Multidimensional electrochemically active structures for battery electrodes

• US 9,172,088 B2
• Filed: 05/24/2011
• Issued: 10/27/2015
• Est. Priority Date: 05/24/2010
• Status: Active Grant

• Current Assignee: Amprius Technologies Incorporated (Amprius, Inc.)
• Original Assignee: Amprius, Inc.
• Inventors: Loveness, Ghyrn E., Stefan, Constantin I., Han, Song
• Primary Examiner(s): DOUYETTE, KENNETH J
• Application Number:
  US13/114,413
• Publication Number:
  US 20110287318A1
• Time in Patent Office: 1,617 Days
• Field of Search: 429/218.1, 429/209, 429/231.8, 429/231.95, 427/77, 427/58, 427/528
• US Class Current: 1/1
• 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 4/0428 Chemical vapour deposition
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/66 Selection of materials
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 4/70 characterised by shape or form
• CPC Class Codes: H01M 4/75 Wires, rods or strips
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

Provided are novel multidimensional electrode structures containing high capacity active materials for use in rechargeable electrochemical cells. These structures include main support structures and multiple nanowires attached to the support structures and extending into different directions away from these supports. The active material may be deposited as a layer (uniform or non-uniform) surrounding the nanowires and, in certain embodiments, the main supports and even substrate. The active material layer may be sufficiently thin to prevent pulverization of the layer at given operating conditions. Interconnections between the electrode structures and/or substrate may be provided by overlaps formed during deposition of the active layer. Silicide-based nano wires structures may be formed on the main supports in a fluidized bed reactor by suspending the metal-containing main supports in a silicon-containing process gas. A layer of silicon may be then deposited over these silicide nanowires.

Claims

1. A battery electrode structure for use in a battery, the battery electrode structure comprising:

a conductive substrate; and

a plurality of multidimensional electrochemically active structures attached to and in electronic communication with the conductive substrate, wherein each of the multidimensional electrochemically active structures comprises;

a support comprising metal;

nanowires comprising support-rooted ends attached to the support and free ends extending in different directions away from the support, the nanowires comprising metal silicide of the metal; and

a layer coating the nanowires, the layer comprising an electrochemically active material for inserting and releasing electrochemically active ions during cycling of the battery.

2. The battery electrode structure of claim 1, wherein the metal silicide is selected from the group consisting of nickel silicide, cobalt silicide, copper silicide, silver silicide, chromium silicide, titanium silicide, aluminum silicide, zinc silicide, and iron silicide.

3. The battery electrode structure of claim 1, wherein the metal silicide comprises at least two different nickel silicide phases selected from the group consisting of Ni₂Si, NiSi, and NiSi₂.

4. The battery electrode structure of claim 1, wherein the electrochemically active material is selected from the group consisting of crystalline silicon, amorphous silicon, a silicon oxide, a silicon oxy-nitride, a tin containing material, a germanium containing material, and a carbon containing material.

5. The battery electrode structure of claim 1, wherein the nanowires are between about 1 micrometer and 200 micrometers in length on average.

6. The battery electrode structure of claim 1, wherein the nanowires are less than about 100 nanometers in diameter on average.

7. The battery electrode structure of claim 1, wherein the layer of the electrochemically active material is at least about 100 nanometers in thickness on average.

8. The battery electrode structure of claim 1, wherein a volume ratio of the electrochemically active material to the metal silicide is at least about 5.

9. The battery electrode structure of claim 1, wherein, prior to cycling of the battery, the electrochemically active material is doped with one or more materials selected from the group consisting of:

phosphorous, boron, gallium, and lithium.

10. The battery electrode structure of claim 1, further comprising a shell formed over the layer of the electrochemically active material, the shell comprising one or more materials selected from the group consisting of carbon, copper, fluorine, a polymer, a sulfide, Lithium Phosphorous Oxynitride (LIPON), and a metal oxide.

