High-capacity silicon nanowire based anode for lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-10403889-B2
Application number	US-201515520526-A
Country	US
Kind code	B2
Filing date	Oct 21, 2015
Priority date	Oct 21, 2014
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

The present invention provides anodes comprising an electrically conductive substrate, comprising at least one non-uniform surface; and a random network of silicon nanowires (Si NWs) chemically grown on said at least one non-uniform surface of the substrate, wherein the Si NWs have at least about 30% amorphous morphology, and methods of manufacturing of the anodes. Further provided are lithium ion batteries comprising said anodes.

First claim

The invention claimed is:

1. An anode comprising:
an electrically conductive substrate, comprising at least one continuous non-uniform surface; and
a random network of silicon nanowires (SiNWs) chemically grown on the at least one non-uniform surface of the substrate,

wherein the SiNWs have at least about 30% amorphous morphology.

2. The anode according to claim 1 , wherein said anode is a lithium ion battery anode.

3. The anode according to claim 1 , wherein from about 30% to about 95% of the mass of each SiNW is amorphous.

4. The anode according to claim 1 , wherein the SiNWs have a core-shell structure, wherein the shell is amorphous.

5. The anode according to claim 1 , wherein the SiNWs have a thickness of from about 10 nm to about 500 nm and a length of from about 1 μm to about 200 μm.

6. The anode according to claim 1 , having a silicon loading on the substrate of from about 0.5 mg/cm 2 to about 20 mg/cm 2 .

7. The anode according to claim 1 , wherein the substrate comprises a non-uniform bulk portion, comprising a plurality of non-uniform surfaces, wherein the SiNWs are chemically grown in the non-uniform bulk portion.

8. The anode according to claim 1 , wherein the at least one non-uniform surface comprises elongated structures, selected from the group consisting of fibers, trenches and combinations thereof.

9. The anode according to claim 8 , wherein the elongated structures have a thickness of from about 0.1 μm to about 100 μm and a length of from about 1 mm to about 10000 mm.

10. The anode according to claim 1 , wherein the substrate comprises a material selected from the group consisting of carbon, graphite, metal, metal alloy and combinations thereof.

11. The anode according to claim 10 , wherein the metal or metal alloy comprises at least one element selected from the group consisting of copper (Cu), nickel (Ni), iron (Fe) and chromium (Cr).

12. The anode according to claim 1 , wherein the substrate is selected from the group consisting of paper, woven cloth, non-woven cloth, film and foil.

13. The anode according to claim 12 , wherein the surface of the film or foil is selected from the group consisting of an etched, carved, scratched, engraved surface and combinations thereof.

14. The anode according to claim 13 , wherein the substrate further comprises a carbon or graphite coating.

15. The anode according to claim 1 , wherein the substrate has a thickness of from about 5 μm to about 500 μm.

16. The anode according to claim 1 , wherein the SiNWs comprise a conducting coating selected from the group consisting of an electron conducting coating, a Li cation conducting coating and a combination thereof.

17. The anode according to claim 16 , wherein the electron conducting coating comprises a material selected from the group consisting of carbon, graphite, reduced graphene oxide and combinations thereof.

18. The anode according to claim 16 , wherein the Li cation conducting coating comprises a solid lithium electrolyte, selected from the group consisting of lithium imide (Li 3 N), lithium oxide (Li 2 O), lithium sulfate (Li 2 SO 4 ), lithium fluoride (LiF), lithium phosphate (Li 3 PO 4 ), lithium carbonate (Li 2 CO 3 ) and combinations thereof; or a ceramic coating selected from the group consisting of aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), titanium oxide (TiO), hafnium oxide (HfO) and combinations thereof.

19. A lithium ion battery comprising the anode according to claim 2 and further comprising an electrolyte, comprising a Li salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (lithium triflate, CF 3 SO 3 Li), lithium bis(perfluoroethylsulfonyl)imide and combinations thereof and at least one cathode selected from the group consisting of lithium iron phosphate (LiFePO 4 ), sulfur-based cathode, lithium metal oxide-based cathode, air cathode and oxygen cathode.

20. The lithium ion battery according to claim 19 , wherein the lithium metal oxide-based cathode comprises a metal selected from the group consisting of nickel (Ni), manganese (Mn), cobalt (Co) and aluminum (Al).

21. The lithium ion battery according to claim 19 , wherein the anode comprises a substrate comprising two opposed non-uniform surfaces, wherein the random network of SiNWs is chemically grown on said two opposed non-uniform surfaces and the anode is disposed between two cathodes.

22. The lithium ion battery according to claim 19 packed in a cell configuration selected from the group consisting of a prismatic cell, pouch cell, cylinder cell and coin cell.

23. A method of manufacturing the anode according to claim 1 , the method comprising:
a. providing an electrically conductive substrate comprising at least one continuous non-uniform surface; and
b. chemically growing a random network of silicon nanowires (SiNWs) on the at least one non-uniform surface of the substrate.

24. The method according to claim 23 , wherein the step of providing an electrically conductive substrate comprises forming a non-uniform surface on an essentially flat substrate.

25. The method according to claim 23 , wherein the substrate comprises a non-uniform bulk portion, comprising a plurality of non-uniform surfaces, and wherein the step of chemically growing a random network of SiNWs further comprises growing said SiNWs in the non-uniform bulk portion of the substrate.

26. The method according to claim 23 , wherein the process of chemically growing a random network of SiNWs comprises a Chemical Vapor Deposition (CVD) process.

27. The method according to claim 25 , wherein the process of chemically growing a random network of SiNWs comprises a step of depositing catalytic nanoparticles on the at least one non-uniform surface of the substrate and in the non-uniform bulk portion of the substrate.

28. The method according to claim 27 , wherein the deposition of the catalytic nanoparticles is performed by immersing the substrate into an aqueous colloidal solution of the catalytic nanoparticles or by electroless deposition of metal nanoparticles.

29. The method according to claim 28 , wherein the substrate is immersed in the aqueous colloidal solution for at least about 5 min.

30. The method according to claim 23 , further comprising a step of coating the SiNWs with a conducting coating by using a technique selected from the group consisting of CVD, Physical Vapor Deposition (PVD), pyrolysis of a precursor, salt precipitation combined with thermal treatment, and combinations thereof.

Assignees

• Univ Ramot
• Ramot At Tel Aviv Unlversity Ltd

Inventors

• Peled Emanuel
• Patolsky Fernando
• Golodnitsky Diana
• Freedman Kathrin
• Davidi Guy
• Schneier Dan

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M4/0428

  Chemical vapour deposition · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/1395

  of electrodes based on metals, Si or alloys · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title