COPOLYMER ELECTROLYTES FOR SECONDARY BATTERY, METHOD FOR PREPARING THE SAME AND USE THEREOF

• US 20150288027A1
• Filed: 07/11/2014
• Published: 10/08/2015
• Est. Priority Date: 04/08/2014
• Status: Active Grant

• Current Assignee: Seoul National University R&DB Foundation (Seoul National University)
• Original Assignee: Seoul National University R&DB Foundation (Seoul National University)
• Inventors: LEE, Jong-Chan, BAIK, Ji-Hoon, KIM, Dong-Gyun, SHIM, Jimin
• Granted Patent: US 9,887,433 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 220/286 and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
• CPC Class Codes: C08F 220/302 and two or more oxygen atoms in the alcohol moiety
• 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 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides copolymers of polyethylene oxide methacrylate and alkenyl group-containing methacrylate, method for preparing the same and use thereof. The copolymers may be used for preparing solid phase electrolytes having high ionic conductivity and enhanced physical properties.

Claims

1. A polymer having the following structure:

2. The polymer according to claim 1,

wherein the bond is amide bond (—

NHCO—

), ester bond (—

COO—

) thioester bond (—

COS—

), ether bond (—

O—

), thioether bond (—

S—

), or disulfide bond (—

S—

S—

).

3. The polymer according to claim 1,

wherein the divalent radical is an aliphatic radical having carbon numbers between 2 to 10, or an aromatic radical.

4. The polymer according to claim 1,

wherein the ratio of the n and m is 17:

1 to 1;

1.

5. The polymer according to claim 1,

wherein the A is cardanol, an alkenyl group or an unsaturated fatty acids

6. The polymer according to claim 5,

wherein the cardanol has the following structure:

7. The polymer according to claim 5,

wherein the alkenyl group may be monounsaturated aliphatic hydrocarbon or polyunsaturated aliphatic hydrocarbon.

8. The polymer according to claim 5,

wherein the unsaturated fatty acid may be 5-dodecenoic acid (12:

1(n-7)), 7-tetradecenonic acid (14;

1(n-7)), palmitoleic acid (16;

1(n-7)), vaccenic acid (18;

1(n-7)), paullinic acid (20;

1(n-7)), oleic acid (18;

1(n-9)), elaidic acid (18;

1(n-9)), eicosenoic acid (20;

1(n-9)), erucic acid (22;

1(n-9)), nervonic acid (24;

1(n-9)), linoleic acid (18;

2(n-6)), gamma-linolenic acid (18;

3(n-6)), dihomo gamma-linolenic acid (18;

3(n-6)), arachidonic acid (20;

4(n-6)), alpha-linolenic acid (18;

3(n-3)), eicosapentaenic acid, EPA (20;

5(n-3)), or docosahexaenic acid, DHA (22;

6(n-3)), or a combination of at least two fatty acid among above.

13. A solid phase electrolyte composition comprising a crosslinked polymer prepared by crosslinking the polymer of claim 1 with a photo-crosslinker;

and an alkali metal salt dispersed in the polymer.

14. The solid phase electrolyte composition according to claim 13,

wherein the photo-crosslinker is 2-hydroxy-2-methylpropiophenone (HMPP), camphorquinone, acroyl chloride, trimethylopropane triacrylate (TPT), polyethylene glycol diacrylate (PEGDA), AIBN, BPO or 2,2-dimethoxy-2-phenylacetophenone (DMPA), or a combination of at least two photo-crosslinkers among the above photo-crosslinkers.

15. The solid phase electrolyte composition according to claim 13,

wherein the alkali metal salt is a lithium salt, sodium salt or potassium salt, or a combination thereof.

16. The solid phase electrolyte composition according to claim 15,

wherein the lithium salt is lithium bis(tetrafluoromethanesulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF₆), lithium perchlorate (LiClO₄), Lithium triflate (LiTf), lithium bis(oxaloto)borate (LiBOB), lithium tetrafluoroborate (LiBF₄), lithium oxalyldifluoroborate (LiODFB), or lithium fluoroalkylphosphate (LiFAP), or a combination thereof

17. The solid phase electrolyte composition according to claim 15,

wherein the sodium salt is sodium tetrafluoroborate (NaBF₄), sodium hexafluorophosphate (NaPF₆), sodium perchlorate (LiClO₄), 4,5-dicyano-2(trifluormethyl)imidazolate (NaTDI), or sodium 4,5-dicyano-2-(pentafluoroethyl)imidazolate (NaPDI), or a combination thereof.

18. The solid phase electrolyte composition according to claim 15,

wherein the potassium salt is potassium tetrafluoroborate (KBF₄), potassium perchlorate (KClO₄), or potassium hexafluorophosphate (KPF₆), or a combination thereof.

20. A secondary battery comprising the solid phase electrolyte composition of claim 13.

9. A method for preparing the polymer, the method comprises:

preparing PEGMA (polyethylene glycol methacrylate) monomers and methacrylic acid monomers substituted with a moiety comprising alkenyl group having 12 to 22 carbon atoms, wherein the alkenyl group has 1 to 6 double bond (ACMA); and

copolymerizing the monomers by mixing the PEGMA monomers and the ACMA monomers in organic solvent and adding an initiator to the mixture.

10. The method according to claim 9,

wherein the molar ratio of the PEGMA monomers and ACMA monomers may be 17:

1 to 1;

1.

11. The method according to claim 9,

wherein the organic solvent is water, tetrahydrofuran (THF), methanol, ethanol, isopropanol, dimethyl formamide (DMF), dimethylsulfoxide (DMSO), propylene glycol methyl ether acetate (PGMEA), n-butyl acetate (NBA), ethyl acetate (EtAc), n-hexane, cyclohexane, benzene, toluene, benzonitrile or anisole, or a combination of at least two solvents among the above solvents, or a two phase solvent system using a polar solvent and a nonpolar solvent.

12. The method according to claim 9,

wherein the initiator is azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile (ADMVN), dilauroyl peroxide (DLP), benzoyl peroxide (BPO), acetyl peroxide, t-butyl peracetate, cumyl peroxide, t-butyl peroxide, t-butyl hydroperoxide, or bis(4-tert-butylcyclohexyl) peroxydicarbonate, or a combination of at least two initiators among the above initiators.

19. A method for preparing the solid phase electrolyte composition, the method comprises:

mixing the polymer, an alkali metal salt and a photo-crosslinker; and

inducing photo-crosslinking between the polymers by irradiating light to the mixture.