# US 12,218,312 B2 · All-solid-state secondary battery and method of charging the same

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- Number: US 12,218,312 B2
- Document ID: US12218312B2
- Status: Granted
- Kind: B2
- Application number: 18/483,856
- Filed: 2023-10-10
- Published: 2024-02-08
- Granted: 2025-02-04
- Earliest claimed: 2017-11-21
- Assignees: Samsung Electronics Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.
- Inventors: Naoki Suzuki; Nobuyoshi Yashiro; Takanobu Yamada; Yuichi Aihara
- Web page: https://patentgrep.com/patent/US12218312B2

## CPC

- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/364: {as mixtures}
- H01M 4/366: {as layered products}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/667: {in the form of layers, e.g. coatings}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0562: Solid materials
- H01M 10/44: Methods for charging or discharging (circuits for charging H02J7/00)
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/027: {Negative electrodes}
- H01M 2010/4292: {Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode}
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

An all-solid-state secondary battery including: a cathode including a cathode active material layer; an anode including an anode current collector, and an anode active material layer on the anode current collector, wherein the anode active material layer includes an anode active material which is alloyable with lithium or forms a compound with lithium; and a solid electrolyte layer between the cathode and the anode, wherein a ratio of an initial charge capacity (b) of the anode active material layer to an initial charge capacity (a) of the cathode active material layer satisfies a condition of Equation 1: 0.01<(b/a)<0.5, wherein a is the initial charge capacity of the cathode active material layer determined from a first open circuit voltage to a maximum charging voltage, and b is the initial charge capacity of the anode active material layer determined from a second open circuit voltage to 0.01 volts vs. Li/Li+.

## Claims

### Claim 1

An all-solid-state secondary battery comprising:
a cathode comprising a cathode active material layer, the cathode active material layer comprises a cathode active material and a solid electrolyte;
an anode comprising
an anode current collector, and
an anode active material layer on the anode current collector,
wherein the anode active material layer comprises
an anode active material comprising amorphous carbon, and
a binder,
wherein the anode active material layer has a thickness of about 1 micrometer to about 20 micrometers; and
a solid electrolyte layer between the cathode and the anode.

### Claim 2 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein a ratio of an initial charge capacity of the anode active material layer to an initial charge capacity of the cathode active material layer satisfies Equation 1:
0.01<(b/a)<0.5 Equation 1
wherein a is the initial charge capacity of the cathode active material layer, determined from a first open circuit voltage to a maximum charging voltage vs. Li/Li+, and
wherein b is the initial charge capacity of the anode active material layer, determined from a second open circuit voltage to 0.01 Volts vs. Li/Li+.

### Claim 3 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the anode active material is in a form of a particle, wherein the anode active material has an average particle diameter of about 4 micrometers or less.

### Claim 4 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the amorphous carbon comprises at least one of furnace black, acetylene black, Ketjen black, or graphene, and has an average particle diameter D50 of about 4 micrometers or less.

### Claim 5 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the anode active material further comprises at least one of gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, or zinc.

### Claim 6 (depends on 5)

The all-solid-state secondary battery of claim 5, wherein the anode active material comprises
a mixture of a first particle comprising the amorphous carbon and a second particle comprising the at least one of gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, or zinc, and
wherein an amount of the second particle is about 8 weight percent to about 60 weight percent, based on a total weight of the mixture.

### Claim 7 (depends on 6)

The all-solid-state secondary battery of claim 6, wherein a weight ratio of the amorphous carbon to the second particle is about 10:1 to about 1:2.

### Claim 8 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the binder comprises at least one of styrene butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, or polyethylene, and an amount of the binder ranges from about 0.3 weight percent to about 15 weight percent, based on a total weight of the anode active material.

### Claim 9 (depends on 1)

The all-solid-state secondary battery of claim 1, further comprising a metal layer between the anode active material layer and the anode current collector, wherein the metal layer comprises at least one of lithium or a lithium alloy.

### Claim 10 (depends on 9)

The all-solid-state secondary battery of claim 9, wherein
the metal layer is disposed within the anode active material layer, between the anode active material layer and the anode current collector, or both, and
the metal layer has a thickness of about 1 micrometer to about 200 micrometers.

### Claim 11 (depends on 1)

The all-solid-state secondary battery of claim 1, further comprising a plating layer on the anode current collector and between the anode current collector and the anode active material layer, the plating layer comprising an element alloyable with lithium,
wherein the plating layer comprises at least one of gold, silver, zinc, tin, indium, silicon, aluminum, or bismuth, and has a thickness of about 1 nanometer to about 500 nanometers.

### Claim 12 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the anode current collector, the anode active material layer, and a region therebetween are Li-free regions at an initial state of or after discharge of the all-solid-state secondary battery.

### Claim 13 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the solid electrolyte layer comprises a solid electrolyte, and
the solid electrolyte of the solid electrolyte layer is amorphous, crystalline, or in a mixed form.

### Claim 14 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the all-solid-state secondary battery is a lithium battery, and the maximum charging voltage is about 3 volts to about 5 volts versus Li/Li+.

### Claim 15 (depends on 1)

The all-solid-state secondary battery of claim 1, wherein the anode current collector comprises a material that does not form a compound with lithium.

### Claim 16 (depends on 15)

The all-solid-state secondary battery of claim 15, wherein the anode current collector comprises at least one of titanium, copper, iron, cobalt, or nickel.

### Claim 17 (depends on 1)

A method of charging an all-solid-state secondary battery, the method comprising:
charging the all-solid-state secondary battery of claim 1,
wherein an initial charge capacity of the anode active material layer is exceeded,
a metal layer is formed between the anode active material layer and the anode current collector during the charging of the all-solid-state secondary battery, and
the metal layer comprises at least one of lithium or a lithium alloy.

### Claim 18 (depends on 17)

The method of claim 17,
wherein a charge capacity of the all-solid-state secondary battery is about two times to about 100 times greater than an initial charge capacity of the anode active material layer.

### Claim 19 (depends on 17)

The method of claim 17, wherein when the initial charge capacity of the anode active material layer is exceeded, a content of lithium in the metal layer comprising at least one of lithium or a lithium alloy is increased.

### Claim 20 (depends on 19)

The method of claim 19, wherein the metal layer is disposed within the anode active material layer, between the anode active material layer and the anode current collector, or both.