Novel macromolecular material for use in realizing electrolytes and/or electrodes

• US 4,758,483 A
• Filed: 09/11/1985
• Issued: 07/19/1988
• Est. Priority Date: 03/11/1983
• Status: Expired due to Term

• Current Assignee: Societe Nationale Elf Aquitaine (Cook Composites and Polymers), Hydro-Quebec (Province of Québec)
• Original Assignee: Societe Nationale Elf Aquitaine (Cook Composites and Polymers), Hydro-Quebec (Province of Québec)
• Inventors: Armand, Michel, Harvey, Paul E., Muller, Daniel, Duval, Michel, Chabagno, Jean M.
• Primary Examiner(s): Walton, Donald L.
• Application Number:
  US06/774,915
• Time in Patent Office: 1,042 Days
• Field of Search: 429/192, 252/62.2
• US Class Current: 429/312
• CPC Class Codes: C08G 65/04 from cyclic ethers only
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 6/181 with polymeric electrolytes

Abstract

A solid polymeric electrolyte comprises a macromolecular material in which there is dissolved an ionic compound, particularly an ionic compound in solution in a copolymer of ethylene oxide and a second unit selected so that the copolymer chain maintains a polyether characteristic. Also a high performance composite electrode embodying this electrolyte, and a process for obtaining this electrolyte.

Claims

1. An improved amorphous, single phase solid electrolyte which possesses improved ionic conductivity, absence of crystallinity, thermo dynamical stability, high cation solubility and improved elasticity at ambient temperatures, which electrolyte is a random polyether copolymer of ethylene oxide and an ether oxide selected from the group consisting of a substituted ether oxide of the formula ##STR7## wherein R is Ra, wherein Ra is alkyl, alkenyl, or alkynyl having 1 to 12 carbon atoms or --CH₂ --O--Re--Ra wherein Ra is defined above, Re is a polyether of the formula --(CH₂ --CH₂ --O)_p -- wherein p is an integer from 0 to 10 and a cyclic ether wherein the ring has more than 3 carbon atoms.

2. The electrolyte of claim 1 wherein said copolymer is cross-linked.

3. The electrolyte of claim 2 wherein the cross-linking is by means of a short cross-linking agent.

4. The electrolyte of claim 3 wherein the short cross-linking agent is selected from the group of a metal, or a non-metal atom which is at least divalent.

5. The electrolyte of claim 4 wherein the short cross-linking agent is selected from the group consisting of silicon, cadmium, boron, titanium, aluminum, zinc, magnesium and tin.

6. The electrolyte of claim 4 wherein the cross-linking agent is linked to a polymer chain by an oxygen atom.

7. The electrolyte of claim 1 wherein the proportion of ether oxide is less than 30 mole percent.

8. The electrolyte of claim 1 wherein the polyether is --CH₂ --O--Re--Ra, wherein Re and Ra are defined in claim 1.

9. The electrolyte of claim 1 wherein the ether oxide is selected from the group of tetrahydrofurane, dioxolane and their derivatives.

10. The electrolyte of claim 1 wherein the ether oxide is a cyclic ether oxide.

11. The electrolyte of claim 1 wherein Ra is an alkyl.

12. The electrolyte of claim 1 which comprises an ionizable salt.

13. The electrolyte of claim 12 wherein the salt is selected from the group consisting of lithium perchlorate and lithium trifluoromethanesulfonate.

14. The electrolyte of claim 13 wherein the salt is present in the range from about 1.5 to 25% by weight.

15. An electrochemical secondary or primary cell wherein the electrode material includes an improved amorphous, single phase solid electrolyte which possesses improved ionic conductivity, absence of crystallinity, thermo dynamical stability, high cation solubility and improved elasticity at ambient temperatures, which electrolyte is a random polyether copolymer of ethylene oxide and an ether oxide selected from the group consisting of a substituted ether oxide of the formula ##STR8## wherein R is RA, wherein Ra is alkyl, alkenyl, or alkynyl having 1 to 12 carbon atoms or --CH₂ --O--Re--Ra wherein Ra is defined above, Re is a polyether of the formula --(CH₂ --CH₂ --O)_p -- wherein p is an integer from 0 to 10 and a cyclic ether wherein the ring has more than 3 carbon atoms.

16. The electrochemical cell of claim 15 wherein said copolymer is cross-linked.

17. The electrochemical cell of claim 16 wherein the cross-linking is by means of a short cross-linking agent selected from the group consisting of silicon, cadmium, boron, titanium, aluminum, zinc, magnesium and tin.

18. The electrochemical cell of claim 15 wherein the ether oxide is a cyclic ether oxide.

19. The electrochemical cell of claim 15 which comprises an ionizable salt.

20. An electrochemical generator which comprises a negative electrode and a positive electrode separated from each other by an improved amorphous, single phase solid electrolyte which possesses improved ionic conductivity, absence of crystallinity, thermo dynamical stability, high cation solubility and improved elasticity at ambient temperatures, which electrolyte is a random polyether copolymer of ethylene oxide and an ether oxide selected from the group consisting of a substituted ether oxide of the formula ##STR9## wherein R is Ra, wherein Ra is alkyl, alkenyl, or alkynyl having 1 to 12 carbon atoms or --CH₂ --O--Re--Ra wherein Ra is defined above, Re is a polyether of the formula --(CH₂ --CH₂ O)_p -- wherein p is an integer from 0 to 10 and a cyclic ether wherein the ring has more than 3 carbon atoms.

21. The electrochemical generator of claim 20 wherein said copolymer is cross-linked.

22. The electrochemical generator of claim 21 wherein the cross-linking is by means of a short cross-linking agent selected from the group consisting of silicon, cadmium, boron, titanium, aluminum, zinc, magnesium and tin.

23. The electrochemical generator of claim 20 wherein the ether oxide is a cyclic ether oxide.

24. The electrochemical generator of claim 20 which comprises an ionizable salt.