Composite electrolyte and solid-state battery containing same

Patent metadata

Field	Value
Publication number	US-12113167-B2
Application number	US-202318311904-A
Country	US
Kind code	B2
Filing date	May 4, 2023
Priority date	Dec 28, 2021
Publication date	Oct 8, 2024
Grant date	Oct 8, 2024

Abstract

A composite electrolyte, including a sulfide electrolyte, a polymer electrolyte, and a functional additive material are provided. In some embodiments, the functional additive material is selected from polymers represented by the following structural R 1 —O—R 2 -A. In some embodiments, R 1 is selected from at least one of polyvinyl group, polypropylene group, polyacrylate group, polyvinylcarbonate group, polyacrylonitrile group, and polystyrene group; R 2 is a straight-chain or branched alkyl group with 3-10 carbon atoms; A is selected from at least one aromatic hydrocarbon group of benzene group, biphenyl group, triphenyl group, naphthalene group, anthracene group, phenanthrene group, and pyrene group; and X is selected from at least one of hydrogen atom, halogen atom, mercapto group, hydroxyl group, amine group, and aldehyde group.

First claim

The invention claimed is:

1. A composite electrolyte, comprising a sulfide electrolyte, a polymer electrolyte, and a functional additive material, wherein the functional additive material is selected from one or more polymers represented by the following structural formula (1):
R 1 —O—R 2 -A-X, wherein R 1 represents a main chain of the polymer, and —O—R 2 -A-Z represents a side chain of the polymer,
R 1 is selected from at least one of polyvinyl main chain group, polypropylene main chain group, polyacrylate main chain group, polyvinylcarbonate main chain group, polyacrylonitrile main chain group, and polystyrene main chain group;
R 2 is a straight-chain or branched alkyl group with 3-10 carbon atoms;
A is selected from at least one aromatic hydrocarbon group of benzene group, biphenyl group, triphenyl group, naphthalene group, anthracene group, phenanthrene group, and pyrene group; and
X is selected from at least one of halogen atom, mercapto group, hydroxyl group, amine group, and aldehyde group.

2. The composite electrolyte according to claim 1 , wherein
a percentage of the functional additive material in the composite electrolyte is 0.5 wt %-5 wt %.

3. The composite electrolyte according to claim 1 , wherein
a percentage of the sulfide electrolyte in the composite electrolyte is 65 wt %-90 wt %.

4. The composite electrolyte according to claim 1 , wherein
a percentage of the polymer electrolyte in the composite electrolyte is 8 wt %-34 wt %.

5. The composite electrolyte according to claim 1 , wherein
X is selected from at least one electron-rich group of halogen atom, mercapto group, hydroxyl group, amine group, and aldehyde group, optionally at least one of halogen atom, mercapto group, and hydroxyl group, and further optionally fluorine atom, chlorine atom, or mercapto group.

6. The composite electrolyte according to claim 1 , wherein
a weight average molecular weight of the functional additive material is 2000-20000.

7. The composite electrolyte according to claim 1 , wherein
the sulfide electrolyte is selected from one or more sulfide containing PS 4 groups of Li 3 PS 4 , Li 6 PS 5 Cl, Li 10 GeP 2 S 12 , and Li 7 P 3 S 11 .

8. The composite electrolyte according to claim 1 , wherein
the polymer electrolyte is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polysulfone, polyvinylpyrrolidone, polyethylene-vinyl acetate copolymer, and polyvinyl butyral, and optionally one or more of polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, and polyacrylonitrile.

9. A preparation method of composite electrolyte, comprising:
(1) providing a sulfide electrolyte and a functional additive material, mixing them uniformly, and dispersing them in a weak polar solvent to form an initial mixed solution;
(2) subjecting the initial mixed solution to heat treatment to remove the weak polar solvent to obtain a premixed composite material; and
(3) mixing the premixed composite material and a polymer electrolyte through ball milling to obtain a composite electrolyte; wherein
the composite electrolyte comprises the sulfide electrolyte, the polymer electrolyte, and the functional additive material, wherein the functional additive material is selected from one or more polymers represented by the following structural formula (1):
R 1 —O—R 2 -A-X formula (1), wherein R 1 represents a main chain of the polymer, and —O—R 2 -A-Z represents a side chain of the polymer,
R 1 is selected from at least one of polyvinyl main chain group, polypropylene main chain group, polyacrylate main chain group, polyvinylcarbonate main chain group, polyacrylonitrile main chain group, and polystyrene main chain group;
R 2 is a straight-chain or branched alkyl group with 3-10 carbon atoms;
A is selected from at least one aromatic hydrocarbon group of benzene group, biphenyl group, triphenyl group, naphthalene group, anthracene group, phenanthrene group, and pyrene group; and
X is selected from at least one of halogen atom, mercapto group, hydroxyl group, amine group, and aldehyde group.

10. The preparation method according to claim 9 , wherein
the weak polar solvent is selected from one or more of toluene, xylene, trimethylbenzene, n-hexane, cyclohexane, dichloromethane, and heptane, and optionally toluene, xylene, trimethylbenzene, and heptane.

11. A solid-state battery, comprising the composite electrolyte according to claim 1 .

12. A battery module, comprising the solid-state battery according to claim 11 .

13. A battery pack, comprising the battery module according to claim 12 .

14. An electric apparatus, comprising at least one of the solid-state batteries according to claim 11 .

15. The composite electrolyte according to claim 1 , wherein the functional additive material is selected from the group consisting of a polymer of chlorophenyl butyl vinyl ether, a polymer of chlorophenyl butoxyl styrene, a polymer of chlorophenylbutyl acrylate, a polymer of chlorophenylpropyl vinyl ether, a polymer of chlorophenylhexyl vinyl ether, a polymer of fluorophenylbutyl vinyl ether, a polymer of mercaptophenylbutyl vinyl ether, a polymer chlorobiphenylbutyl vinyl ether, a polymer of chloronaphthalene butyl vinyl ether, and any combinations thereof.

16. The preparation method according to claim 9 , wherein the functional additive material is selected from the group consisting of a polymer of chlorophenyl butyl vinyl ether, a polymer of chlorophenyl butoxyl styrene, a polymer of chlorophenylbutyl acrylate, a polymer of chlorophenylpropyl vinyl ether, a polymer of chlorophenylhexyl vinyl ether, a polymer of fluorophenylbutyl vinyl ether, a polymer of mercaptophenylbutyl vinyl ether, a polymer chlorobiphenylbutyl vinyl ether, a polymer of chloronaphthalene butyl vinyl ether, and any combinations thereof.

Assignees

• Contemporary Amperex Technology Co Ltd

Inventors

• Hu Bobing
• Liu Chengyong
• Liao Shangju
• He Xiaoning
• Xue Wenwen
• Xie Zhangdi
• Huang Shengyuan
• Zou Jieliang

Classifications

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M10/0567

  characterised by the additives · CPC title