# US 12,763,332 B2 · Positive electrode

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- Number: US 12,763,332 B2
- Document ID: US12763332B2
- Status: Granted
- Kind: B2
- Application number: 18/268,339
- Filed: 2021-12-23
- Published: 2024-02-08
- Granted: 2026-10-13
- Earliest claimed: 2020-12-24
- Assignees: Umicore AG & Co. KG
- Applicants: Umicore
- Inventors: Shinichi Kumakura; Jihoon Kang
- Web page: https://patentgrep.com/patent/US12763332B2

## CPC

- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- C08G 77/46: containing polyether sequences
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0082: Organic polymers
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## 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.

## Claims

### Claim 1

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 R1 and R2, equal to or different from each other and at each occurrence, is C1-6 alkanediyl wherein said C1-6 alkanediyl, is optionally substituted with one or more substituents selected from halide, C1-4 alkyl, C3-6 cycloalkyl, CF3, OR8, and wherein each of R8, equal to or different from each other and at each occurrence, is independently selected from the group consisting of hydrogen and C1-4 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 R3, R4, R5, R6 and R7, equal to or different from each other and at each occurrence, is independently selected from the group consisting of C1-6 alkyl, C3-6 cycloalkyl, aryl, C1-6 alkoxy, heterocyclyl, wherein said C1-6 alkyl, C3-6 cycloalkyl, aryl, C1-6 alkoxy, and heterocyclyl are optionally substituted with one or more substituents selected from halide, C1-4 alkyl, C3-6 cycloalkyl, CF3, and OR8, and wherein each of R9, equal to or different from each other and at each occurrence, is independently selected from the group consisting of hydrogen, C1-4 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—CH2 moiety of monomer (M) with the H—Si moiety of the polysiloxane compound having the formula (III).

### Claim 2 (depends on 1)

The positive electrode according to claim 1, wherein from 80.0% by moles to 99.0% by moles of the recurring units of the polymer (P) are EO units.

### Claim 3 (depends on 1)

The positive electrode according to claim 1, wherein from 0.5% by moles to 6.0% by moles of the recurring units of the polymer (P) are PO units.

### Claim 4 (depends on 1)

The positive electrode according to claim 1, wherein from 1.2% by moles to 4.0% 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 R1, R2, n and X are as defined in claim 1.

### Claim 5 (depends on 1)

The positive electrode according to claim 1, wherein the monomer (M) is of formula (II)
wherein each of R1 and R2, equal to or different from each other and at each occurrence, is a C1-2 alkanediyl and n is an integer 0 or 1.

### Claim 6 (depends on 1)

The positive electrode according to claim 1, wherein each of R3, R4, and R7, equal to or different from each other and at each occurrence, is independently C1-6 alkyl; each of R5 and R6, equal to or different from each other and at each occurrence, is independently selected from C1-4 alkyl or phenyl, wherein said C1-4 alkyl is optionally substituted with one or more substituents selected from halide, C1-4 alkyl, and CF3; m is an integer of at least 5 and at most 1000.

### Claim 7 (depends on 1)

The positive electrode according to claim 1, 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═CH2 moiety of monomer (M) with the H—Si moiety of the polysiloxane compound having the formula (III).

### Claim 8 (depends on 1)

The positive electrode according to claim 1, wherein the weight ratio of the polymer electrolyte to the positive electrode active material is between 5% and 50%.

### Claim 9 (depends on 1)

The positive electrode according to claim 1, wherein the positive electrode further comprises at least one lithium salt selected from: LiTFSI, LiFSI, LiPF6, LiBF4, and LiClO4.

### Claim 10 (depends on 1)

The positive electrode according to claim 1, wherein A is Al and the atomic ratio of A to the total amount of Ni, Mn, and/or Co is higher than 0.

### Claim 11 (depends on 1)

A polymer battery comprising the positive electrode according to claim 1.

### Claim 12 (depends on 1)

An electrochemical cell comprising the positive electrode according to claim 1.

### Claim 13 (depends on 12)

A battery comprising the electrochemical cell according to claim 12.

### Claim 14

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 R1 and R2, equal to or different from each other and at each occurrence, is C1-6 alkanediyl wherein said C1-6 alkanediyl, is optionally substituted with one or more substituents selected from halide, C1-4 alkyl, C3-6 cycloalkyl, CF3, and OR8, and wherein each of R8, equal to or different from each other and at each occurrence, is independently selected from the group consisting of hydrogen and C1-4 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 R3, R4, R5, R6 and R7, equal to or different from each other and at each occurrence, is independently selected from the group consisting of C1-6 alkyl, C3-6 cycloalkyl, aryl, C1-6 alkoxy, and heterocyclyl, wherein said C1-6 alkyl, C3-6 cycloalkyl, aryl, C1-6 alkoxy, heterocyclyl are optionally substituted with one or more substituents selected from halide, C1-4 alkyl, C3-6 cycloalkyl, CF3, and OR9, and wherein each of R9, equal to or different from each other and at each occurrence, is independently selected from the group consisting of hydrogen, C1-4 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═CH2 moiety of monomer (M) with the H—Si moiety of the polysiloxane compound having the formula (III).

### Claim 15 (depends on 14)

Battery or electrochemical cell according to claim 14, comprising at least one lithium salt selected from: LiTFSI, LiFSI, LiPF6, LiBF4, and LiClO4.

### Claim 16 (depends on 1)

The positive electrode according to claim 1, wherein A is Al.

### Claim 17 (depends on 14)

The battery or electrochemical cell according to claim 14, wherein A is Al.