Template electrode structures for depositing active materials

• US 9,172,094 B2
• Filed: 06/10/2013
• Issued: 10/27/2015
• 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): DOUYETTE, KENNETH J
• Application Number:
  US13/914,491
• Publication Number:
  US 20130344383A1
• Time in Patent Office: 869 Days
• Field of Search: 429/211, 429/218.1, 429/223, 429/220, 429/219, 429/231.5, 429/229, 429/221, 252/182.1
• 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 4/136 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, the nanostructured template comprising nanowires rooted to a substrate, the nanowires comprising substrate-rooted ends and free-ends; and

non-silicide, electrochemically active material shells coating the nanowires, the non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500mAh/g, wherein the shells are disjoined at the substrate.

2. The electrochemically active electrode material of claim 1, wherein the shells are at least twice as thick at the free-ends of the nanowires as they are at the substrate-rooted ends.

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

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, silicon oxides, silicon oxy-nitrides, tin-containing material, and germanium-containing material.

5. The electrochemically active electrode material of claim 1, wherein the shells comprise porous silicon.

6. The electrochemically active electrode material of claim 1, further comprising a dopant in the non-silicide electrochemically active material.

7. 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, the nanostructured template comprising nanowires rooted to a substrate, the nanowires comprising substrate-rooted ends and free-ends; and

non-silicide, electrochemically active material shells coating the nanowires, the non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500mAh/g, wherein the shells are at least twice as thick at the free-ends of the nanowires as they are at the substrate-rooted ends, wherein the thickness of the shells increases continuously from the substrate rooted ends to the free ends of the nanowires.

8. The electrochemically active electrode material of claim 7, wherein the thickness of the shells increases abruptly from the substrate rooted ends to the free ends of the nanowires.

9. The electrochemically active electrode material of claim 7, further comprising a dopant in the non-silicide electrochemically active material.

10. The electrochemically active electrode material of claim 9, wherein the dopant is selected from the group consisting of boron, aluminum, gallium, indium, thallium, phosphorous, arsenic, antimony, bismuth, sulfur, and selenium.

11. The electrochemically active electrode material of claim 7, wherein the thickness of the shells increases gradually from the substrate rooted ends to the free ends of the nanowires.

12. The electrochemically active electrode material of claim 7, wherein the metal silicide is selected from a group consisting of nickel silicide, cobalt silicide, copper silicide, silver silicide, chromium silicide, titanium silicide, aluminum silicide, zinc silicide, and iron silicide.

13. The electrochemically active electrode material of claim 7, wherein the electrochemically active material is selected from the group consisting of crystalline silicon, amorphous silicon, silicon oxides, silicon oxy-nitrides, tin-containing material, and germanium-containing material.

14. The electrochemically active electrode material of claim 7, wherein the shells comprise porous silicon.

15. The electrochemically active electrode material of claim 7, wherein the nanowires are uncoated with electrochemically active material at or near their interfaces with the substrate.

16. The electrochemically active electrode material of claim 7, wherein the nanowires are coated with electrochemically active material at their interfaces with the substrate.

17. 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, the nanostructured template comprising nanowires rooted to a substrate, the nanowires comprising substrate-rooted ends and free-ends; and

non-silicide, electrochemically active material shells coating the nanowires, the non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500 mAh/gu, wherein the shells are at least twice as thick at the free-ends of the nanowires as they are at the substrate-rooted ends, wherein the thickness of the shells increases, not continuously, from the substrate rooted ends to the free ends of the nanowires.

18. The electrochemically active electrode material of claim 17, wherein the thickness of the shells increases abruptly from the substrate rooted ends to the free ends of the nanowires.

19. The electrochemically active electrode material of claim 18, wherein the shells comprise porous silicon.

20. The electrochemically active electrode material of claim 17, wherein the nanowires are uncoated with electrochemically active material at or near their interfaces with the substrate.

21. The electrochemically active electrode material of claim 17, wherein the thickness of the shells increases gradually from the substrate rooted ends to the free ends of the nanowires.

22. The electrochemically active electrode material of claim 17, wherein the nanowires are coated with electrochemically active material at their interfaces with the substrate.

23. The electrochemically active electrode material of claim 17, wherein the metal silicide is selected from a group consisting of nickel silicide, cobalt silicide, copper silicide, silver silicide, chromium silicide, titanium silicide, aluminum silicide, zinc silicide, and iron silicide.

24. The electrochemically active electrode material of claim 17, wherein the electrochemically active material is selected from the group consisting of crystalline silicon, amorphous silicon, silicon oxides, silicon oxy-nitrides, tin-containing material, and germanium-containing material.

25. The electrochemically active electrode material of claim 17, wherein the shells comprise porous silicon.

26. The electrochemically active electrode material of claim 17, further comprising a dopant in the non-silicide electrochemically active material.

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

a current collector substrate;

a nanostructured template comprising a metal silicide, the nanostructured template comprising nanowires rooted to the current collector substrate, the nanowires comprising substrate-rooted ends and free-ends; and

non-silicide, electrochemically active material shells coating the nanowires, the non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500mAh/g, wherein the shells are at least twice as thick at the free-ends of the nanowires as they are at the substrate-rooted ends, wherein the thickness of the shells increases continuously from the substrate rooted ends to the free ends of the nanowires.

28. A lithium ion cell comprising:

a current collector substrate;

a nanostructured template comprising a metal silicide, the nanostructured template comprising nanowires rooted to the current collector substrate, the nanowires comprising substrate-rooted ends and free-ends; and

non-silicide, electrochemically active material shells coating the nanowires, the non-silicide electrochemically active material having a theoretical lithiation capacity of at least about 500 mAh/g, wherein the shells are at least twice as thick at the free-ends of the nanowires as they are at the substrate-rooted ends, wherein the thickness of the shells increases continuously from the substrate rooted ends to the free ends of the nanowires.