Method for the production of MSnx nanoparticles as anode materials for a rechargeable battery

Patent metadata

Field	Value
Publication number	US-10259046-B2
Application number	US-201615214050-A
Country	US
Kind code	B2
Filing date	Jul 19, 2016
Priority date	Jul 30, 2015
Publication date	Apr 16, 2019
Grant date	Apr 16, 2019

Abstract

A method for the production of MSnx nanoparticles, wherein M is an element selected from the group consisting of Co, Mn, Fe, Ni, Cu, In, Al, Ge, Pb, Bi, Ga, and 0<x≤10, the method including synthesizing Sn nanoparticles by reducing a tin salt with a solution of a hydride in an anhydrous polar solvent, separating the solid Sn nanoparticles formed from the solution, and washing the Sn nanoparticles, synthesizing M nanoparticles by reducing a metal salt with a solution of a hydride in an anhydrous polar solvent, separating the solid M nanoparticles formed from the solution, and washing the M nanoparticles, mechanical mixing the Sn nanoparticles and the M nanoparticles to convert them into MSnx nanoparticles.

First claim

What is claimed is:

1. A method for producing MSnx nanoparticles, wherein:
M is an element selected from the group consisting of Co, Mn, Fe, Ni, Cu, In, Al, Ge, Pb, Bi, Ga;
0<x≤10; and
the MSnx nanoparticles are amorphous nanoparticles,

the method comprising:
separately synthesizing Sn nanoparticles and M nanoparticles by, in either order:
synthesizing the Sn nanoparticles by reducing a tin salt with a solution of a first hydride in a first anhydrous polar solvent, separating solid Sn nanoparticles formed from the solution, and washing the Sn nanoparticles, and
synthesizing the M nanoparticles by reducing a metal salt with a solution of a second hydride in a second anhydrous polar solvent, separating solid M nanoparticles formed from the solution, and washing the M nanoparticles; and then

mechanically mixing the Sn nanoparticles and the M nanoparticles to obtain the amorphous MSnx nanoparticles.

2. The method according to claim 1 , wherein a molar ratio of the M nanoparticles and the Sn nanoparticles in the mechanical mixing is 1:1 to 1:3.

3. The method according to claim 1 , wherein the mechanical mixing occurs by ball-milling.

4. The method according to claim 3 , wherein the ball-milling is performed in the presence of an inert gas.

5. The method according to claim 4 , wherein the ball-milling is performed in the presence of nitrogen.

6. The method according to claim 3 , wherein the ball-milling is performed in air.

7. The method according to claim 1 , wherein M is Co.

8. The method according to claim 1 , wherein the reducing of the tin salt occurs at a temperature from 50° C. to 70° C.

9. The method according to claim 1 , wherein the reducing of the metal salt occurs at a temperature from 60° C. to 180° C.

10. The method according to claim 1 , wherein the first hydride is selected from the group consisting of NaBH4, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, tributyltinhydride, diisobutyl aluminum hydride, lithium aluminum hydride, lithium triethylborohydride and mixtures thereof.

11. The method according to claim 10 , wherein the first hydride is NaBH4.

12. The method according to claim 10 , wherein the second hydride is NaBH4.

13. The method according to claim 1 , wherein the first anhydrous polar solvent is selected from the group consisting of 1-methyl-2-pyrrolidone (NMP), hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, dimethylsulfoxide, sulfolane, glyme, diglyme, triethylene glycol dimethylether, and mixtures thereof.

14. The method according to claim 13 , wherein the first anhydrous polar solvent is 1-methyl-2-pyrrolidone (NMP).

15. The method according to claim 13 , wherein the second anhydrous polar solvent is 1-methyl-2-pyrrolidone (NMP).

16. The method according to claim 1 , wherein the tin salt is selected from the group consisting of tin chloride, tin fluoride, tin bromide, tin iodide, tin oxide, tin sulfide, sodium stannate trihydrate, tetrabutyltin, and mixtures thereof.

