# US 12,603,274 B2 · Lithium ion secondary battery and manufacturing method for negative electrode for lithium ion secondary battery

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- Number: US 12,603,274 B2
- Document ID: US12603274B2
- Status: Granted
- Kind: B2
- Application number: 18/040,707
- Filed: 2021-09-21
- Published: 2023-09-14
- Granted: 2026-04-14
- Earliest claimed: 2021-03-03
- Assignees: Vehicle Energy Japan Inc.
- Applicants: Vehicle Energy Japan Inc.
- Inventors: Takeshi Miki; Shuichi Suzuki; Yusuke Tachikawa
- Web page: https://patentgrep.com/patent/US12603274B2

## CPC

- H01M 4/364: {as mixtures}
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/48: of inorganic oxides or hydroxides
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- 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 4/587: for inserting or intercalating light metals
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- 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
- H01M 2004/027: {Negative 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

A lithium ion secondary battery is provided which has a sufficient discharge capacity and has a low internal resistance in a low SOC range. The lithium ion secondary battery includes: a positive electrode including a positive electrode mixture containing a positive electrode active material represented by the following formula: Li1+xMAO2; (where X satisfies −0.15≤X≤0.15, MA represents a group of elements including at least one selected from the group consisting of Mn and Al, Ni, and Co.); and a negative electrode including a negative electrode mixture containing a negative electrode active material containing a carbon-based material, a negative electrode additive containing a copper oxide, and a binder, in which the negative electrode mixture contains the copper oxide in an amount of 0.5 wt % or more and 15 wt % or less based on the total weight of the negative electrode active material and the negative electrode additive.

## Claims

### Claim 1

A lithium ion secondary battery comprising:
a positive electrode comprising a positive electrode mixture containing a positive electrode active material represented by formula (1):
Li1+xMAO2 (1),
where (X satisfies −0.15≤X≤0.15 and MA represents a group of elements including at least one selected from the group consisting of Manganese (Mn), Aluminum (Al), Nickel (Ni), and Cobalt (Co); and
a negative electrode comprising a negative electrode mixture,
wherein the negative electrode mixture comprises: a negative electrode active material containing a carbon-based material, a negative electrode additive containing a copper oxide, and a binder,
wherein the negative electrode active material comprises electrically connected particulate material that suppresses increases in an internal resistance of the lithium ion secondary battery,
wherein the negative electrode mixture contains the copper oxide in an amount of 0.5 wt % or more and 15 wt % or less based on a total weight of the negative electrode active material and the negative electrode additive, and
wherein the negative electrode additive has a median diameter smaller than a median diameter of the negative electrode active material and within the range of 1 μm to 10 μm.

### Claim 2 (depends on 1)

The lithium ion secondary battery according to claim 1, wherein the copper oxide is Cu2O, and
wherein the negative electrode mixture contains the copper oxide in the amount of 0.9 wt % or more and 15 wt % or less based on the total weight of the negative electrode active material and the negative electrode additive.

### Claim 3 (depends on 2)

The lithium ion secondary battery according to claim 2, wherein the negative electrode mixture contains the copper oxide in the amount of 1.4 wt % or more and 12 wt % or less based on the total weight of the negative electrode active material and the negative electrode additive.

### Claim 4 (depends on 1)

The lithium ion secondary battery according to claim 1, wherein the copper oxide is CuO, and
wherein the negative electrode mixture contains the copper oxide in the amount of 0.5 wt % or more and 8.3 wt % or less based on the total weight of the negative electrode active material and the negative electrode additive.

### Claim 5 (depends on 4)

The lithium ion secondary battery according to claim 4, wherein the negative electrode mixture contains the copper oxide in the amount of 0.78 wt % or more and 6.7 wt % or less based on the total weight of the negative electrode active material and the negative electrode additive.

### Claim 6 (depends on 1)

The lithium ion secondary battery according to claim 1, wherein both the negative electrode active material and the negative electrode additive are particulate, and
wherein the negative electrode active material and the negative electrode additive are separate particles that are not composited with each other.

### Claim 7

A manufacturing method for a negative electrode for a lithium ion secondary battery, the manufacturing method comprising the steps of:
preparing a mixture of a negative electrode active material containing a carbon-based material, a negative electrode additive containing a copper oxide, and a binder; and
applying the mixture to a negative electrode current collector;
wherein the mixture contains the copper oxide in an amount of 0.5 wt % or more and 15 wt % or less based on the total weight of the negative electrode active material and the negative electrode additive, and
wherein the negative electrode additive has a median diameter smaller than the median diameter of the negative electrode active material and within the range of 1 to 10 μm
wherein the negative electrode active material comprises electrically connected particulate material that suppresses increases in an internal resistance of the lithium ion secondary battery.

### Claim 8 (depends on 7)

The manufacturing method according to claim 7, wherein the negative electrode active material and the negative electrode additive are separate particles which are not composited with each other.

### Claim 9 (depends on 1)

The lithium ion secondary battery according to claim 1, wherein MA comprises Zirconium (Zr) to reduce the internal resistance of the lithium ion secondary battery.

### Claim 10 (depends on 1)

The lithium ion secondary battery according to claim 1, wherein the negative electrode active material are electrically connected particulate material without inhibiting the negative electrode additive having a high electrical resistance.

### Claim 11

A lithium ion secondary battery comprising:
a positive electrode comprising a positive electrode mixture containing a positive electrode active material represented by the following formula (1):
Li1+xMAO2 (1),
where X satisfies −0.15≤X≤0.15 and MA represents a group of elements including at least one selected from the group consisting of Manganese (Mn), Aluminum (Al), Nickel (Ni), and Cobalt (Co); and
a negative electrode comprising a negative electrode mixture, wherein the negative electrode mixture comprises, as separate particulates:
containing a negative electrode active material containing electrically connected particulate material that suppresses increases in an internal resistance of the lithium ion secondary battery,
a negative electrode additive containing a copper oxide, and
a binder,
wherein the negative electrode mixture contains the copper oxide in an amount of 0.5 wt % or more and 15 wt % or less based on a total weight of the negative electrode active material and the negative electrode additive, and
wherein the lithium ion secondary battery comprises a discharging capacity and the internal resistance affected by a low state of charge range.