Garnet materials for Li secondary batteries and methods of making and using garnet materials

• US 10,439,251 B2
• Filed: 10/11/2017
• Issued: 10/08/2019
• Est. Priority Date: 10/07/2013
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Holme, Tim, Donnelly, Niall, Iyer, Sriram, Winoto, Adrian, Singh, Mohit, Hudson, Will, Choi, Dong Hee Anna, Karpenko, Oleh, Kerman, Kian
• Primary Examiner(s): Cano, Milton I
• Assistant Examiner(s): Ojo-Amoo, Abibatu O
• Application Number:
  US15/730,583
• Publication Number:
  US 20180069263A1
• Time in Patent Office: 727 Days
• Field of Search: 429332
• CPC Class Codes: C01G 25/006 Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C04B 2235/3203 Lithium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3205 Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
• CPC Class Codes: C04B 2235/3208 Calcium oxide or oxide-forming salts thereof, e.g. lime
• CPC Class Codes: C04B 2235/3213 Strontium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3215 Barium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3222 Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
• CPC Class Codes: C04B 2235/3227 Lanthanum oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3229 Cerium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3244 Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3248 Zirconates or hafnates, e.g. zircon
• CPC Class Codes: C04B 2235/3251 Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3255 Niobates or tantalates, e.g. silver niobate
• CPC Class Codes: C04B 2235/3256 Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
• CPC Class Codes: C04B 2235/3258 Tungsten oxides, tungstates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3294 Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
• CPC Class Codes: C04B 2235/6025 Tape casting, e.g. with a doctor blade
• CPC Class Codes: C04B 2235/656 characterised by specific heating conditions during heat treatment
• CPC Class Codes: C04B 2235/6567 : Treatment time
• CPC Class Codes: C04B 2235/661 : Multi-step sintering
• CPC Class Codes: C04B 2235/666 : Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
• CPC Class Codes: C04B 2235/764 : Garnet structure A3B2(CO4)3
• CPC Class Codes: C04B 2235/786 : Micrometer sized grains, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/96 : Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 35/117 : Composites
• CPC Class Codes: C04B 35/486 : Fine ceramics
• CPC Class Codes: C04B 35/4885 : with aluminium oxide
• CPC Class Codes: C04B 35/495 : based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
• CPC Class Codes: C04B 35/62218 : obtaining ceramic films, e.g. by using temporary supports
• CPC Class Codes: C04B 35/6261 : Milling
• CPC Class Codes: C04B 35/6262 : of calcined, sintered clinker or ceramics
• CPC Class Codes: C04B 35/64 : Burning or sintering processes C04B33/32 takes precedence ; powder metallurgy B22F
• CPC Class Codes: C04B 35/645 : Pressure sintering
• CPC Class Codes: C04B 35/65 : Reaction sintering of free metal- or free silicon-containing compositions C04B35/573, C04B35/591 take precedence
• CPC Class Codes: C04B 41/009 : characterised by the material treated
• CPC Class Codes: C04B 41/5027 : Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
• CPC Class Codes: H01M 10/052 : Li-accumulators
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/056 : characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0561 : the electrolyte being constituted of inorganic materials only
• CPC Class Codes: H01M 10/0562 : Solid materials
• CPC Class Codes: H01M 10/0585 : of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 2300/0071 : Oxides
• CPC Class Codes: H01M 2300/0091 : in the form of mixtures
• CPC Class Codes: H01M 4/366 : as layered products
• CPC Class Codes: H01M 4/8657 : layered
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells

Abstract

Disclosed herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Also disclosed herein are lithium-stuffed garnet thin films having fine grains therein. Also disclosed herein are methods of making and using lithium-stuffed garnets as catholytes, electrolytes and/or anolytes for all solid state lithium rechargeable batteries. Also disclosed herein are electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also disclosed herein are methods for preparing dense thin (<50 um) free standing membranes of an ionically conducting material for use as a catholyte, electrolyte, and, or, anolyte, in an electrochemical device, a battery component (positive or negative electrode materials), or a complete solid state electrochemical energy storage device. Also disclosed herein are sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.

Claims

1. A sintered film comprising:

a first layer comprising a sintered lithium-stuffed garnet; and

a second layer in direct contact with the first layer, the second layer comprising a sintered metal;

wherein the sintered film thickness is less than 200 μ

m and greater than 1 nm.