17. The method according to claim 16 , wherein the tin salt is tin chloride.

18. The method according to claim 1 , wherein the metal salt is selected from the group consisting of M chlorides and mixtures thereof.

19. The method according to claim 18 , wherein the metal salt is Co chloride.

20. The method according to claim 1 , wherein the reducing of the tin salt occurs in inert gas.

21. The method according to claim 20 , wherein the reducing of the tin salt occurs under nitrogen.

22. The method according to claim 20 , wherein the reducing of the metal salt occurs under nitrogen.

23. The method according to claim 1 , wherein the reducing of the tin salt occurs in air.

24. The method according to claim 1 , wherein the synthesizing of the Sn nanoparticles comprises:
preparing the solution of the first hydride in the first anhydrous polar solvent and at least one solution of the tin salt in the first anhydrous solvent;
heating the solution of the first hydride to a reaction temperature of the reducing of the tin salt; and
starting the reducing when the reaction temperature is reached by adding the at least one solution of the tin salt into the solution of the first hydride to generate a reaction mixture.

25. The method according to claim 24 , wherein the reaction mixture is cooled to room temperature immediately after the adding.

26. The method according to claim 1 , wherein the synthesizing the Sn nanoparticles comprises:
preparing a solution of at least one tin salt in the first anhydrous polar solvent and at least one solution of the first hydride in the first anhydrous polar solvent;
heating the solution of the at least one tin salt to a reaction temperature of the reducing of the tin salt; and
starting the reducing when the reaction temperature is reached by adding the solution of the first hydride into the at least one solution of the tin salt to generate a reaction mixture.

27. The method according to claim 1 , wherein the synthesizing the M nanoparticles comprises:
preparing the solution of the second hydride in the second anhydrous polar solvent and at least one solution of the metal salt in the second anhydrous polar solvent;
heating the solution of the second hydride to a reaction temperature of the reducing of the metal salt; and
starting the reducing when the reaction temperature of the reducing of the metal salt is reached by adding the at least one solution of the metal salt into the solution of the second hydride to generate a reaction mixture.

28. The method according to claim 1 , wherein the synthesizing the M nanoparticles comprises:
preparing a solution of at least one metal salt in the second anhydrous polar solvent and at least one solution of the second hydride in the second anhydrous polar solvent;
heating the solution of the at least one metal salt to a reaction temperature of the reducing of the at least one metal salt; and
starting the reducing when the reaction temperature of the reducing of the at least one metal salt is reached by adding the at least one solution of the second hydride into the solution of the at least one metal salt to generate a reaction mixture.

29. A method for producing an anode, the method comprising:
performing the method of claim 1 for producing the MSnx nanoparticles;
mixing the MSnx nanoparticles, carbon black, carboxy methyl cellulose (CMC) and water, to obtain an aqueous slurry;
coating the aqueous slurry on a current collector, to obtain a coated current collector; and
drying the coated current collector to obtain the anode.

30. The method according to claim 1 , wherein the second hydride is selected from the group consisting of NaBH4, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, tributyltinhydride, diisobutyl aluminum hydride, lithium aluminum hydride, lithium triethylborohydride and mixtures thereof.

31. The method according to claim 1 , wherein the second anhydrous polar solvent is selected from the group consisting of 1-methyl-2-pyrrolidone (NMP), hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, dimethylsulfoxide, sulfolane, glyme, diglyme, triethylene glycol dimethylether, and mixtures thereof.

Assignees

• Belenos Clean Power Holding Ag

Inventors

• Kovalenko Maksym
• Walter Marc

Classifications

• B22F1/054

  Nanosized particles · CPC title

• B22F1/08

  Metallic powder characterised by particles having an amorphous microstructure · CPC title

• H01M10/36

  Accumulators not provided for in groups H01M10/05-H01M10/34 · CPC title

• H01M4/1395

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

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title