Nanoporous Silicon Network Thin Films as Anodes for Lithium Ion Batteries

• US 20150140427A1
• Filed: 11/14/2014
• Published: 05/21/2015
• Est. Priority Date: 11/15/2013
• Status: Abandoned Application

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Zhang, Xiang, Zhu, Jia, Gladden, Christopher, Barth, David
• Application Number:
  US14/542,145
• Publication Number:
  US 20150140427A1
• Time in Patent Office: Days
• US Class Current: 429/218.1
• CPC Class Codes: C01B 33/02 Silicon forming single crystals or homogeneous polycrystalline material with defined structure C30B
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Various embodiments of the invention describe nanoporous silicon (Si) network thin films with controllable porosity and thickness that are fabricated by a robust and scalable electrochemical process, and then released from Si wafers and transferred to flexible and conductive substrates. These nanoporous Si network thin films serve as high performance Li-ion battery electrodes, with an initial discharge capacity of 2570 mA h g⁻¹, above 1000 mA h g⁻¹ after 200 cycles without any electrolyte additives.

Claims

1. A composition of matter comprising:

a nanoporous silicon (Si) network thin film.

2. The composition of claim 1, wherein a pore size of the thin film is approximately uniform.

3. The composition of claim 1, wherein the thin film comprises approximately 0.01-0.02 Ω

-cm p-type silicon.

4. The composition of claim 1, wherein the thin film comprises a boron impurity concentration of approximately 3×

10¹⁸-8×

10¹⁸ cm<sup>−

3</sup>.

5. The composition of claim 1, wherein the thin film comprises single crystalline silicon.

6. The composition of claim 1, wherein an average pore size is between 10 nm to 30 nm.

7. The composition of claim 6, wherein the average pore size is approximately 20 nm.

8. The composition of claim 1, wherein an average thin film thickness is approximately between 0.5 um-1.5 um.

9. The composition of claim 8, wherein the average thin film thickness is approximately 1 um.

10. The composition of claim 1, wherein an average porosity is approximately between 70% to 90%.

11. The composition of claim 10, wherein the average porosity is approximately 80%.

12. An electrode comprising:

a current collector; and

a nanoporous silicon (Si) network thin film in contact with the current collector.

13. A battery comprising:

an anode comprising a current collector and a nanoporous silicon (Si) network thin film in contact with the current collector; and

a cathode.

14. The battery of claim 13, wherein a specific capacity is approximately 2570 mAh/g.

15. The battery of claim 13, wherein a coulombic efficiency is approximately 96 to 99.9%.

16. The battery of claim 13, wherein a discharge capacity is approximately 1800 mAh/g.

17. A method of manufacturing a nanoporous silicon (Si) network thin film comprising:

providing a doped p-type silicon substrate;

providing a constant current power source in electrical contact with the doped p-type silicon substrate;

etching the doped p-type silicon substrate in a hydrofluoric (HF) acid and ethanol (EtOH) solution for a predetermined etching time period at a predetermined etching electrical current and voltage to produce the nanoporous Si network thin film; and

transferring the nanoporous Si network thin film to a receiver substrate.

18. The method of claim 17, further comprising providing a light illumination to control a porosity of the nanoporous Si network thin film.

19. The method of claim 18, wherein the porosity of the nanoporous Si network thin film is controlled by adjusting an etching current and a light illumination intensity.

20. The method of claim 19, wherein increasing an etching current uniformly increases the porosity, while increasing the light illumination intensity decreases the porosity of the nanoporous Si network.

21. The method of claim 17, further comprising rinsing the doped p-type silicon substrate with ethanol to remove residual HF, followed by submersion in hexane and air-drying.

22. The method of claim 17, further comprising providing an approximately 20:

1 ethanol;

HF solution and etching at an increased voltage for approximately between 2-10 minutes to undercut the nanoporous Si network thin film to and cause separation from the doped p-type silicon substrate.

23. The method of claim 22, further comprising etching at approximately 30 volts to undercut the nanoporous Si network thin film.

24. The method of claim 17, wherein the etching current is approximately between 280-600 mA/cm² and the etching time is approximately between 15-120 seconds.

25. The method of claim 17, wherein the hydrofluoric (HF) acid and ethanol (EtOH) solution is approximately 3:

1 HF;

EtOH.

26. The method of claim 17, wherein the doped p-type silicon substrate comprises a resistivity of approximately between 0.01-0.02 Ω

cm and a boron impurity concentration of approximately between 3×

10¹⁸-8×

10¹⁸ cm<sup>−

3</sup>.

27. The method of claim 17, wherein the constant current power source is in electrical contact with the doped p-type silicon substrate with a positive terminal connected to an electrode that contacts a backside of the doped p-type silicon substrate, and a negative terminal is connected to an electrode that is positioned approximately at a top portion of the solution.

28. The method of claim 27, wherein the positive terminal is connected to an aluminum foil electrode and the negative terminal is connected to a platinum ring electrode.