Solid polymer electrolyte, battery and solid-state electric double layer capacitor using the same as well as processes for the manufacture thereof

• US 5,874,184 A
• Filed: 07/11/1997
• Issued: 02/23/1999
• Est. Priority Date: 06/03/1993
• Status: Expired due to Term

• Current Assignee: Showa Denko KK (Resonac Holdings Corp.)
• Original Assignee: Showa Denko KK (Resonac Holdings Corp.)
• Inventors: Tamura, Eri, Noguchi, Jun, Ueda, Miyuki, Yashima, Hideo, Takeuchi, Masataka, Tokita, Koji, Ooga, Kazuhiko
• Primary Examiner(s): NUZZOLILLO, MARIA
• Application Number:
  US08/892,849
• Time in Patent Office: 592 Days
• Field of Search: 429/192, 429/212, 429/213, 429/218, 29/623.1, 29/623.5, 252/62.6, 252/500, 252/518, 361/523, 361/212, 361/301.1, 361/305, 361/306.3, 361/311, 361/361
• US Class Current: 429/314
• CPC Class Codes: C08F 290/062 Polyethers
• CPC Class Codes: C08F 290/142 Polyethers
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/2835 having less than 5 ether groups
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 18/4837 and other oxyalkylene units
• CPC Class Codes: C08G 18/4883 containing cyclic groups having at least one oxygen atom in the ring
• CPC Class Codes: C08G 18/8116 esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• CPC Class Codes: C08G 65/329 with organic compounds
• CPC Class Codes: C08G 65/3322 acyclic
• CPC Class Codes: C08G 65/33348 containing isocyanate group
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01G 11/64 characterised by additives
• CPC Class Codes: H01G 9/025 Solid electrolytes H01G11/54 takes precedence
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 4/621 Binders
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: H01M 6/40 : Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y10S 977/948 : Energy storage/generating using nanostructure, e.g. fuel cell, battery
• CPC Class Codes: Y10T 29/49108 : Electric battery cell making

Abstract

A solid polymer electrolyte comprising a composite of (a) a polymeric component which comprises (i) a polymer obtained from at least one compound represented by general formula (IA), (IIA) and/or (IIIA) as described in the specification; or (ii) a polymer obtained from at least one compound having alcoholic hydroxyl groups wherein at least one hydrogen atom of said alcoholic hydroxyl groups is replaced by a unit represented by general formula (X) or (XI) as described in the specification, and (b) at least one electrolyte salt, which has a high ionic conductivity and can be made into a thin film. The present invention is also directed to an electrode comprising the solid polymer electrolyte and an electroactive substance or polarizable material; as well as a process for manufacturing the same. In addition, the present invention is directed to a primary an secondary battery having the solid polymer electrolyte, as well as a process for manufacturing the same. The battery of the present invention has a high capacity, high current density, and, in the case of a secondary battery, has good cyclability. Finally, the present invention is directed to a solid-state electric double layer capacitor comprising the solid polymer electrolyte, as well as a process for manufacturing the same. The electric double layer capacitor has a high output voltage and a large take-out current.

Claims

1. A polymerizable composition useful in forming an ion conductive polymeric composite, comprising (i) at least one compound having at least three organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, and (ii) a salt.

5. A polymerizable composition useful in forming an ion conductive polymeric composite as claimed in any one of claims 1 to 4, wherein said ethylencially unsaturated group is a group having an ethylenically unsaturated unit selected from the group consisting of CH₂ ═

C(R¹)--, CH₂ ═

C(R¹)C(═

O)-- and CH₂ ═

C(R¹)C(═

O)O--, wherein R¹ represents a hydrogen atom or a methyl group.

2. A polymerizable composition useful in forming an ion conductive polymeric composite, comprising (i) at least one compound having at least three organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, (ii) a salt, and (iii) a solvent.

3. A polymerizable composition useful in forming an ion conductive polymeric composite, comprising (i) at least one compound having at least four organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, and (ii) a salt.

4. A polymerizable composition useful in forming an ion conductive polymeric composite, comprising (i) at least one compound having at least four organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, (ii) a salt, and (iii) a solvent.

6. A method for forming an ion conductive polymeric composite, which comprises providing a polymerizable composition comprising (i) at least one compound having at least three organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group and (ii) a salt, and subjecting said composition to heating and/or irradiation to thereby crosslink said composition.

10. A method for forming an ion conductive polymeric composite as claimed in any one of claims 6 to 9, wherein said ethylencially unsaturated group is a group having an ethylencially unsaturated unit selected from the group consisting of CH₂ ═

C(R¹)--, CH₂ ═

C(R¹)C(═

O)-- and CH₂ ═

C(R¹)C(═

O)O--, wherein R¹ represents a hydrogen atom or a methyl group.

11. An electrochemical apparatus comprising an ion conductive polymeric composite produced according to the method as claimed in any one of claims 6 to 9.

12. A battery comprising an ion conductive polymeric composite produced according to the method as claimed in any one of claims 6 to 9.

13. A capacitor comprising an ion conductive polymeric composite produced according to the method as claimed in any one of claims 6 to 9.

7. A method for forming an ion conductive polymeric composite, which comprises providing a polymerizable composition comprising (i) at least one compound having at least three organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, (ii) a salt and (iii) a solvent, and subjecting said composition to heating and/or irradiation to thereby crosslink said composition.

8. A method for forming an ion conductive polymeric composite, which comprises providing a polymerizable composition comprising (i) at least one compound having at least four organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group and (ii) a salt, and subjecting said composition to heating and/or irradiation to thereby crosslink said composition.

9. A method for forming an ion conductive polymeric composite, which comprises providing a polymerizable composition comprising (i) at least one compound having at least four organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, (ii) a salt, and (iii) a solvent, and subjecting said composition to heating and/or irradiation to thereby crosslink said composition.

14. A compound having at least three organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group.

15. A compound having at least four organic chains, wherein said organic chain comprises an ethylenically unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group.

16. A method for producing a compound having at least three organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, comprising providing a compound having at least three alcoholic hydroxyl groups and replacing at least three hydrogen atoms of said alcoholic hydroxy groups by a unit represented by an organic chain containing an ethylenically unsaturated group and a --O--(C═

O)--NH-- group.

20. A method for producing a compound having at least three organic chains according to the method as claimed in any one of claims 16 to 19, wherein said compound is a compound having at least four said organic chains, and the reacting compound is a compound having at least four alcoholic hydroxyl groups.

17. A method for producing a compound having at least three organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, comprising reacting a compound having at least three alcoholic hydroxyl groups with an isocyanide compound having an ethylencially unsaturated group and an oxyalkylene group.

18. A method for producing a compound having at least three organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, comprising reacting a compound having at least three alcoholic hydroxyl groups and at least one oxyalkylene group with an isocyanate compound having an ethylenically unsaturated group.

19. A method for producing a compound having at least three organic chains, wherein said organic chain comprises an ethylencially unsaturated group, a --O--(C═

O)--NH-- group and at least one oxyalkylene group, comprising reacting a compound having at least three alcoholic hydroxyl groups and at least one oxyalkylene group with an isocyanide compound having an ethylencially unsaturated group and an oxyalkylene group.