# US 12,603,287 B2 · Electrode active material for secondary battery and method of manufacturing same

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- Number: US 12,603,287 B2
- Document ID: US12603287B2
- Status: Granted
- Kind: B2
- Application number: 18/020,746
- Filed: 2021-08-19
- Published: 2023-09-28
- Granted: 2026-04-14
- Earliest claimed: 2020-08-21
- Assignees: LG Energy Solution, Ltd.
- Applicants: LG Energy Solution, Ltd.
- Inventors: Joon Koo Kang; Il Ha Lee; Ki Hwan Kim
- Web page: https://patentgrep.com/patent/US12603287B2

## CPC

- H01M 4/622: {being polymers}
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/366: {as layered products}
- 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 4/60: of organic compounds
- H01M 4/602: {Polymers}
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/624: {Electric conductive fillers}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 10/052: Li-accumulators
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present application provides an electrode active material having excellent electrical conductivity and ionic conductivity as well as excellent mechanical flexibility by forming a unique conductive polymer layer on an active material core, while preventing side reactions between the active material core and an electrolyte from occurring, and an electrode comprising the same. Accordingly, it is possible to provide a lithium secondary battery having an excellent capacity retention ratio (lifetime characteristics) according to charging/discharging while having a high energy density. The conductive polymer layer includes a thiophene-based polymer having one or more functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group and a flowable functional group.

## Claims

### Claim 1

An electrode active material comprising:
an active material core; and
a conductive polymer layer on a surface of the active material core,
wherein the conductive polymer layer comprises a thiophene-based polymer,
wherein the thiophene-based polymer has a weight average molecular weight in a range of 500 g/mol to 20,000 g/mol,
wherein the thiophene-based polymer comprises a polymerization unit of Formula 3:
wherein L3 and L4 are each independently a single bond or an alkylene group, R2 is a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, or a flowable functional group, and R3 is hydrogen, a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, or a flowable functional group,
wherein the flowable functional group is an alkyl group comprising 3 or more carbon atoms, an alkoxy group comprising 3 or more carbon atoms, a carbonyl group comprising an alkyl group comprising 3 or more carbon atoms, a carbonyloxy group comprising an alkyl group comprising 3 or more carbon atoms, or a functional group of Formula 2:
wherein L1 is a single bond or an alkylene group, L2 is an alkylene group, R1 is an alkyl group, and n is a number in a range of 1 to 10.

### Claim 2 (depends on 1)

The electrode active material according to claim 1, wherein the active material core comprises a lithium nickel-manganese-cobalt oxide represented by Formula 1 below:
LixMyO2 [Formula 1]
wherein M is represented by Ni1-a-bMnaCOb, a is in a range of 0.05 to 0.4, b is in a range of 0.05 to 0.4, 1-a-b is in a range of 0.2 to 0.9, x is 0.95 to 1.15, and y is 2-x.

### Claim 3 (depends on 1)

The electrode active material according to claim 1, wherein in the thiophene-based polymer, a ratio (M/S) of a mole number (M) of one or more functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, and a flowable functional group relative to a mole number(S) of sulfur is in a range of 0.1 to 10.

### Claim 4 (depends on 1)

The electrode active material according to claim 1, wherein the thiophene-based polymer simultaneously comprises a first functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, and a carbonyl group, and a second functional group which is the flowable functional group.

### Claim 5 (depends on 4)

The electrode active material according to claim 4, wherein in the thiophene-based polymer, a ratio ((M1+M2)/S) of a sum of a mole number (M1) of the first functional group (M1) and a mole number (M2) of the second functional group to a mole number (S) of sulfur is in a range of 0.1 to 10.

### Claim 6 (depends on 1)

The electrode active material according to claim 1, wherein at least one of L3 and L4 is an alkylene group and a number of carbon atoms present in L3 and L4 is in a range of 2 to 10.

