RU2218359C2 - Fluorinated graft copolymer, polymeric electrolyte containing this copolymer, lithium accumulator battery with the polymeric electrolyte - Google Patents

Fluorinated graft copolymer, polymeric electrolyte containing this copolymer, lithium accumulator battery with the polymeric electrolyte Download PDF

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RU2218359C2
RU2218359C2 RU2002105381/04A RU2002105381A RU2218359C2 RU 2218359 C2 RU2218359 C2 RU 2218359C2 RU 2002105381/04 A RU2002105381/04 A RU 2002105381/04A RU 2002105381 A RU2002105381 A RU 2002105381A RU 2218359 C2 RU2218359 C2 RU 2218359C2
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copolymer
range
polyethylene glycol
vinylidene fluoride
monomethyl ether
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RU2002105381A (en
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Миунг-донг ЧО
Н.В. Каричковская
В.С. Колосницын
До-янг СЕУНГ
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Самсунг Сди Ко., Лтд.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

FIELD: chemical industry; production of fluorinated graft copolymer; polymeric electrolyte containing it and lithium accumulator batteries. SUBSTANCE: invention presents fluorinated graft copolymer, the polymeric electrolyte containing this copolymer, and lithium accumulator battery with the polymeric electrolyte. The graft copolymer of monomethylic ether of polyethylene glycol and copolymer trifluoroethylenechloride and vinylidene fluoride is described by formula I:

Description

Текст описания в факсимильном виде (см. графическую часть). Description text in facsimile form (see graphic part).

Claims (14)

1. Привитой сополимер монометилового эфира полиэтиленгликоля и трифторэтиленхлорида и винилиденфторида, описываемый формулой 11. A grafted copolymer of monomethyl ether of polyethylene glycol and trifluoroethylene chloride and vinylidene fluoride described by formula 1
Figure 00000031
Figure 00000031
 где n = 1-10;where n = 1-10; m = 1-5;m is 1-5; а = 3-25;a = 3-25; 1 = 50-337.1 = 50-337. 2. Способ получения привитого сополимера монометилового эфира полиэтиленгликоля и трифторэтиленхлорида и винилиденфторида, описываемого формулой 12. A method of obtaining a grafted copolymer of monomethyl ether of polyethylene glycol and trifluoroethylene chloride and vinylidene fluoride described by formula 1
Figure 00000032
Figure 00000032
 где n = 1-10;where n = 1-10; m = 1-5; m is 1-5; а = 3-25;a = 3-25; 1 = 50-337,1 = 50-337, причем способ включает (a) растворение сополимера трифторэтиленхлорида и винилиденфторида и монометилового эфира полиэтиленгликоля в органическом растворителе, причем их массовое отношение находится в диапазоне между 1:0,5 и 1::2,5 соответственно, и (b) добавление к смеси, получаемой в результате на стадии (а), основания или щелочного металла в количестве 1,05 и 1,3 моль в расчете на 1 моль монометилового эфира полиэтиленгликоля с получением продукта.moreover, the method includes (a) dissolving the copolymer of trifluoroethylene chloride and vinylidene fluoride and polyethylene glycol monomethyl ether in an organic solvent, and their mass ratio is in the range between 1: 0.5 and 1 :: 2.5, respectively, and (b) adding to the mixture obtained as a result, in step (a), a base or an alkali metal, in an amount of 1.05 and 1.3 mol per 1 mol of polyethylene glycol monomethyl ether to obtain a product. 3. Способ по п.2, отличающийся тем, что основанием на стадии (b) является по меньшей мере одно соединение, выбираемое из группы, состоящей из гидроксида натрия, гидроксида калия, гидроксида кальция, оксида цинка, оксида магния и триэтиламина.3. The method according to claim 2, characterized in that the base in step (b) is at least one compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc oxide, magnesium oxide and triethylamine. 4. Способ по п.2, отличающийся тем, что щелочным металлом на стадии (b) является по меньшей мере один, выбираемый из группы, состоящей из натрия, калия и лития.4. The method according to claim 2, characterized in that the alkali metal in stage (b) is at least one selected from the group consisting of sodium, potassium and lithium. 5. Способ по п.2, отличающийся тем, что в реакционную смесь на стадии (b) дополнительно добавляют от 10 до 15 мас.ч. межфазного катализатора в расчете на 100 мас.ч. сополимера трифторэтиленхлорида и винилиденфторида.5. The method according to claim 2, characterized in that from 10 to 15 parts by weight are additionally added to the reaction mixture in step (b). interfacial catalyst per 100 wt.h. a copolymer of trifluoroethylene chloride and vinylidene fluoride. 6. Способ по п.5, отличающийся тем, что межфазным катализатором предпочтительно является по меньшей мере один, выбираемый из группы, состоящей из N-децилпиридинилбромида и хлорида бензилтриэтиламмония.6. The method according to claim 5, characterized in that the interfacial catalyst is preferably at least one selected from the group consisting of N-decylpyridinyl bromide and benzyltriethylammonium chloride. 7. Способ по п.2, отличающийся тем, что средневесовая молекулярная масса сополимера трифторэтиленхлорида и винилиденфторида находится в диапазоне от 10000 до 500000, а средневесовая молекулярная масса монометилового эфира полиэтиленгликоля находится в диапазоне от 100 до 2000.7. The method according to claim 2, characterized in that the weight average molecular weight of the copolymer of trifluoroethylene chloride and vinylidene fluoride is in the range from 10,000 to 500,000, and the weight average molecular weight of the polyethylene glycol monomethyl ether is in the range from 100 to 2000. 8. Способ по п.2, отличающийся тем, что растворителем на стадии (а) является по меньшей мере один, выбираемый из группы, состоящей из ацетона, метилэтилкетона, тетрагидрофурана и диметилсульфоксида, а его содержание предпочтительно находится в диапазоне от 500 до 1500 мас.ч. в расчете на 100 мас.ч. сополимера.8. The method according to claim 2, characterized in that the solvent in stage (a) is at least one selected from the group consisting of acetone, methyl ethyl ketone, tetrahydrofuran and dimethyl sulfoxide, and its content is preferably in the range from 500 to 1500 wt. .h. based on 100 parts by weight copolymer. 9. Способ по п.2, отличающийся тем, что температура реакции на стадии (b) находится в диапазоне от 0 до 70°С.9. The method according to claim 2, characterized in that the reaction temperature in stage (b) is in the range from 0 to 70 ° C. 10. Полимерный электролит, содержащий привитой сополимер монометилового эфира полиэтиленгликоля и трифторэтиленхлорида и винилиденфторида, описываемый формулой 110. A polymer electrolyte containing a grafted copolymer of polyethylene glycol monomethyl ether and trifluoroethylene chloride and vinylidene fluoride, described by formula 1
Figure 00000033
Figure 00000033
 где n = 1-10;where n = 1-10; m = 1-5;m is 1-5; а = 3-25;a = 3-25; l = 50-337,l = 50-337, и литиевую соль, содержание которой находится в диапазоне от 5 до 30 мас.ч. в расчете на 100 мас.ч. привитого сополимера.and lithium salt, the content of which is in the range from 5 to 30 parts by weight based on 100 parts by weight grafted copolymer. 11. Полимерный электролит по п.10, отличающийся тем, что литиевой солью являются одна или несколько, выбираемых из группы, состоящей из LiCF3SO3, LiPF6, LiBF4, LiClO4 и LiN (CF3SO2)2.11. The polymer electrolyte of claim 10, wherein the lithium salt is one or more selected from the group consisting of LiCF 3 SO 3 , LiPF 6 , LiBF 4 , LiClO 4 and LiN (CF 3 SO 2 ) 2 . 12. Полимерный электролит по п.10, отличающийся тем, что дополнительно содержит по меньшей мере один пластификатор, выбираемый из группы, состоящей из пропиленкарбоната, монометилового эфира полиэтилгликоля, этиленкарбоната и сульфолана, а его содержание находится в диапазоне от 5 до 30 мас.ч. в расчете на 100 мас.ч. привитого сополимера монометилового эфира полиэтиленгликоля и сополимера трифторэтиленхлорида и винилиденфторида, описываемого формулой 1.12. The polymer electrolyte according to claim 10, characterized in that it further comprises at least one plasticizer selected from the group consisting of propylene carbonate, monomethyl ether of polyethylene glycol, ethylene carbonate and sulfolane, and its content is in the range from 5 to 30 wt.h . based on 100 parts by weight a grafted copolymer of polyethylene glycol monomethyl ether and a copolymer of trifluoroethylene chloride and vinylidene fluoride described by formula 1. 13. Полимерный электролит по п.10, отличающийся тем, что средневесовая молекулярная масса привитого сополимера монометилового эфира полиэтиленгликоля и трифторэтиленхлорида и винилиденфторида, описываемого формулой 1, находится в диапазоне от 30000 до 600000.13. The polymer electrolyte according to claim 10, characterized in that the weight average molecular weight of the grafted copolymer of polyethylene glycol monomethyl ether and trifluoroethylene chloride and vinylidene fluoride described by formula 1 is in the range from 30,000 to 600,000. 14. Литиевая аккумуляторная батарея, в которой в качестве покрытия используют полимерный электролит по любому из пп.10-13.14. A lithium secondary battery in which a polymer electrolyte according to any one of claims 10 to 13 is used as a coating.
RU2002105381/04A 2002-02-27 2002-02-27 Fluorinated graft copolymer, polymeric electrolyte containing this copolymer, lithium accumulator battery with the polymeric electrolyte RU2218359C2 (en)

