# US 12,191,444 B2 · All-solid secondary battery and method of manufacturing the same

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- Number: US 12,191,444 B2
- Document ID: US12191444B2
- Status: Granted
- Kind: B2
- Application number: 17/376,243
- Filed: 2021-07-15
- Published: 2022-02-10
- Granted: 2025-01-07
- Earliest claimed: 2020-08-06
- Assignees: Samsung Electronics Co., Ltd.; Corning Incorporated
- Applicants: Samsung Electronics Co., Ltd.; Corning Incorporated
- Inventors: Jusik Kim; Myungjin Lee; Sewon Kim; Michael Edward Badding; Jaemyung Chang; Zhen Song
- Web page: https://patentgrep.com/patent/US12191444B2

## CPC

- H01M 10/0562: Solid materials
- H01M 4/0407: {by coating on an electrolyte layer}
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/366: {as layered products}
- H01M 4/38: of elements or alloys
- H01M 4/405: {Alloys based on lithium}
- 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 4/583: Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- 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 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2300/0071: Oxides
- 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 secondary battery including: a cathode layer including a cathode active material layer; an anode layer; and a solid electrolyte layer between the cathode layer and the anode layer, and the solid electrolyte layer including a solid electrolyte, wherein the anode layer includes an anode current collector, a first anode active material layer in contact with the solid electrolyte layer, and a second anode active material layer between the anode current collector and the first anode active material layer, wherein the first anode active material layer is a lithium-containing first metal layer, wherein the second anode active material layer includes a carbon-containing anode active material or a carbon-containing anode active material and a second metal, and wherein a surface of the solid electrolyte layer adjacent to the first anode active material layer has a porosity of 40 percent or less.

## Claims

### Claim 1

An all-solid secondary battery comprising:
a cathode layer comprising a cathode active material layer;
an anode layer; and
a solid electrolyte layer between the cathode layer and the anode layer, the solid electrolyte layer comprising a solid electrolyte,
wherein the anode layer comprises
an anode current collector,
a first anode active material layer in contact with the solid electrolyte layer, and
a second anode active material layer between the anode current collector and the first anode active material layer,
wherein the first anode active material layer is a lithium-containing first metal layer comprising lithium and a first metal,
wherein the second anode active material layer comprises
a carbon-containing anode active material, or
a carbon-containing anode active material and a second metal, and
wherein
the solid electrolyte layer has an outermost surface adjacent to the first anode active material layer and an opposite second surface adjacent to the cathode layer, the solid electrolyte layer having a porous portion extending from the outermost surface in a direction towards the opposite second surface, and the porous portion having a porosity of 1 percent to 20 percent, and
the first metal of the lithium-containing first metal layer is present in a pore of the porous portion of the solid electrolyte layer and has a particle size of about 10 nanometers to about 900 nanometers,
wherein, the solid electrolyte layer comprises lithium, and a content of lithium of the solid electrolyte layer in an area within a 1 micrometer distance from the outermost surface of the solid electrolyte layer adjacent to the first anode active material layer is depleted by about 5 atomic percent to about 20 atomic percent, based on a total lithium content of the solid electrolyte.

### Claim 2 (depends on 1)

The all-solid secondary battery of claim 1, a thickness of the porous portion of the solid electrolyte layer is about 1% to about 50% of the total thickness of the solid electrolyte layer extending from the outermost surface of the solid electrolyte layer.

### Claim 3 (depends on 2)

The all-solid secondary battery of claim 2, wherein the porous portion of the solid electrolyte layer is an area within about 1 micrometer from the outermost surface of the solid electrolyte layer.

### Claim 4 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first metal and the second metal independently comprise indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, zinc, or a combination thereof.

### Claim 5 (depends on 1)

The all-solid secondary battery of claim 1, wherein the lithium-containing first metal layer comprises a lithium-first metal alloy interlayer adjacent to the solid electrolyte layer and a first metal layer adjacent to the lithium-first metal alloy interlayer, and
wherein the lithium-first metal alloy interlayer has a thickness of 7 micrometers or less.

