Thermally protective salt material for thermal spraying of electrode materials

• US 6,794,086 B2
• Filed: 02/28/2001
• Issued: 09/21/2004
• Est. Priority Date: 02/28/2000
• Status: Expired due to Fees

• Current Assignee: National Technology & Engineering Solutions Of Sandia LLC (Honeywell International Inc.), US Nanocorp, Inc. (The Nano Group, Inc.)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation), US Nanocorp, Inc. (The Nano Group, Inc.)
• Inventors: Dai, Jinxiang, Guidotti, Ronald A., Xiao, Tongsan D., Reisner, David E.
• Primary Examiner(s): Yuan, Dah-Wei
• Application Number:
  US09/795,696
• Publication Number:
  US 20020018929A1
• Time in Patent Office: 1,301 Days
• Field of Search: 429/209, 429/218.6, 429/231.9, 429/231.95
• US Class Current: 429/231.95
• CPC Class Codes: C23C 4/04 characterised by the coating material
• CPC Class Codes: C23C 4/11 Oxides
• CPC Class Codes: H01M 4/08 Processes of manufacture
• CPC Class Codes: H01M 6/36 containing electrolyte and made operational by physical means, e.g. thermal cells

Abstract

A method for the manufacture of an electrode for an energy storage or conversion device comprises thermally spraying a feedstock mixture comprising an effective quantity of a source of a thermally protective salt and an active material or active material precursor onto a substrate to produce a film of the active material and salt. The film can have a thickness of about 1 to about 1000 microns.

In a particularly advantageous feature, the active materials which ordinarily decompose or are unavailable at the high temperatures used during thermal spray processes, such as metal chalcogenides such as pyrite, CoS₂, WS₂, Ni(OH)₂, MnO₂, and the like may be thermally sprayed to form an electrode when the feedstock mixture employs an effective amount of a source of the thermally protective salt coating. The active material feedstock may comprise microstructured or nanostructured materials, which after thermal spray results in electrodes having microstructured or nanostructured active materials, respectively.

Claims

1. A method for the manufacture of an electrode for an energy storage and conversion device, comprising

thermally spraying a feedstock mixture comprising an effective quantity of a source of a thermally protective salt and an active material or active material precursor onto a substrate to produce a film of the active material and salt wherein the film has a thickness of about 1 to about 1000 microns wherein the source of the thermally protective salt is a LiCl—

KCl eutectic, LiBr—

KBr—

LiF, LiCl—

LiBr—

LiF, a carbonate-based system with a melting point below about 500°

C., or a sulfate-based system with a melting point below about 500°

C.

2. The method of claim 1, wherein the source of the thermally protective salt is LiCl—

KCl eutectic.

3. The method of claim 1, wherein the active material film comprises a metal chalcenogide.

4. The method of claim 3, wherein the active material film comprises a metal sulfide.

5. The method of claim 3, wherein the active material film comprises FeS₂.

6. The method of claim 3, wherein the active material film comprises FeS₂, CoS₂, WS₂, Ni(OH)₂, or MnO₂.

7. The method of claim 1, wherein thermal spraying is by DC arc plasma spray.

8. The method of claim 1, wherein the films thickness is about 1 to about 200 microns.

9. The method of claim 1, wherein the film thickness is about 5 to about 114 microns.

10. The method of claim 1, wherein the active material film is nanostructured.

11. The method of claim 1 further comprising removing the thermally protective salt from the film by leaching with a solvent.

12. The method of claim 1 wherein the feedstock mixture further comprises Li₂O.

13. The method of claim 1 further comprising adding Li₂O to the film of active material after thermally spraying the feedstock mixture.

