# US 12,113,209 B2 · Negative electrode active material with metal dopant, and negative electrode, and lithium secondary battery including the same

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- Number: US 12,113,209 B2
- Document ID: US12113209B2
- Status: Granted
- Kind: B2
- Application number: 17/265,605
- Filed: 2019-08-23
- Published: 2021-06-03
- Granted: 2024-10-08
- Earliest claimed: 2018-08-23
- Assignees: LG Energy Solution, Ltd.
- Applicants: LG Energy Solution Ltd.
- Inventors: Se Mi Park; Yong Ju Lee; Dong Hyuk Kim
- Web page: https://patentgrep.com/patent/US12113209B2

## CPC

- C01B 33/02: Silicon (forming single crystals or homogeneous polycrystalline material with defined structure C30B)
- H01M 4/366: {as layered products}
- C01B 33/113: Silicon oxides; Hydrates thereof {(preparing monoxide by reduction of siliceous material C01B33/182)}
- C01B 33/18: Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof (preparation of aerogels by dehydrating gels C01B33/158; treatment to enhance the pigmenting or filling properties C09C)
- H01M 4/0428: {Chemical vapour deposition}
- H01M 4/0459: {Electrochemical doping, intercalation, occlusion or alloying}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/364: {as mixtures}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/483: {for non-aqueous cells (H01M4/485 takes precedence)}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/625: {Carbon or graphite}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2004/60: Particles characterised by their size
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 2004/027: {Negative electrodes}
- Y02E 60/10: Energy storage using batteries
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to a negative electrode active material including a silicon-based core, a first coating layer positioned on the silicon-based core, and a second coating layer positioned on the first coating layer, wherein the second coating layer includes a metal material doped onto a surface thereof.

## Claims

### Claim 1

A negative electrode active material comprising:
a silicon-based core;
a first coating layer positioned on the silicon-based core; and
a second coating layer positioned on the first coating layer,
wherein the second coating layer includes a metal material doped onto a surface of the second coating layer, and
wherein the metal material is positioned on the surface of the second coating layer, which is opposite to a surface of the second coating layer which contacts with the first coating layer.

### Claim 2 (depends on 1)

The negative electrode active material of claim 1, wherein the silicon-based core includes one or more selected from the group consisting of Si, a silicon oxide particle (SiOx, 0≤x<2), and a mixture thereof.

### Claim 3 (depends on 2)

The negative electrode active material of claim 2, wherein the silicon oxide particle (SiOx, 0≤x<2) is a composite composed of amorphous SiO2 and crystalline Si.

### Claim 4 (depends on 1)

The negative electrode active material of claim 1, wherein an average particle size (D50) of the silicon-based core is in a range of 0.01 μm to 30 μm.

### Claim 5 (depends on 1)

The negative electrode active material of claim 1, wherein the first coating layer includes one or more selected from the group consisting of amorphous carbon, natural graphite, artificial graphite, activated carbon, mesocarbon microbeads (MCMB), carbon fiber, and a carbon-based material made by heat-treating coal tar pitch, petroleum pitch, and an organic material as raw materials.

### Claim 6 (depends on 1)

The negative electrode active material of claim 1, wherein
the second coating layer is formed by carbonizing a polymer, and
the polymer includes one or more selected from the group consisting of polyethylene oxide, polyvinyl pyrrolidone, polyacrylic acid, polyvinyl alcohol, polyethyleneimine, polyacetylene, polyparaphenylene, polypyrrole, polyaniline, polyacrylonitrile, polyurea, and polythiophene.

### Claim 7 (depends on 1)

The negative electrode active material of claim 1, wherein the metal material comprises one or more selected from the group consisting of Li, Mg, Ca, Al, Ti, and Na.

### Claim 8 (depends on 1)

The negative electrode active material of claim 1, wherein the metal material is included in an amount of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the negative electrode active material.

### Claim 9 (depends on 1)

A negative electrode for a lithium secondary battery comprising the negative electrode active material of claim 1.

### Claim 10 (depends on 9)

A lithium secondary battery comprising the negative electrode of claim 9.

### Claim 11 (depends on 1)

A method of preparing the negative electrode active material of claim 1, the method comprising:
forming a first coating layer on a silicon-based core;
coating a polymer on the first coating layer to form a polymer layer and carbonizing the polymer layer to form a second coating layer; and
doping a surface of the second coating layer with a metal material.

### Claim 12 (depends on 11)

The method of claim 11, wherein the metal material is one or more selected from the group consisting of Li, Mg, Ca, Al, Ti, and Na.