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

• US 9,806,372 B2
• Filed: 11/03/2014
• Issued: 10/31/2017
• 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): SMITH, JEREMIAH R
• Application Number:
  US14/531,929
• Publication Number:
  US 20150200420A1
• Time in Patent Office: 1,093 Days
• 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 thin and free standing sintered garnet film, wherein the film thickness is less than 50 μ

m and greater than 10 nm, wherein the film comprises a garnet characterized by the formula Li_xLa₃Zr₂O₁₂•

yAl₂O₃, wherein x ranges from 5.5 to 9, and y ranges from 0.05 to 1.0, and wherein the film is not adhered or fixed to a substrate.

2. The film of claim 1, wherein the film has a surface roughness of less than 5 μ

m.

3. The film of claim 1, wherein the garnet has a median grain size of between 0.1 μ

m and 10 μ

m.

4. The film of claim 1, wherein the film has an area specific resistance (ASR) of less than 10 Ω

cm².

5. The film of claim 1, wherein the film has an area specific resistance (ASR) of less than 10 Ω

cm² at 80°

C.

6. The film of claim 1, wherein the carbon content is less than 5 atomic %.

7. The film of claim 1, wherein the molar ratio of Al₂O₃:

Li_xLa₃Zr₂O₁₂, is 0.35, 0.5, 0.67 or 1.0.

8. The film of claim 1, wherein the film thickness is about 49 μ

m.