Preparation of metal chalcogenides

Patent metadata

Field	Value
Publication number	US-11208334-B2
Application number	US-201815998266-A
Country	US
Kind code	B2
Filing date	Jul 26, 2018
Priority date	Aug 1, 2017
Publication date	Dec 28, 2021
Grant date	Dec 28, 2021

Abstract

A method embodiment involves preparing single metal or mixed transition metal chalcogenide using exfoliation of two or more different bulk transition metal dichalcogenides in a manner to form an intermediate hetero-layered transition metal chalcogenide structure, which can be treated to provide a single-phase transition metal chalcogenide.

First claim

We claim:

1. A method for preparing a transition metal chalcogenide, comprising the step of exfoliating and concurrently self-combining two or more starting transition metal chalcogenides having compositions that differ with respect to at least one of a transition metal constituent and a chalcogen constituent to produce a hetero-layered structure having a mix of different layers with different compositions.

2. The method of claim 1 wherein exfoliating is conducted by mechanical processing of the starting transition metal chalcogenides together.

3. The method of claim 2 wherein the exfoliating is conducted by dry mechanical processing of the two or more starting transition metal chalcogenides together.

4. The method of claim 2 wherein dry mechanical processing is carried out in an inert gaseous atmosphere or gaseous atmosphere that is non-reactive towards the two or more starting transition metal chalcogenides and the produced hetero-layered structure.

5. The method of claim 2 wherein the exfoliating and self-combining are conducted by mechanical processing in the presence of a liquid medium.

6. The method of claim 5 wherein the liquid medium comprises at least one of isopropanol, water, dimethylsulphoxide, N-vinyl-pyrrolidinonc, N-methyl-pyrrolidinone, benzonitrile or any solvent that does not react with exfoliated chalcogenide materials under the processing conditions.

7. The method of claim 2 wherein mechanical processing is carried out using pestle and mortar, shaker ball mills of any configuration, planetary ball mills of any configurations, any type of laboratory or industrial grinders, sonication, or other milling, or grinding equipment.

8. The method of claim 1 wherein the exfoliating and sell-combining form the hetero-layered structure which is three dimensional.

9. The method of claim 1 wherein the exfoliated starting transition metal chalcogenides are concurrently mixed as they are exfoliated to self-combine to form the hetero-layered structure.

10. The method of claim 9 where the hetero-layered structure is converted into single-phase, chalcogenide material by subjecting it to thermal annealing treatment or mechanical processing including at least one of milling, grinding, cold or hot rolling, or extrusion, high hydrostatic pressure, combined with thermal annealing treatment.

11. The method of claim 10 wherein the thermal treatment is carried out by heating in the temperature range between 100° C. and 1500° C.

12. The method of claim 1 wherein the exfoliating and concurrent self-combing are carried out by ultrasonic irradiation.

13. The method of claim 1 including the further step of treating the hetero-layered structure to form a substantially single-phase, chalcogenide structure.

14. The method of claim 13 wherein the hetero-layered structure is substantially devoid of separate phases of the two or more starting transition metal chalcogenides.

15. The method of claim 13 wherein a substantially homogenous solid solution of the two or more starting transition metal chalcogenides is produced.

16. The method of claim 13 wherein the hetero-layered structure is treated by heat treating at a temperature for a time to achieve a substantially single-phase chalcogenide structure.

17. The method of claim 16 wherein heat treating is conducted at elevated temperatures between 100 and 1500 degrees C. in an inert or non-reactive gaseous atmosphere to produce a single-phase transition metal chalcogenide.

18. The method of claim 16 wherein the heat treating time is between 1 minute to 72 hours or longer.

19. The method of claim 16 wherein heat treating is conducted in an atmosphere comprising at least one of helium, argon, krypton, xenon, nitrogen, and any other gas, which shows no reactivity towards the starting transition metal chalcogenides or the hetero-layered structure.

20. The method of claim 13 including the further step of exfoliating the substantially single phase, chalcogenide structure.

21. The method of claim 1 wherein the starting transition metal chalcogenides comprise transition metal dichalcogenides selected from the group consisting of the group 4 transition metal dichalcogenides (M=Ti, Zr, Hf), group 5 transition metal dichalcogenides (M=V, Nb, Ta) or group 6 transition metal dichalcogenides (M=Cr, Mo, W), group 7 transition metal dichalcogenides (M=Mn, Re), group 10 transition metal dichalcogenides (M=Pd, Pt)J, group 11 transition metal dichalcogenides (Cu, Ag), group 12 transition metal dichalcogenides (Zn, Cd), group 13 transition metal dichalcogenides (e.g., M= 1 n, Ga) as well as lanthanum group metals chalcogenides (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu).

22. The method of claim 1 that produce a hetero-layered transition metal chalcogenide having a chemical composition represented by (M a M 2 b M 3 c. . . n )(X d X 2 e X 3 f ), where the formula unit includes two or more different metals (M), and X, X 2 and X 3 represent S, Se, or Te, whereby the sum of a+b+c+. . . n is between 1 and 3 and the sum of d+e+f is between 1 and 6.

23. The method of claim 1 where the hetero-layered structure comprises at least two or more of a mixed metal dichalcogenide material, a mixed metal tricbalcogenide material, a same metal dichalcogenide material, or a same metal trichalcogenide material.

24. The method of claim 23 the metal is selected from the group consisting of Ti, Zr, Hf, Nb, Ta, Mo, W, Re, Pd, Pt, In, Ga and Sn.

25. The method of claim 1 wherein the exfoliating and self-combining occur in the presence of at least one of graphite, black phosphorus, and boron nitride.

26. The method of claim 1 wherein exfoliating is conducted using at least one of ultrasonic irradiation, liquid-assisted mechanical processing that includes grinding or milling, electrical force liquid-phase electrochemical exfoliation, or chemical exfoliation.

Assignees

• Univ Iowa State Res Found Inc

Inventors

• Balema Viktor
• Hlova Ihor
• Pecharsky Vitalij K

Classifications

• C01G39/06 Primary

  Sulfides · CPC title

• C01P2002/88

  by thermal analysis data, e.g. TGA, DTA, DSC · CPC title

• C01B19/002

  Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions · CPC title

• C01P2004/30

  extending in three dimensions · CPC title

• C01G41/00

  Compounds of tungsten · CPC title