# US 11,908,994 B2 · Metal and nitrogen-including argyrodite solid electrolyte, electrochemical cell including solid electrolyte, and method of preparing solid electrolyte oxide

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- Number: US 11,908,994 B2
- Document ID: US11908994B2
- Status: Granted
- Kind: B2
- Application number: 16/993,760
- Filed: 2020-08-14
- Published: 2021-05-13
- Granted: 2024-02-20
- Earliest claimed: 2019-11-07
- Assignees: Samsung SDI Co., Ltd.
- Applicants: Samsung SDI Co., Ltd.
- Inventors: Soyeon Kim; Hyunseok Kim; Seoksoo Lee
- Web page: https://patentgrep.com/patent/US11908994B2

## CPC

- H01M 10/0562: Solid materials
- C01B 25/14: Sulfur, selenium, or tellurium compounds of phosphorus
- 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 4/134: Electrodes based on metals, Si or alloys
- H01M 4/366: {as layered products}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/405: {Alloys based on lithium}
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/624: {Electric conductive fillers}
- 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}
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0068: inorganic
- H01M 2300/0071: Oxides
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A solid electrolyte including a compound represented by Formula 1: (Li1-aMa)7-d+xPS6-d-x+kNxXd Formula 1 wherein, in Formula 1, M is Na, K, Ca, Fe, Mg, Ag, Cu, Zr, Zn, or a combination thereof; X is Cl, Br, F, I, a pseudohalogen, or a combination thereof; and 0<x<1, 0≤a<1, 0<d≤1.8, and 0≤k<1, and wherein the compound has an argyrodite crystal structure.

## Claims

### Claim 1

K all-solid-state secondary battery comprising:
a cathode layer;
an anode layer; and
a solid electrolyte layer disposed between the cathode layer and the anode layer,
wherein, the solid electrolyte layer and the cathode layer comprise a solid electrolyte, and the solid electrolyte comprises a compound represented by Formula 1, and
the solid electrolyte of the cathode layer has an average particle diameter, which is smaller than an average particle diameter of the solid electrolyte used in the solid electrolyte layer:
(Li1-aMa)7-d+xPS6-d-x+kNxXd Formula 1
wherein, in Formula 1,
M is Na or K, or a combination thereof;
X is at least two of CI, Br, F, I, or a pseudohalogen; and
0.1≤x≤0.125, 0<a<1, 0<d≤1, and 0≤k<1, and
wherein the compound has an argyrodite crystal structure.

### Claim 2

An all-solid-state secondary battery comprising:
a cathode layer;
an anode layer; and
a solid electrolyte layer disposed between the cathode layer and the anode layer,
wherein, the solid electrolyte layer and the cathode layer comprises a solid electrolyte, and the solid electrolyte comprising a compound represented by Formula 1, and
the solid electrolyte of the cathode layer has an average particle diameter, which is smaller than an average particle diameter of the solid electrolyte used in the solid electrolyte layer:
(Li1-aMa)7-d+xPS6-d-x+kNxXd Formula 1
wherein, in Formula 1,
M is Na, K, Ca, Fe, Mg, Ag, Cu, Zr, Zn, or a combination thereof,
X is at least two of CI, Br, F, I, or a pseudohalogen, and
0.1≤x≤0.125, 0<a<1, 0<d≤1, and 0≤k<1, and
wherein the compound has an argyrodite crystal structure.

### Claim 3 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein an ion conductivity of the solid electrolyte at 25° C. is equal to or greater than about 1 millisiemen per centimeter.

### Claim 4 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein a thickness of the solid electrolyte is about 10 micrometers to about 200 micrometers.

### Claim 5 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein X is Cl and at least one of F, Br, or I.

### Claim 6 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein, in Formula 1, Xd is (Br1-x1Clx1)d, wherein 0<x1<1 and 0<d≤1.

### Claim 7 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein the compound represented by Formula 1 is Li6Na0.125PS4.875N0.125Cl0.5Br0.5, Li6K0.125PS4.875N0.125Cl0.5Br0.5, Li6Na0.125PS4.875N0.125Cl0.16Br0.84, Li6K0.125PS4.875N0.125Cl0.16Br0.84, or a combination thereof.

### Claim 8 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein the compound is a compound represented by Formula 1-1:
(Li1-aMa)7-d+xPS6-d-xNxXd Formula 1-1
wherein, in Formula 1-1,
M is sodium (Na), potassium (K), calcium (Ca), iron (Fe), magnesium (Mg), silver (Ag), copper (Cu), zirconium (Zr), zinc (Zn), or a combination thereof;
X is at least two of chlorine (CI), bromine (Br), fluorine (F), iodine (I), or a pseudohalogen; and
0.1≤x≤0.125, 0<a<1, and 0<d≤1.

