Lithium stuffed garnet setter plates for solid electrolyte fabrication

• US 10,422,581 B2
• Filed: 10/26/2017
• Issued: 09/24/2019
• 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): Wiese, Noah S
• Application Number:
  US15/794,948
• Publication Number:
  US 20180045465A1
• Time in Patent Office: 698 Days
• 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, e.g. orthophosphate or 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 setter plate for fabricating solid electrolytes of a rechargeable battery, the setter plate comprising at least two members selected from the group consisting of Li₂ZrO₃, Li₂SiO₃, LiLaO₂, LiAlO₂, Li₂O, Li₃PO₄, and a Li-stuffed garnet compound characterized by the formula Li_ALa_BM′

_cM″

_DZr_EO_F, wherein 4<

A<

8.5, 1.5<

B<

4, 0≤

C≤

2, 0≤

D≤

2;

0≤

E<

2, 10<

F<

13, and M′ and

M″

are each, independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta;

a surface defined by a first lateral dimension from 1 cm to 96 cm and a second lateral dimension from 1 cm to 96 cm; and

a thickness from 0.1 mm to 100 mm.

2. The setter plate of claim 1, wherein the first lateral dimension is from 3 cm to 30 cm and the second lateral dimension is from 3 cm to 30 cm.

3. The setter plate of claim 1, wherein the thickness is from 0.1 mm to 10 mm.

4. The setter plate of claim 1, wherein the surface has a surface roughness from 1.0 μ

m Ra to 4 μ

m Ra, wherein Ra is an arithmetic average of absolute values of sampled surface roughness amplitudes.

5. The setter plate of claim 1, having a flatness of between 0.1 μ

m and 100 μ

m.

6. The setter plate of claim 1, having a flatness of between 0.5 μ

m and 20 μ

m.

16. The setter plate of claim 1, wherein the setter plate comprises a Li-stuffed garnet compound characterized by the formula Li_ALa_BM′

_cM″

_DZr_EO_F, wherein 4<

A<

8.5, 1.5<

B<

4, 0≤

C≤

2, 0≤

D≤

2;

0≤

E<

2, 10<

F<

13, and M′ and

M″

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

7. A setter plate used for fabricating solid electrolytes of a rechargeable battery, the setter plate comprising:

an oxide material with lithium concentration greater than 0.02 mol/cm³ and a melting point above 1100°

C.;

a surface defined by a first lateral dimension from 3 cm to 30 cm and a second lateral dimension from 3 cm to 30 cm; and

a thickness from 0.1 mm to 100 mm,

wherein the oxide material comprises at least two members selected from the group consisting of Li₂ZrO₃, LiLaO₂, LiAlO₂, Li₂O, Li₃PO₄, and a Li-stuffed garnet compound characterized by the formula Li_ALa_BM′

_cM″

_DZr_EO_F, wherein 4<

A<

8.5, 1.5<

B<

4, 0≤

C≤

2, 0≤

D≤

2;

0≤

E<

2, 10<

F<

13, and M′ and

M″

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

8. The setter plate of claim 7, wherein the oxide material comprises LiLaO₂.

9. The setter plate of claim 7, wherein the oxide material further comprises Al₂O₃.

10. The setter plate of claim 7, wherein the oxide material further comprises ZrO₂.

11. The setter plate of claim 7, wherein the oxide material further comprises La₂O₃.

12. The setter plate of claim 7, wherein the oxide material comprises LiAlO₂.

13. The setter plate of claim 7, wherein the oxide material comprises Li₂O.

14. The setter plate of claim 7, wherein the oxide material comprises Li₃PO₄.

15. The setter plate of claim 7, wherein the oxide material comprises at least two members selected from the group consisting of LiLaO₂, LiAlO₂, Li₂O, Li₃PO₄, a Li-stuffed garnet compound characterized by the formula Li_xLa_yZr_zO_t.qAl₂O₃, wherein 4<

x<

10, 1<

y<

4, 1<

z<

3, 6<

t<

14, 0<

q<

1, and a combination thereof.

17. The setter plate of claim 7, wherein the setter plate comprises a Li-stuffed garnet compound characterized by the formula Li_ALa_BM′

_cM″

_DZr_EO_F, wherein 4<

A<

8.5, 1.5<

B<

4, 0≤

C≤

2, 0≤

D≤

2;

0≤

E<

2, 10<

F<

13, and M′ and

M″

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