Thin film lithium conducting powder material deposition from flux

• US 9,362,546 B1
• Filed: 01/03/2014
• Issued: 06/07/2016
• Est. Priority Date: 01/07/2013
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Donnelly, Niall, Holme, Tim
• Primary Examiner(s): Murata, Austin
• Application Number:
  US14/146,728
• Time in Patent Office: 886 Days
• Field of Search: None
• US Class Current: 1/1
• 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 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C04B 2235/3203 Lithium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3227 Lanthanum oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/764 Garnet structure A3B2(CO4)3
• CPC Class Codes: C04B 2235/787 Oriented grains
• CPC Class Codes: C04B 35/00 Shaped ceramic products characterised by their composition porous ceramic products C04B38/00; ceramic articles characterised by particular shape, see the relevant classes, e.g. linings for casting ladles, tundishes, cups or the like B22D41/02; ceramic substrates for microelectronic semi-conductors H01L23/15; Ceramics compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides other than as macroscopic reinforcing agents C22C; shaping of ceramics B28B; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products chemical preparation of powders of inorganic compounds C01; infiltration of sintered ceramic preforms with molten metal C04B41/51
• CPC Class Codes: C04B 35/486 Fine ceramics
• CPC Class Codes: C04B 35/62218 obtaining ceramic films, e.g. by using temporary supports
• CPC Class Codes: C04B 35/62645 Thermal treatment of powders or mixtures thereof other than sintering
• CPC Class Codes: C04B 35/653 Processes involving a melting step
• 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 10/058 Construction or manufacture
• CPC Class Codes: H01M 4/0409 by a doctor blade method, slip-casting or roller coating
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

The present invention is directed to battery technologies and processing techniques thereof. In various embodiments, ceramic electrolyte powder material (or component thereof) is mixed with two or more flux to form a fluxed powder material. The fluxed powder material is shaped and heated again at a temperature less than 1100° C. to form a dense lithium conducting material. There are other variations and embodiments as well.

Claims

1. A method for making a material, the method comprising:

providing a lithium-ion conducting ceramic powder material at a first quantity, the lithium-ion conducting ceramic powder material being characterized by a first density, the lithium-ion conducting ceramic powder material being characterized by a median particle size of about 100 nm to 10 μ

m;

providing a first flux material at a second quantity, the second quantity being less than 51% of the first quantity, the first flux material comprising lithium-ion ceramic powder material, the first flux material being characterized by a melting temperature of about 500-1000°

C.;

providing a second flux material at a third quantity, the second flux material being characterized by a melting temperature of about 500-1000°

C.;

mixing at least the first flux material and the second flux material to form a eutectic mixture, the eutectic mixture being characterized by a melting point of less than 800°

C.;

subjecting the eutectic mixture to a temperature of about 100 to 1100°

C.;

mixing the eutectic mixture with the lithium-ion conducting ceramic powder material to form a fluxed ceramic powder material;

shaping the fluxed ceramic powder material into a predetermine shape;

heating the shaped fluxed ceramic powder material to a temperature of less than 1100°

C.; and

forming a dense lithium-ion conducting material, the dense lithium-ion conducting material being characterized by a second density, the second density is at least 20% higher than the first density;

wherein the lithium-ion conducting ceramic powder material comprises electrolyte component powders selected from one or more of metal oxides, nitrates, carbonates, sulfates, borates, or hydroxides; and

wherein the electrolyte component powders is characterized by a quantity less than the second quantity.

2. The method of claim 1 wherein the first flux material comprises inorganic salts of lithium-ion conducting material.

3. The method of claim 1 wherein the second density is at least 40% higher than the first density.

4. The method of claim 1 further comprising melting the lithium-ion conducting ceramic powder material by the eutectic mixture at a temperature of less than 800°

C.

5. The method of claim 1 further comprising dissolving the lithium-ion conducting ceramic powder material by the eutectic mixture at a temperature of less than 800°

C.

6. The method of claim 1 wherein the eutectic material comprises less than 80% of a total mass of the fluxed ceramic powder material.

7. The method of claim 1 wherein the predetermined shape is disc, sheet, cylinder, or pellet.

8. The method of claim 1 wherein the second quantity being about 15˜

30% of the first quantity.

9. The method of claim 1 wherein the first flux material comprises one or more materials selected from LiOH, LiCl, LiBr, LiNO₃, Li₃BO₃ or LiSO₄.

10. The method of claim 1 wherein the second flux material comprises one or more materials selected from NaOH, NaCl, NaNO₃, NaSO₄, NaBr, or Na₂CO₃.

11. The method of claim 1 wherein the eutectic mixture is characterized by a melting point of about 200 to 800°

C.

12. The method of claim 1 further comprising subjecting the flux material to a temperature of about 200 to 1000°

C.

13. The method of claim 1 wherein the lithium-ion conducting ceramic powder material being characterized by a median particle size of about 100 nm to 2 um.

14. The method of claim 1 wherein the lithium-ion conducting ceramic powder material comprises a garnet material.

15. The method of claim 1 wherein the lithium-ion conducting ceramic powder material comprises a perovskite material.

16. The method of claim 1 wherein the lithium-ion conducting ceramic powder material comprises Nasicon material, Lisicon material, and/or a Tungsten Bronze material.

17. The method of claim 1 further comprising providing a third flux material at a third quantity, the third flux material comprising KOH, KCl, KNO₃, KSO₄, KBr, and/or K₂CO.

18. The method of claim 1 further comprising removing the first flux material and the second flux material by subjecting the dense lithium-ion conducting material to one or more solvent washings, the one or more solvent comprising water, ethanol, isopropanol, acetone, acetonitrile, an acid, and/or a base.

19. The method of claim 1 wherein the dense lithium-ion conducting material is deposited on a metal conductive material.

20. The method of claim 1 further comprising:

providing a substrate material, the substrate material comprises a layer of metal conductive material, wherein the lithium-ion conducting ceramic powder material is provided on the layer of metal conductive material.

21. A method for depositing lithium garnet material, the method comprising:

providing components of lithium-ion conducting ceramic powder material at a first quantity, the components being characterized by a first density, the components being characterized by a median particle size of about 100 nm to 10 um;

providing a first flux material at a second quantity, the second quantity being more than 100% of the first quantity, the flux material comprising inorganic salts of lithium-ion conducting material, the first flux material being characterized by melting temperature of about 500-1000°

C.;

provide a second flux material at a third quantity, the second flux material being characterized by melting temperature of about 500-1000°

C.;

mixing the first flux material and the second flux material with the components to form the fluxed ceramic powder material;

shaping the fluxed ceramic powder material in to a predetermine shape;

heating the shaped fluxed ceramic powder material to a temperature of less than 1100°

C.; and

forming a dense lithium-ion conducting material, the dense lithium-ion conducting material being characterized by a second density, the second density is at least 20% higher than the first density.