Lithium stuffed garnet setter plates for solid electrolyte fabrication

• US 9,970,711 B2
• Filed: 10/05/2016
• Issued: 05/15/2018
• Est. Priority Date: 04/16/2015
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Iyer, Sriram, Holme, Tim, Donnelly, Niall
• Primary Examiner(s): SNELTING, ERIN LYNN
• Application Number:
  US15/286,509
• Publication Number:
  US 20170062873A1
• Time in Patent Office: 587 Days
• Field of Search: 264671-672
• CPC Class Codes: B28B 7/0097 Press moulds; Press-mould and press-ram assemblies
• CPC Class Codes: B30B 15/34 Heating or cooling presses or parts thereof
• CPC Class Codes: C04B 2235/3203 Lithium oxide 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 2235/3244 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 2235/447 Phosphates or phosphites calcium phosphates C04B2235/3212, e.g. orthophosphate, hypophosphite
• CPC Class Codes: C04B 2235/6025 Tape casting, e.g. with a doctor blade
• CPC Class Codes: C04B 2235/65 Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
• CPC Class Codes: C04B 2235/764 Garnet structure A3B2(CO4)3
• CPC Class Codes: C04B 2235/77 Density
• CPC Class Codes: C04B 2235/785 Submicron sized grains, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 2235/786 Micrometer sized grains, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/94 Products characterised by their shape
• CPC Class Codes: C04B 2235/9623 Ceramic setters properties
• CPC Class Codes: C04B 2235/963 Surface properties, e.g. surface roughness
• CPC Class Codes: C04B 35/10 based on aluminium oxide
• CPC Class Codes: C04B 35/119 with zirconium oxide
• CPC Class Codes: C04B 35/44 : based on aluminates
• CPC Class Codes: C04B 35/48 : based on zirconium or hafnium oxides, zirconates, zircon or hafnates
• CPC Class Codes: C04B 35/486 : Fine ceramics
• CPC Class Codes: C04B 35/4885 : with aluminium oxide
• CPC Class Codes: C04B 35/64 : Burning or sintering processes C04B33/32 takes precedence ; powder metallurgy B22F
• CPC Class Codes: C08K 2003/2203 : of lithium
• CPC Class Codes: C08K 3/105 : Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
• CPC Class Codes: C08K 5/09 : Carboxylic acids; Metal salts thereof; Anhydrides thereof
• CPC Class Codes: C08K 5/12 : of cyclic polycarboxylic acids
• CPC Class Codes: F27B 17/02 : specially designed for laboratory use
• CPC Class Codes: F27B 21/02 : Sintering grates or tables
• CPC Class Codes: F27D 2005/0081 : Details
• CPC Class Codes: F27D 5/0006 : Composite supporting structures
• CPC Class Codes: H01M 10/0481 : Compression means other than compression means for stacks of electrodes and separators
• 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 10/0562 : 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 2300/0068 : inorganic
• CPC Class Codes: H01M 2300/0071 : Oxides
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Setter plates are fabricated from Li-stuffed garnet materials having the same, or substantially similar, compositions as a garnet Li-stuffed solid electrolyte. The Li-stuffed garnet setter plates, set forth herein, reduce the evaporation of Li during a sintering treatment step and/or reduce the loss of Li caused by diffusion out of the sintering electrolyte. Li-stuffed garnet setter plates, set forth herein, maintain compositional control over the solid electrolyte during sintering when, upon heating, lithium is prone, to diffuse out of the solid electrolyte.

Claims

1. A method of using a setter plate to fabricate a Li-stuffed garnet solid electrolyte film for a rechargeable battery, the method comprising:

placing a green film of unsintered Li-stuffed garnet precursor materials between two setter plates; and

sintering the green film between and in contact with the two setter plates;

wherein the setter plates comprise a Li-stuffed garnet;

wherein the thickness of each of the two setter plates is about 0.5 mm to about 100 mm.

2. The method of claim 1, further comprising placing a metal foil or metal powder between at least one setter plate and the green film prior to the sintering the green film.

3. The method of claim 1, wherein the green film has a surface defined by a first lateral dimension from 1 cm to 50 cm and a second lateral dimension from 1 cm to 50 cm.

4. The method of claim 1, wherein the sintering comprises heating the green film and the two setter plates and exposing the green film and the two setter plates to an Argon:

H₂ mixed atmosphere.

5. The method of claim 1, wherein the sintering produces a sintered Li-stuffed garnet solid electrolyte less than 100 microns thick and more than 1 nm thick.

6. The method of claim 1, wherein the sintered Li-stuffed garnet solid electrolyte has an ASR between 0.1 Ω

·

cm² to 10 Ω

·

cm² at 50°

C.

7. A method of using a setter plate to fabricate a Li-stuffed garnet solid electrolyte for a rechargeable battery, the method comprising:

placing a green film of unsintered Li-stuffed garnet precursor materials between two setter plates, wherein each of the two setter plate individually comprises a member selected from Li₂ZrO₃, xLi₂O-(1−

x)SiO₂ (where x=0.01-0.99), aLi₂O-bB₂O₃-cSiO₂ (where a+b+c=1), LiLaO₂, LiAlO₂, Li₂O, Li₃PO₄, a Li-stuffed garnet, and combinations thereof; and

sintering the green film between and in contact with the two setter plates;

wherein the thickness of each of the two setter plates is about 0.5 mm to about 100 mm.

8. The method of claim 7, wherein the green film is a tape-cast film.

9. The method of claim 7, wherein the sintering atmosphere comprises, Air, Argon, Nitrogen, an Argon:

H₂ mixture, or an Argon;

H₂;

H₂O mixture.

10. The method of claim 7, further comprising placing a metal foil or metal powder between the setter plate and the green film prior to the sintering the green film.

11. The method of claim 10, wherein the metal is Ni, Cu, Fe, Al, Ag, combinations thereof, or alloys thereof.

12. The method of claim 7, wherein the green film has a surface defined by a first lateral dimension from 1 cm to 50 cm and a second lateral dimension from 1 cm to 50 cm.

13. The method of claim 7, wherein the green film has a thickness between 1 μ

m to about 100 μ

m.

14. The method of claim 7, wherein the sintering comprises heating the green electrolyte film and the two setter plates to between 450°

C. and 1300°

C.

15. The method claim 7, wherein the sintering comprises heating the green film and the two setter plates and exposing the green film and the two setter plates to an Argon:

H₂ mixed atmosphere.

16. The method of claim 7, wherein the sintering produces a sintered Li-stuffed garnet solid electrolyte less than 50 microns thick.

17. The method of claim 7, further comprising providing a rechargeable battery comprising the Li-stuffed garnet solid electrolyte.