2. The film of claim 1, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_ALa_BM′

_CM″

_DZr_EO_F, Li_ALa_BM′

_CM″

_DTa_EO_F, and Li_ALa_BM′

_CM″

_DNb_EO_F, wherein 4<

A<

8.5, 1.5<

B<

4, 0≤

C<

2, 0≤

D<

2;

0<

E<

2.5, 10<

F<

14, and wherein M′ and

M″

are each, independently, selected from the group consisting of Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta.

3. The film of claim 1, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_ALa_BZr_CAl_DMe″

_EO_F wherein 4<

A<

8.5, 1.5<

B<

4, 0≤

C≤

2.5, 0≤

D≤

2, 0≤

E<

2, and 10<

F<

14, and wherein Me″

is a metal selected from the group consisting of Nb, Ta, W, Mo, and Sb.

4. The film of claim 3, wherein E=0.

5. The film of claim 4, wherein 10<

F<

13.

6. The film of claim 3, wherein A<

7.

7. The film of claim 4, wherein 0.3<

D<

1.

8. The film of claim 5, wherein 0.3<

D<

1.

9. The film of claim 1, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂.y½

Al₂O₃;

wherein 5.0<

x<

9 and 0.1<

y<

1.5.

10. The film of claim 9, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂.0.35Al₂O₃.

11. The film of claim 9, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂.0.5Al₂O₃.

12. The film of claim 9, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li₇La₃Zr₂O₁₂.0.5Al₂O₃.

13. The film of claim 1, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂+yAl₂O₃;

wherein 5.5≤

x≤

9, and 0≤

y≤

1.

14. The film of claim 13, wherein the lithium-stuffed garnet comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂.Al₂O₃.

15. The film of claim 13, wherein the lithium-stuffed garnet comprises Li₇La₃Zr₂O₁₂.0.35Al₂O₃.

16. The film of claim 13, wherein the lithium-stuffed garnet comprises Li₇La₃Zr₂O₁₂.0.65Al₂O₃.

17. The film of claim 1, wherein the lithium-stuffed garnet comprises Li₇La₃Zr₂O₁₂.0.67Al₂O₃.

18. The film of claim 1, wherein the lithium-stuffed garnet comprises Li₇La₃Zr₂O₁₂.Al₂O₃.

19. The film of claim 1, wherein the lithium-stuffed garnet comprises Li₇La₃Zr₂O₁₂ doped with alumina.

20. The film of claim 1, wherein the film has a conductivity greater than 10⁻

4 S/cm at room temperature.

21. The film of claim 1, wherein the metal of the second layer is nickel, aluminum, iron, steel, stainless steel, copper, an alloy of nickel, an alloy of copper, an alloy of iron, an alloy of aluminum, an alloy of steel, or a combination thereof.

22. The film of claim 1, wherein the lithium-stuffed garnet of has a median grain size of between 0.5 nm and 10 μ

m.

23. The film of claim 1, wherein the lithium-stuffed garnet of has a median grain size of between 10 nm and 10 μ

m.

24. The film of claim 1, wherein the lithium-stuffed garnet of has a median grain size of between 100 nm and 10 μ

m.

25. The film of claim 1, wherein the sintered film thickness is between 100 nm and 30 μ

m.

26. The film of claim 1, wherein the porosity of first layer is less than 20%.

27. The film of claim 1, wherein the porosity of the first layer is less than 10%.

28. The film of claim 1, wherein the porosity of first layer is less than 5%.

29. The film of claim 1, wherein the porosity of first layer is less than 3%.

30. The film of claim 1, wherein the film has an area specific resistance (ASR) of less than 100 Ω

cm² at 80°

C. when bonded to lithium.

31. The film of claim 1, further comprising a sintered third layer, the third layer comprising a lithium-stuffed garnet, and the third layer interfacing the second layer.

32. The film of claim 31, wherein the lithium-stuffed garnet of the third layer comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂.y½

Al₂O₃;

wherein 5.0<

x<

9 and 0.1<

y<

1.5.

33. The film of claim 31, wherein the lithium-stuffed garnet of the third layer comprises at least one member selected from the group consisting of Li_xLa₃Zr₂O₁₂.0.35Al₂O₃.

34. The film of claim 31, wherein the lithium-stuffed garnet of the third layer comprises Li₇La₃Zr₂O₁₂.0.35Al₂O₃.

35. The film of claim 31, wherein the lithium-stuffed garnet of the third layer comprises Li₇La₃Zr₂O₁₂ doped with alumina.

36. The film of claim 31, wherein the film has a conductivity greater than 10⁻

4 S/cm at room temperature.