Method of making silicon anode material for rechargeable cells

• US 8,962,183 B2
• Filed: 05/07/2010
• Issued: 02/24/2015
• Est. Priority Date: 05/07/2009
• Status: Active Grant

• Current Assignee: Nexeon Limited
• Original Assignee: Nexeon Limited
• Inventors: Rayner, Philip John
• Primary Examiner(s): SIDDIQUEE, MUHAMMAD S
• Application Number:
  US13/266,683
• Publication Number:
  US 20120129049A1
• Time in Patent Office: 1,754 Days
• Field of Search: 429/218.1, 429/226, 216/13
• US Class Current: 429/218.1
• CPC Class Codes: C22C 21/02 with silicon as the next major constituent
• CPC Class Codes: C22C 21/04 Modified aluminium-silicon alloys
• 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 4/0492 Chemical attack of the support material
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• 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 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10T 428/24149 Honeycomb-like
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

A method of forming a silicon anode material for rechargeable cells includes providing a metal matrix that includes no more than 30 wt % of silicon, including silicon structures dispersed therein. The metal matrix is at least partially etched to at least partially isolate the silicon structures.

Claims

1. A method of forming a silicon anode material for a rechargeable cell, which method comprises:

providing a metal-silicon alloy comprising a metal matrix and silicon structures dispersed in the metal matrix, the metal-silicon alloy including no more than 30 wt % silicon,

at least partially etching the metal matrix to release particulate silicon structures from the metal matrix, and

collecting the particulate silicon structures to provide the silicon anode material.

2. A method according to claim 1 wherein the metal matrix including silicon structures dispersed therein is made by a process comprising solidifying a molten metal-silicon alloy.

3. A method according to claim 1, wherein the metal-silicon alloy comprises 7-25 wt % silicon.

4. A method according to claim 1 wherein the metal is aluminium or an aluminium alloy containing at least 50 wt % aluminium.

5. A method according to claim 4 wherein the etching is performed chemically or electrochemically using an etchant comprising one or more acids, one or more alkali, or using an ionic solution optionally in combination with at least one alkali.

6. A method according to claim 1, wherein the particulate silicon structures comprise crystalline silicon.

7. A method according to claim 1, wherein the particulate silicon structures comprise structural elements and at least 80% of the structural elements have a size and shape such that they have an aspect ratio of at least 5, and a minor dimension (i.e. the smallest dimension of the structural element) of 0.1-2 μ

m and a major dimension (i.e. the largest dimension of the structural element) of at least 5 μ

m.

8. A method according to claim 7 wherein the metal-silicon alloy is made by a process comprising cooling step and wherein the cooling step is controlled so that the matrix is cooled at a predetermined rate in order to provide silicon structures having the said size and shape.

9. A method according to claim 7 wherein the metal matrix also includes one or more modifiers selected from Sb, Cu, Mg, Zn, Mn, Cr, Co, Mo, Ni, Be, Zr, Fe, Na, Sr, and P, to provide structural elements having the said size and shape.

10. A method according to claim 7 which comprises the step of tempering the metal-silicon alloy prior to etching to provide structural elements having the said size and shape.

11. The method of claim 1 wherein the released particulate silicon structures are porous.

12. The method of claim 1 wherein the released particulate silicon structures include residual metal from the metal matrix.

19. The method of claim 11, wherein the porous particulate silicon structures comprise a plurality of interconnected structural elements.

20. The method of claim 19, wherein at least 80% of the structural elements have a size and shape such that they have an aspect ratio of at least 5, and a minor dimension (i.e. the smallest dimension of the structural element) of 0.1-2 μ

m and a major dimension (i.e. the largest dimension of the structural element) of at least 5 μ

m.

23. The method of claim 19, wherein the metal matrix is substantially etched away.

13. A method of forming a silicon anode material for rechargeable cells, which method comprises:

providing particles comprising a metal-silicon alloy comprising a metal matrix and silicon structures dispersed in the metal matrix, the metal-silicon alloy including no more than 30 wt % silicon, and

at least partially etching the metal matrix of the metal-silicon alloy of the particles to form porous silicon particles by removal of metal from the metal-silicon alloy, the porous silicon particles comprising a plurality of interconnected structural elements.

14. The method of claim 13 wherein the interconnected structural elements of the porous silicon particles have aspect ratios of at least five.

15. The method of claim 13 wherein the porous silicon particles include residual metal from the metal matrix.

22. The method of claim 13, wherein at least 80% of the structural elements have a size and shape such that they have an aspect ratio of at least 5, and a minor dimension (i.e. the smallest dimension of the structural element) of 0.1-2 μ

m and a major dimension (i.e. the largest dimension of the structural element) of at least 5 μ

m.

25. The method of claim 13, wherein the metal matrix is substantially etched away.

27. The method of claim 13, wherein the metal matrix is aluminium or an aluminium alloy containing at least 50 wt % aluminium.

29. The method of claim 13, further comprising collecting the porous silicon structure to provide the silicon anode material.

30. The method of claim 14, wherein the metal matrix also includes one or more modifiers selected from Sb, Cu, Mg, Zn, Mn, Cr, Co, Mo, Ni, Be, Zr, Fe, Na, Sr, and P, to provide structural elements having the said aspect ratio.

16. A method of forming a silicon anode material for rechargeable cells, which method comprises:

providing a metal-silicon alloy comprising a metal matrix and silicon structures dispersed in the metal matrix, the metal-silicon alloy including no more than 30 wt % silicon, and

at least partially etching the metal matrix of the metal-silicon alloy to form a porous silicon structure by removal of metal from the metal-silicon alloy, the porous silicon structure comprising a plurality of interconnected structural elements.

17. The method of claim 16 wherein the interconnected structural elements of the porous silicon structure have aspect ratio of at least five.

18. The method of claim 16 wherein the porous structure includes residual metal from the metal matrix.

21. The method of claim 16, wherein at least 80% of the structural elements have a size and shape such that they have an aspect ratio of at least 5, and a minor dimension (i.e. the smallest dimension of the structural element) of 0.1-2 μ

m and a major dimension (i.e. the largest dimension of the structural element) of at least 5 μ

m.

24. The method of claim 16, wherein the metal matrix is substantially etched away.

26. The method of claim 16, wherein the metal matrix is aluminium or an aluminium alloy containing at least 50 wt % aluminium.

28. The method of claim 16, further comprising collecting the porous silicon particles to provide the silicon anode material.

31. The method of claim 17, wherein the metal matrix also includes one or more modifiers selected from Sb, Cu, Mg, Zn, Mn, Cr, Co, Mo, Ni, Be, Zr, Fe, Na, Sr, and P, to provide structural elements having the said aspect ratio.