Silicon nanostructure active materials for lithium ion batteries and processes, compositions, components and devices related thereto
View Patent ↗The present invention relates to nanostructured materials for use in rechargeable energy storage devices such as lithium batteries, particularly rechargeable secondary lithium batteries, or lithium-ion batteries (LIBs). The present invention includes materials, components, and devices, including nanostructured materials for use as battery active materials, and lithium ion battery (LIB) electrodes comprising such nanostructured materials, as well as manufacturing methods related thereto. Exemplary nanostructured materials include silicon-based nanostructures such as silicon nanowires and coated silicon nanowires, nanostructures disposed on substrates comprising active materials or current collectors such as silicon nanowires disposed on graphite particles or copper electrode plates, and LIB anode composites comprising high-capacity active material nanostructures formed on a porous copper and/or graphite powder substrate.
1. A method of forming a lithium-ion battery (LIB)
component, comprising: providing at least one substrate structure; and
electrochemically depositing a plurality of nanostructures directly onto one or more surfaces of the at least one substrate structure, wherein the nanostructures are formed via electrochemical deposition without a growth template, and the nanostructures are comprised of crystalline Si and are substantially free of amorphous Si or polycrystalline Si upon formation.
2. The method of claim 1 , wherein the LIB component is a LIB anode component.
3. The method of claim 1 , wherein the plurality of nanostructures form at least one LIB anode active material.
4. The method of claim 3 , wherein the nanostructures further comprise one or more intermetallic compounds and/or alloys of Si, tin (Sn), one or more intermetallic compounds and/or alloys of Sn, or Si and Sn,
wherein the one or more intermetallic compounds of Si are a silicon-copper (Si-Cu) intermetallic compound, a silicon-nickel (Si-Ni) intermetallic compound, or any combination thereof; and
wherein the one or more intermetallic compounds of Sn are a tin-copper (Sn-Cu) intermetallic compound, a tin-nickel (Sn-Ni) intermetallic compound, a tin-manganese (Sn-Mn) intermetallic compound intermetallic compound, or any combination thereof.
5. The method of claim 1 , wherein the substrate structure comprises at least one current collector structure.
6. The method of claim 5 , wherein the at least one current collector structure comprises at least one copper (Cu) structure and/or at least one graphite structure and/or at least one carbon structure.
7. The method of claim 5 , wherein the at least one current collector structure comprises one or more of a Cu film, Cu foil, a Cu mesh structure, and a Cu sponge structure.
8. The method of claim 5 , wherein the at least one current collector structure comprises one or more of a graphite film, carbon paper, a graphite foil structure, graphite powder, and carbon powder.
9. The method of claim 1 , wherein the substrate structure comprises at least one active material structure.
10. The method of claim 9 , wherein the at least one active material substrate structure comprises graphite, wherein the at least one active substrate structure comprises graphite, wherein the graphite active material substrate structure comprises graphite powder having a plurality of graphite flakes or particles, and wherein the graphite powder is combined with one or more binder materials to adhere the graphite particles or flakes together.
11. The method of claim 10 , wherein the one or more binder materials include one or more of carboxylmethyl cellulose (CMC), polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), or polyacrylic acid (PAA).
12. The method of claim 10 , wherein the combining is performed prior to electrochemically depositing the plurality of nanostructures on one or more surfaces of the graphite powder.
13. The method of claim 10 , wherein the plurality of nanostructures are electrochemically deposited on one or more surfaces of the graphite powder prior to combining the graphite powder with one or more binder materials to adhere the graphite particles or flakes together.
14. The method of claim 1 , wherein the providing at least one substrate structure comprises coating graphite powder onto a graphite foil structure or a porous Cu structure.
15. The method of claim 14 , wherein the coating comprises coating a graphite powder and one or more binder materials onto the graphite foil or porous Cu structure.
16. The method of claim 1 , wherein the providing at least one substrate structure comprises disposing graphite powder comprising a plurality of graphite particles or graphite flakes between two or more porous Cu structures.
17. The method of claim 16 , wherein the providing further comprises combining the graphite powder with at least one binder material prior to disposing the graphite powder between the two or more porous Cu structures.
18. The method of claim 1 , wherein the plurality of nanostructures are electrochemically deposited directly onto the one or more surfaces of the at least one substrate structure, wherein the nanostructures are in direct physical contact with the one or more surfaces of the at least one substrate structure.
19. The method of claim 1 , wherein no further processing is required to achieve the crystalline structure of the nanostructure.
