Nanostructured battery active materials and methods of producing same
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.
1. A method comprising:
providing a carbon-based porous substrate comprising a population of particles comprising at least one of natural graphite particles, synthetic graphite particles, graphene particles, or carbon black particles;
mixing deionized water with a copper source and a chelating agent to form a first aqueous solution comprising copper ions, wherein the copper source comprises at least one of copper sulfate, copper nitrate, copper chloride, or copper acetate and wherein the chelating agent comprises at least one of potassium sodium tartrate, EDTA, or polyols;
mixing deionized water with a reducing agent to form a second aqueous solution, wherein the reducing agent comprises at least one of sodium ascorbate or ascorbic acid;
mixing the first aqueous solution with the second aqueous solution to form Cu 2 O colloidal nanoparticles in an alkaline plating solution, the Cu 2 O colloidal nanoparticles formed via chemical reduction of the copper source, and wherein the pH and concentrations are adjusted to control the size distribution of the Cu 2 O colloidal nanoparticles;
depositing the Cu 2 O colloidal nanoparticles onto a surface of the carbon-based porous substrate by stirring a solution comprising the Cu 2 O colloidal nanoparticles and the carbon-based porous substrate until the solution is substantially depleted of the Cu 2 O colloidal nanoparticles;
loading the carbon-based porous substrate with the Cu 2 O nanoparticles deposited thereon into a reaction vessel, wherein the carbon-based porous substrate with the Cu 2 O nanoparticles deposited thereon form a packed bed in the reaction vessel; and
growing, in the reaction vessel, nanostructures on the carbon-based porous substrate from the Cu 2 O 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 nanostructure growing process; and wherein the nanostructures comprise silicon, germanium or a combination thereof.
2. The method of claim 1 further comprising, prior to immersing, setting the pH of the alkaline plating solution between 8 and 11 and setting the copper ions concentration up to 5 millimolar.
3. The method of claim 1 , wherein the particles in the population of particles in the carbon-based porous substrate have an average diameter between 0.5 μm and 50 μm.
4. The method of claim 1 , wherein the particles in the population of particles in the carbon-based porous substrate have an average diameter between 2 μm and 10 μm.
5. The method of claim 1 , wherein depositing further comprises depositing the formed Cu 2 O colloidal nanoparticles onto the surface of the carbon-based porous substrate until the concentration of copper ions in the alkaline plating solution is less than 1 ppm.
6. The method of claim 1 , wherein the formed Cu 2 O nanoparticles in the alkaline plating solution have an average size between 5 nm and 100 nm as measured by a light scattering measurement or by electron microscopy.
7. The method of claim 1 , wherein the formed Cu 2 O nanoparticles in the alkaline plating solution have an average size between 20 nm and 50 nm as measured by a light scattering measurement or by electron microscopy.
8. The method of claim 1 , wherein the formed Cu 2 O nanoparticles in the alkaline plating solution have an average size between 20 nm and 40 nm as measured by a light scattering measurement or by electron microscopy.
9. The method of claim 1 , further comprising filtering the plating solution to recover the carbon-based porous substrate with the Cu 2 O nanoparticles deposited thereon and drying the carbon-based porous substrate in an oven.
10. The method of claim 1 , further comprising setting the copper ions concentration up to 5 millimolar.
11. The method of claim 1 , wherein the nanostructures comprise at least one of nanowires or nanoparticles.
12. The method of claim 1 , wherein the one or more reactant gas comprises silane (SiH 4 ).
13. The method of claim 1 , further comprising, after growing, applying a carbon coating or an oxide coating to the nanostructures.
14. The method of claim 1 , further comprising, after growing, incorporating the carbon-based porous substrate with the nanostructure grown thereon into a battery slurry.
15. The method of claim 1 , further comprising, after growing, incorporating the carbon-based porous substrate with the nanostructure grown thereon into a battery anode.
16. The method of claim 1 , further comprising, after growing, incorporating the carbon-based porous substrate with the nanostructure grown thereon into a battery.
17. The method of claim 1 , further comprising:
recovering, by filtration, the carbon-based porous substrate with the Cu 2 O nanoparticles deposited thereon.
18. The method of claim 17 , further comprising, after recovering, drying the carbon-based porous substrate with the nanoparticles deposited thereon in an oven at 120° C. for at least 12 hours.