# US 10,483,587 B2 · Sulfide solid electrolyte

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- Number: US 10,483,587 B2
- Document ID: US10483587B2
- Status: Granted
- Kind: B2
- Application number: 16/239,140
- Filed: 2019-01-03
- Published: 2019-05-09
- Granted: 2019-11-19
- Earliest claimed: 2016-09-12
- Assignees: Idemitsu Kosan Co., Ltd.
- Applicants: Idemitsu Kosan Co., Ltd.
- Inventors: Kota Terai; Futoshi Utsuno; Takashi Umeki; Masaru Nakagawa; Hiroshi Yamaguchi
- Web page: https://patentgrep.com/patent/US10483587B2

## CPC

- H01M 10/0562: Solid materials
- C01B 25/14: Sulfur, selenium, or tellurium compounds of phosphorus
- H01B 1/06: mainly consisting of other non-metallic substances
- H01B 1/10: sulfides
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 10/052: Li-accumulators
- 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 4/5815: {Sulfides}
- H01M 2300/0068: inorganic
- 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
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- 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

A sulfide solid electrolyte containing lithium, phosphorus, sulfur, and two or more of elements X selected from halogen elements, where the sulfide solid electrolyte includes an argyrodite-type crystal structure, and a molar ratio of the sulfur to the phosphorus “b (S/P)” and a molar ratio of the element X to the phosphorus “c (X/P)” satisfy the following formula (1): 0.23<c/b<0.57 (1).

## Claims

### Claim 1

A sulfide solid electrolyte, comprising lithium, phosphorus, sulfur, and two or more of elements X selected from the group consisting of halogen elements,
wherein the sulfide solid electrolyte comprises an argyrodite-type crystal structure, and
wherein a molar ratio of the sulfur to the phosphorus, b (S/P), and a molar ratio of the elements X to the phosphorus, c (X/P), satisfy formula (1):
0.23<c/b<0.57 (1).

### Claim 2 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein the molar ratio of the sulfur to the phosphorus, b (S/P),and the molar ratio of the elements X to the phosphorus, c (X/P), satisfy formula (1a):
0.25≤c/b≤0.43 (1a).

### Claim 3 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein the molar ratio of the sulfur to the phosphorus, b (S/P), and the molar ratio of the elements X to the phosphorus, c (X/P), satisfy formula (1b):
0.30≤c/b≤0.41 (1b).

### Claim 4 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein at least one of the elements X is chlorine.

### Claim 5 (depends on 4)

The sulfide solid electrolyte according to claim 4, satisfying formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X.

### Claim 6 (depends on 4)

The sulfide solid electrolyte according to claim 4,
wherein the sulfide solid electrolyte satisfies formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X; and
wherein at least one of the elements X is bromine.

### Claim 7 (depends on 4)

The sulfide solid electrolyte according to claim 4,
wherein the sulfide solid electrolyte satisfies formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X;
wherein at least one of the elements X is bromine; and
wherein a molar ratio of the lithium to the phosphorus, a (Li/P), the molar ratio of the sulfur to the phosphorus, b (S/P), and the molar ratio of the elements X to the phosphorus, c (X/P), satisfy formulas (A) to (C):
5.0≤a≤7.5 (A)
6.5≤a+c≤7.5 (B)
0.5≤a−b≤1.5 (C)
wherein b>0 and c>0 are satisfied.

### Claim 8 (depends on 4)

The sulfide solid electrolyte according to claim 4,
wherein the sulfide solid electrolyte satisfies formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X;
wherein at least one of the elements X is bromine; and
wherein the sulfide solid electrolyte comprises a composition represented by formula (3):
Lia(P1-αMα)SbXc (3)
wherein:
M is one or more of elements selected from the group consisting of Si, Ge,Sn, Pb, B, Al, Ga, As, Sb and Bi, and X is two or more of elements selected from the group consisting of F, Cl, Br and I;
a to c satisfy formulas (A) to (C); and
α satisfies 0≤α≤0.3:
5.0≤a≤7.5 (A)
6.5≤a+c≤7.5 (B)
0.5≤a−b≤1.5 (C)
wherein b>0 and c>0 are satisfied.

