# US 2021/0242490 A1 · All-solid secondary battery and method of preparing same

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- Number: US 2021/0242490 A1
- Document ID: US20210242490A1
- Status: Published application
- Kind: A1
- Application number: 16/927,097
- Filed: 2020-07-13
- Published: 2021-08-05
- Earliest claimed: 2020-01-31
- Assignees: Samsung SDI Co., Ltd.
- Applicants: Samsung SDI Co., Ltd.
- Inventors: Junhwan KU; Toshinori SUGIMOTO
- Web page: https://patentgrep.com/patent/US20210242490A1

## CPC

- H01M 10/0562: Solid materials
- H01M 4/366: {as layered products}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- 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 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/623: {fluorinated polymers}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/663: {containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/058: Construction or manufacture
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0068: inorganic
- H01M 2300/008: Halides
- H01M 2300/0094: in the form of layered products, e.g. coatings
- 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 includes a solid electrolyte layer disposed between an anode layer and a cathode layer, where the solid electrolyte layer contains a first solid electrolyte layer including a first solid electrolyte and a second electrolyte layer including a second solid electrolyte, where the first solid electrolyte is disposed proximate to the anode layer, the second solid electrolyte layer is disposed proximate to the cathode layer, and the first solid electrolyte has a lithium ion conductivity greater than a lithium ion conductivity of the second solid electrolyte, where a difference between the lithium ion conductivity of the first solid electrolyte and the lithium ion conductivity of the second solid electrolyte is equal to or greater than about 2 mS/cm.

## Claims

### Claim 1

An all-solid secondary battery comprising:
a solid electrolyte layer disposed between an anode layer and a cathode layer,
wherein the solid electrolyte layer comprises
a first solid electrolyte layer comprising a first solid electrolyte, and
a second solid electrolyte layer comprising a second solid electrolyte, wherein
the first solid electrolyte layer is disposed proximate to the anode layer,
the second solid electrolyte layer is disposed proximate to the cathode layer, and
the first solid electrolyte has a lithium ion conductivity which is greater than a lithium ion conductivity of the second solid electrolyte, and
a difference between the lithium ion conductivity of the first solid electrolyte and the lithium ion conductivity of the second solid electrolyte is equal to or greater than about 2 millisiemens per centimeter.

### Claim 2 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first solid electrolyte layer is disposed directly on the anode layer, and the second solid electrolyte layer is disposed directly on the cathode layer.

### Claim 3 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first solid electrolyte and the second solid electrolyte are each independently a sulfide solid electrolyte having an argyrodite crystal structure.

### Claim 4 (depends on 1)

The all-solid secondary battery of claim 1, wherein
the first solid electrolyte and the second solid electrolyte each independently has an argyrodite crystal structure and comprises Cl and Br, I, or a combination thereof, and
an amount of the Br, I, or a combination thereof in the first solid electrolyte is greater than an amount of Br, I, or a combination thereof in the second solid electrolyte.

### Claim 5 (depends on 1)

The all-secondary battery of claim 1,
wherein the first solid electrolyte layer comprises the first solid electrolyte and the second solid electrolyte layer comprises the second solid electrolyte,
wherein the first solid electrolyte and the second solid electrolyte each independently has an argyrodite crystal structure and comprises Cl and Br, I, or a combination thereof, and
wherein a ratio of the Br, I, or a combination thereof to Cl of the first solid electrolyte is greater than a ratio of the Br, I, or a combination thereof to CI of the second solid electrolyte.

### Claim 6 (depends on 1)

The all-solid secondary battery of claim 1, wherein the first solid electrolyte and the second solid electrolyte each independently has an argyrodite crystal structure represented by Formula 1,
LiaMxPSbXcCld Formula 1
wherein, in Formula 1,
M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof;
X is Br, I, or a combination thereof; and
0≤x≤0.07, 5≤a≤6, 4≤b≤6, c>0, d>0, 0<(c+d)≤2, and 5≤(a+x)≤6.

### Claim 7 (depends on 6)

The all-solid secondary battery of claim 6, wherein the second solid electrolyte includes a compound having an argyrodite crystal structure and represented by Formula 2, Formula 2-1, or a combination thereof.
LiaMxPSb(Cl)d Formula 2
wherein, M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof; and
0≤x≤0.07, a is a number from 5 to 6, b is a number from 4 to 6, 0<d≤2, and 5≤a+x≤6,
LiaMxPSb(X1)c1(Cl)d1 Formula 2-1
wherein, in Formula 2-1, M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof;
X1 is Br, I, or a combination thereof; and
0≤x≤0.07, a is a number from 5 to 6, b is a number from 4 to 6, c1>0, d1>0, 0<c1+d1≤2, and 5≤a+x≤6.

### Claim 8 (depends on 1)

The all-solid secondary battery of claim 1, wherein the difference in the lithium ion conductivity of the first solid electrolyte and the lithium ion conductivity of the second solid electrolyte is about 2 millisiemens per centimeter to about 20 millisiemens per centimeter.

