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

• US 11,139,503 B2
• Filed: 06/20/2019
• Issued: 10/05/2021
• Est. Priority Date: 10/07/2013
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Battery Incorporated
• Inventors: Karpenko, Oleh, Donnelly, Niall, Holme, Tim, Hudson, Will, Iyer, Sriram, Choi, Dong Hee Anna, Singh, Mohit, Winoto, Adrian
• Primary Examiner(s): Slifka, Sarah A.
• Application Number:
  US16/447,886
• Publication Number:
  US 20190372158A1
• Time in Patent Office: 838 Days
• Field of Search: None
• 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

Set forth 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 set forth herein are lithium-stuffed garnet thin films having fine grains therein. Disclosed herein are novel and inventive 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 novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also set forth herein are methods for preparing novel structures, including 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, the methods set forth herein disclose novel 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 method for sintering a thin and free standing garnet film, comprising the following steps:

providing a green tape thin film by casting a garnet slurry;

wherein the slurry comprises a lithium-stuffed garnet and a binder; and

wherein the slurry further comprises at least one member selected from the group consisting of a solvent, a plasticizer, a surfactant, a dispersant, and combinations thereof;

sintering the green tape thin film between setter plates;

wherein at least one of the setter plates is a ceramic setter plate comprising a material having a lithium concentration that is at least 10 atomic percent of the material;

wherein the sintering is heat, spark plasma, or field assisted sintering;

wherein sintering optionally includes applying pressure to the film with the setter plates; and

wherein one of the setter plates comprises ZrO₂, SiO₂, Al₂O₃, LiAlO₂, LiLaO₂, lithium-stuffed garnet, or Li₂ZrO₃.

2. The method of claim 1, wherein the slurry comprises milled and calcined lithium-stuffed garnet.

3. The method of claim 1, wherein the solid loading of the green tape is at least 30% v/v.

4. The method of claim 1, wherein the solid loading of the green tape is at least 40% v/v.

5. The method of claim 1, wherein the solid loading of the green tape is at least 50% v/v.

6. The method of claim 1, wherein the solid loading of the green tape is at least 60% v/v.

7. The method of claim 1, wherein the solid loading of the green tape is at least 65% v/v.

8. The method of claim 1, wherein the film is sintered directly onto a metal.

9. The method of claim 8, wherein the metal is a metal powder or a metal foil.

10. The method of claim 9, wherein the metal is a metal powder between and in contact with one side of the green tape and one setter plate.

11. The method of claim 9, wherein the metal is a metal powder layer positioned between and in contact with two green tapes, and wherein the green tapes are between and in contact with the setter plates.

12. The method of claim 8, wherein the metal is Ni or Cu powder.

13. The method of claim 1, wherein a source of Li in addition to the setter plates is placed in proximity of the sintered film during sintering.

14. The method of claim 1, wherein one of the setter plates comprises lithium-stuffed garnet, and wherein the lithium-stuffed garnet is characterized by the empirical 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, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta.

15. The method of claim 1, wherein the pressure applied to the film with the setter plates is between 1 and 1000 PSI.

16. The method of claim 1, wherein the solvent is selected from ethanol, isopropanol, toluene, ethyl acetate, methyl acetate, acetone, acetonitrile, or combinations thereof.