Method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries

• US 9,184,438 B2
• Filed: 10/02/2009
• Issued: 11/10/2015
• Est. Priority Date: 10/10/2008
• Status: Expired due to Fees

• Current Assignee: Nexeon Limited
• Original Assignee: Nexeon Limited
• Inventors: Green, Mino, Liu, Feng-Ming
• Primary Examiner(s): Ahmed, Shamim
• Application Number:
  US13/123,356
• Publication Number:
  US 20110269019A1
• Time in Patent Office: 2,230 Days
• Field of Search: 216/99, 216/104, 216/106, 438/753
• US Class Current: 1/1
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/049 Manufacturing of an active layer by chemical means
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/362 Composites
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A process for etching silicon to form silicon pillars on the etched surfaces, includes treating silicon with an etching solution that includes 5 to 10M HF 0.01 to 0.1M Ag⁺ ions and 0.02 to 0.2M NO₃⁻ ions. Further, NO₃⁻ ions in the form of alkali metal, nitric acid or ammonium nitrate salt is added to maintain the concentration of nitrate ions within the above range. The etched silicon is separated from the solution. The process provides pillars, especially for use as the active anode material in lithium ion batteries. The process is advantageous because it uses an etching bath containing only a small number of ingredients whose concentration needs to be controlled and it can be less expensive to operate than previous processes.

Claims

1. A process of etching silicon to form silicon structures on the etched surfaces, the process comprising:

treating silicon with an initial etching solution comprising;

5 to 10M HF,

0.01 to 0.1 M Ag⁺ ions,

a concentration within a range of 0.02 to 0.2M NO₃⁻

ions, and

subsequently adding further NO₃⁻

ions in the form of an alkali metal nitrate or ammonium nitrate salt, or in the form of nitric acid, to maintain the concentration of NO₃⁻

ions within the range specified for the initial etching solution; and

separating the etched silicon from the solution.

2. The process of claim 1, wherein the further NO₃⁻

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

3. The process of claim 1, wherein the solution contains less than 0.05% by weight of iron ions, wherein said iron ions are ferric or ferrous.

4. The process of claim 1, wherein the solution contains less than 0.5% by volume of an alcohol.

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

5 to 10 M 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 or ammonium ions, and

incidental additions and impurities.

6. The process of claim 1, which is conducted in a single bath.

7. The process of claim 1, wherein the solution used initially has a concentration of HF of 6.5 to 9M.

8. The process of claim 1, further including a step of adjusting the composition by adding a base or nitric acid.

9. The process of claim 1, wherein the silicon that is treated with said etching solution is in the form of granules or bulk material.

10. The process of claim 1, wherein the silicon has a purity of 90.00% or over by mass.

11. The process of claim 1, wherein the silicon is in granular form.

12. The process of claim 11, wherein the granules have a particle size in the range of 5 to 500 μ

m to produce silicon particles having structures formed on their surfaces, the structures having a height in the range of 1 to 100 μ

m.

13. The process of claim 1 wherein the structures have a diameter at their bases in the range of 0.08 to 0.70 μ

m.

14. The process of claim 1, which includes the step of detaching the structures from the underlying silicon to form silicon fibres.

15. The process of claim 8, wherein the base is selected from the group consisting of NaOH and NH₄OH.