### Claim 9 (depends on 4)

The sulfide solid electrolyte according to claim 4,
wherein the sulfide solid electrolyte satisfies formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X;
wherein diffraction peaks are measured at 2θ=25.2±0.5 deg and 29.7±0.5 deg in powder X-ray diffraction using CuKα rays; and
wherein, in powder X-ray diffraction using CuKα rays, the sulfide solid electrolyte does not have a diffraction peak derived from lithium halide, or if the sulfide solid electrolyte has a diffraction peak derived from lithium halide, said diffraction peak satisfies formula (4):
0<IA/IB<0.1 (4)
wherein IA represents an intensity of a diffraction peak of lithium halide, and IB represents an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 10 (depends on 4)

The sulfide solid electrolyte according to claim 4,
wherein the sulfide solid electrolyte satisfies formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X;
wherein diffraction peaks are measured at 2θ=25.2±0.5 deg and 29.7±0.5 deg in powder X-ray diffraction using CuKα rays; and
wherein, in powder X-ray diffraction using CuKα rays, the sulfide solid electrolyte does not have a diffraction peak at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg, or if the sulfide solid electrolyte has a diffraction peak at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg, said diffraction peak satisfies formula (5):
0<IC/ID<0.05 (5)
wherein IC represents an intensity of a diffraction peak which is not a diffraction peak of an argyrodite-type crystal structure between the diffraction peaks at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg, and ID represents an intensity of a diffraction peak at 2θ=29.7±0.5 deg.

### Claim 11 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein diffraction peaks are measured at 2θ=25.2±0.5 deg and 29.7±0.5 deg in powder X-ray diffraction using CuKα rays.

### Claim 12 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein at least one of the elements X is bromine.

### Claim 13 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein a molar ratio of the lithium to the phosphorus, a (Li/P), the molar ratio of the sulfur to the phosphorus, b (S/P), and the molar ratio of the elements X to the phosphorus, c (X/P), satisfy formulas (A) to (C):
5.0≤a≤7.5 (A)
6.5≤a+c≤7.5 (B)
0.5≤a−b≤1.5 (C)
wherein b>0 and c>0 are satisfied.

### Claim 14 (depends on 1)

The sulfide solid electrolyte according to claim 1, comprising a composition represented by formula (3):
Lia(P1-αMα)SbXc (3)
wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi, and X is two or more of elements selected from the group consisting of F, Cl, Br and I;
a to c satisfy formulas (A) to (C); and
a satisfies 0≤α≤0.3:
5.0≤a≤7.5 (A)
6.5≤a+c≤7.5 (B)
0.5≤a−b≤1.5 (C)
wherein b>0 and c>0 are satisfied.

### Claim 15 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
at least one of the elements X is chlorine; and
at least one of the elements X is bromine.

### Claim 16 (depends on 1)

The sulfide solid electrolyte according to claim 1,
wherein at least one of the elements X is chlorine;
wherein at least one of the elements X is bromine; and
wherein a molar ratio of the lithium to the phosphorus, a (Li/P), the molar ratio of the sulfur to the phosphorus, b (S/P), and the molar ratio of the elements X to the phosphorus, c (X/P), satisfy formulas (A) to (C):
5.0≤a≤7.5 (A)
6.5≤a+c≤7.5 (B)
0.5≤a−b≤1.5 (C)
wherein b>0 and c>0 are satisfied.

### Claim 17 (depends on 1)

The sulfide solid electrolyte according to claim 1,
wherein at least one of the elements X is bromine;
wherein the sulfide solid electrolyte satisfies formula (2):
0.25<XCl<1 (2)
wherein XCl represents a molar ratio of the chlorine to the elements X; and
wherein the sulfide solid electrolyte comprises a composition represented by formula (3):
Lia(P1-αMα)SbXc (3)
wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi, and X is two or more of elements selected from the group consisting of F, Cl, Br and I;
a to c satisfy formulas (A) to (C); and
a satisfies 0≤α≤0.3:
5.0≤a≤7.5 (A)
6.5≤a+c≤7.5 (B)
0.5≤a−b≤1.5 (C)
wherein b>0 and c>0 are satisfied.

### Claim 18 (depends on 1)

An electrode mix, comprising the sulfide solid electrolyte according to claim 1 and an active material.

### Claim 19 (depends on 18)

A lithium ion battery, comprising the electrode mix according to claim 18.

### Claim 20 (depends on 1)

A lithium ion battery, comprising the sulfide solid electrolyte according to claim 1.