyhexafluorobutanoyloxy-) ethylmethacrylate ions, thereby to overcome problems associated with mobile anions. The cation is preferably Li<+> and a polymer such as poly (ethylene oxide) may be blended into the electrolyte to improve its mechanical properties.

Description

SPECIFICATION Solid state electrochemical cell The invention relates to a solid state electrochemical cell; the cell comprises an anode having at least one alkali metal as its active material, a cathode and an electrolyte comprising an anion and a cation comprising at least one electrolytically active alkali metal ion.
South African Patent Application No 79/6263 describes an electrochemical cell wherein the electrolyte comprises a solid solution of an ionic compound (e.g. a salt of an alkali metal and a strong acid anion) in a solid plastic polymeric macromolecular material.
Such electrolytes are not, however, pure cation conductors and it is possible that mobility of the anion can lead, in operation of such a cell, to problems such as the formation of undesirable discharge products at the electrodes and compositional changes in the polymer, e.g. in the form of a membrane thereof.
The invention provides a solid state electrochemical cell comprising an anode having at least one alkali metal as its active material, a cathode and an electrolyte comprising an anion and a cation comprising at least one electrolytically active alkali metal ion, wherein the anion constitutes part of the chain of a polymer and is thereby at least partially immobilised .
Immobilisation of the anion in the invention enables the abovementioned problems associated with electrolytes having mobile anions to be overcome. The electrolyte in the invention has been found to have a high ionic conductivity.
Examples of suitable anions are anions having the structures (I) and (II below.
where n represents chain lengths and is 1,000 in both cases.
In each of the above, the anion is part of the chain of a polymer and is therefore immobile.
The anion of the structure (I) above may be made by neutralising poly(methacryloyl-oxybenzoic acid), referred to hereinafter as PMBA, and the anion of the structure (II) by neutralising poly (2-(4-carboxyhexafluorobutanoyl-oxy-) ethyl methalcrylic acid), referred to hereinafter as PCHFEM.
The electrolytically active alkali metal ion is preferably lithium or sodium and is most preferably lithium. The lithium salts of the abovementioned anions of PMBA and of PCHFEM may not, in themselves, be useful as electrolytes in an electrochemical cell because of inappropriate mechanical properties. In such cases, it may be necessary to blend the salt with another material to produce appropriate mechanical properties for the above purpose. Thus, each of the abovementioned Li salts may be blended with a polymer such as poly (ethylene oxide) to provide an electrolyte for use in the invention.
PMBA and PCHFEM may be made by methods known in the art and the cell of the invention may be fabricated by methods known in the art. Furthermore, the electrodes in the cell may be constituted by materials known in the art for this purpose, for example the anode may be made of Li or an alloy thereof and the cathode by an intercalation compound such as TiS2.
Several ways of carrying out the invention will be described in detail below by way of example only.
Example t (i) Preparation of PMBA Methacryloyl chloride was reacted with phydroxy benzoic acid that had been neutralised with NaOH solution to give sodium methacryloyl-oxy-benzoate in about 50% yield.
Treatment with hydrochloric acid gave methacryloyl-oxy-benzoic acid which was purified by re-crystallisation from glacial acetic acid, ethanol and acetone respectively. The acid was polymerised at 90 C in dimethyl formamide solution in a sealed degassed ampoule using benzoyl peroxide as initiator. This gave PMBA which was separated from residual monomer by dissolving the latter in diethyl ether.
(ii) Preparation of Electrolyte The PMBA was neutralised with LiOH and 75% by weight of poly (ethylene oxide) in a methanol/water solution added. The solvents were removed under vacuum at 1 30 C.
(iii) Properties of Electrolyte A differential scanning calorimetric investigation of the electrolyte showed a reduction in crystallite size and a decrease in the degree of crystallinity of the poly (ethylene oxide). This may be due to interaction between Lis ions and the ether-oxygen atoms along the poly (ethylene oxide) chains. A possible structure of the electrolyte is thereof:
Conductivity measurements as a function of frequency were carried out using a frequency response analyser. A value of ca. 3 X 10-5 Sl~'cm~' was observed at 93 p.
Example 2 (i) Preparation of PCHFEM An excess of hexafluoroglutaric anhydride was reacted with dried 2-hydroxy ethyl methacrylate. The excess was removed by vacuum distillation at ca. 50 C. The resulting acid was polymerised at 90 C in ethyl acetate in a sealed degassed ampoule using benzoyl peroxide as intiator.
(ii) Preparation of Electrolyte The PCHFEM was neutralised with LiOMe in ethyl acetate to give the Li salt thereof (PCHFEM-Li). An appropriate amount of poly (ethylene oxide) was added, so that the ratio of ether oxygens in the poly (ethylene oxide) to Lie ions of the PCHFEM-Li was 0/Lie = 18.
The solvent was removed by evaporation and by heating under vacuum at 1 30 C.
The ionic conductivity at 1 00 C of the final product was found to be ~10-5 -1l2-1 using the method as in Example 1.