### Claim 9 (depends on 1)

The all-solid secondary battery of claim 1,
wherein, a ratio of a packing density to a true density in each of the first solid electrolyte layer and the second solid electrolyte layer is about 0.6:1 or more,
the ratio of the packing density to the true density of the first solid electrolyte layer is less than a ratio of packing density to the true density of the second solid electrolyte layer, and
a difference between the ratio of the packing density to the true density of the first solid electrolyte layer and the ratio of the packing density to the true density of the second solid electrolyte layer is about 0.02:1 to about 0.05:1.

### Claim 10 (depends on 1)

The all-solid secondary battery of claim 1, wherein a ratio of a thickness of the first solid electrolyte layer to a thickness of the second solid electrolyte layer is about 1:1 to about 1:10.

### Claim 11 (depends on 1)

The all-solid secondary battery of claim 1, wherein
a thickness of the second solid electrolyte layer is greater than a thickness of the first solid electrolyte, and
a thickness of the first solid electrolyte layer is about 1 micrometer to about 35 micrometers and a thickness of the second solid electrolyte layer is about 10 micrometers to about 60 micrometers.

### Claim 12 (depends on 1)

The all-solid secondary battery of claim 1, wherein a total thickness of the solid electrolyte layer is about 11 micrometers to about 200 micrometers.

### Claim 13 (depends on 6)

The all-solid secondary battery of claim 6, wherein first solid electrolyte comprising Formula 1 is represented by Formula 3,
LiaMxPSbBrcCld Formula 3
wherein, in Formula 3,
M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof, and
0≤x≤0.07, 5≤a≤6, 4≤b≤6, c>0, d>0, 0<(c+d)≤2, and 5≤(a+x)≤6.

### Claim 14 (depends on 13)

The all-solid secondary battery of claim 13, wherein 0≤x≤0.05.

### Claim 15 (depends on 6)

The all-solid secondary battery of claim 6, wherein the first solid electrolyte comprising Formula 1 is represented by Formula 4,
(Li1-x1Mx1)7-yPS6-y(Br1-x2Clx2)y Formula 4
wherein, in Formula 4,
M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof, and
0≤x<1, 0<x2<1, and 0≤y≤2.

### Claim 16 (depends on 6)

The all-solid secondary battery of claim 6, wherein a compound represented by Formula 1 is Li5.5PS4.5Cl0.75Br0.75, Li5.5PS4.5Cl0.25Br1.25, Li5.5PS4.5Cl1.25Br0.25, Li5.5PS4.5Cl0.1Br1.4, Li5.45Na0.05PS4.5Cl0.25Br1.25, Li5.5PS4.5Cl0.25Br1.25, Li5.45Na0.05PS4.5Cl0.1Br1.4, Li5.45Na0.05PS4.5Cl0.1Br1.4, Li5Na0.05PS4Cl0.01Br1.99, Li5.74PS4.74Cl0.01Br1.25, Li5PS4Cl0.01Br1.99, Li5.45K0.05PS4.5Cl0.25Br1.25, Li5.45K0.05PS4.5Cl0.1Br1.4, Li5.45K0.05PS4.5Cl0.1Br1.4, Li5K0.05PS4Cl0.01Br10.99, or a combination thereof.

### Claim 17 (depends on 7)

The all-solid secondary battery of claim 7, wherein the second solid electrolyte comprises Li5.75PS4.75Cl1.25, Li5.75PS4.5Cl1.5, Li5.5PS4.5Cl1.5, Li5.45Na0.05PS4.5Cl1.5, Li5.45K0.05PS4.5Cl10.5, Li5.74PS4.74Cl1.26, Li5Na0.05PS4Cl2, Li5K0.05PS4Cl2, Li5.8PS4.8Cl1.2, Li5.7Na0.05PS4.75Cl1.25, Li5.7Cu0.05PS4.75Cl1.25, Li5.65Cu0.1PS4.75Cl1.25, or a combination thereof.

### Claim 18 (depends on 1)

The all-solid secondary battery of claim 1, wherein an ion conductivity of both the first solid electrolyte and the second solid electrolyte are about 1 millisiemens per centimeter or greater at 25° C.

### Claim 19 (depends on 1)

The all-solid secondary battery of claim 1, wherein an ion conductivity of the first solid electrolyte is about 3 millisiemens per centimeter to about 7 millisiemens per centimeter at 25° C., about 10 millisiemens per centimeter to about 15 millisiemens per centimeter at 45° C., or about 16 millisiemens per centimeter to about 20 millisiemens per centimeter at 60° C.

### Claim 20 (depends on 1)

The all-solid secondary battery of claim 1, wherein an ion conductivity of the second solid electrolyte is about 1 millisiemen per centimeter to about 5 millisiemens per centimeter at 25° C., about 3 millisiemens per centimeter to about 8 millisiemens per centimeter at 45° C., or about 5 millisiemens per centimeter to about 12 millisiemens per centimeter at 60° C.

### Claim 21 (depends on 1)

The all-solid secondary battery of claim 1,
wherein the first solid electrolyte layer and the second solid electrolyte layer each independently comprises a binder, and
wherein the binder comprises styrene-butadiene-styrene copolymer, acrylic resin, styrene-butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, a vinylidene fluoride/hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, or a combination thereof.

