IP Library Granted Patent US 9,346,966
Granted Patent B2
US 9,346,966 · App. 13/645,551 · Granted May 24, 2016

Liquid silane-based compositions and methods for producing silicon-based materials

Inventors: Douglas L. Schulz (Fargo, ND); Justin Hoey (Fargo, ND); Xiangfa Wu (Fargo, ND); Iskander Akhatov (West Fargo, ND); Philip Boudjouk (Fargo, ND); Xuliang Dai (Solon, OH); Larry Pederson (West Fargo, ND); Jeremiah Smith (Fargo, ND); Arumugasamy Elangovan (Fargo, ND); Sijin Han (Milpitas, CA)
Assignee: NDSU RESEARCH FOUNDATION
C09D11/00B29D99/0078C01B33/021D01D5/0038D01D5/34D01F1/10D01F9/14D04H1/4209D04H1/4382D04H1/728D06M11/74H01M4/134H01M4/366H01M4/38H01M4/625B82Y40/00H01L21/02532H01L21/02603H01L21/02628Y02E60/122Y02P70/54Y10S977/895
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 9,346,966
App. No.
13/645,551
Granted
May 24, 2016
Kind
B2
Abstract

Described herein are synthesis schemes and methods for producing silicon based nanostructures and materials, including compositions and methods for synthesis of silicon-based nanowires and composites from three-component and four-component liquid silane/polymer inks. Materials and methods for producing silicon based micro and nanofibers that can be used in a variety of applications including material composites, electronic devices, sensors, photodetectors, batteries, ultracapacitors, and photosensitive substrates, and the like.

Claims (42)

1. A method for synthesizing silicon nanofibers, comprising:

combining a liquid silane, a polymer and a solvent to form a viscous solution;

passing a stream of viscous solution through a high electric field to form fibers;

depositing the formed fibers onto a substrate; and

transforming the deposited fibers.

2. A method as recited in claim 1 , wherein said liquid silane is a cyclosilane of the formula Si n H 2n selected from the group of cyclosilanes consisting of cyclopentasilane, cyclohexasilane and 1-silylcyclopentasilane.

3. A method as recited in claim 1 , wherein said liquid silane is a linear or branched cyclosilane of the formula Si n H 2n+2 .

4. A method as recited in claim 1 , wherein said polymer is selected from the group of polymers consisting of poly(methyl methacrylate), polycarbonate, poly(vinylidene fluoride-co-hexafluoropropylene), and polyvinyl butryal.

5. A method as recited in claim 1 , wherein said solvent is selected from the group of solvents consisting of toluene, xylene, cyclooctane, 1,2,4-trichlorobenzene, dichloromethane or mixtures thereof.

6. A method as recited in claim 1 , wherein said substrate is selected from the group of substrates consisting of a carbon fiber matte, a metal foil, and a mandrel.

7. A method as recited in claim 1 , wherein the deposited fibers are transformed using thermal processing at temperatures from 150° C. to 300° C. to produce polysilane-containing materials.

8. The method recited in claim 1 , wherein the deposited fibers are transformed using thermal processing at temperatures from 300° C. to 850° C. to produce amorphous silicon-containing materials.

9. The method as recited in claim 1 , wherein the deposited fibers are transformed using thermal processing at temperatures from 850° C. to 1414° C. to produce crystalline silicon-containing materials.

10. The method as recited in claim 1 , wherein the deposited fibers are transformed using laser processing to give crystalline silicon-containing materials.

11. A method for synthesizing silicon nanofibers, comprising:

combining a liquid silane, a polymer, a solid phase and a solvent to form a viscous solution;

passing a stream of viscous solution through a high electric field to form fibers;

depositing the formed fibers onto a substrate; and

transforming the deposited fibers.

12. A method as recited in claim 11 , wherein said liquid silane is a cyclosilane of the formula Si n H 2n selected from the group of cyclosilanes consisting of cyclopentasilane, cyclohexasilane and 1-silylcyclopentasilane.

13. A method as recited in claim 11 , wherein said liquid silane is a linear or branched cyclosilane of the formula Si n H 2n+2 .

14. A method as recited in claim 11 , wherein said solid phase is a metallic particle selected from the group of metal particles consisting of metallic particles of Al, Au, Ag, Cu, In—Sn—O, fluorine-doped tin oxide and carbon black.