### Claim 6 (depends on 5)

The all-solid secondary battery of claim 5, wherein the first metal in the lithium-first metal interlayer comprises indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, zinc, or a combination thereof.

### Claim 7 (depends on 1)

The all-solid secondary battery of claim 1, wherein, the first metal is uniformly dispersed in porous portion of the solid electrolyte layer.

### Claim 8 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first anode active material layer further comprises a third metal in an area adjacent to the solid electrolyte layer, and
a content of the third metal is 30 atomic percent or less, based on the total atomic weight of the first anode active material layer.

### Claim 9 (depends on 8)

The all-solid secondary battery of claim 8, wherein the third metal comprises lanthanum, titanium, zirconium, or a combination thereof.

### Claim 10 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first anode active material layer does not comprise a binder, and
the second anode active material layer comprises a binder.

### Claim 11 (depends on 1)

The all-solid secondary battery of claim 1, wherein the carbon-containing anode active material has a particle form, and
the carbon-containing anode active material has a particle size of about 5 micrometers or less.

### Claim 12 (depends on 1)

The all-solid secondary battery of claim 1, wherein the carbon-containing anode active material comprises amorphous carbon.

### Claim 13 (depends on 1)

The all-solid secondary battery of claim 1, wherein
the second anode active material layer comprises a composite comprising first particles comprising amorphous carbon and second particles comprising a second metal, and
wherein a content of the second particles is about 1 weight percent to about 60 weight percent based on a total weight of the composite.

### Claim 14 (depends on 1)

The all-solid secondary battery of claim 1, wherein each of a thickness of the first anode active material layer and a thickness of the second anode active material layer are 50% or less of a thickness of the cathode active material layer, and
wherein the thickness of the first anode active material layer is about 1 micrometer to about 10 micrometers, and the thickness of the second anode active material layer is about 10 nanometers to about 10 micrometers.

### Claim 15 (depends on 1)

The all-solid secondary battery of claim 1, wherein a thickness of the first anode active material layer is less than a thickness of the second anode active material layer.

### Claim 16 (depends on 1)

The all-solid secondary battery of claim 1, further comprising a third anode active material layer
between the anode current collector and the second anode active material layer, or
between the first anode active material layer and the second anode active material layer, or
between the anode current collector and the second anode active material layer and between the first anode active material layer and the second anode active material layer,
wherein the third anode active material layer is a metal layer comprising lithium or a lithium alloy.

### Claim 17 (depends on 1)

The all-solid secondary battery of claim 1, wherein
the anode current collector, the first anode active material layer, the second anode active material layer, and an area therebetween are free of lithium, and do not comprise lithium in an initial state or a post-discharge state.

### Claim 18 (depends on 1)

The all-solid secondary battery of claim 1, wherein the solid electrolyte is an oxide-containing solid electrolyte or a sulfide-containing solid electrolyte.

### Claim 19 (depends on 18)

The all-solid secondary battery of claim 18, wherein the oxide-containing solid electrolyte comprises Li1+x+yAlxTi2−xSiyP3−yO12 wherein 0<x<2, 0≤y<3, Li3PO4, LixTiy(PO4)3 wherein 0<x<2 and 0<y<3, LixAlyTiz(PO4)3 wherein 0<x<2, 0<y<1 and 0<z<3, Li1+x+y(AlaGa1−a)x(TibGe1−b)2-xSiyP3−yO12 wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, LixLayTiO3 wherein 0<x<2 and 0<y<3, Li2O, LiOH, Li2CO3, LiAlO2, Li2O—Al2O—SiO2—P2O5—TiO2—GeO2, Li3+xLa3M2O12 wherein M is Te, Nb, or Zr, and 0≤x≤10, or a combination thereof.

