Method of fabricating structured particles composed of silicon or a silicon-based material

• US 8,932,759 B2
• Filed: 10/02/2009
• Issued: 01/13/2015
• Est. Priority Date: 10/10/2008
• Status: Active Grant

• Current Assignee: Nexeon Limited
• Original Assignee: Nexeon Limited
• Inventors: Green, Mino, Liu, Feng-Ming
• Primary Examiner(s): Ruddock, Ula C.
• Assistant Examiner(s): MARKS, JACOB B
• Application Number:
  US13/123,363
• Publication Number:
  US 20110250498A1
• Time in Patent Office: 1,929 Days
• Field of Search: 429/219
• US Class Current: 429/219
• CPC Class Codes: C09K 13/08 containing a fluorine compound
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 4/049 Manufacturing of an active layer by chemical means
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A process of etching silicon includes treating silicon, e.g. granules or bulk material, with an etching solution, including HF, Ag⁺ ions and nitrate ions thereby etching the silicon to form silicon having etched pillars on its surface, which silicon includes a surface deposit of silver. The etched silicon is then separated from the spent etching solution. The silver from the etched silicon is dissolved using nitric acid to form a solution containing Ag⁺ ions and nitrate ions. The solution containing Ag⁺ ions and nitrate ions is mixed with further HF to form a further etching solution. The further etching solution is used to treat further silicon. The pillars may be used as an anode material in a Li-ion battery.

Claims

1. A process of etching silicon, the process comprising:

treating silicon, e.g. granules or bulk material, with a solution comprising HF, Ag⁺ ions and nitrate ions,

forming silicon having etched structures on its surface, which silicon includes a surface deposit of silver,

separating the etched silicon from a spent etching solution,

dissolving the silver from the etched silicon using nitric acid to form a solution containing Ag⁺ ions and nitrate ions,

mixing the solution containing Ag⁺ ions and nitrate ions with further HF to form a further solution, and

using the further solution to treat further silicon.

2. The process of claim 1, wherein the further HF is composed of the spent etching solution and additional HF.

3. The process of claim 1, wherein the etched silicon separated from the spent etching solution is washed and drained prior to dissolving the silver from the etched silicon.

4. The process of claim 1, wherein the solution comprises:

5 to 10M HF

0.01 to 0.1 M Ag⁺ ions

0.02 to 0.2M NO₃⁻

ions.

5. The process of claim 1, wherein the silicon is granular silicon having a particle size in the range 5 to 500 μ

m.

6. The process of claim 1, which is conducted at a temperature of 0°

C. to 70°

C.

7. The process of claim 1, wherein further NO₃⁻

ions are added to the solution during at least one of the steps of treating and forming in one or several steps, e.g. further NO₃⁻

ions are added after about 35% to 65% of the overall process time.

8. The process of claim 7, wherein the further NO₃⁻

ions are added in the form of an alkali metal nitrate salt.

9. The process of claim 1, wherein the forming step is conducted for at least 10 mins.

10. The process of claim 1, wherein the solution has a concentration of HF of 6-9M.

11. The process of claim 1, wherein the concentration of Ag⁺ in the solution is in the range of 0.02M to 0.06M.

12. The process of claim 1, wherein NO₃⁻

is present in the solution in an amount of 0.04M to 0.08M.

13. The process of claim 1, which includes adjusting the composition of the further solution so that it has approximately the same composition of Ag⁺ ions, NO₃⁻

ions and HF as the first solution.

14. The process of claim 1, wherein the solution consists essentially of:

5 to 10M HF

0.01 to 0.1 M Ag⁺ ions

0.02 to 0.2M NO₃⁻

ions

water, hydrogen and hydroxyl ions

and optionally;

SiF₆²⁻

ions

alkali metal and/or ammonium ions, and

incidental additions and impurities.

15. The process of claim 1, wherein the spent etching solution from two or more processes is collected together and the resulting collected etched silicon is treated with nitric acid as a batch.

16. The process of claim 1, which includes the further step of detaching the structures from the resulting etched silicon to form silicon fibres by one or more of scraping, agitating (especially by ultrasonic vibration) or chemical etching.

17. Etched silicon structures obtained from the process of claim 1.

18. An electrode containing the structures of claim 17 as one of its active materials.

19. An electrochemical cell containing an electrode as claimed in claim 18.

20. A process of etching silicon to form silicon having etched structures on its surface, the process comprising:

(i) depositing silver onto silicon with a solution comprising HF, Ag+ ions and nitrate ions;

(ii) etching the silver deposited silicon to give etched silicon having a surface deposit of silver;

(iii) separating the etched silver deposited silicon from a spent etching solution;

(iv) removing the surface deposit of silver by treatment with nitric acid to form a solution containing Ag+ ions and nitrate ions;

(v) mixing the solution containing Ag+ ions and nitrate ions with further HF to form a further solution, and

(vi) using the further solution to treat further silicon.