15. A method as recited in claim 11 , wherein said solid phase is a semiconducting particle selected from the group of semiconducting particles consisting of carbon nanotubes, silicon nanowires, polydihydrosilane (Si n H 2 ) n , CdSe, CdTe, PbS, PbSe, ZnO and Si.

16. A method as recited in claim 11 , wherein said solid phase is a metal reagent selected from the group of metal reagents consisting of CaH 2 , CaBr 2 , Cp 2 Ti(CO) 2 , TiCl 4 , V(CO) 6 , Cr(CO) 6 , Cp 2 Cr, Mn 2 (CO) 10 , CpMn(CO) 3 , Fe(CO) 5 , Fe 2 (CO) 9 , Co 2 (CO) 8 , CO 4 (CO) 12 , Cp 2 Co, Cp 2 Ni, Ni(COD) 2 , BaH 2 , [Ru(CO) 4 ] ∞ , Os 3 (CO) 12 , Ru 3 (CO) 12 , HFeCo 3 (CO) 12 , and H 2 FeRu 3 (CO) 13 .

17. A method as recited in claim 11 , wherein said solid phase is a photoactive particle selected from the group of photoactive particles consisting of a carbon fullerene, a quantum dot of CdSe, PbS, Si or Ge, and a core-shell quantum dot of ZnSe/CdSe or Si/Ge.

18. A method as recited in claim 11 , further comprising:

coating the transformed fibers with a coherent, conductive coating.

19. A method as recited in claim 11 , wherein the coating is a coating selected from the group of coatings consisting of graphite, carbon black, KB Carbon, carbon nanotubes and graphene.

20. A method of making silicon-containing composite wires comprising:

combining a polymer and a solvent to form a viscous solution;

flowing liquid silane through the inner annulus of a coaxial delivery tube while flowing the viscous polymer solution through the outer annulus;

exposing the viscous mixture to a high electric field where continuous fibers are formed and deposited onto a substrate; and

transforming the deposited fibers into a composite material that contains on the inside a polysilane, an amorphous silicon and/or a crystalline silicon fraction and on the outside a carbon coating.

21. A method as recited in claim 20 , wherein the liquid silane flowing through the inner annulus is selected from the group of cyclosilanes consisting of Si 6 H 12 cyclohexasilane, Si 6 H 12 1-silyl-cyclopentasilane and Si 5 H 10 cyclopentasilane.

22. A method as recited in claim 20 , wherein the liquid silane flowing through the inner annulus is selected from the group of linear and branched silanes having the formula Si n H 2n+2 .

23. A method as recited in claim 20 , wherein the solution flowing through the outer annulus is polyacrylonitrile in dimethylformamide.

24. A method for making silicon-containing battery electrode composite, comprising:

combining a liquid silane of the formula Si n H 2n , with a polymer and a solvent to form a viscous solution;

expelling the viscous solution through a high electric field wherein continuous fibers are formed and deposited onto a metal foil substrate;

transforming the deposited fibers by thermal treatment under inert gas;

forming a coherent, ion conductive coating on the transformed fibers; and mixing

the coated silicon nanofibers with a binder and KB carbon to form an electrode.

Assignments (3)
CONFIRMATORY LICENSE Recorded Jun 18, 2015
From: NORTH DAKOTA STATE UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 035930/0855 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 28, 2012
From: NORTH DAKOTA STATE UNIVERSITY
To: NDSU RESEARCH FOUNDATION
Reel/Frame 029417/0468 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 2, 2012
From: SCHULZ, DOUGLAS L.; HOEY, JUSTIN; WU, XIANGFA; AKHATOV, ISKANDER; BOUDJOUK, PHILIP; DAI, XULIANG; PEDERSON, LARRY; SMITH, JEREMIAH; ELANGOVAN, ARUMUGASAMY; HAN, SIJIN
To: NORTH DAKOTA STATE UNIVERSITY
Reel/Frame 029260/0451 →
Continuity (3)
Continuation PCTUS2011031478 · Apr 6, 2011
Provisional Application 61321338 · Apr 6, 2010
Related Publication 20130093122A1 · Apr 18, 2013