Method of making anhydrous metal sulfide nanocrystals

Patent metadata

Field	Value
Publication number	US-2021261411-A1
Application number	US-202117180479-A
Country	US
Kind code	A1
Filing date	Feb 19, 2021
Priority date	Feb 21, 2020
Publication date	Aug 26, 2021
Grant date	—

Abstract

Methods of forming Li2S and other MSn nanocrystals are provided. The methods employ low-cost lithium salts as a reagent and utilizes one or more metathesis reactions that occur either in solution, preferably at or near ambient conditions, or in the solid-state at elevated temperatures.

First claim

1 . A method of producing Li 2 S comprising:
mixing a first sulfide salt and a first lithium salt; allowing sufficient time to form Li 2 S and a product salt; and recovering the Li 2 S.

2 . The method of claim 1 , wherein the first sulfide salt and the first lithium salt are mixed in a first solution, wherein the product salt is insoluble in or only sparingly soluble in the first solution, and wherein the product salt is separated from the first solution prior to recovering the Li 2 S.

3 . The method of claim 2 , wherein the first solution comprises a polar solvent having a boiling point of about 150° C. or less, and wherein the Li 2 S is recovered via solvent evaporation in an inert atmosphere or in the presence of H 2 S.

4 . The method of claim 2 , wherein the first sulfide salt and the first lithium salt spontaneously react to form the Li 2 S at room temperature.

5 . The method of claim 1 , wherein the first sulfide salt and the first lithium salt are mixed, without the addition of a solvent, and the mixture is heated to a temperature of at least 400° C., wherein the Li 2 S and the product salt are added to a first solution, wherein the product salt is insoluble in or only sparingly soluble in the first solution, and wherein the product salt is separated from the first solution prior to recovering the Li 2 S.

6 . The method of claim 5 , wherein the first solution comprises a polar solvent having a boiling point of about 150° C. or less, and wherein the Li 2 S is recovered via solvent evaporation in an inert atmosphere or in the presence of H 2 S.

7 . The method of claim 1 , further comprising annealing the recovered Li 2 S at a temperature of about 150° C. to about 300° C. in an inert atmosphere or in the presence of H 2 S.

8 . The method of claim 1 , wherein the Li 2 S is in the form of nanocrystals have a volume-averaged mean particle size (D 50 ) from 5 nm to 50 nm.

9 . The method of claim 1 , wherein the first sulfide salt is selected from the group consisting of Na 2 S, K 2 S, Rb 2 S, Cs 2 S, Fr 2 S, (NH 4 ) 2 S, P 2 S 5 , NiS, and combinations thereof.

10 . The method of claim 1 , wherein the first lithium salt is selected from the group consisting of a lithium halide, lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium sulfate (Li 2 SO 4 ), lithium sulfite (Li 2 SO 3 ), lithium amide (LiNH 2 ), lithium nitride (LiN 3 ), lithium nitrate (LiNO 3 ), lithium phosphate (Li 3 PO 4 ), and combinations thereof.

11 . The method of claim 1 , further comprising:
mixing the recovered Li 2 S and a non-lithium containing salt; allowing sufficient time to form a metal or metalloid sulfide (MS n ) and a second lithium salt; and recovering the MS n .

12 . The method of claim 11 , wherein the recovered Li 2 S and non-lithium containing salt are mixed in a second solution, wherein the MS n is insoluble in or only sparingly soluble in the second solution, wherein the MS n is separated from the second solution.

13 . The method of claim 12 , wherein the second solution comprises a polar aprotic solvent having a boiling point of about 150° C. or less.

14 . The method of claim 11 , wherein the recovered Li 2 S and non-lithium containing salt are mixed, without the addition of a solvent, and the mixture is heated to a temperature of at least 400° C., wherein the MS n and the product salt are added to a second solution, wherein the MS n is insoluble in or only sparingly soluble in the second solution, and wherein the MS n is separated from the second solution.

15 . The method of claim 14 , wherein the second solution comprises a polar aprotic solvent having a boiling point of about 150° C. or less.

16 . The method of claim 11 , wherein the non-lithium containing salt comprises a metal or metalloid cation and an anion selected from the group consisting of a halide, hydroxide, carbonate, sulfate, sulfite, nitrate, nitrite, phosphate, acetate, citrate, and combinations thereof.

17 . The method of claim 11 , wherein the MS n is selected from the group consisting of Cr 2 S 3 , M n S, ReS 2 , FeS 2 , RuS 2 , OsS 2 , CoS 2 , RhS 2 , IrS 3 , NiS 2 , PdS, PtS, HfS 2 , NbS 2 , TaS 2 , GeS 2 , SiS 2 , TiS 2 , SnS 2 , MoS 2 , ZrS 2 , CdS, ZnS, VS 2 , WS 2 , Al 2 S 3 , CaS, and MgS.

18 . The method of claim 11 , further comprising recovering the second lithium salt and recycling the second lithium salt second to be used as the first lithium salt.

19 . A method of producing Li 2 S nanocrystals comprising:
mixing a first sulfide salt and a first lithium salt in a first solution comprising a polar solvent; allowing sufficient time to form Li 2 S and a product salt precipitate; separating the product salt precipitate from the first solution; recovering the Li 2 S via solvent evaporation, and annealing the recovered Li 2 S at a temperature of about 150° C. to about 250° C., wherein the Li 2 S is in the form of nanocrystals have a volume-averaged mean particle size (D 50 ) from 5 nm to 50 nm.

20 . A method of producing metal or metalloid sulfide (MS n ) nanocrystals comprising:
mixing a first sulfide salt and a first lithium salt in a first solution comprising a polar solvent; allowing sufficient time to form Li 2 S and a product salt precipitate; separating the product salt precipitate from the first solution; recovering the Li 2 S from the first solution; mixing the recovered Li 2 S with a non-lithium containing salt in a second solution comprising a polar aprotic solvent; allowing sufficient time to form MS n nanocrystals and a second lithium salt; and recovering the MS n nanocrystals from the second solution, wherein the MS n nanocrystals are selected from the group consisting of Cr 2 S 3 , M n S, ReS 2 , FeS 2 , RuS 2 , OsS 2 , CoS 2 , RhS 2 , IrS 3 , NiS 2 , PdS, PtS, HfS 2 , NbS 2 , TaS 2 , GeS 2 , SiS 2 , TiS 2 , SnS 2 , MoS 2 , ZrS 2 , CdS, ZnS, VS 2 , WS 2 , Al 2 S 3 , CaS, and MgS.

Assignees

• Colorado School Of Mines

Inventors

• Wolden Colin A
• Smith William H

Classifications

• C01B17/40 Primary

  Making shaped products, e.g. granules · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title