Template electrode structures for depositing active materials

• US 8,257,866 B2
• Filed: 03/02/2011
• Issued: 09/04/2012
• Est. Priority Date: 05/07/2009
• Status: Active Grant

• Current Assignee: Amprius Technologies Incorporated (Amprius, Inc.)
• Original Assignee: Amprius, Inc.
• Inventors: Loveness, Ghyrn E., DelHagen, William S., Fasching, Rainer, Han, Song, Liu, Zuqin
• Primary Examiner(s): Crepeau, Jonathan
• Assistant Examiner(s): DOUYETTE, KENNETH J
• Application Number:
  US13/039,031
• Publication Number:
  US 20110159365A1
• Time in Patent Office: 552 Days
• Field of Search: 429/231.95, 429/209, 429/122, 429/212, 429/213, 429/233, 429/229, 429/231.3, 429/220, 429/221, 429/223
• US Class Current: 429/223
• 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 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• 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 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• 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 4/75 Wires, rods or strips
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

Provided are examples of electrochemically active electrode materials, electrodes using such materials, and methods of manufacturing such electrodes. Electrochemically active electrode materials may include a high surface area template containing a metal silicide and a layer of high capacity active material deposited over the template. The template may serve as a mechanical support for the active material and/or an electrical conductor between the active material and, for example, a substrate. Due to the high surface area of the template, even a thin layer of the active material can provide sufficient active material loading and corresponding battery capacity. As such, a thickness of the layer may be maintained below the fracture threshold of the active material used and preserve its structural integrity during battery cycling.

Claims

1. An electrochemically active electrode material for use in a lithium ion cell, the electrochemically active electrode material comprising:

a nanostructured template comprising a metal silicide; and

a layer of a non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500 mAh/g coating the nanostructured template, the electrochemically active material configured to take in and release lithium ions during cycling of the lithium ion cell,

wherein the nanostructured template facilitates conduction of electrical current to and from the electrochemically active material and provides support to the layer of the electrochemically active material.

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

3. The electrochemically active electrode material of claim 2, wherein the metal silicide comprises at least two different nickel silicide phases selected from the group consisting of Ni₂Si, NiSi, and NiSi₂.

4. The electrochemically active electrode material 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, and a germanium containing material.

5. The electrochemically active electrode material of claim 1, wherein the nanostructured template comprises silicide containing nanowires.

6. The electrochemically active electrode material of claim 5, wherein the silicide containing nanowires are between about 1 micrometer and 200 micrometers in length on average.

7. The electrochemically active electrode material of claim 5, wherein the silicide containing nanowires are less than about 100 nanometers in diameter on average.

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

9. The electrochemically active electrode material of claim 1, wherein a volume ratio of the active material to the template is at least about 5.

10. The electrochemically active electrode material of claim 1, wherein the layer of the electrochemically active material comprises amorphous silicon, the layer having a thickness of at least about 100 nanometers on average;

and wherein the nanostructured template comprises nickel silicide nanowires that are between about 10 micrometers and 50 micrometers in length on average and less than about 50 nanometers in diameter on average.

11. The electrochemically active electrode material of claim 1, wherein, prior to cycling the electrochemical active electrode material in the lithium ion cell, the layer of the electrochemically active material is doped with one or more of the following materials:

phosphorous, boron, gallium, and lithium.

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

13. The electrochemically active electrode material of claim 1, wherein the electrochemically active material has a theoretical lithiation capacity of at least about 1000 mAh/g.

14. The electrochemically active material of claim 1, wherein a mass ratio of the electrochemically active material to the metal silicide is at least about 5.

15. The electrochemically active material of claim 1, wherein a mass ratio of the electrochemically active material to the metal silicide is at least about 10.

16. A lithium ion electrode for use in a lithium ion cell, the lithium ion electrode comprising:

an electrochemically active electrode material comprising;

a nanostructured template comprising a metal silicide; and

a layer of a non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500 mAh/g coating the nanostructured template, the electrochemically active material configured to take in and release lithium ions during cycling of the lithium ion cell, wherein the nanostructured template facilitates conduction of electrical current to and from the electrochemically active material; and

a current collector substrate in electrical communication with the electrochemically active electrode material and comprising the metal of the metal silicide.

17. The lithium ion electrode of claim 16, wherein the nanostructured template comprises nanowires rooted to the substrate, the nanowires comprising free-ends and substrate-rooted ends.

18. The lithium ion electrode of claim 17, wherein the layer of the electrochemically active material is at least twice as thick at the free-ends of the nanowires than at the substrate-rooted ends.

19. The lithium ion electrode of claim 17, 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 substrate-rooted ends.

20. The lithium ion electrode of claim 16, further comprising an intermediate sub-layer positioned between the nanostructured template and the current collector substrate and configured to improve metallurgical attachment and electronic conductivity between the nanostructured template and the current collector substrate.

21. The lithium ion electrode of claim 16, further comprising an intermediate sub-layer positioned between the nanostructured template and the layer of the electrochemically active material and configured to improve metallurgical attachment and electronic conductivity between the nanostructured template and the layer of the electrochemically active material.

22. The lithium ion electrode of claim 16, further comprising an intermediate sub-layer positioned between the nanostructured template and the layer of the electrochemically active material and configured to provide an elastic interface between the nanostructured template and the layer of the electrochemically active material.

23. The lithium ion electrode of claim 16, wherein a ratio of a surface area of the nanostructured template to a surface area of the substrate is at least about 20.

24. The lithium ion electrode of claim 16, wherein the substrate comprises a base layer adjacent to the substrate, the base layer being substantially free of the metal of the metal silicide.

25. The lithium ion electrode of claim 16, wherein the substrate comprises one or more material selected from the group consisting of copper, nickel, titanium, and stainless steel.

26. The lithium ion electrode of claim 16, wherein the lithium ion electrode is a negative electrode.

27. The lithium ion electrode of claim 16, wherein the lithium ion electrode is a positive electrode.

28. A lithium ion cell comprising:

an electrochemically active electrode material comprising;

a nanostructured template comprising a metal silicide; and

a layer of non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500 mAh/g coating the nanostructured template, the electrochemically active material configured to take in and release lithium ions during cycling of the lithium ion cell, wherein the nanostructured template facilitates conduction of electrical current to and from the electrochemically active material; and

a current collector substrate in electrical communication with the electrochemically active electrode material and comprising the metal of the metal silicide.