Composite electrolytes

Patent metadata

Field	Value
Publication number	US-10374254-B2
Application number	US-201615192960-A
Country	US
Kind code	B2
Filing date	Jun 24, 2016
Priority date	Jun 24, 2015
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

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 necked particles of inorganic material which form a percolation network for lithium ion conduction through the electrolyte; wherein the organic material has a lithium ion conductivity of less than 10 −8 S/cm at 80° C.;
wherein the inorganic material comprises a surface species which reacts with a functional group selected from an epoxide, a carboxylic acid, an ester, an amide, an amine, a sulfonic acid, a phosphate, a phosphine oxide, a phosphoric acid, an alkoxide, a nitrile, a thioether, thiol, and combinations thereof.

2. The electrolyte of claim 1 , wherein the electrolyte has a fracture strength of greater than 5 MPa and less than 250 MPa, as measured in a ring-on-ring test as specified in the ASTM C1499-09 standard.

3. The electrolyte of claim 1 , wherein the organic material is bonded to, adsorbed on, molded around, or entangled with the surface of the inorganic material, a surface attached species on the surface of the inorganic material, or an inorganic material particle.

4. The electrolyte of claim 1 , wherein the organic material is bonded to the surface of the inorganic material by covalent, ionic, electrostatic, or van Der Waals bonds.

5. 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.

6. The electrolyte of claim 1 , wherein the surface species is selected from a thiol, a hydroxide, a sulfide, an oxide, and a combination thereof.

7. The electrolyte of claim 1 , wherein the organic material has polar functional groups.

8. The electrolyte of claim 1 , wherein the organic material is entangled with the inorganic material.

9. The electrolyte of claim 1 , wherein the organic material is entangled with a surface species which is present on the inorganic material.

10. The electrolyte of claim 9 , wherein the surface species is a monomer, oligomer, or polymer attached to the surface of the inorganic material.

11. The electrolyte of claim 1 , wherein the electrolyte is a thin film having a thickness between 1 nm and 100 μm.

12. The electrolyte of claim 1 , wherein the inorganic material is a solid state electrolyte selected from a lithium-stuffed garnet oxide, an antiperovskite oxide, a lithium borohydride, a lithium iodide-containing material and a lithium sulfide-containing material.

13. The electrolyte of claim 12 , wherein the inorganic material is a solid state electrolyte of a lithium-stuffed garnet oxide characterized by the formula Li u La v Zr x O y .zAl 2 O 3 , wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14; and
z is a rational number from 0 to 1;
wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

14. The electrolyte of claim 12 , wherein the lithium-stuffed garnet oxide is characterized by the formula Li u La 3 Zr 2 O 12 .zAl 2 O 3 , wherein 4≤u≤10 and 0<z≤1.

15. The electrolyte of claim 12 , wherein the lithium-stuffed garnet oxide is characterized by the formula Li 6.75-7.1 La 3 Zr 2 O 12 .0.5Al 2 O 3 or Li 6.4-7.7 La 3 Zr 2 O 12 . 0.11Al 2 O 3 .

16. The electrolyte of claim 12 , wherein the inorganic material is a solid state electrolyte selected from a lithium sulfide characterized by one of the following 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 ;
Li g As h Sn j S k O l , wherein 2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and 0≤1≤10;
Li m P n S p I q , wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; or
a mixture of (Li 2 S):(P 2 S 5 ) having a molar ratio from about 10:1 to about 6:4 and
LiI, wherein the ratio of [(Li 2 S):(P 2 S 5 )]:LiI is from 95:5 to 50:50;
a mixture of LiI and Al 2 O 3 ;
Li 3 N;
LPS+X, wherein X is selected from Cl, I, or Br;
vLi 2 S+wP 2 S 5 +yLiX;
vLi 2 S+wS i S 2 +yLiX;
vL i2 S+wB 2 S 3 +yLiX;
a mixture of LiBH 4 and LiX wherein X is selected from Cl, I, or Br; or
vLiBH 4 +wLiX+yLiNH 2 , wherein X is selected from Cl, I, or Br; and
wherein coefficients v, w, and y are rational numbers from 0 to 1.

17. The electrolyte of claim 12 , wherein the inorganic material is a solid state electrolyte selected from a lithium sulfide characterized by Li 10 Si 0.5 Sn 0.5 P 2 S 12 and Li 7.4 P 1.6 S 7.2 I.

18. The electrolyte of claim 1 , wherein the organic material is a polymer.

19. The electrolyte of claim 1 , wherein the organic material is a polymer selected from the group consisting of polyolefins, natural rubbers, synthetic rubbers, polybutadiene, polyisoprene, epoxidized natural rubber, polyisobutylene, polypropylene oxide, polyacrylates, polymethacrylates, polyesters, polyvinyl esters, polyurethanes, styrenic polymers, epoxy resins, epoxy polymers, poly(bisphenol A-co-epichlorohydrin), vinyl polymers, polyvinyl halides, polyvinyl alcohol, polyethyleneimine, poly(maleic anhydride), silicone polymers, siloxane polymers, polyacrylonitrile, polyacrylamide, polychloroprene, polyvinylidene fluoride, polyvinyl pyrrolidone, polyepichlorohydrin, and blends or copolymers thereof.

20. The electrolyte of claim 19 , wherein the molecular weight of the polymer is greater than 50,000 g/mol.

21. 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.

22. The electrolyte of claim 1 , wherein the organic material comprises one or more crosslinkable members selected from the group consisting of diglycidyl ethers, epoxy resins, polyamines, and mixtures thereof.

23. The electrolyte of claim 1 , wherein the organic material comprises one or more polymerizable monomers selected from the group consisting of vinyl esters, acrylates, methacrylates, and styrenic monomers.

24. The electrolyte of claim 1 , wherein the organic material comprises one or more crosslinkable members selected from the group consisting of diglycidyl ethers, triglycidyl ethers, epoxy resins, and polyamines.

25. The electrolyte of claim 1 , wherein the organic material comprises one or more crosslinkable oligomers selected from the group consisting of vinyl-functionalized oligomers of polybutadiene, polysiloxanes, and mixtures thereof.

26. The electrolyte of claim 1 , where the organic material comprises an epoxy resin.

27. The electrolyte of claim 1 , where 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.

28. The electrolyte of claim

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M10/0562

  Solid materials · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M6/185

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

• H01M6/181

  with polymeric electrolytes · CPC title