Sulfide solid electrolyte and method of producing the same

Patent metadata

Field	Value
Publication number	US-11990583-B2
Application number	US-202017606776-A
Country	US
Kind code	B2
Filing date	Dec 25, 2020
Priority date	Dec 27, 2019
Publication date	May 21, 2024
Grant date	May 21, 2024

Abstract

Provided are a sulfide solid electrolyte having a small particle size and a low specific surface area; an electrode composite material, a slurry and a battery in each of which the sulfide solid electrolyte is used; and a method of producing the sulfide solid electrolyte. The sulfide solid electrolyte contains lithium (Li), phosphorus (P) and sulfur (S) elements and has: a median diameter D 50 of 0.10 μm or more and 2.0 μm or less; and a value of the formula: (A×B)/C, wherein A represents a BET specific surface area (m 2 /g), B represents a true density (g/cm 3 ), and C represents a CS value (m 2 /cm 3 ), of 1.0 or more and 2.5 or less.

First claim

The invention claimed is:

1. A sulfide solid electrolyte, comprising lithium (Li), phosphorus (P) and sulfur (S) elements, wherein the sulfide solid electrolyte has: a median diameter D 50 , which is a particle size at a cumulative volume of 50 vol % in a volume-based particle size distribution measured by a laser diffraction scattering particle size distribution measurement method, of 0.10 μm or more and 2.0 μm or less; a BET specific surface area of 2.0 m 2 /g or more and 20 m 2 /g or less; and a value of the formula: (A×B)/C, wherein A represents the BET specific surface area (m 2 /g), B re presents a true density (g/cm 3 ), and C represents a CS value (m 2 /cm 3 ), of 1.5 or more and 2.1 or less.

2. The sulfide solid electrolyte according to claim 1 , wherein:
the content of the lithium (Li) element is 41 mol % or more and 50 mol % or less, based on the total molar amount of constituent elements of the sulfide solid electrolyte;
the content of the phosphorus (P) element is 7.0 mol % or more and 20 mol % or less, based on the total molar amount of constituent elements of the sulfide solid electrolyte; and
the content of the sulfur (S) element is 31 mol % or more and 43 mol % or less, based on the total molar amount of constituent elements of the sulfide solid electrolyte.

3. The sulfide solid electrolyte according to claim 1 , further comprising at least one halogen (X) element.

4. The sulfide solid electrolyte according to claim 3 , wherein the at least one halogen (X) element comprises at least one of chlorine (Cl) and bromine (Br) elements.

5. The sulfide solid electrolyte according to claim 3 , wherein the content of the at least one halogen (X) element is 3.7 mol % or more and 19 mol % or less, based on the total molar amount of constituent elements of the sulfide solid electrolyte.

6. The sulfide solid electrolyte according to claim 1 , wherein, in a X-ray diffraction pattern measured with CuKα1 radiation, peaks are present at positions of 2θ=25.19°±1.00° and 29.62°±1.00°.

7. The sulfide solid electrolyte according to claim 6 , wherein, in the X-ray diffraction pattern, a peak is present at a position selected from 2θ=15.34°±1.00°, 17.74°±1.00°, 30.97°±1.00°, 44.37°±1.00°, 47.22°±1.00° and 51.70°±1.00°.

8. The sulfide solid electrolyte according to claim 1 , wherein:
the sulfide solid electrolyte comprises a crystal phase having an argyrodite-type crystal structure; and
the crystal phase has a composition represented by the following formula:
Li a PS b X c

wherein X represents at least one halogen element, a represents 3.0 or more and 6.5 or less, b represents 3.5 or more and 5.5 or less, and c represents 0.50 or more and 3.0 or less.

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

10. A slurry, comprising the sulfide solid electrolyte according to claim 1 and a dispersion medium.

11. A battery, comprising a positive electrode layer, a negative electrode layer and a solid electrolyte layer located between the positive electrode layer and the negative electrode layer,
wherein the solid electrolyte layer comprises the sulfide solid electrolyte according to claim 1 .

12. A method of producing the sulfide solid electrolyte according to claim 1 , the method comprising the steps of:
(1-1) providing as an intermediate a sulfide solid electrolyte that comprises lithium (Li), phosphorus (P) and sulfur (S) elements and has a median diameter D 50 of 0.10 μm or more and 2.0 μm or less, a BET specific surface area of 3.0 m 2 /g or more and 25 m 2 /g or less, and a value of the formula: (A×B)/C, wherein A represents the BET specific surface area (m 2 /g), B represents a true density (g/cm 3 ), and C represents a CS value (m 2 /cm 3 ), of more than 2.5 and 5.0 or less, and
(1-2) subjecting the intermediate to thermal treatment and pulverizing the resulting thermally-treated product to obtain a pulverized product that has a median diameter D 50 of 0.10 μm or more and 2.0 μm or less.

13. A method of producing the sulfide solid electrolyte according to claim 1 , the method comprising the steps of:
(2-1) providing a raw material powder that comprises lithium (Li), phosphorus (P) and sulfur (S) elements and has a median diameter D 50 of 0.10 μm or more and 2.0 μm or less and a D 95 of 0.30 μm or more and 5.0 μm or less; and
(2-2) subjecting the raw material powder to thermal treatment and pulverizing the resulting thermally-treated product to obtain a pulverized product that has a median diameter D 50 of 0.10 μm or more and 2.0 μm or less.

Assignees

• Mitsui Mining & Smelting Co Ltd

Inventors

• Nakayama Yuki
• Ito Takahiro
• Takahashi Tsukasa

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M4/0407

  by coating on an electrolyte layer · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2300/0068

  inorganic · CPC title