Method of manufacturing sulfide-based solid electrolyte through wet process

Patent metadata

Field	Value
Publication number	US-10290896-B2
Application number	US-201715482378-A
Country	US
Kind code	B2
Filing date	Apr 7, 2017
Priority date	Nov 16, 2016
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

A method of manufacturing a sulfide-based solid electrolyte through a wet process is provided. The method includes preparing a slurry by adding a solvent to a mixture including lithium sulfide and a sulfide of a group 14 or group 15 element and amorphizing the mixture by milling the slurry. The slurry is dried in order to remove the solvent. The dried mixture is crystallized by heat-treating to form the sulfide-based solid electrolyte.

First claim

What is claimed is:

1. A method of manufacturing a sulfide-based solid electrolyte through a wet process, the method comprising:
preparing a slurry by adding a solvent to a mixture including lithium sulfide and a sulfide of a group 14 or group 15 element, wherein preparing the slurry further comprises mixing nickel sulfide to the mixture, wherein the nickel sulfide comprises Ni 3 S 2 , NiS, or NiS 2 , and wherein the mixture includes 60 mol % to 80 mol % of the lithium sulfide, 10 mol % to 32 mol % of the sulfide of the group 14 or group 15 element, and 4 mol % to 20 mol % of the nickel sulfide;
amorphizing the mixture by milling the slurry;
drying the slurry in order to remove the solvent to form a dried mixture, wherein the drying of the slurry comprises primarily drying the slurry in a vacuum state for 10 mins to 20 hrs at 25° C. to 60° C.: and secondary drying the slurry, wherein the secondary drying is performed at a secondary drying temperature, wherein the secondary drying temperature is higher than a melting point of the solvent, lower than a crystallization temperature of the amorphized mixture, and between 130° C. and 190° C., and wherein the secondary drying is performed for a time between 10 mins and 4 hrs; and
crystallizing the dried mixture by heat-treating to form the sulfide-based solid electrolyte.

2. The method of claim 1 , wherein the lithium sulfide is Li 2 S and the sulfide of the group 14 or group 15 element is at least one of P 2 S 3 , P 2 S 5 , SiS 2 , GeS 2 , As 2 S 3 and Sb 2 S 3 .

3. The method of claim 1 , wherein the solvent is selected from a group consisting of
at least one hydrocarbon-based solvent of pentane, hexane, 2-ethyl hexane, heptane, octane, cyclohexane, and methyl cyclohexane;
at least one BTX-based solvent of benzene, toluene, xylene, and ethylbenzene;
at least one ether-based solvent of diethyl ether, tetrahydrofuran, and 1,4-dioxane;
at least one ester-based solvent of ethyl propionate and propyl propionate; or
a mixed solvent thereof.

4. The method of claim 1 , wherein the solvent is added to the mixture so that a solid content of the slurry is 10 wt % to 15 wt %.

5. The method of claim 1 , wherein the amorphizing is performed by milling the slurry under conditions of 300 RPM to 800 RPM and 4 hrs to 40 hrs by using planetary mill.

6. The method of claim 1 , wherein the residue of the solvent becomes more than 0 wt % and equal to or less than 5 wt % by drying the slurry.

7. The method of claim 1 , wherein the heat-treating is performed under conditions of 200° C. to 500° C. and 30 mins to 10 hrs.

8. A method of manufacturing a solid-state battery, the method comprising:
preparing a mixture including lithium sulfide and a sulfide of a group 14 or group 15 element;
preparing a slurry by adding a solvent to the mixture, wherein preparing the slurry further comprises mixing nickel sulfide to the mixture, wherein the nickel sulfide comprises Ni 3 S 2 , NiS, or NiS 2 , wherein the mixture includes 60 mol % to 80 mol % of the lithium sulfide, 10 mol % to 32 mol % of the sulfide of the group 14 or group 15 element, and 4 mol % to 20 mol% of nickel sulfide;
milling the slurry to amorphize the mixture;
forming a dried mixture by removing the solvent from the slurry using a drying process, wherein the drying process comprises primarily drying the slurry in a vacuum state for 10 mins to 20 hrs at 25° C. to 60° C.; and secondary drying the slurry, wherein the secondary drying is performed at a secondary drying temperature, wherein the secondary drying temperature is higher than a melting point of the solvent, lower than a crystallization temperature of the amorphized mixture, and between 130° C. and 190° C., and wherein the secondary drying is performed for a time between 10 mins and 4 hrs; and
crystallizing the dried mixture by heat-treating to form a sulfide-based solid electrolyte of the solid-state battery.

9. The method of claim 8 , wherein the milling comprises using a planetary mill.

10. The method of claim 9 , wherein milling using the planetary mill is performed by injecting zirconia (ZrO 2 ) balls into the slurry.

11. The method of claim 8 , wherein the lithium sulfide is Li 2 S and the sulfide of the group 14 or group 15 element is at least one of P 2 S 3 , P 2 S 5 , SiS 2 , GeS 2 , As 2 S 3 and Sb 2 S 3 .

12. The method of claim 8 , wherein the solvent added to the mixture comprises a solvent selected from a group consisting of:
a hydrocarbon-based solvent of pentane, hexane, 2-ethyl hexane, heptane, octane, cyclohexane, or methyl cyclohexane;
a BTX-based solvent of benzene, toluene, xylene, or ethylbenzene;
an ether-based solvent of diethyl ether, tetrahydrofuran, or 1,4-dioxane; and
an ester-based solvent of ethyl propionate or propyl propionate.

13. A method of manufacturing a lithium ion solid-state battery, the method comprising:
preparing a mixture including lithium sulfide and a sulfide comprising a group 14 or group 15 element;
preparing a slurry by adding a solvent to the mixture, wherein preparing the slurry further comprises mixing nickel sulfide to the mixture, wherein the nickel sulfide comprises Ni 3 S 2 , NiS, or NiS 2 , wherein the mixture includes 60 mol % to 80 mol % of the lithium sulfide, 10 mol % to 32 mol % of the sulfide of the group 14 or group 15 element, and 4 mol % to 20 mol % of nickel sulfide;
milling the slurry to amorphize the mixture;
forming a dried mixture by removing the solvent from the slurry using a drying process, wherein the drying process comprises a first drying process and a second drying process,
wherein the first drying process is performed in a vacuum at a first drying temperature between 25° C. and 60° C., wherein the first drying process is performed for a time between 10 mins to 20 hrs,
wherein the second drying process is performed at a second drying temperature, wherein the second drying temperature is higher than a melting point of the solvent, lower than a crystallization temperature of the amorphized mixture, and between 130° C. and 190° C., and wherein the second drying process is performed for a time between 10 mins and 4 hrs; and
crystallizing the dried mixture by heat-treating to form a sulfide-based solid electrolyte of the lithium ion solid-state battery.

14. The method of claim 13 , wherein the milling is performed under conditions of 300 RPM to 800 RPM and 4 hrs to 40 hrs by using planetary mill.

15. The method of claim 13 , wherein the milling comprises using a planetary mill.

16. The method of claim 15 , wherein milling using the planetary mill is performed by injecting zirconia (ZrO 2 ) balls into the slurry.

17. The method of claim 13 , wherein the lithium sulfide is Li 2 S and the sulfide of the group 14 or group 15 element is at least one of P 2 S 3 , P 2 S 5 , SiS 2 , GeS 2 , As 2 S 3 and Sb 2 S 3 .

18. The method of claim 13 , wherein the solvent added to the mixture comprises a solvent selected from a group consisting of:
a hydrocarbon-based solvent of pentane, hexane, 2-ethyl hexane, heptane, octane, cyclohexane, or methyl cyclohexane;
a BTX-based solvent of benzene, toluene, xylene, or ethylbenzene;
an ether-based solvent of diethyl ether, tetrahydrofuran, or 1,4-dioxane; and
an ester-based solvent of ethyl propionate or propyl propionate.

Assignees

• Hyundai Motor Co Ltd

Inventors

• Sung Ju Young
• Lee Ho Taek
• Lim Jae Min
• Jang Yong Jun

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• C03C3/321

  Chalcogenide glasses, e.g. containing S, Se, Te · CPC title

• C04B2235/446

  Sulfides, tellurides or selenides · CPC title

• C04B35/547

  based on sulfides or selenides {or tellurides} · CPC title

• H01B1/10

  sulfides · CPC title