Thermopolymerizable composition for battery use

• US 6,562,513 B1
• Filed: 09/08/1999
• Issued: 05/13/2003
• Est. Priority Date: 09/17/1998
• Status: Expired due to Term

• Current Assignee: Showa Denko KK
• Original Assignee: Showa Denko KK
• Inventors: Naijo, Shuichi, Takeuchi, Masataka
• Primary Examiner(s): Maples, John S.
• Application Number:
  US09/391,155
• Time in Patent Office: 1,343 Days
• Field of Search: 429/189, 429/317, 429/314, 526/230.5, 526/227, 526/310
• US Class Current: 429/189
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 20/10 Esters
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides (1) a thermopolymerizable composition containing a thermopolymerizable compound having (meth)acrylate having a moiety consisting of oxyalkylene, fluorocarbon, oxyfluorocarbon and/or carbonate group within the molecule, an electrolyte salt, an organic polymerization initiator having no benzene ring, and a polymerization retarder having vinyl group within the molecule, (2) a solid electrolyte obtained by heat-curing the composition, (3) a primary battery, a secondary battery and an electric double-layer capacitor each using the solid electrolyte, and processes for manufacturing the same.

Claims

1. A thermopolymerizable composition comprising at least one thermopolymerizable compound having a polymerizable functional group and capable of forming a polymer having a cross-linked and/or side chain structure by the polymerization, at least one electrolyte salt, at least one polymerization initiator and at least one polymerization retarder having a vinyl group.

2. The thermopolymerizable composition as claimed in claim 1, wherein said polymerization retarder is a compound having a structure represented by the following formula (1):

wherein A represents a linear, branched or cyclic alkylene group having from 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having from 2 to 20 carbon atoms or a linear, branched or cyclic alkynyl group having from 2 to 10 carbon atoms;

Ar represents an aryl group which may have a substituent;

a represents an integer of 0 or 1; and

the Ar groups may be the same or different.

3. The thermopolymerizable composition as claimed in claim 1, wherein said polymerization initiator is an organic peroxide represented by the following formula (2):

wherein X represents a linear, branched or cyclic alkyl or alkoxy group which may have a substituent;

Y represents a linear, branched or cyclic alkyl group which may have a substituent; and

m and n each independently represents 0 or 1, provided that the combination of (m,n)=(0,1) is excluded.

4. The thermopolymerizable composition as claimed in claim 3, wherein said organic peroxide has an active oxygen amount of from about 1 to about 1,000 ppm based on the thermopolymerizable composition.

5. The thermopolymerizable composition as claimed in claim 3, wherein said organic peroxide is selected from the group consisting of diacyl peroxides, peroxydicarbonates and peroxy esters each containing no benzene ring.

6. The thermopolymerizable composition as claimed in claim 1, wherein said thermopolymerizable compound comprises a compound having an ethylenically unsaturated polymerizable group.

7. The thermopolymerizable composition as claimed in claim 1, wherein said thermopolymerizable compound comprises a polymerizable compound having either one of the polymerizable functional groups represented by the following formulae (3) and/or (4):

wherein R¹ and R³ each represents hydrogen atom or an alkyl group;

R² and R⁵ each represents a divalent group containing oxyalkylene, fluorocarbon, oxyfluorocarbon or a carbonate group;

R⁴ represents a divalent group having 10 or less carbon atoms;

provided that R², R⁴ and R⁵ each may contain a hetero atom and may have any of linear, branched and cyclic structures;

x represents 0 or an integer of from 1 to 10;

provided that when a plurality of polymerizable functional groups represented by formula (3) or (4) are contained in the same molecule, R¹, R², R³, R⁴, R⁵ or x in each polymerizable functional group may be the same or different.

8. The thermopolymerizable composition as claimed in claim 7, which further comprises at least one organic solvent selected from the group consisting of carbonic esters, aliphatic esters, ethers, lactones, sulfoxides and amides.

9. The thermopolymerizable composition as claimed in claim 1, wherein the content of an organic solvent is from about 300 to about 1,500 wt % based on the thermopolymerizable compound.

10. The thermopolymerizable composition as claimed in claim 1, which comprises at least one kind of inorganic fine particle having an average particle size of from about 0.005 to about 100 μ

m.

11. The thermopolymerizable composition as claimed in claim 1, wherein said electrolyte salt is at least one selected from the group consisting of alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, transition metal salts and protonic acids.

12. The thermopolymerizable composition as claimed in claim 11, wherein at least one electrolyte salt is selected from the group consisting of LiPF₆, LiBF₄, LiAsF₆ and LiN(R-SO2)₂ (wherein R represents a perfluoroalkyl group having from 1 to 10 carbon atoms).

13. The thermopolymerizable composition as claimed in claim 2, wherein said polymerization retarder is a compound having a structure represented by formula (1) where A is a linear, branched or cyclic alkylene group having from 1 to 20 carbon atoms;

Ar is a phenyl group which may have a substituent;

a is an integer of 0 or 1; and

the Ar groups may be the same or different.

14. The thermopolymerizable composition as claimed in claim 3, wherein said polymerization initiator is an organic peroxide,represented by formula (2) where X and Y each is a linear, branched or cyclic alkyl group which may have a substituent;

and m and n each independently is 0 or 1, provided that the combination of (m,n)=(0,1) is excluded.

15. A solid polymer electrolyte obtained by thermopolymerizing a thermopolymerizable composition comprising at least one thermopolymerizable compound having a polymerizable functional group and capable of forming a polymer having a cross-linked and/or side chain structure by the polymerization, at least one electrolyte salt, at least one polymerization initiator and at least one polymerization retarder having a vinyl group.

16. A battery using a solid polymer electrolyte obtained by thermopolymerizing a thermopolymerizable composition comprising at least one thermopolymerizable compound having a polymerizable functional group and capable of forming a polymer having a cross-linked and/or side chain structure by the polymerization, at least one electrolyte salt, at least one polymerization initiator and at least one polymerization retarder having a vinyl group.

17. The battery as claimed in claim 16, wherein at least one material selected from the group consisting of lithium, lithium alloys, carbon materials capable of occluding or releasing lithium ion, inorganic compounds capable of occluding or releasing lithium ion and electrically conducting polymers capable of occluding or releasing lithium ion is used as a negative electrode of the battery.

18. The battery as claimed in claim 16, wherein at least one material selected from the group consisting of electrically conducting polymers, metal oxides, metal sulfides and carbon materials is used as a positive electrode of the battery.