GB2118763A - Solid state electrochemical cell - Google Patents
Solid state electrochemical cell Download PDFInfo
- Publication number
- GB2118763A GB2118763A GB8309140A GB8309140A GB2118763A GB 2118763 A GB2118763 A GB 2118763A GB 8309140 A GB8309140 A GB 8309140A GB 8309140 A GB8309140 A GB 8309140A GB 2118763 A GB2118763 A GB 2118763A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyether
- complex
- solid state
- electrochemical cell
- state electrochemical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007787 solid Substances 0.000 title claims abstract description 10
- -1 poly(ethylene oxide) Polymers 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 5
- 239000011149 active material Substances 0.000 claims abstract description 3
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
A solid state electrochemical cell comprises an anode having Li as its active material, a cathode and an electrolyte comprising a complex of a polyether with lithium. The polyether is atactic, has a low glass transition temperature and is capable of forming a complex with Li<+> ions but not with Na<+> ions. An example of such a polyether is polyvinyl methyl ether. The complex may be blended with another polymer such as a poly(ethylene oxide)- LiClO4 complex to improve mechanical properties for fabrication into the electrolyte.
Description
SPECIFICATION
Solid state electrochemical cell
The invention relates to an electrochemical cell incorporating a solid electrolyte; the electrolyte comprises a complex of a polyether with lithium.
Complexes of poly(ethylene oxide) and a lithium salt have been studied and observed to have high ionic conductivities. See, for example, a paper by M. D. Armand et al) presented to the 2nd
International Conference on Solid Electrolytes at
St. Andrews' University UK in 1978. There is, however, interest in improving the performance of
Li polymer complexes for their use as electrolyte in solid state electrochemical cells.
The invention provides a solid state electrochemical cell comprising an anode having lithium as its active material, a cathode and an electrolyte comprising a complex of a polyether with lithium, the polyether being an atactic polyether having a glass transition temperature of substantially less than 00C and being capable of forming a complex with Li+ ions but not with Na+ ions.
The electrolytes of the invention have been found, in certain test experiments described herein, to have higher ionic conductivities than certain known Li polymer complexes. This is believed to be due to the polyethers of the invention, being atactic, i.e., having no stereo regularity, having an enhanced proportion of amorphous regions. Thus, it is believed that high ionic conductivity may occur via such amorphous regions. Moreover, because the polyether of the invention are not capable of forming complexes with Na+, it is believed that the Li+ ions in the electrolyte will be more loosely bound to the polyether than say in the case of poly(ethylene oxide), which does form complexes with Na+ thereby giving rise to higher lithium ion conductivity.
An example of a polyether useful in the invention is polyvinyl methyl ether, referred to hereinafter as PVME, which has a low glass transistion temperature (-300C) and is an atactic material with amorphous characteristics.
Moreover, PVME is capable of forming complexes with Li salts such Lilo4, e.g. by simple addition thereof, but not with Na salts such as NaSCN.
Polyethers useful in the invention may not necessarily be mechanically suitable in themselves for fabrication into electrolytes suitable for use in electrochemical cells. It may, therefore, be necessary to blend such a polyether with another material to produce appropriate mechanical properties for the above purpose. For example, PVME may be in the form of a viscous liquid at room temperature and may therefore have to be blended with another polymer such as a saturated poly(ethylene oxide)-LiCI04 complex.
Electrochemical cells of the invention may be made by methods known in the art and the electrodes may be constituted by materials known in the art. For example, the anode may be made of Li or of an alloy thereof and the cathode of 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 1 (i) Preparation of electrolyte
A complex of PVME, LiClO4 and poly(ethylene oxide) was prepared by addition of the above constituents in methanolic solution. The methanol was then removed under vacuum at 1 000C. The resulting electrolyte had a ratio of 0 atoms in the poly(ethylene oxide) to Li+ ions of 3.9 and had 10% by weight of the PVME in relation to the poly(ethylene oxide).
(ii) Properties of electrolyte
The specific ionic conductivity of the electrolyte was measured and found to be ca.
1 x 10-4 ~1cm~ at 930C. This compares with a value of ca. 6x 1 0~5Q~'cm~1 for a known poly(ethylene oxide)-LiSCN complex having a
O/Li+ ratio of 5.0 and a value of ca.
6x10-5S2-1cm-1 for a known polyethylene oxide)-LiBF4 complex with a O/Li+ ratio of 4.0.
Example 2
The procedure of step (i) of Example 1 was repeated except that the electrolyte produced had 50% by weight of PVME in relation to
poly(ethylene oxide) and an O/Li+ ratio of 3.8. The specific ionic conductivity was found to be ca.