### Claim 7 (depends on 1)

The electrode active material according to claim 1, wherein the thiophene-based polymer simultaneously comprises a polymerization unit of Formula 4 below and a polymerization unit of Formula 5 below:
wherein L5 and L6 are each independently a single bond or an alkylene group, R4 is a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, or a carbonyl group, and R5 is hydrogen, a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, or a carbonyl group:
wherein L7 and L8 are each independently a single bond or an alkylene group, R6 is a flowable functional group, and R7 is hydrogen or a flowable functional group wherein the flowable functional group is an alkyl group comprising 3 or more carbon atoms, an alkoxy group comprising 3 or more carbon atoms, a carbonyl group comprising an alkyl group comprising 3 or more carbon atoms, a carbonyloxy group comprising an alkyl group comprising 3 or more carbon atoms, or a functional group of Formula 2:
wherein L1 is a single bond or an alkylene group, L2 is an alkylene group, R1 is an alkyl group, and n is a number in a range of 1 to 10.

### Claim 8 (depends on 7)

The electrode active material according to claim 7, wherein a ratio (M4/M5) of a mole number (M4) of the polymerization unit of Formula 4 to a mole number (M5) of the polymerization unit of Formula 5 is in a range of 0.1 to 10.

### Claim 9 (depends on 1)

The electrode active material according to claim 1, wherein the thiophene-based polymer has an oxidation potential in a range of 2.0V to 4.2V.

### Claim 10 (depends on 1)

The electrode active material according to claim 1, wherein a coverage of the conductive polymer layer to the active material core is 80% or more.

### Claim 11 (depends on 1)

The electrode active material according to claim 1, wherein the conductive polymer layer has a thickness in a range of 1 nm to 1 μm.

### Claim 12 (depends on 1)

The electrode active material according to claim 1, comprising 0.1 to 150 parts by weight of the conductive polymer layer relative to 100 parts by weight of the active material core.

### Claim 13

A method of manufacturing an electrode active material comprising a step of mixing a thiophene-based polymer with an active material core, wherein
the thiophene-based polymer has a weight average molecular weight in a range of 500 g/mol to 20,000 g/mol,
wherein the thiophene-based polymer comprises a polymerization unit of Formula 3:
wherein L3 and L4 are each independently a single bond or an alkylene group, R2 is a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, or a flowable functional group, and R3 is hydrogen, a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, or a flowable functional group,
wherein the flowable functional group is an alkyl group comprising 3 or more carbon atoms, an alkoxy group comprising 3 or more carbon atoms, a carbonyl group comprising an alkyl group comprising 3 or more carbon atoms, a carbonyloxy group comprising an alkyl group comprising 3 or more carbon atoms, or a functional group of Formula 2:
wherein L1 is a single bond or an alkylene group, L2 is an alkylene group, R1 is an alkyl group, and n is a number in a range of 1 to 10.

### Claim 14 (depends on 13)

The method of manufacturing an electrode active material according to claim 13, wherein the thiophene-based polymer is formed by polymerizing a thiophene-based monomer comprising one or more functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, and a flowable functional group in a presence of an oxidizing agent.

### Claim 15 (depends on 14)

The method of manufacturing an electrode active material according to claim 14, wherein the thiophene-based monomer is represented by Formula 6 below:
wherein L3 and L4 are each independently a single bond or an alkylene group, R2 is a carboxyl group, a hydroxyl group, an amine group, a nitro group, an ether group, a carbonyl group, or a flowable functional group, R3 is hydrogen, a carboxyl group, a hydroxyl group, an amine a group, a nitro group, an ether group, a carbonyl group, or a flowable functional group, and R8 and R9 are each independently hydrogen or halogen wherein the flowable functional group is an alkyl group comprising 3 or more carbon atoms, an alkoxy group comprising 3 or more carbon atoms, a carbonyl group comprising an alkyl group comprising 3 or more carbon atoms, a carbonyloxy group comprising an alkyl group comprising 3 or more carbon atoms, or a functional group of Formula 2:
wherein L1 is a single bond or an alkylene group, L2 is an alkylene group, R1 is an alkyl group, and n is a number in a range of 1 to 10.

### Claim 16 (depends on 1)

An electrode, comprising:
a current collector; and
an electrode active material layer formed on one side of the current collector,
wherein the electrode active material layer comprises the electrode active material of claim 1, a conductive material, and a binder.