A positive electrode

Patent metadata

Field	Value
Publication number	US-2024047679-A1
Application number	US-202118268339-A
Country	US
Kind code	A1
Filing date	Dec 23, 2021
Priority date	Dec 24, 2020
Publication date	Feb 8, 2024
Grant date	—

Abstract

A positive electrode for lithium-ion secondary batteries, comprising a positive electrode active material and at least one polymer electrolyte being polyether polymer, said positive electrode active material comprising at least elements selected from Li, M′, and oxygen, wherein the metal M′ has a formula: Ni1-x-y-zMnxCoyAz with 0.00≤x≤0.70, 0.00≤y≤0.40, and 0.00≤z≤0.10, wherein A, when present, is different than Ni, Mn, Co and Li, and is preferably at least one of: B, Mg, Al, Nb, Ti, Y, W, S, Ba, Sr, and Zr.

First claim

1 - 15 . (canceled)

16 . A positive electrode for lithium-ion secondary batteries, comprising a positive electrode active material and at least one polymer electrolyte, said positive electrode active material comprising Ni, Mn, Co and A, said positive electrode material having a Ni:(Mn+Co+A) molar ratio of (1−x−y−z):(x+y+z) wherein 0.00≤x≤0.70, 0.00≤y≤0.40, and 0.00≤z≤0.10 as measured by ICP, wherein A, when present, is different than Ni, Mn, Co and Li, and is at least one of: B, Mg, Al, Nb, Ti, Y, W, S, Ba, Sr, and Zr, and said polymer electrolyte being obtained by reaction between:
i. at least one polyether polymer [hereinafter polymer (P)], said polymer (P) comprising:
at least 70.0% by moles of oxyethylene units (EO);
from 0.0 to 10.0% by moles of oxypropylene units (PO); and
from 1.00 to 4.0% by moles of recurring units derived from at least one monomer [hereafter, 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 , 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 consisting of 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, heterocyclyl, wherein said C 1-6 alkyl, C 3-6 cycloalkyl, aryl, C 1-6 alkoxy, and 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 an 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).

17 . The positive electrode according to claim 16 , wherein from 80.0% by moles to 99.0% by moles of the recurring units of the polymer (P) are EO units.

18 . The positive electrode according to claim 16 , wherein from 0.5% by moles to 6.0% by moles or 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.

19 . The positive electrode according to claim 16 , 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 16 .

20 . The positive electrode according to claim 16 , 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.

21 . The positive electrode according to claim 16 , 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, and CF 3 ; m is an integer of at least 5 and at most 1000.

22 . The positive electrode according to claim 16 , 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).

23 . The positive electrode according to claim 16 , wherein the weight ratio of the polymer electrolyte to the positive electrode active material is between 5% and 50%.

24 . The positive electrode according to claim 16 , wherein the positive electrode further comprises at least one lithium salt selected from: LiTFSI, LiFSI, LiPF 6 , LiBF 4 , and LiClO 4 .

25 . The positive electrode according to claim 16 , wherein A is Al and the atomic ratio of A to the total amount of Ni, Mn, and/or Co is higher than 0.

26 . A polymer battery comprising the positive electrode according to claim 16 .

27 . An electrochemical cell comprising the positive electrode according to claim 16 .

28 . A battery comprising the electrochemical cell according to claim 27 .

29 . A battery or an electrochemical cell comprising a positive electrode active material and a polymer electrolyte, said positive electrode active material comprising Ni, Mn, Co and A, said positive electrode material having a Ni:(Mn+Co+A) molar ratio of (1−x−y−z):(x+y+z) wherein 0.00≤x≤0.70, 0.00≤y≤0.40, and 0.00≤z≤0.10 as measured by ICP, wherein A, when present, is different than Ni, Mn, Co and Li, and is at least one of: B, Mg, Al, Nb, Ti, Y, W, S, Ba, Sr, and Zr, and said polymer electrolyte being obtained by reaction between:
i. at least one polyether polymer [hereinafter polymer (P)], said polymer (P) comprising:
at least 70.0% by moles of oxyethylene units (EO);
from 0.0 to 10.0% by moles of oxypropylene units (PO); and
from 1.00 to 4.0% by moles of recurring units derived from at least one monomer [hereafter, 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 consisting of 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,

Assignees

• Umicore Nv

Inventors

• Kumakura Shinichi
• Kang Jihoon

Classifications

• H01M4/62 Primary

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0565

  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