### Claim 9 (depends on 8)

The all-solid-state secondary battery of claim 8, wherein the compound is a compound represented by Formula 3:
(Li1-aNaa)7-d+xPS6-d-xNxXd Formula 3
wherein, in Formula 3,
X is at least two of chlorine (CI), bromine (Br), fluorine (F), iodine (I), or a pseudohalogen; and
0.1≤x≤0.125, 0<a<1, and 0<d≤1.

### Claim 10 (depends on 8)

The all-solid-state secondary battery of claim 8, wherein the compound is a compound represented by Formula 4:
(Li1-aKa)7-d+xPS6-d-xNxXd Formula 4
wherein, in Formula 4,
X is at least two of chlorine (CI), bromine (Br), fluorine (F), iodine (I), or a pseudohalogen; and
0.1≤x≤0.125, 0<d≤1, and 0<a<1.

### Claim 11 (depends on 8)

The all-solid-state secondary battery of claim 8, wherein the compound is a compound represented by Formula 5:
Li7-d+xPS6-d-xNx(Br1-x1Clx1)d Formula 5
wherein, in Formula 5, 0.1≤x≤0.125, 0<d≤1, and 0<x1<1.

### Claim 12 (depends on 2)

The all-solid-state secondary battery of claim 2, wherein the cathode layer comprises a cathode active material.

### Claim 13 (depends on 12)

The all-solid-state secondary battery of claim 12, wherein a capacity retention is greater than about 85% at a 100th cycle after charging to equal to or greater than 4 Volts and discharging to 2.5 Volts the all-solid-state secondary battery in a constant-temperature chamber of 25° C.

### Claim 14 (depends on 12)

The all-solid-state secondary battery of claim 12, wherein the cathode active material is at least one of a lithium transition metal oxide having a layered crystal structure, a lithium transition metal oxide having an olivine crystal structure, or a lithium transition metal oxide having a spinel crystal structure.

### Claim 15 (depends on 12)

The all-solid-state secondary battery of claim 12, wherein the cathode layer further comprises a conducting agent.

### Claim 16 (depends on 15)

The all-solid-state secondary battery of claim 15, wherein an amount of the 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 active material.

### Claim 17 (depends on 12)

The all-solid-state secondary battery of claim 12, wherein the anode layer comprises
an anode current collector, and
a first anode active material layer disposed on the anode current collector, wherein the first anode active material layer comprises a first anode active material.

### Claim 18 (depends on 17)

The all-solid-state secondary battery of claim 17 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.

### Claim 19 (depends on 18)

The all-solid-state secondary battery of claim 18, wherein the second anode active material layer is a metal in the form of a layer comprising at least one of lithium metal or a lithium alloy.

### Claim 20 (depends on 17)

The all-solid-state secondary battery of claim 17, wherein the anode active material comprises at least one of a carbonaceous anode active material, a metal, or a metalloid.

### Claim 21 (depends on 20)

The all-solid-state secondary battery of claim 20, wherein the carbonaceous anode active material comprises at least one of an amorphous carbon or a crystalline carbon.

### Claim 22 (depends on 20)

The all-solid-state secondary battery of claim 20, wherein the metal or the metalloid anode active material comprises at least one of Au, Pt, Pd, Si, Ag, Al, Bi, Sn, or Zn.

### Claim 23

A method of preparing a solid electrolyte comprising a compound of Formula 1, the method comprising:
providing a Li precursor, a S precursor, a P precursor, an X precursor, a N precursor, and an M precursor;
mixing the Li precursor, the S precursor, the P precursor, the X precursor, the N precursor, and the M precursor, to prepare a solid electrolyte precursor; and
heat-treating the solid electrolyte precursor at a temperature equal to or greater than about 300° C. to prepare the solid electrolyte comprising a compound of Formula 1,
(Li1-aMa)7-d+xPS6-d-x+kNxXd Formula 1
wherein, in Formula 1,
M is Na, K, Ca, Fe, Mg, Ag, Cu, Zr, Zn, or a combination thereof;
X is at least two of CI, Br, F, I, or a pseudohalogen; and
0.1≤x≤0.125, 0<a<1, 0<d≤1, and 0≤k<1,
wherein the compound of Formula 1 has an argyrodite crystal structure.

### Claim 24 (depends on 23)

The method of claim 23, wherein the X in the X precursor is at least two of CI, Br, F, I, or a pseudohalogen.

### Claim 25 (depends on 23)

The method of claim 23, wherein the solid electrolyte precursor comprises the M precursor, and wherein M is Na, K, Ca, Fe, Mg, Ag, Cu, Zr, Zn, or a combination thereof.

### Claim 26 (depends on 23)

The method of claim 23, wherein the heat-treating comprises heat-treating at a temperature of about 300° C. to about 600° C.