Methods for mass-producing silicon nano powder and graphene-doped silicon nano powder

Patent metadata

Field	Value
Publication number	US-9728777-B2
Application number	US-201313987450-A
Country	US
Kind code	B2
Filing date	Jul 26, 2013
Priority date	Jul 26, 2013
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

Disclosed is a facile and cost effective method of producing nano silicon powder or graphene-doped silicon nano powder having a particle size smaller than 100 nm. The method comprises: (a) preparing a silicon precursor/graphene nano composite; (b) mixing the silicon precursor/graphene nano composite with a desired quantity of magnesium; (c) converting the silicon precursor to form a mixture of graphene-doped silicon and a reaction by-product through a thermal and/or chemical reduction reaction; and (d) removing the reaction by-product from the mixture to obtain graphene-doped silicon nano powder.

First claim

We claim:

1. A method of producing graphene-doped silicon nano powder having a silicon particle size smaller than 100 nm, said method comprising: (a) mixing a graphene material with a silicon precursor to form a silicon precursor/graphene nano composite, wherein said graphene material is selected from pristine graphene, graphene fluoride, graphene bromide, graphene iodide, chemically functionalized graphene, or a combination thereof, wherein pristine graphene is a non-oxidized graphene that is produced without chemical intercalation or oxidation; (b) mixing the silicon precursor/graphene nano composite with a quantity of magnesium; (c) converting said silicon precursor/graphene nano composite to form a mixture of graphene-doped silicon and a reaction by-product by a chemical or thermal reduction reaction; and (d) removing the reaction by-product from the mixture to obtain said graphene-doped silicon nano powder.

2. The method of claim 1 , wherein said graphene material is selected from a single-layer sheet or few-layer platelet of pristine graphene, graphene fluoride, graphene bromide, graphene iodide, chemically functionalized graphene, or a combination thereof, wherein few layer is defined as less than 10 layers of graphene planes.

3. The method of claim 1 , wherein said silicon precursor contains tetraethyl orthosilicate (TEOS), sodium silicate, silica, silicon-halogen compound, or a combination thereof, and said reaction by-product contains MgO or a magnesium-halogen compound.

4. The method of claim 1 , wherein said silicon precursor contains silicon fluoride and said reaction by-product contains MgF 2 .

5. The method of claim 1 , wherein said step (a) of preparing a silicon precursor/graphene nano composite includes dispersing or dissolving a silicon precursor in an acidic graphene solution to form a hybrid suspension, removing a liquid component from said hybrid suspension, and/or chemically or thermally converting said hybrid suspension to form said silicon precursor/graphene nano composite.

6. The method of claim 1 , wherein said step (a) of preparing a silicon precursor/graphene nano composite includes nucleation and growth of silicon precursor particles on a graphene surface.

7. The method of claim 1 , wherein said step (b) of mixing the silicon precursor/graphene nano composite with a quantity of magnesium includes liquid solution mixing, melt mixing, grinding, mechanical milling, air milling, or ball-milling.

8. The method of claim 1 , wherein the step (d) of removing the reaction by-product from the mixture comprises etching the reaction product by an acid solution.

9. The method of claim 8 wherein etching of said reaction by-product includes etching MgO in an acid-resistant container that is equipped with a mechanical stirring system.

10. The method of claim 8 wherein etching of said reaction by-product includes using an acid selected from HCl, H 2 SO 4 , HF, HNO 3 , or a combination thereof.

11. The method of claim 1 , further comprising filtration, washing, and/or drying after step (d).

12. The method of claim 11 wherein the drying process is selected from oven drying, vacuum drying, vaporizing, spray drying, or fluidized bed drying.

13. The method of claim 1 further comprising a heating process to purify the graphene-doped silicon nano powder or to remove graphene for forming pure silicon nano powder.

14. The method of claim 13 , wherein the removal of graphene is conducted in a rotating furnace or a fluidized bed furnace.

15. A method of producing graphene-doped silicon nano powder having a silicon particle size smaller than 100 nm, said method comprising: (a) mixing a graphene material with a silicon precursor to form a silicon precursor/graphene nano composite; (b) mixing the silicon precursor/graphene nano composite with a quantity of magnesium; (c) converting said silicon precursor/graphene nano composite to form a mixture of graphene-doped silicon and a reaction by-product by a chemical or thermal reduction reaction; and (d) removing the reaction by-product from the mixture to obtain said graphene-doped silicon nano powder, wherein said step (a) of preparing a silicon precursor/graphene nano composite includes (i) dispersing or dissolving a silicon precursor in an acidic graphene solution to form a hybrid suspension, (ii) adding an alkaline chemical to said hybrid suspension to form a gel, and (iii) drying the gel to form said silicon precursor/graphene nano composite.

16. The method of claim 15 , wherein the alkaline chemical is selected from ammonia water, sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, or a combination thereof.

17. The method of claim 15 wherein the step of drying includes spray drying or fluidized bed drying.

18. The method of claim 17 wherein said chamber contains a thermally stable material selected from a stainless steel, a nickel alloy, a titanium alloy, a cobalt alloy, a superalloy, or a high-temperature or refractory alloy that does not react with magnesium at a high temperature in the range of from 500° C. to 1000° C.

19. A method of producing graphene-doped silicon nano powder having a silicon particle size smaller than 100 nm, said method comprising: (a) mixing a graphene material with a silicon precursor to form a silicon precursor/graphene nano composite; (b) mixing the silicon precursor/graphene nano composite with a quantity of magnesium; (c) converting said silicon precursor/graphene nano composite to form a mixture of graphene-doped silicon and a reaction by-product by a chemical or thermal reduction reaction; and (d) removing the reaction by-product from the mixture to obtain said graphene-doped silicon nano powder, wherein said step (b) of mixing the silicon precursor/graphene nano composite with a quantity of magnesium includes coating the silicon precursor with magnesium to form magnesium-coated silicon precursor/graphene nano composite powder.

20. The method of claim 19 wherein said graphene material is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene bromide, graphene iodide, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof.

21. The method of claim 19 , wherein said step (c) of converting said silicon precursor includes placing the magnesium-coated silicon precursor/graphene nano composite powder in a sealed chamber and purging the powder to a heating apparatus that allows the reaction between magnesium and silicon precursor to occur therein for forming a mixture of graphene-doped silicon and a reaction by-product.

22. The method of claim 19 , wherein said silicon precursor contains SiO 2 .

23. The method of claim 19 wherein said heating apparatus comprises a holding chamber or a temporary holding chamber, a pulsed purging control system, a vacuum system, insulating materials, a heating element, a vacuum chamber, and a cooling system.

Assignees

• Jang Bor Z
• Wang Yanbo
• Zhamu Aruna
• Nanoteck Instr Inc

Inventors

• Jang Bor Z
• Wang Yanbo
• Zhamu Aruna

Classifications

• H01M4/386 Primary

  Silicon or alloys based on silicon · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title