### Claim 22 (depends on 21)

The all-solid secondary battery of claim 21, wherein an amount of the binder in the first solid electrolyte layer is less than an amount of a binder in the second solid electrolyte layer, wherein a difference between the amount of the binder in the first solid electrolyte and the amount of the binder in the second solid electrolyte layer is about 0.5 weight percent to about 1.5 weight percent.

### Claim 23 (depends on 22)

The all-solid secondary battery of claim 22, wherein
an amount of the binder in the first solid electrolyte layer is about 0.5 part by weight to about 1.5 parts by weight or less, based on 100 parts by weight of a total weight of the first solid electrolyte comprising the binder, and
an amount of the binder in the second solid electrolyte layer is about 1 part by weight to about 2 parts by weight, based on 100 parts by weight of a total weight of the second solid electrolyte comprising the binder.

### Claim 24 (depends on 1)

The all-solid secondary battery of claim 1, wherein the anode layer comprises a first anode active material layer comprising an anode current collector and an anode active material disposed on the anode current collector,
wherein the anode active material comprises a carbonaceous anode active material, a metal-containing anode active material, a metalloid-containing anode active material, or a combination thereof.

### Claim 25 (depends on 24)

The all-solid secondary battery of claim 24, wherein the carbonaceous anode active material comprises amorphous carbon, crystalline carbon, or a combination thereof, and
the metal-containing anode active material or the metalloid-containing anode active material comprises gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or a combination thereof.

### Claim 26 (depends on 24)

The all-solid secondary battery of claim 24, further comprising a second anode active material layer disposed between the anode current collector and the first anode active material layer or between the solid electrolyte layer and the first anode active material layer,
wherein the second anode active material layer is a metal layer comprising lithium metal or a lithium alloy.

### Claim 27 (depends on 1)

The all-solid secondary battery of claim 1, wherein the cathode layer comprises a cathode active material,
wherein the cathode active material is a lithium transition metal oxide having a layered crystal structure, a lithium transition metal oxide having an olivine crystal structure, a lithium transition metal oxide having a spinel crystal structure, or a combination thereof.

### Claim 28 (depends on 1)

The all-solid secondary battery of claim 1, wherein the cathode layer comprises a compound represented by Formula 1, a compound represented by Formula 2, or a combination thereof:
LiaMxPSbXcCld Formula 1
wherein, in Formula 1,
M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof;
X is Br, I, or a combination thereof; and
0≤x≤0.07, 5≤a≤6, 4≤b≤6, c>0, d>0, 0<(c+d)≤2, and 5≤(a+x)≤6,
LiaMxPSbCld Formula 2
wherein, in Formula 2,
M is Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof; and
0≤x≤0.07, 5≤a≤6, 4≤b≤6, 0<d≤2, and 5≤(a+x)≤6.

### Claim 29 (depends on 1)

The all-solid secondary battery of claim 1, wherein the cathode layer comprises a cathode active material, a sulfide solid electrolyte, and a conductive agent,
wherein an amount of the sulfide solid electrolyte in the cathode layer is about 2 parts by weight to about 70 parts by weight, based on 100 parts by weight of the cathode layer.

### Claim 30 (depends on 1)

A method of preparing the all-solid secondary battery of claim 1, the method including:
providing a cathode layer;
providing an anode layer;
contacting a first solid electrolyte and a binder to form a first composition;
contacting a second solid electrolyte and a binder to form a second composition;
disposing the first composition on a surface of the anode layer facing the cathode layer to form a first solid electrolyte layer, and
disposing the second composition on a surface of the cathode layer facing the anode layer to form a second electrolyte layer to provide the all-solid secondary battery.

### Claim 31 (depends on 30)

The all-solid secondary battery of claim 30, wherein the disposing of the first composition comprises:
coating the first composition on a surface of the anode layer, and
drying the first composition on a surface of the anode layer.

### Claim 32 (depends on 30)

The all-solid secondary battery of claim 30, wherein the disposing of the second composition comprises:
coating the second composition on a substrate;
drying the second composition on a substrate to form a dried composition,
separating the dried composition from the substrate; and
placing the dried composition on a surface of the cathode layer facing the anode layer.

### Claim 33

An all-solid secondary battery comprising:
a solid electrolyte layer disposed between an anode layer and a cathode layer,
wherein the solid electrolyte layer comprises a first solid electrolyte layer comprising a first solid electrolyte and a second solid electrolyte layer comprising a second solid electrolyte,
wherein the first solid electrolyte layer is disposed proximate to the anode layer,
the second solid electrolyte layer is disposed proximate to the cathode layer,
the first solid electrolyte has a lithium ion conductivity greater than a lithium ion conductivity of the second solid electrolyte, and
wherein the solid electrolyte layer has an argyrodite structure represented by Formula 6:
Li+12-n-xAX6-xY′x Formula 6
wherein, in Formula 6,
A is P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, Ta, or a combination thereof,
X is S, Se, Te, or a combination thereof,
Y′ is Cl, Br, I, F, CN, OCN, SCN, N3, or a combination thereof,
1≤n≤6 and 0<x<2, wherein n is an oxidation number of A.