A polymer electrolyte

Patent metadata

Field	Value
Publication number	US-2024063433-A1
Application number	US-202118268293-A
Country	US
Kind code	A1
Filing date	Dec 23, 2021
Priority date	Dec 24, 2020
Publication date	Feb 22, 2024
Grant date	—

Abstract

A polymer electrolyte suitable for use in lithium-ion secondary batteries is obtained by reaction between: at least one polyether polymer [polymer (P)], said polymer (P) comprising: at least 70.0% by moles of oxyethylene units; from 0.0 to 10.0% by moles of oxypropylene units; and from 1.00 to 4.0% by moles of recurring units derived from at least one monomer and at least one polysiloxane compound. Said at least one polysiloxane compound is grafted to said at least one polymer (P) through reaction of at least a fraction of the —CH═CH 2 moiety of monomer (M) with the H—Si moiety of the polysiloxane compound.

First claim

1 - 10 . (canceled)

11 . A polymer electrolyte suitable for use in lithium-ion secondary batteries being obtained by reaction between:
i. at least one polyether polymer [hereinafter polymer (P)], said polymer (P) comprising:
a) at least 70.0% by moles of oxyethylene units (EO);
b) from 0.0 to 10.0% by moles of oxypropylene units (PO); and
c) from 1.00 to 4.0% by moles of recurring units derived from at least one monomer [hereinafter, monomer (M)] of general formula (I) or of general formula (II):

wherein
each of R 1 and R 2 , equal to or different from each other and at each occurrence, is C 1-6 alkanediyl wherein said C 1-6 alkanediyl, is optionally substituted with one or more substituents selected from halide, C 1-4 alkyl, C 3-6 cycloalkyl, CF 3 , and OR 8 , and wherein each of R 8 , equal to or different from each other and at each occurrence, is independently selected from the group hydrogen and C 1-4 alkyl; n is an integer 0 or 1 or 2;
each of X is a leaving group selected from the group consisting of halide, trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate and methanesulfonate;

and
ii. at least one polysiloxane compound having the formula (III):

wherein
each of R 3 , R 4 , R 5 , R 6 and R 7 , equal to or different from each other and at each occurrence, is independently selected from the group consisting of C 1-6 alkyl, C 3-6 cycloalkyl, aryl, C 1-6 alkoxy, and heterocyclyl, wherein said C 1-6 alkyl, C 3-6 cycloalkyl, aryl, C 1-6 alkoxy, heterocyclyl are optionally substituted with one or more substituents selected from halide, C 1-4 alkyl, C 3-6 cycloalkyl, CF 3 , and OR 9 , and wherein each of R 9 , equal to or different from each other and at each occurrence, is independently selected from the group consisting of hydrogen, C 1-4 alkyl, and a hydroxyl protecting group,
m is an integer of at least 3; and
wherein said at least one polysiloxane compound having the formula (III) is grafted to said at least one polymer (P) through reaction of at least a fraction of the —CH═CH 2 moiety of monomer (M) with the H—Si moiety of the polysiloxane compound having the formula (III).

12 . The polymer electrolyte according to claim 11 , wherein from 80.0% by moles to 99.0% by moles of the recurring units of the polymer (P) are EO units.

13 . The polymer electrolyte according to claim 11 , wherein from 0.5% by moles to 5.0% by moles, or from 0.5% by moles to 4.0% by moles, or from 1.0% by moles to 4.0% by moles, or from 1.0% by moles to 3.0% by moles of the recurring units of the polymer (P) are PO units.

14 . The polymer electrolyte according to claim 11 , wherein from 1.2% by moles to 4.0% by moles, or from 1.5% by moles to 3.5% by moles, or from 1.5% by moles to 3.0% by moles of the recurring units of the polymer (P) are recurring units derived from the monomer (M) of general formula (I) or of general formula (II) wherein R 1 , R 2 , n and X are as defined in claim 11 .

15 . The polymer electrolyte according to claim 11 , wherein the monomer (M) is of formula (II)

wherein
each of R 1 and R 2 , equal to or different from each other and at each occurrence, is a C 1-2 alkanediyl and n is an integer 0 or 1.

16 . The polymer electrolyte according to claim 11 , wherein the polymer (P) is a random copolymer, having an Mn (number average molecular weight) of at least 10 000 g/mol and at most 150 000 g/mol.

17 . The polymer electrolyte according to claim 11 , wherein each of R 3 , R 4 , and R 7 , equal to or different from each other and at each occurrence, is independently C 1-6 alkyl; each of R 5 and R 6 , equal to or different from each other and at each occurrence, is independently selected from C 1-4 alkyl or phenyl, wherein said C 1-4 alkyl is optionally substituted with one or more substituents selected from halide, C 1-4 alkyl, or CF 3 ; m is an integer of at least 5 and at most 1000.

18 . The polymer electrolyte according to claim 11 , wherein the polymer (P) and the polysiloxane having formula (III) are at least partially dissolved in an organic solvent selected from the group consisting of benzene, toluene, xylene, and cymene.

19 . The polymer electrolyte according to claim 11 , wherein the polysiloxane compound having the formula (III) is grafted to the polymer (P) in the presence of a catalyst.

20 . The polymer electrolyte according to claim 11 , wherein the polysiloxane compound having formula (III) is grafted to polymer (P) through reaction of at least 10% and at most 90% by moles, of the —CH═CH 2 moiety of monomer (M) with the H—Si moiety of the polysiloxane compound having the formula (III).

21 . The polymer electrolyte according to claim 19 , wherein the catalyst is a hydrosilylation catalyst selected from the group consisting of a Karstedt's catalyst, a Wilkinson catalyst, a Speier catalyst, and mixtures thereof.

Assignees

• Umicore Nv

Inventors

• Kumakura Shinichi
• Kubo Masataka

Classifications

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M4/622

  being polymers · CPC title

• H01M10/052

  Li-accumulators · CPC title