Preparation of ion conductive solid electrolyte

• US 4,908,283 A
• Filed: 04/24/1989
• Issued: 03/13/1990
• Est. Priority Date: 10/09/1986
• Status: Expired due to Fees

• Current Assignee: UBE Industries Limited 12-32 Nishihonmachi 1-Chome Ube-Shi
• Original Assignee: UBE Industries Limited
• Inventors: Suehiro, Tsuomu, Takahashi, Toru, Shimizu, Ryuichi, Ashitaka, Hidetomo
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US07/342,122
• Time in Patent Office: 323 Days
• Field of Search: 429/192, 429/217
• US Class Current: 429/317
• CPC Class Codes: H01M 6/181 with polymeric electrolytes

Abstract

An improved ion conductive solid electrolyte favorably emplolyable for an solid electrolyte cell comprises a cured product of an acryloyl-denatured polyalkylene oxide having a molecular weight of 200-3,000 and an inorganic ion salt. Another improved ion conductive solid electrolyte comprises a cured product of an acryloyl-denatured polyalkylene oxide having a molecular weight of 200-3,000, an inorganic ion salt and a polyalkylene glycol.

Claims

1. A process for the preparation of an ion conductive solid electrolyte, which comprises curing a composition comprising an acryloyl-denatured polyalkylene oxide having a molecular weight of 200 to 3,000 which comprises an acryloyl group having the formula:

##STR5## wherein R¹ is hydrogen or a lower alkyl group having 1-6 carbon atoms; and

R² is hydrogen or an aromatic group;

and a polyalkylene oxide chain having the formula;

space="preserve" listing-type="equation">(CH.sub.2 CHRO).sub.n

wherein

n is an integer of from 1 to 30; and

R is hydrogen or a lower alkyl group having 1-6 carbon atoms,

and an inorganic ion salt by irradiating the composition with active rays.

2. The process as claimed in claim 1, wherein said inorganic ion salt contains at least one atom selected from the group consisting of Li, Na, K, Cs, Ag, Cu and Mg.

3. The process as claimed in claim 1, wherein said composition contains the inorganic ion salt in an amount of 0.05-50 molar % based on the alkylene oxide unit of the acryloyl-denatured polyalkylene oxide.

4. The process as claimed in claim 1, wherein said composition contains an organic solvent selected from the group consisting of propylene carbonate, γ

-butyrolactone, ethylene carbonate, tetrahydrofuran, acetonitrile, dimethoxyethane, dimethylsulfoxide, dioxolane and sulfolane in an amount of not more than 200 weight % based on the amount of composition.

5. The process as claimed in claim 1, wherein said composition contains a photopolymerization initiator.

6. A solid electrolyte cell using a solid electrolyte film and a negative pole comprising lithium metal or lithium alloy, wherein said electrolyte film is a cured product prepared by irradiating a composition comprising an acryloyl-denatured polyalkylene oxide and an inorganic ion salt with active rays, said acryloyl-denatured polyalklene oxide having a molecular weight of 200 to 3,000 and comprising an acryloyl group having the formula:

##STR6## wherein R¹ is hydrogen or a lower alkyl group having 1-6 carbon atoms; and

R² is hydrogen or an aromatic group;

and a polyalkylene oxide chain having the formula;

space="preserve" listing-type="equation">(CH.sub.2 CHRO).sub.n

wherein

n is an integer of from 1 to 30; and

R is hydrogen or a lower alkyl group having 1-6 carbon atoms.

7. The solid electrolyte cell as claimed in claim 6, wherein said composition contains the inorganic ion salt in an amount of 0.05-50 molar % based on the alkylene oxide unit of the acryloyl-denatured polyalkylene oxide.

8. The solid electolyte cell as claimed in claim 6, wherein said composition contains an organic solvent selected from the group consisting of propylene carbonate, γ

-butyrolactone, ethylene carbonate, tetrahydrofuran, acetonitrile, dimethoxyethane, dimethylsulfoxide, dioxolane and sulfolane in an amount of not more than 200 weight % based on the amount of composition.

9. An ion conductive solid electrolyte, which comprises a cured product of a composition comprising:

an acryloyl-denatured polyalkylene oxide having a molecular weight of 200 to 3,000 which comprises an acryloyl group having the formula;

##STR7## wherein R¹ is hydrogen or a lower alkyl group having 1-6 carbon atoms,

and a polyalkylene oxide chain having the formula;

space="preserve" listing-type="equation">(CH.sub.2 CHRO).sub.n

wherein

n is an integer of from 1 to 30; and

R is hydrogen or a lower alkyl group having 1-6 carbon atoms;

an inorganic ion salt; and

a polyalkylene glycol having the formula;

space="preserve" listing-type="equation">(R.sup.3 O(CH.sub.2 CHR.sup.4 O).sub.n R.sup.5

wherein

n is an integer of from 2 to 30; and

each of R³, R⁴ and R⁵ independently is hydrogen or a lower alkyl group having 1-6 carbon atoms.

10. The ion conductive solid electrolyte as claimed in claim 9, wherein said inorganic ion salt contains an atom selected from the group consisting of Li, Na, K, Cs, Ag, Cu and Mg.

11. The ion conductive solid electrolyte as claimed in claim 9, wherein said composition contains the inorganic ion salt in an amount of 0.05-50 molar % based on the alkylene oxide unit of the acryloyl-denatured polyalkylene oxide.

12. The ion conductive solid electrolyte as claimed in claim 9, wherein said composition contains the polyalkylene glycol an amount of 1-500 weight % based on the acryloyl-denatured polyalkylene oxide.

13. A solid electrolyte cell using a negative pole comprising lithium metal or lithium alloy and a positive pole, wherein said positive pole is a cured product of a composition comprising:

an active material of positive pole;

an acryloyl-denatured polyalkylene oxide having a molecular weight of 200 to 3,000 which comprises an acryloyl group having the formula;

##STR8## wherein R¹ is hydrogen or a lower alkyl group having 1-6 carbon atoms,

and a polyalkylene oxide chain having the formula;

space="preserve" listing-type="equation">(CH.sub.2 CHRO).sub.n

wherein

n is an integer of from 1 to 30; and

R is hydrogen or a lower alkyl group having 1-6 carbon atoms;

an inorganic ion salt; and

a polyalkylene glycol having the formula;

space="preserve" listing-type="equation">R.sup.3 O(CH.sub.2 CHR.sup.4 O).sub.n R.sup.5

wherein

n is an integer of from 3 to 30; and

each of R³, R⁴ and R⁵ independently is hydrogen or a lower alkyl group having 1-6 carbon atoms.

14. The solid electrolyte cell as claimed in claim 13, wherein said inorganic ion salt contains an atom of Li.

15. The solid electrolyte cell as claimed in claim 13, wherein said composition contains the inorganic ion salt in an amount of 0.05-50 molar % based on the alkylene oxide unit of the acryloyl-denatured polyalkylene oxide.

16. The solid electrolyte cell as claimed in claim 13, wherein said composition contains the polyalkylene glycol an amount of 1-500 weight % based on the acryloyl-denatured polyalkylene oxide.