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CN113993920A (en) * 2019-08-08 2022-01-28 株式会社Lg新能源 Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery comprising the same

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KR100756457B1 (en) * 2005-11-01 2007-09-07 주식회사 엘지화학 Block copolymers containing perfluorocyclobutane rings and electrolyte membranes using the same
CN105322239A (en) * 2015-10-09 2016-02-10 桂林理工大学 Electrolyte containing N,N'-di[2-(1,3-triethylene glycol methyl ether) propyl] perylene diimide and preparation method of electrolyte
KR102590176B1 (en) 2018-07-10 2023-10-16 주식회사 엘지에너지솔루션 Solid electrolyte composition for secondary battery and solid electrolyte
CN109326822B (en) * 2018-11-05 2020-11-17 珠海冠宇电池股份有限公司 Preparation method of all-solid fluoropolymer electrolyte membrane and lithium ion battery

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JPH09231977A (en) * 1996-02-27 1997-09-05 Elf Atochem Japan Kk Electrode and its manufacture
JPH10120738A (en) * 1996-10-17 1998-05-12 Toagosei Co Ltd Production of fluorine-containing graft polymer
JPH11329441A (en) * 1998-05-13 1999-11-30 Toshiba Corp Non-aqueous electrolyte secondary cell
JP2001143752A (en) * 1999-11-19 2001-05-25 Nippon Mektron Ltd Gel electrolyte for lithium ion cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113993920A (en) * 2019-08-08 2022-01-28 株式会社Lg新能源 Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery comprising the same
CN113993920B (en) * 2019-08-08 2024-03-26 株式会社Lg新能源 Copolymer for polymer electrolyte, gel polymer electrolyte including the same, and lithium secondary battery

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