1 0-6#-1cm-1 at 250C This is an order of magnitude higher than the value found for a known poly(ethylene oxide)-LiClO4 complex
having a O/Li+ ratio of 4.5.
Claims (5)
1. A solid state electrochemical cell comprising an anode having lithium as its active material, a cathode and an electrolyte comprising a complex of a polyether with lithium, the polyether being an atactic polyether having a glass transition temperature of substantially less than 00C and being capable of forming a complex with Li+ ions but not with Na+ ions.
2. A solid state electrochemical cell as claimed in claim 1 wherein the polyether is polyvinyl methyl ether.
3. A solid state electrochemical cell as claimed in either of the preceding claims wherein the polyether is blended with another polymer for improving the mechanical properties of the polyether.
4. A solid state electrochemical cell as claimed in claim 4 wherein the other polymer is poly(ethylene oxide).
5. A solid state electrochemical cell as claimed in claim 4 wherein the electrolyte comprises a complex of polyvinyl methyl ether with LiClO4 blended with a complex of poly(ethylene oxide) with LiClO4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8309140A GB2118763B (en) | 1982-04-16 | 1983-04-05 | Solid state electrochemical cell |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8211146 | 1982-04-16 | ||
| GB8309140A GB2118763B (en) | 1982-04-16 | 1983-04-05 | Solid state electrochemical cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2118763A true GB2118763A (en) | 1983-11-02 |
| GB2118763B GB2118763B (en) | 1986-11-26 |
Family
ID=26282577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8309140A Expired GB2118763B (en) | 1982-04-16 | 1983-04-05 | Solid state electrochemical cell |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2118763B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2568574A1 (en) * | 1984-07-31 | 1986-02-07 | Comp Generale Electricite | Ionically conductive polymer and solid electrolyte employing it |
| FR2570224A1 (en) * | 1984-09-11 | 1986-03-14 | Elf Aquitaine | SOLID ELECTROLYTE POLYMER CONSTITUTED BY A RETICULATED COPOLYMER |
| 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 |
| US4970012A (en) * | 1988-12-16 | 1990-11-13 | Nippon Oil Company, Ltd. | Polymeric solid electrolytes and production process thereof |
| EP0411693A1 (en) * | 1989-08-01 | 1991-02-06 | ENIRICERCHE S.p.A. | Solid polymeric electrolyte and devices which incorporate it |
| EP0312160A3 (en) * | 1987-10-16 | 1991-05-29 | ENIRICERCHE S.p.A. | Solid polymeric electrolyte and electrochemical generators containing it |
| EP0418066A3 (en) * | 1989-09-13 | 1991-12-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for electrostatic coating of a resin molding |
| EP0421612A3 (en) * | 1989-09-11 | 1992-08-19 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Method for improving electric conductivity of a resin molding |
-
1983
- 1983-04-05 GB GB8309140A patent/GB2118763B/en not_active Expired
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2568574A1 (en) * | 1984-07-31 | 1986-02-07 | Comp Generale Electricite | Ionically conductive polymer and solid electrolyte employing it |
| FR2570224A1 (en) * | 1984-09-11 | 1986-03-14 | Elf Aquitaine | SOLID ELECTROLYTE POLYMER CONSTITUTED BY A RETICULATED COPOLYMER |
| EP0174894A1 (en) * | 1984-09-11 | 1986-03-19 | Societe Nationale Elf Aquitaine | Polymeric solid electrolyte based on a reticulated copolymer |
| 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 |
| EP0312160A3 (en) * | 1987-10-16 | 1991-05-29 | ENIRICERCHE S.p.A. | Solid polymeric electrolyte and electrochemical generators containing it |
| US4970012A (en) * | 1988-12-16 | 1990-11-13 | Nippon Oil Company, Ltd. | Polymeric solid electrolytes and production process thereof |
| EP0411693A1 (en) * | 1989-08-01 | 1991-02-06 | ENIRICERCHE S.p.A. | Solid polymeric electrolyte and devices which incorporate it |
| EP0421612A3 (en) * | 1989-09-11 | 1992-08-19 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Method for improving electric conductivity of a resin molding |
| EP0418066A3 (en) * | 1989-09-13 | 1991-12-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for electrostatic coating of a resin molding |
| US5137748A (en) * | 1989-09-13 | 1992-08-11 | Dai-Ichi Kogyo Keiyaku Co. | Method for electrostatic coating of a resin molding |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2118763B (en) | 1986-11-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |