Silicon-sulfur polymer, solid electrolyte and solid-state lithium-ion battery

Patent metadata

Field	Value
Publication number	US-9000117-B2
Application number	US-201213709051-A
Country	US
Kind code	B2
Filing date	Dec 9, 2012
Priority date	Sep 24, 2012
Publication date	Apr 7, 2015
Grant date	Apr 7, 2015

Abstract

The present disclosure discloses a silicon-sulfur polymer, a solid electrolyte comprising the silicon-sulfur polymer, and a corresponding solid-state lithium-ion battery. The silicon-sulfur polymer of the present disclosure is a polymer compound comprising both an inorganic backbone-chain structure and an organic side-chain structure, and has the characteristics of both the organic polymer and the inorganic polymer as well as many unique properties. Therefore, the solid electrolyte formed by the silicon-sulfur polymer and the solid-state lithium-ion battery thereof have many good characteristics including a good lithium-ion-conduction capability, better thermal endurance, a wider range of operating temperatures, and better thermostability.

First claim

What is claimed is:

1. A silicon-sulfur polymer for a solid electrolyte, comprising at least one structure unit as shown by Formula 1 or Formula 2:

wherein R 1 and R 2 represent substituting groups which are respectively independently selected from alkyl, alkoxy, a polyether group and a terminal group with a —YA structure, at least one of the substituting groups R 1 and R 2 is the terminal group with the —YA structure, R 3 represents alkyl or aryl, n is an integer greater than 1, and in the terminal group with the —YA structure, Y represents an anion and A represents a cation.

2. The silicon-sulfur polymer of claim 1 , wherein the anion Y is at least one selected from —S − ,

—N—R x —O − , —O—R x —NH − ,—O—R x —O − ,

—S—R x —S − ,

—N—R x —S − , —S—R x —NH − , —S—R x —O − and —O—R x —S − , where R x and R y represent alkyl or aryl.

3. The silicon-sulfur polymer of claim 1 , wherein the cation A is at least one selected from Li + , Na + , K + and a quaternary ammonium cation.

4. The silicon-sulfur polymer of claim 1 , wherein at least one of the substituting groups R 1 and R 2 is —S − Li + .

5. The silicon-sulfur polymer of claim 1 , wherein the substituting group R 1 or R 2 comprises at least one crosslinking group which is formed by a crosslinking monomer having a polymerizing function, and the crosslinking monomer is at least one selected from H—S—H, HO—R x —OH, HS—R x —OH, HO—R x —NH 2 , H 2 N—R x —NH 2 ,

HS—R x —SH,

and HS—R x —NH 2 , where R x and R y represent alkyl or aryl.

6. A solid electrolyte, comprising the silicon-sulfur polymer of claim 1 .

7. A solid-state lithium-ion battery, comprising a cathode which comprises a cathode active material, an anode which comprises an anode active material, and the solid electrolyte of claim 6 .

8. A preparation method of the silicon-sulfur polymer, wherein the silicon-sulfur polymer is prepared through a reaction of a silicon-containing polymeric monomer, a sulfur-containing polymeric monomer and an alkoxide in a solvent; the silicon-sulfur polymer comprises at least one structure unit as shown by Formula (1) or Formula (2):

wherein R 1 and R 2 represent substituting groups which are respectively independently selected from alkyl, alkoxy, a polyether group and a terminal group with a —YA structure at least one of the substituting groups R 1 and R 2 is the terminal group with the —YA structure, R 3 represents alkyl or aryl, n is an integer greater than 1, and in the terminal group with the —YA structure, Y represents an anion and A represents a cation.

9. The preparation method of the silicon-sulfur polymer of claim 8 , wherein the silicon-containing polymeric monomer is at least one selected from LSi(OCH 2 X) 3 , L 2 Si(OCH 2 X) 2 and Si(OCH 2 X) 4 , where X represents methyl, ethyl, propyl, butyl or phenyl, L represents methyl, ethyl, propyl, phenyl, —SH,

—N—R x —OH, —O—R x —OH, —S—R x —SH,

—N—R x —SH, —S—R x —NH 2 , —S—R x —OH, or —O—R x —SH, and R x represent alkyl or aryl.

10. The preparation method of the silicon-sulfur polymer of claim 9 , wherein the silicon-containing polymeric monomer is at least one selected from LSi(OCH 3 ) 3 , L 2 Si(OCH 3 ) 2 and Si(OCH 3 ) 4 .

11. The preparation method of the silicon-sulfur polymer of claim 10 , wherein the silicon-containing polymeric monomer is at least one selected from CH 3 Si(OCH 3 ) 3 and (CH 3 ) 2 Si(OCH 3 ) 2 .

12. The preparation method of the silicon-sulfur polymer of claim 8 , wherein the silicon-containing polymeric monomer is at least one selected from LSiCl 3 , L 2 SiCl 2 and SiCl 4 , where L represents methyl, ethyl, propyl, phenyl, —SH,

—N—R x —OH, —N—R x —OH, —S—R x —SH,

—N—R x —SH, —S—R x —NH 2 , —S—R x —OH or —O—R x —SH, and R x represent alkyl or aryl.

13. The preparation method of the silicon-sulfur polymer of claim 12 , wherein the silicon-containing polymeric monomer is at least one selected from CH 3 SiCl 3 and (CH 3 ) 2 SiCl 2 .

14. The preparation method of the silicon-sulfur polymer of claim 8 , wherein the silicon-containing polymeric monomer further comprises a control monomer which is at least one selected from TSi(OCH 3 ) 3 and T 2 Si(OCH 3 ) 2 , where T represents methyl, ethyl, propyl, butyl or phenyl.

15. The preparation method of the silicon-sulfur polymer of claim 14 , wherein the control monomer is at least one selected from CH 3 Si(OCH 3 ) 3 and (CH 3 ) 2 Si(OCH 3 ) 2 .

16. The preparation method of the silicon-sulfur polymer of claim 8 , wherein the sulfur-containing polymeric monomer is at least one selected from H 2 S and a compound having thiohydroxy, thiohydroxy and hydroxyl, or thiohydroxy and amido at both terminals of a molecule thereof.

17. The preparation method of the silicon-sulfur polymer of claim 16 , wherein the sulfur-containing polymeric monomer is at least one selected from —H—S—H, —HS—R x —OH, —HS—R x —SH,

and —HS—R x —NH 2 , where R x and R y represent alkyl or aryl.

18. The preparation method of the silicon-sulfur polymer of claim 17 , wherein the sulfur-containing polymeric monomer is at least one selected from H—S—H, HS—CH 2 CH 2 —OH, HS—CH 2 CH 2 —SH,

and HS—CH 2 CH 2 —NH 2 .

19. The preparation method of the silicon-sulfur polymer of claim 8 , wherein the alkoxide is at least one selected from alkoxides having a structure of

where R a , R b and R c are selected from hydrogen, alkyl, alkylene and aryl, and A is selected from Li + , Na + , K + and a quaternary ammonium cation.

20. The preparation method of the silicon-sulfur polymer of claim 19 , wherein the alkoxide is at least one selected from a methoxide and an ethylate of Li + , Na + , K + or the quaternary ammonium cation.

Assignees

• Microvast New Materials Huzhou Co Ltd
• Microvast Power Systems Co Ltd

Inventors

• Zhou Xiaoping

Classifications

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M10/0525

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

• Y02E60/122

  Cross-Sectional Technologies · mapped topic

• Y02E60/10

  Energy storage using batteries · CPC title

• C08J5/20

  Manufacture of shaped structures of ion-exchange resins · CPC title