Claims (5)

1. A solid state electrochemical cell comprising an anode having at least one alkali metal as its active material, a cathode, and an electrolyte comprising an anion and a cation comprising at least one electrolytically active alkali metal ion, wherein the anion constitutes part of the chain of a polymer and is thereby at least partially immobilised.
2. A solid state electrochemical cell as claimed in claim 1 wherein the electrochemically active alkali metal ion is lithium.
3. A solid state electrochemical cell as claimed in claim 1 or claim 2 wherein the anion constitutes part of the chain of poly (methacryloyl-oxy-benzoate) .
4. A solid state electrochemical cell as claimed in claim 1 or claim 2 wherein the anion constitutes part of the chain of poly (2 (4-cargoxyhexafluorobutanoyl-oxy-) ethyl methacrylate).
5. A solid state electrochemical cell as claimed in claim 3 or claim 4 wherein the electrolyte is blended with poly (ethylene oxide).
GB8309139A 1982-04-16 1983-04-05 Solid state electrochemical cell Expired GB2119162B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8309139A GB2119162B (en) 1982-04-16 1983-04-05 Solid state electrochemical cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8211145 1982-04-16
GB8309139A GB2119162B (en) 1982-04-16 1983-04-05 Solid state electrochemical cell

Publications (2)

Publication Number Publication Date
GB2119162A true GB2119162A (en) 1983-11-09
GB2119162B GB2119162B (en) 1985-11-20

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GB8309139A Expired GB2119162B (en) 1982-04-16 1983-04-05 Solid state electrochemical cell

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2584868A1 (en) * 1985-07-12 1987-01-16 Elf Aquitaine Ionic conduction macromolecular material
EP0213985A1 (en) * 1985-07-12 1987-03-11 Societe Nationale Elf Aquitaine Macromolecular material with ion conductivity
FR2591391A1 (en) * 1985-12-11 1987-06-12 Elf Aquitaine Macromolecular material with high cationic conduction
US4908283A (en) * 1986-10-09 1990-03-13 Ube Industries, Ltd. Preparation of ion conductive solid electrolyte
EP0376466A2 (en) * 1988-11-22 1990-07-04 Associated Universities, Inc. Solvent-free solid polymer electrolyte and process for its preparation
US5240791A (en) * 1989-08-28 1993-08-31 Yuasa Battery Co., Ltd. Solid polymer electrolyte
EP0572099A2 (en) * 1987-06-30 1993-12-01 Yuasa Battery Company Limited Polymer solid electrolyte and polymer solid electrolyte battery
WO1996021953A2 (en) * 1995-01-13 1996-07-18 Sri International Single-ion conducting solid polymer electrolytes
EP1349178A1 (en) * 2002-03-27 2003-10-01 Hitachi, Ltd. Cationic polymeric conductors, their monomers and utilisation in lithium secondary batteries

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2584868A1 (en) * 1985-07-12 1987-01-16 Elf Aquitaine Ionic conduction macromolecular material
EP0213985A1 (en) * 1985-07-12 1987-03-11 Societe Nationale Elf Aquitaine Macromolecular material with ion conductivity
US4914161A (en) * 1985-07-12 1990-04-03 Societe Nationale Elf Aquitaine Ionically conductive macromolecular material
FR2591391A1 (en) * 1985-12-11 1987-06-12 Elf Aquitaine Macromolecular material with high cationic conduction
US4908283A (en) * 1986-10-09 1990-03-13 Ube Industries, Ltd. Preparation of ion conductive solid electrolyte
EP0572099A3 (en) * 1987-06-30 1996-04-24 Yuasa Battery Co Ltd Polymer solid electrolyte and polymer solid electrolyte battery
EP0572099A2 (en) * 1987-06-30 1993-12-01 Yuasa Battery Company Limited Polymer solid electrolyte and polymer solid electrolyte battery
EP0376466A3 (en) * 1988-11-22 1991-11-27 Associated Universities, Inc. Solvent-free solid polymer electrolyte and process for its preparation
EP0376466A2 (en) * 1988-11-22 1990-07-04 Associated Universities, Inc. Solvent-free solid polymer electrolyte and process for its preparation
US5240791A (en) * 1989-08-28 1993-08-31 Yuasa Battery Co., Ltd. Solid polymer electrolyte
WO1996021953A2 (en) * 1995-01-13 1996-07-18 Sri International Single-ion conducting solid polymer electrolytes
WO1996021953A3 (en) * 1995-01-13 1996-09-12 Stanford Res Inst Int Single-ion conducting solid polymer electrolytes
EP1349178A1 (en) * 2002-03-27 2003-10-01 Hitachi, Ltd. Cationic polymeric conductors, their monomers and utilisation in lithium secondary batteries
US7300991B2 (en) 2002-03-27 2007-11-27 Hitachi, Ltd. Cationic conductor, its intermediate, and lithium secondary battery using the conductor
US7704642B2 (en) 2002-03-27 2010-04-27 Hitachi, Ltd. Cationic conductor, its intermediate, and lithium secondary battery using the conductor

Also Published As

Publication number Publication date
GB2119162B (en) 1985-11-20

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