# US 10,374,253 B2 · Sulfide solid electrolyte

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- Number: US 10,374,253 B2
- Document ID: US10374253B2
- Status: Granted
- Kind: B2
- Application number: 16/239,645
- Filed: 2019-01-04
- Published: 2019-05-09
- Granted: 2019-08-06
- Earliest claimed: 2016-09-12
- Assignees: Idemitsu Kosan Co., Ltd.
- Applicants: Idemitsu Kosan Co., Ltd.
- Inventors: Futoshi Utsuno; Kota Terai; Takashi Umeki; Masaru Nakagawa; Hiroshi Yamaguchi
- Web page: https://patentgrep.com/patent/US10374253B2

## 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 that contains lithium, phosphorus, sulfur, chlorine and bromine, wherein in powder X-ray diffraction analysis using CuKα rays, it has a diffraction peak A at 2θ=25.2±0.5 deg and a diffraction peak B at 2θ=29.7±0.5 deg, the diffraction peak A and the diffraction peak B satisfy the following formula (A), and a molar ratio of the chlorine to the phosphorus “c (Cl/P)” and a molar ratio of the bromine to the phosphorus “d (Br/P)” satisfies the following formula (1): 1.2<c+d<1.9 (1) 0.845<SA/SB<1.200 (A) where SA is an area of the diffraction peak A and SB is an area of the diffraction peak B.

## Claims

### Claim 1

A sulfide solid electrolyte, comprising lithium, phosphorus, sulfur, chlorine and bromine, wherein
in powder X-ray diffraction analysis using CuKα rays, the sulfide solid electrolyte has a diffraction peak A at 2θ=25.2±0.5 deg and a diffraction peak B at 2θ=29.7±0.5 deg,
the diffraction peak A and the diffraction peak B satisfy formula (A), and
a molar ratio of the chlorine to the phosphorus, c (Cl/P), and a molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formula (1):
1.2<c+d<1.9 (1)
0.845<SA/SB<1.200 (A)
wherein SA is an area of the diffraction peak A and SB is an area of the diffraction peak B.

### Claim 2 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein the molar ratio of the bromine to the phosphorus, d (B/P), is 0.15 or more and 1.6 or less.

### Claim 3 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formula (2):
0.08<d/(c+d)<0.8 (2).

### Claim 4 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein a molar ratio of the lithium to the phosphorus, a (Li/P), a molar ratio of the sulfur to the phosphorus, b (S/P), the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formulas (3) to (5):
5.0≤a≤7.5 (3)
6.5≤a+c+d≤7.5 (4)
0.5≤a−b≤1.5 (5)
with the proviso that b>0, c>0 and d>0.

### Claim 5 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein, in powder X-ray diffraction analysis 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 (B):
0<IC/IA<0.08 (B)
wherein IC is an intensity of a diffraction peak of lithium halide, and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 6 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein, in powder X-ray diffraction analysis using CuKα rays, the sulfide solid electrolyte does not have a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg or, if the sulfide solid electrolyte has a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg, said diffraction peak satisfies formula (C):
0<ID/IA<0.09 (C)
wherein ID is an intensity of a diffraction peak at 2θ=14.4±0.5 deg and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 7 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein the sulfide solid electrolyte contains an argyrodite type crystal structure and a lattice constant of the argyrodite type crystal structure is 9.800 Å or more and 9.920 Å or less.

### Claim 8 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the bromine to the phosphorus, d (B/P), is 0.15 or more and 1.6 or less; and
the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formula (2):
0.08<d/(c+d)<0.8 (2).

### Claim 9 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the bromine to the phosphorus, d (B/P), is 0.15 or more and 1.6 or less; and
a molar ratio of the lithium to the phosphorus, a (Li/P), a molar ratio of the sulfur to the phosphorus, b (S/P), the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formulas (3) to (5):
5.0≤a≤7.5 (3)
6.5≤a+c+d≤7.5 (4)
0.5≤a−b≤1.5 (5)
with the proviso that b>0, c>0 and d>0.

### Claim 10 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formula (2):
0.08<d/(c+d)<0.8 (2); and
a molar ratio of the lithium to the phosphorus, a (Li/P), a molar ratio of the sulfur to the phosphorus, b (S/P), the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formulas (3) to (5):
5.0≤a≤7.5 (3)
6.5≤a+c+d≤7.5 (4)
0.5≤a−b≤1.5 (5)
with the proviso that b>0, c>0 and d>0.

### Claim 11 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the bromine to the phosphorus, d (B/P), is 0.15 or more and 1.6 or less; and
in powder X-ray diffraction analysis 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 (B):
0<IC/IA<0.08 (B)
wherein IC is an intensity of a diffraction peak of lithium halide, and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 12 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formula (2):
0.08<d/(c+d)<0.8 (2); and
in powder X-ray diffraction analysis 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 (B):
0<IC/IA<0.08 (B)
wherein IC is an intensity of a diffraction peak of lithium halide, and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 13 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the bromine to the phosphorus, d (B/P), is 0.15 or more and 1.6 or less; and
in powder X-ray diffraction analysis using CuKα rays, the sulfide solid electrolyte does not have a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg or, if the sulfide solid electrolyte has a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg, said diffraction peak satisfies formula (C):
0<ID/IA<0.09 (C)
wherein ID is an intensity of a diffraction peak at 2θ=14.4±0.5 deg and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 14 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
the molar ratio of the chlorine to the phosphorus, c (Cl/P), and the molar ratio of the bromine to the phosphorus, d (Br/P), satisfy formula (2):
0.08<d/(c+d)<0.8 (2); and
in powder X-ray diffraction analysis using CuKα rays, the sulfide solid electrolyte does not have a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg or, if the sulfide solid electrolyte has a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg, said diffraction peak satisfies formula (C):
0<ID/IA<0.09 (C)
wherein ID is an intensity of a diffraction peak at 2θ=14.4±0.5 deg and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 15 (depends on 1)

The sulfide solid electrolyte according to claim 1, wherein:
in powder X-ray diffraction analysis 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 (B):
0<IC/IA<0.08 (B)
wherein IC is an intensity of a diffraction peak of lithium halide, and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg; and
in powder X-ray diffraction analysis using CuKα rays, the sulfide solid electrolyte does not have a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg or, if the sulfide solid electrolyte has a diffraction peak at 2θ=14.4±0.5 deg and 33.8±0.5 deg, said diffraction peak satisfies formula (C):
0<ID/IA<0.09 (C)
wherein ID is an intensity of a diffraction peak at 2θ=14.4±0.5 deg and IA is an intensity of a diffraction peak at 2θ=25.2±0.5 deg.

### Claim 16 (depends on 1)

The sulfide solid electrolyte according to claim 1, produced by a process comprising:
applying a mechanical stress to raw materials to obtain an intermediate containing a glass component; and
heat-treating the intermediate.

### Claim 17 (depends on 1)

The sulfide solid electrolyte according to claim 1, produced by a process comprising:
applying a mechanical stress to raw materials to obtain an intermediate containing a glass component; and
heat-treating the intermediate at a temperature of 350 to 480° C. in an inert gas atmosphere.

### 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.