Composite electrolytes

Patent metadata

Field	Value
Publication number	US-11955603-B2
Application number	US-202117465642-A
Country	US
Kind code	B2
Filing date	Sep 2, 2021
Priority date	Jun 24, 2015
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

Set forth herein are electrolyte compositions that include both organic and inorganic constituent components and which are suitable for use in rechargeable batteries. Also set forth herein are methods and systems for making and using these composite electrolytes.

First claim

What is claimed is:

1. An electrolyte comprising an inorganic material embedded in an organic material; wherein:
the inorganic material comprises particles of inorganic material which form a percolation network for lithium ion conduction through the electrolyte, wherein the inorganic material has a particle size of about 50 nm to about 500 nm;
the organic material has a lithium conductivity of less than 10 −8 S/cm at 80° C.,
wherein the inorganic material comprises necked-particles of inorganic material,
the inorganic material is a solid state electrolyte, and wherein the solid state electrolyte is a sulfide electrolyte characterized by the formula:
Li a Si b Sn c P d S e O f , wherein 2≤ a≤ 8, b+c= 1,0.5≤ d≤ 2.5,4≤ e≤ 12, and 0< f≤ 10.

2. The electrolyte of claim 1 , wherein the electrolyte has a fracture strength of greater than 5 MPa and less than 250 MPa.

3. The electrolyte of claim 1 , wherein the organic material is molded around the inorganic material.

4. The electrolyte of claim 1 , wherein the organic material comprises a functional group selected from a carboxylic acid, an ester, an amide, an amine, a silane, sulfonic acid, a phosphate, a phosphine oxide, a phosphoric acid, an alkoxide, a nitrile, a thioether, thiol, and combinations thereof; or wherein the organic material has polar functional groups.

5. The electrolyte of claim 1 , wherein:
the organic material is polymerized around the inorganic material; wherein the organic material is entangled with the inorganic material; or
the organic material is entangled with a surface species which is present on the inorganic material.

6. The electrolyte of claim 1 , wherein:
the organic material is a polymer;
wherein one or more component of the organic material is a polymer selected from the group consisting of natural rubbers, synthetic rubbers, polyisoprene, epoxidized natural rubber, polyisobutylene, polyacrylates, polymethacrylates, polyesters, polyvinyl esters, polyurethanes, styrenic polymers, epoxy resins, epoxy polymers, poly(bisphenol A-co-epichlorohydrin), polyvinyl alcohol, polyethyleneimine, poly(maleic anhydride), silicone polymers, polyacrylonitrile, polyacrylamide, polychloroprene, polyvinyl pyrrolidone, polyepichlorohydrin, and blends or copolymers thereof; or
the polymer is preformed and selected from the group consisting of polyisoprene, epoxidized natural rubber, and poly(butadiene-co-acrylonitrile); and
the molecular weight of the polymer is greater than 50,000 g/mol.

7. The electrolyte of claim 1 , wherein:
the organic material comprises one or more polymerizable or crosslinkable members selected from the group consisting of vinyl esters, acrylates, methacrylates, styrenic monomers, vinyl-functionalized oligomers of polybutadiene, vinyl-functionalized oligomers of polysiloxanes, and mixtures thereof;
the organic material comprises one or more crosslinkable members selected from the group consisting of diglycidyl ethers, epoxy resins, polyamines, and mixtures thereof;
the organic material comprises one or more polymerizable monomers selected from the group consisting of vinyl esters, acrylates, methacrylates, styrenic monomers;
the organic material comprises one or more crosslinkable members selected from the group consisting of diglycidyl ethers, triglycidyl ethers, epoxy resins, polyamines; or
the organic material comprises one or more crosslinkable oligomers selected from the group consisting of vinyl-functionalized oligomers of polybutadiene, polysiloxanes, and mixtures thereof.