11. The battery electrode structure of claim 1, further comprising a substrate layer formed over the conductive substrate and comprising the electrochemically active material, the substrate layer forming joint structures with the layer coating the nanowires, the joint structures provide attachment to some of the plurality of multidimensional electrochemically active structures to the conductive substrate and electronic communication with the conductive substrate.

12. The battery electrode structure of claim 1, wherein portions of the layer of the electrochemical active materials coating the nanowires form joint structures with each other.

13. The battery electrode structure of claim 1, further comprising a polymeric binder attaching the plurality of multidimensional electrochemically active structures to the conductive substrate.

14. The battery electrode structure of claim 1, wherein the battery is a lithium ion battery.

15. The battery electrode structure of claim 1, wherein the electrochemically active material has a theoretical lithiation capacity of at least about 800 mAh/g.

16. The battery electrode structure of claim 1, further comprising a nanostructure template including template nanowires rooted to the substrate, wherein the layer of the electrochemically active material coats the template nanowires and the template nanowires provide attachment and electronic communication to the plurality of multidimensional electrochemically active structures with respect to the conductive substrate.

17. The battery electrode structure of claim 1, wherein the layer of the electrochemically active material is at least twice as thick at the free ends of the nanowires than at the support-rooted ends.

18. The battery electrode structure of claim 1, wherein the layer of the electrochemically active material comprises amorphous silicon and germanium, and wherein the layer has more silicon and less germanium at the free ends of the nanowires than at the support-rooted ends.

19. The battery electrode structure of claim 1, further comprising an intermediate sub-layer positioned between the nanowires and the layer of the electrochemically active material and configured to improve metallurgical attachment and electronic conductivity between the nanowires and the layer of the electrochemically active material.

20. The battery electrode structure of claim 1, further comprising an intermediate sub-layer positioned between the nanowires and the layer of the electrochemically active material and configured to provide an elastic interface between the nanowires and the layer of the electrochemically active material.

21. The battery electrode structure of claim 1, further comprising a base sub-layer adjacent to the substrate, the base sub-layer being substantially free of the metal of the metal silicide.

22. The battery electrode structure of claim 1, wherein the conductive substrate comprises one or more material selected from the group consisting of copper, nickel, titanium, and stainless steel.

23. The battery electrode structure of claim 1, wherein the battery electrode structure is a part of a negative electrode.

24. The battery electrode structure of claim 1, wherein the battery electrode structure is a part of a positive electrode.

26. The battery electrode structure of claim 1, further comprising an intermediate sublayer positioned between the nanowires and the layer of the electrochemically active material.

27. The battery electrode structure of claim 26, wherein the intermediate sub-layer comprises a metal alloy.

28. The battery electrode structure of claim 26, wherein the intermediate sub-layer comprises one or more of titanium, copper, nickel, aluminum, zinc, and alloys thereof.

25. A lithium ion cell comprising:

a conductive substrate; and

a plurality of multidimensional electrochemically active structures attached to and in electronic communication with the conductive substrate, wherein each of the multidimensional electrochemically active structures comprises;

a support comprising metal;

nanowires comprising support-rooted ends attached to the support and free-ends extending in different directions away from the support, the nanowires comprising a material selected from the group consisting of metal silicide of the metal, carbon nanotubes, and combinations thereof; and

a layer coating the nanowires, the layer comprising an electrochemically active material for inserting and releasing electrochemically active ions during cycling of the lithium ion cell.

29. A method of fabricating multidimensional electrochemically active structures, the method comprising:

receiving supports comprising metal;

forming nanowires comprising support-rooted ends attached to the supports and free-ends extending into different directions away from the supports, the nanowires comprising metal silicide of the metal; and

forming a layer coating the nanowires, the layer comprising an electrochemically active material for inserting and releasing electrochemically active ions during cycling of the electrochemically active material.

30. The method of claim 29, wherein the supports have one or more shapes selected from the group consisting of particles, rods, and flakes.