Nanostructured battery active materials and methods of producing same

• US 10,243,207 B2
• Filed: 07/24/2012
• Issued: 03/26/2019
• Est. Priority Date: 07/26/2011
• Status: Active Grant

• Current Assignee: ONED Material Incorporated
• Original Assignee: OneD Material LLC
• Inventors: Cao, Wanqing, Robbins, Virginia, Zhu, Yimin
• Primary Examiner(s): Usyatinsky, Alexander
• Application Number:
  US14/234,565
• Publication Number:
  US 20150086871A1
• Time in Patent Office: 2,436 Days
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 37/0211 using a colloidal suspension
• CPC Class Codes: C01B 33/02 Silicon forming single crystals or homogeneous polycrystalline material with defined structure C30B
• CPC Class Codes: C01B 33/021 Preparation chemical coating from the vapour phase C23C16/00
• CPC Class Codes: C01B 33/029 by decomposition of monosilane
• CPC Class Codes: C01P 2004/16 Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C30B 11/12 Vaporous components, e.g. vapour-liquid-solid-growth
• CPC Class Codes: C30B 25/005 Growth of whiskers or needles
• CPC Class Codes: C30B 29/06 Silicon
• CPC Class Codes: C30B 29/60 characterised by shape
• CPC Class Codes: H01M 4/0428 Chemical vapour deposition
• CPC Class Codes: H01M 4/0495 Chemical alloying
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/36 Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Methods for producing nanostructures from copper-based catalysts on porous substrates, particularly silicon nanowires on carbon-based substrates for use as battery active materials, are provided. Related compositions are also described. In addition, novel methods for production of copper-based catalyst particles are provided. Methods for producing nanostructures from catalyst particles that comprise a gold shell and a core that does not include gold are also provided.

Claims

1. A method for producing nanowires, the method comprising:

providing a porous substrate having catalyst nanoparticles disposed thereon, wherein the porous substrate comprises a population of particles comprising at least one of graphite particles, graphene particles, carbon black particles, or carbon nanotubes and wherein the catalyst nanoparticles comprise copper, a copper compound, and/or a copper alloy;

loading the porous substrate into a reaction vessel wherein the population of particles with the catalyst nanoparticles disposed thereon form a packed bed in the reaction vessel; and

growing nanowires on the porous substrate in the reaction vessel from the catalyst nanoparticles via a Vapor-Solid-Solid (VSS) synthesis technique, wherein the growing comprises mixing the packed bed while flowing one or more reactant gases in the reaction vessel during the nanowire growing process.

2. The method of claim 1, wherein the nanowires comprise silicon, germanium, or a combination thereof.

3. The method of claim 2, wherein the nanowires comprise monocrystalline silicon, polycrystalline silicon, amorphous silicon, or a combination thereof.

4. The method of claim 1, wherein the population of particles comprises natural graphite particles, synthetic graphite particles, or a combination thereof.

5. The method of claim 4, wherein the catalyst nanoparticles have an average diameter between about 5 nm and about 100 nm, the particles have an average diameter between about 5 microns and 50 microns, and the nanowires have an average diameter between 10 nm and 100 nm and aspect ratio greater than 10.

6. The method of claim 1, wherein providing a porous substrate having catalyst nanoparticles disposed thereon comprises synthesizing discrete catalyst nanoparticles on the porous substrate through electroless deposition of copper onto the porous substrate by immersing the porous substrate in an electroless plating solution comprising at most 10 millimolar copper ions.

7. The method of claim 1, wherein providing a porous substrate having catalyst nanoparticles disposed thereon comprises immersing the porous substrate in a solution comprising copper ions and/or a copper complex, whereby the copper ions and/or the copper complex are adsorbed on the surface of the substrate, thereby forming discrete nanoparticles on the surface of the substrate.

8. The method of claim 2, wherein, after growing, silicon comprises between 2% and 20% of the total weight of the nanowires and the porous substrate.

9. The method of claim 1, wherein the one or more reactant gases are flown in a plurality of directions to reduce growth variance of the nanowires.

10. The method of claim 1, wherein the one or more reactant gases comprise silane (SiH₄).

11. The method of claim 1, further comprising, after growing, applying a carbon coating or a polymer coating to the nanowires.

12. The method of claim 1, wherein mixing comprises rotating the reaction vessel during the nanowire growing process.

13. The method of claim 12, wherein rotating comprises scraping the population of particles with the catalyst nanoparticles disposed thereon to prevent said particles from sticking to the vessel walls.

14. The method of claim 12, wherein rotating comprises flowing the reactant gases into the reaction vessel through a fixed tube positioned at the center of the reaction vessel.

15. The method of claim 14, wherein rotating comprises braking aggregates of the population of particles with catalyst nanoparticles disposed thereon through two linear arrays of regularly spaced rigid pins, the first array being fixed to the rotating wall of the reaction vessel and the second array being fixed to the fixed tube, the first and the second arrays of pins being offset in an interdigitated fashion so that they do not collide during the rotation of the reaction vessel.

16. The method of claim 14, wherein the one or more reactant gases comprise silane (SiH₄).

17. The method of claim 1, wherein mixing comprises fluidizing the population of particles with the catalyst nanoparticles disposed thereon by ultrasonic or mechanical shaking of the packed bed over the course of the nanowires synthesis reaction.

18. The method of claim 1, wherein mixing comprises recirculating the population of particles with the catalyst nanoparticles disposed thereon using a rotating impeller blade in the reaction vessel.

19. The method of claim 1, wherein mixing comprises recirculating the population of particles with the catalyst nanoparticles disposed thereon faster than the growth rate of the nanowires.

20. The method of claim 1, wherein mixing comprises redistributing the population of particles with the catalyst nanoparticles disposed thereon through a mechanical stirrer in the reaction vessel.

21. The method of claim 1, wherein providing a porous substrate having catalyst nanoparticles disposed thereon comprises synthesizing colloidal nanoparticles comprising copper and/or a copper compound and then depositing the nanoparticles on the porous substrate.