Composite electrolytes

• US 10,374,254 B2
• Filed: 06/24/2016
• Issued: 08/06/2019
• Est. Priority Date: 06/24/2015
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Van Berkel, Kim, Holme, Tim, Singh, Mohit, Mehrotra, Amal, Chen, Zhebo, Kerman, Kian, Hermann, Wes, Hudson, William
• Primary Examiner(s): Cantelmo, Gregg
• Application Number:
  US15/192,960
• Publication Number:
  US 20170005367A1
• Time in Patent Office: 1,138 Days
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0091 in the form of mixtures
• CPC Class Codes: H01M 50/446 Composite material consisting of a mixture of organic and inorganic materials
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

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.

Claims

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<sup>−

8</sup> 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 μ

m.

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_uLa_vZr_xO_y.zAl₂O₃, 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_uLa₃Zr₂O₁₂.zAl₂O₃, 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_6.75-7.1La₃Zr₂O₁₂.0.5Al₂O₃ or Li_6.4-7.7La₃Zr₂O₁₂. 0.11Al₂O₃.

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_aSi_bSn_cP_dS_eO_f, wherein 2≤

a≤

8, b+c=1, 0.5≤

d≤

2.5, 4≤

e≤

12, and 0<

f≤

10 ;

Li_gAs_hSn_jS_kO_l, wherein 2≤

g≤

6, 0≤

h≤

1, 0≤

j≤

1, 2≤

k≤

6, and 0≤

1≤

10;

Li_mP_nS_pI_q, wherein 2≤

m≤

6, 0≤

n≤

1, 0≤

p≤

1, 2≤

q≤

6;

or

a mixture of (Li₂S);

(P₂S₅) having a molar ratio from about 10;

1 to about 6;

4 and

LiI, wherein the ratio of [(Li₂S);

(P₂S₅)];

LiI is from 95;

5 to 50;

50;

a mixture of LiI and Al₂O₃;

Li₃N;

LPS+X, wherein X is selected from Cl, I, or Br;

vLi₂S+wP₂S₅+yLiX;

vLi₂S+wS_iS₂+yLiX;

vL_i2S+wB₂S₃+yLiX;

a mixture of LiBH₄ and LiX wherein X is selected from Cl, I, or Br;

or

vLiBH₄+wLiX+yLiNH₂, 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 Li₁₀Si_0.5Sn_0.5P₂S₁₂and Li_7.4P_1.6S_7.2I.

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 1, further comprising carboxyl-terminated poly(butadiene-co-acrylonitrile), amine-terminated poly(butadiene-co-acrylonitrile), poly(propylene glycol) diglycidyl ether, poly(propylene glycol) bis(2-aminopropyl ether), or combinations thereof.

29. The electrolyte of claim 1, where the organic material comprises

(a) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA), diethylenetriamine (DETA), and amine-terminated poly(butadiene-co-acrylonitrile);

(b) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA), diethylenetriamine;

(c) (DETA), and poly(propylene glycol) bis(2-aminopropyl ether);

(d) an epoxy polymer of bisphenol A diglycidyl ether and diethylenetriamine (DETA);

(e) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA) and poly(propylene glycol) bis(2-aminopropyl ether);

(f) an epoxy polymer of bisphenol A diglycidyl ether and diethylenetriamine (DETA);

or

(g) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA) and poly(propylene glycol) bis(2-aminopropyl ether).

30. The electrolyte of claim 29, wherein the poly(propylene glycol) bis(2-aminopropyl ether) has a molecular weight (g/mol) of about 100 to 50,000.

31. The electrolyte of claim 29, wherein the poly(propylene glycol) bis(2-aminopropyl ether) has a molecular weight (g/mol) of about 230 to 4000.

32. The electrolyte of claim 1, wherein the electrolyte has a fracture strength of 25 MPa to 75 MPa.

33. The electrolyte of claim 1, wherein the electrolyte has a total area specific resistance (ASR) of between 0 Ω

·

cm² and 200 Ω

·

cm² at 45°

C.

34. 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) of at least 1;

1 to 99;

1.

35. 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) of at least 80;

20 to 99;

1.

36. The electrolyte of claim 1, wherein the volumetric ratio of inorganic material to organic material is greater than 1.

37. The electrolyte of claim 1, wherein the volumetric ratio of inorganic material to organic material is greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

38. The electrolyte of claim 1, wherein the necked particles are sintered necked particles.

39. The electrolyte of claim 1, wherein the necked particles are fuse necked particles.

40. A composition comprising the electrolyte of claim 1 and a gel electrolyte;

wherein the composition of claim 1 directly contacts the gel electrolyte.

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

42. An electrochemical cell comprising a positive electrode, a negative electrode, and an electrolyte layer, wherein the electrolyte layer comprises an electrolyte selected from any one of the electrolytes in claim 1.

43. An electrochemical cell comprising a positive electrode, a negative electrode, and a composite electrolyte layer;

wherein the composite electrolyte layer is positioned between the positive electrode and negative electrode;

wherein the composite electrolyte layer comprises a polymer and an inorganic solid state electrolyte;

wherein a volumetric ratio of the inorganic solid state electrolyte to the polymer is greater than 1;

wherein the positive electrode and the negative electrode directly contact the inorganic solid state electrolyte; and

wherein the composite electrolyte is an electrolyte of claim 1.

44. The electrochemical cell of claim 43, wherein the composite electrolyte has a fracture strength of about 50 to 200 MPa.

45. The electrochemical cell of claim 43, wherein the inorganic solid state electrolyte is sintered or necked.

46. The electrochemical cell of claim 43, wherein the solid state electrolyte is a lithium-stuffed garnet electrolyte characterized by the formula Li_yLa₃Zr₂O₁₂.X Al₂O₃, wherein 4≤

y≤

10 and 0<

X≤

1.

47. The electrochemical cell of claim 43, wherein the solid state electrolyte is a sulfide electrolyte characterized by the formula

Li_aSi_bSn_cP_dS_eO_f, wherein 2≤

a≤

8, b+c=1, 0.5≤

d≤

2.5, 4≤

e≤

12, and 0<

f≤

10 ;

Li_gAs_hSn_jS_kO_l, wherein 2≤

g≤

6, 0≤

h≤

1, 0≤

j≤

1, 2≤

k≤

6, and 0≤

1≤

10;

Li_mP_nS_pI_q, wherein 2≤

m≤

6, 0≤

n≤

1, 0≤

p≤

1, 2≤

q≤

6;

or

a mixture of (Li₂S);

(P₂S₅) having a molar ratio from about 10;

1 to about 6;

4 and

LiI, wherein the ratio of [(Li₂S);

(P₂S₅)];

LiI is from 95;

5 to 50;

50;

a mixture of LiI and Al₂O₃;

Li₃N;

LPS+X, wherein X is selected from Cl, I, or Br;

vLi₂S+wP₂S₅+yLiX;

vLi₂S+wS_iS₂+yLiX;

vL_i2S+wB₂S₃+yLiX;

a mixture of LiBH₄ and LiX wherein X is selected from Cl, I, or Br;

or

vLiBH₄+wLiX+yLiNH₂, wherein X is selected from Cl, I, or Br; and

wherein coefficients v, w, and y are rational numbers from 0 to 1.

48. An electrolyte comprising an inorganic material and an organic material, wherein the inorganic material is embedded in the organic material, and the organic material is molded around, adsorbed to, bonded to, or entangled with the surface of the inorganic material or a particle thereof;

and 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<sup>−

8</sup> 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.