8. The electrolyte of claim 1 , wherein:
the organic material comprises an epoxy resin; or
the organic material comprises an epoxy polymer precursor selected from the group consisting of bisphenol A diglycidyl ether (DGEBA), poly(bisphenol A-co-epichlorohydrin) glycidyl end-capped polymers, diethylenetriamine (DETA) and derivatives thereof, tetraethylenepentamine and derivatives thereof, polyethyleneimine, carboxyl-terminated poly(butadiene-co-acrylonitrile), amine-terminated poly(butadiene-co-acrylonitrile), poly(propylene glycol) diglycidyl ether, poly(propylene glycol) bis(2-aminopropyl ether), and combinations thereof; and optionally wherein the organic material comprises an epoxy polymer precursor selected from the group consisting of bisphenol A diglycidyl ether (DGEBA), poly(bisphenol A-co-epichlorohydrin) glycidyl end-capped polymers, diethylenetriamine (DETA) and derivatives thereof, tetraethylenepentamine and derivatives thereof, polyethyleneimine, and combinations thereof.

9. The electrolyte of claim 1 , wherein:
the organic material comprises an epoxy polymer of bisphenol A diglycidyl ether (DGEBA), diethylenetriamine (DETA), and amine-terminated poly(butadiene-co-acrylonitrile); where the organic material comprises an epoxy polymer of bisphenol A diglycidyl ether (DGEBA), diethylenetriamine (DETA), and poly(propylene glycol) bis(2-aminopropyl ether); where the organic material comprises a polymer of bisphenol A diglycidyl ether (DGEBA) and poly(propylene glycol) bis(2-aminopropyl ether); or where the organic material comprises a polymer of bisphenol A diglycidyl ether and diethylenetriamine (DETA);
the poly(propylene glycol) bis(2-aminopropyl ether) optionally has a molecular weight (g/mol) of about 100 to 50,000.

10. The electrolyte of claim 1 , wherein:
the inorganic material has a silane attached to its surface, wherein the silane is selected from trichlorosilanes, trimethoxysilanes, and triethoxysilanes;
the trichlorosilane is 3-methacryloxypropyltrichlorosilane; wherein the trimethoxysilane is 3-acryloxypropyltrichlorosilane; or
the trimethoxysilane is 7-octenyltrimethoxysilane.

11. The electrolyte of claim 1 , wherein the electrolyte is directly in contact with a gel electrolyte.

12. The electrolyte of claim 1 , wherein the electrolyte has a total area-specific resistance (ASR) of between 0 and 100 Ω·cm 2 at 45° C.

13. The electrolyte of claim 1 , wherein the electrolyte comprises an inorganic material and an organic material in a weight ratio of (inorganic material):(organic material) from 1:1 to 99:1.

14. The electrolyte of claim 1 , wherein the organic material is a polymerizable or cross-linkable monomer.

15. An electrochemical device comprising an electrolyte of claim 1 .

16. The electrolyte of claim 1 , wherein:
the organic material is selected from a preformed polymer, a monomer of a polymer, an oligomer, and combinations thereof,
the organic material comprises

wherein n is an integer from 0 to 100,000; or
the composition comprises bisphenol A diglycidyl ether,

or any oligomer, polymer, or repeated unit thereof; and
the electrolyte is prepared by mixing a preformed polymer with the inorganic material, wherein the preformed polymer is optionally cured or crosslinked after mixing with the inorganic material; or wherein the electrolyte is prepared by mixing the monomer of a polymer, the oligomer, or combinations thereof with the inorganic material, and polymerizing or crosslinking the monomer(s), the oligomer, or combinations thereof to form a polymeric organic material in-situ.

17. The electrolyte of claim 16 , wherein:
the preformed polymer is selected from the group consisting of polyolefins, natural rubbers, synthetic rubbers, polybutadiene, polyisoprene, epoxidized natural rubber, polyisobutylene, polypropylene oxide, polyac

Assignees

• Quantumscape Battery Inc

Inventors

• Van Berkel Kim
• Holme Tim
• Singh Mohit
• Mehrotra Amal
• Chen Zhebo
• Kerman Kian
• Hermann Wes
• Hudson William

Classifications

• H01M10/0565 Primary

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

• H01G11/06

  with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC] · CPC title

• H01G11/56

  Solid electrolytes, e.g. gels; Additives therein · CPC title

• H01M6/181

  with polymeric electrolytes · CPC title

• H01M6/185

  with oxides, hydroxides or oxysalts as solid electrolytes · CPC title