20. The method of claim 1 , wherein the nanostructures comprise monocrystalline Si.
21. The method of claim 1 , wherein the nanostructures comprise elongated nanostructures, Si nanowires, Si nanospikes, clusters of Si nanospikes, or clusters of Si nanowires, wherein the elongated nanostructures comprises nanowires, tapered nanowires, nanospikes, clusters of nanospikes, or clusters of nanowires.
22. The method of claim 1 , wherein at least one substrate structure comprises at least one substrate structure comprising plurality of surface features formed on at least one surface of the substrate structure, wherein the depositing comprises forming the one or more nanostructures directly on the one or more surface features.
23. The method of claim 22 , wherein the surface features comprise a plurality of protrusions formed on at least one surface of the one or more substrate structures.
24. The method of claim 22 , wherein the surface features comprise a plurality of indentations or trenches formed on at least one surface of the one or more substrate structures.
25. The method of claim 1 , wherein the electrochemical deposition is performed at about 80° C. or less.
26. The method of claim 1 , further comprising forming a LIB anode component comprising the at least one substrate structure and the plurality of nanostructures formed thereon.
27. The method of claim 26 , wherein the at least one substrate structure comprises graphite powder and the nanostructures comprise Si nanostructures electrochemically deposited on the graphite powder, wherein the LIB anode composite comprises a porous active material composite including the graphite powder and Si nanostructures.
28. The method of claim 27 , wherein the active material composite has a porosity of about 1-50%.
29. The method of claim 28 , wherein the active material composite comprises a binder material, wherein the active material composite consists of less than 10 wt.% of the binder material.
30. The method of claim 29 , wherein the binder material comprises carboxylmethyl cellulose (CMC).
31. The method of claim 1 , wherein the electrochemical deposition is performed at about room temperature.
32. A method of forming a lithium-ion battery (LIB)
component, comprising: providing at least one substrate structure; and
electrochemically depositing a plurality of nanostructures directly onto one or more surfaces of the at least one substrate structure, wherein the nanostructures are nanocrystals comprising at least one active material, wherein the nanocrystals are formed as crystalline nanocrystals and are substantially free of amorphous or polycrystalline nanocrystals immediately upon formation via electrochemical deposition such that no further processing is required after electrochemical deposition to achieve the crystalline structure of the nanocrystals.
33. A method of forming a lithium-ion battery (LIB)
component, comprising: providing at least one substrate structure comprising graphite;
and
electrochemically depositing a plurality of nanostructures directly onto one or more surfaces of the at least one graphite substrate structure, and wherein the nanostructures are comprised of crystalline Si and are substantially free of amorphous Si or polycrystalline Si upon formation.
34. A method of forming a lithium-ion battery (LIB) component, comprising:
providing an electrolytic cell comprising a working electrode, wherein the working electrode comprises at least one substrate structure comprising one or more LIB current collector structures and/or one or more LIB active material structures; and
electrochemically depositing a plurality of Si nanostructures directly onto one or more surfaces of the at least one substrate structure, and wherein the Si nanostructures are comprised of crystalline Si and are substantially free of amorphous Si or polycrystalline Si upon formation.
35. A lithium-ion battery (LIB) comprising:
an anode comprising at least one active material, wherein the at least one active material includes Si and graphite and wherein the Si is comprised of crystalline Si and is substantially free of amorphous Si or polycrystalline Si upon formation of the anode; and
an electrolyte comprising:
at least one liquid solvent selected from the group consisting of diethyl carbonate (DEC), ethylene carbonate (EC), or ethyl methyl carbonate (EMC); and
at least one additive-selected from the group consisting of fluorinated ethylene carbonate (FEC), diallyl pyrocarbonate (DAPC), diethyl pyrocarbonate (DEPC), diallyl carbonate (DAC), diallyl succinate (DAS), tris(pentafluorophenyl) bora (TPFPB), tris(2,2,2-trifluoroethyl) posphite (TTFP), N, N′-dicyclohexylcarbodiimide (DCC), methoxy trimethyl silane (MOTS), dimethoxydimethylsilane (DMOS), trimethoxy methyl silane (TMOS), maleic anhydride (MA), succinimide (SI), n-(benzyloxycaronyloxy)succinimide (NBSI), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), 1,3-propanesultone (PS), polydimethylsiloxane (PDMS), maleic anhydride (MA), and succinic anhydride (SA).
36. The lithium-ion battery of claim 35 , wherein the Si and graphite comprise Si-nanowires attached to graphite particles.
37. The lithium-ion battery of claim 36 , wherein after initial charge and discharge cycles, the Si-nanowires comprise one or more of: crystalline silicon, polycrystalline silicon, and amorphous silicon and said Si-nanowires include one or more coating layers comprising at least one of: SEI materials, binder materials, and conductive materials.