### Claim 20 (depends on 18)

The all-solid secondary battery of claim 18, wherein the oxide-containing solid electrolyte is a garnet-type solid electrolyte comprising Li7La3Zr2O12, Li3+xLa3Zr2−aMaO12 wherein M=Ga, W, Nb, Ta, or Al and 0≤x≤10, or a combination thereof.

### Claim 21 (depends on 18)

The all-solid secondary battery of claim 18, wherein the sulfide-containing solid electrolyte comprises Li2S—P2S5, Li2S—P2S5—LiX wherein X is a halogen, LizS—P2S5—Li2O, Li2S—P2S5—Li2O—LiI, Li2S—SiS2, Li2S—SiS2—LiI, Li2S—SiS2—LiBr, Li2S—SiS2—LiCl, Li2S—SiS2—B2S3—LiI, Li2S—SiS2—P2S5—LiI, Li2S—B2S3, Li2S—P2S5—ZmSn wherein m and n are each independently a positive number, and Z is Ge, Zn, Ga, or a combination thereof, Li2S—GeS2, Li2S—SiS2—Li3PO4, Li2S—SiS2—LipMOq wherein p and q are each independently a positive number, and M is P, Si, Ge, B, Al, Ga, In, or a combination thereof, Li7−xPS6-xClx wherein 0≤x≤2, Li7-xPS6-xBrx wherein 0≤x≤2, Li7−xPS6−xIx wherein 0≤x≤2, or a combination thereof.

### Claim 22 (depends on 18)

The all-solid secondary battery of claim 18, wherein the sulfide-containing solid electrolyte is an argyrodite-type solid electrolyte comprising Li7-xPS6−xClx wherein 0≤x≤2, Li7−xPS6−xBrx wherein 0≤x≤2, Li7-xPS6-xIx wherein 0≤x≤2, or a combination thereof.

### Claim 23 (depends on 1)

A method of manufacturing the all-solid secondary battery of claim 1, the method comprising:
providing the solid electrolyte layer;
disposing a first composition comprising a first metal salt, a C1 to C10 aliphatic aldehyde, and sodium hydroxide on a first surface of the solid electrolyte layer to form a first metal layer;
heat-treating the first metal layer at about 100° C. to about 600° C. to form the first anode active material layer, which is the lithium-containing first metal layer including lithium and the first metal;
coating a second composition on the first anode active material layer, wherein the second composition comprises a carbon-containing anode compound or including a carbon-containing anode compound and the second metal;
drying the second composition to form the second anode active material layer, wherein the second anode active material layer comprises
the carbon-containing anode active material, or
the carbon-containing anode active material and the second metal;
providing the anode current collector on the second anode active material layer to prepare the anode layer; and
providing the cathode active material layer and the cathode current collector on a second surface of the solid electrolyte layer to prepare the cathode layer on the solid electrolyte layer and to provide the all-solid secondary battery.

### Claim 24 (depends on 23)

The method of claim 23, wherein the disposing of the first composition comprises applying the first composition onto the surface of the solid electrolyte layer, wherein the applying comprises solution infiltration, dipping, spin coating, drop casting, spray coating, spray pyrolysis, roll coating, dip coating, flow coating, a doctor blade method, dispensing, inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexoprinting, or lithoprinting.

### Claim 25 (depends on 23)

The method of claim 23, wherein the first metal salt comprises indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, palladium, silver, zinc, or a combination thereof.

### Claim 26 (depends on 23)

The method of claim 23, wherein the first metal layer is formed by a Tollens reaction using a mixture comprising silver nitrate, formaldehyde, and sodium hydroxide.

### Claim 27 (depends on 23)

The method of claim 23, wherein the second metal comprises indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, palladium, silver, zinc, or a combination thereof.

### Claim 28 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first anode active material layer has a thickness of about 3 micrometers to about 7 micrometers.

### Claim 29 (depends on 1)

The all-solid secondary battery of claim 1, wherein an atomic ratio of lithium to the first metal in the lithium-containing layer is about 1:1 to about 10:1.