14. A method for the manufacture of an electrode for an energy storage and conversion device, comprising

ball-milling an active material comprising a metal chalcenogide or metal chalcenogide precursor with about 10% to about 30% by weight based on the total weight of the composition of a source of a thermally protective salt, to provide a feedstock for thermal spray;

and

thermally spraying the feedstock for thermal spray onto a substrate, to produce an active material film wherein the source of the thermally protective salt is a LiCl—

KCl eutectic, LiBr—

KBr—

LiF, LiCl—

LiBr—

LiF, a carbonate-based system with a melting point below about 500°

C., or a sulfate-based system with a melting point below about 500°

C.

15. The method of claim 14, wherein the source of the thermally protective salt is LiCl—

KCl eutectic.

16. The method of claim 14, wherein the thermally protective salt coats particles of the active material prior thermally spray.

17. The method of claim 16, wherein the active material film comprises a metal sulfide.

18. The method of claim 16, wherein the active material film comprises FeS₂.

19. The method of claim 16, wherein the active material film comprises FeS₂, CoS₂, WS₂, Ni(OH)₂, or MnO₂.

20. The method of claim 14, wherein thermal spraying is by DC arc plasma spray.

21. The method of claim 14, wherein the film has a thickness of about 1 to about 200 microns.

22. The method of claim 14, wherein the film has a thickness of about 5 to about 114 microns.

23. The method of claim 14, wherein the active material film is nanostructured.

24. The method of claim 14, further comprising removing the thermally protective salt from the film by leaching with a solvent.

25. The method of claim 14 wherein the feedstock further comprises Li₂O.

26. A electrode for an energy storage and conversion device, comprising

a substrate;

and

a layer of active material comprising a thermally protective salt deposited on the substrate, the layer having a thickness of about 1 to about 200 microns wherein the active material is unsuitable without the thermally protective salt for use in an electrode at thermal spray temperatures further wherein the thermally protective salt is derived from a source of a thermally protective salt which a LiCl—

KCl eutectic, LiBr—

KBr—

LiF, LiCl—

LiBr—

LiF, a carbonate-based system with a melting point below about 500°

C., or a sulfate-based system with a melting point below about 500°

C.

27. The electrode of claim 26, wherein the layer of active material has a thickness of about 5 to about 114 microns.

28. The electrode of claim 26, wherein the layer of active material has a thickness of about 5 to about 114 microns.

29. The electrode of claim 26, wherein the layer of active material comprises FeS₂, CoS₂, WS₂, Ni(OH)₂, or MnO₂.

30. The electrode of claim 29, wherein the layer of active material comprises FeS₂.

31. A method for the manufacture of an electrode, comprising

providing a feedstock comprising pyrite and an effective quantity of a source of a thermally protective salt;

and

thermally spraying the feedstock onto a substrate, to produce a film of salt coated pyrite active material having a thickness of about 1 to about 1000 microns wherein the source of the thermally protective salt is a LiCl—

KCl eutectic, LiBr—

KBr—

LiF, LiCl—

LiBr—

LiF, a carbonate-based system with a melting point below about 500°

C., or a sulfate-based system with a melting point below about 500°

C.

32. The method of claim 31, wherein thermal spraying is by DC arc plasma spray.

33. The method of claim 31, wherein the film has a thickness of about 1 to about 200 microns.

34. The method claim 31, wherein the film has a thickness of about 5 to about 114 microns.

35. A method for the manufacture of a cathode, comprising

ball-milling pyrite with about 10% to about 30% by weight based on the total weight of the composition of a source of a thermally protective salt to provide a feedstock comprising a source of a thermally protective salt coating and pyrite;

and

thermally spraying the feedstock solution onto a substrate to produce a film of salt coated pyrite active material having a thickness of about 1 to about 200 microns wherein the source of the thermally protective salt is a LiCl—

KCl eutectic, LiBr—

KBr—

LiF, LiCl—

LiBr—

LiF, a carbonate-based system with a melting point below about 500°

C., or a sulfate-based system with a melting point below about 500°

C.

36. The method of claim 35, wherein thermal spraying is by DC arc plasma spray.

37. The method of claim 35, wherein the films have a thickness of about 5 to about 114 microns.