Highly reactive, dust-free and free-flowing lithium sulphide and method for the production thereof

Abstract

The invention relates to a highly reactive, high-purity, free-flowing and dust-free lithium sulfide powder having an average particle size between 250 and 1,500 μm and BET surface areas between 1 and 100 m.sup.2/g. The invention, furthermore, relates to a process for its preparation, wherein in a first step, lithium hydroxide monohydrate is heated in a temperature-controlled unit to a reaction temperature between 150° C. and 450° C. in the absence of air, and an inert gas is passed over or through it, until the residual water of crystallization content of the formed lithium hydroxide is less than 5 wt. % and in a second step, the anhydrous lithium hydroxide formed in the first step is mixed, overflowed or traversed by a gaseous sulfur source from the group consisting of hydrogen sulfide, elemental sulfur, carbon disulfide, mercaptans or sulfur nitrides.

Claims

1. A lithium sulfide powder, characterized in that it has an average particle size between 250 and 1,500 μm and BET surface areas between 1 and 100 m.sup.2/g, and contains cationic impurities from the group consisting of alkali metal, alkaline earth metal and transition metal cations in the 0.01-100 ppm range, and anionic impurities from the group consisting of oxoanions of carbon and sulfur, as well as halides in concentrations of 1-1,000 ppm.

2. A process for preparing a lithium sulfide powder according to claim 1, characterized in that in a first step, lithium hydroxide monohydrate having an average particle size in the range of 150-2,000 μm is heated in a temperature-controlled unit to a reaction temperature between 150° C. and 450° C. in the absence of air, and an inert gas is flowed over or through it, until the residual water of crystallization content of the formed lithium hydroxide is less than 5% by weight, wherein the heating rate to reach the reaction temperature is between 1° C. per min. and 1000° C. per min, and wherein the inert gas has a flow rate in the range of 100-1,000 l/h, and in a second step, the anhydrous lithium hydroxide formed in the first step is mixed, overflowed or traversed by a sulfur source from the group consisting of hydrogen sulfide, elemental sulfur, carbon disulfide, mercaptans or sulfur nitrides, wherein when the sulfur source is hydrogen sulfide, the hydrogen sulfide is introduced as a mixture of H.sub.2S and an inert carrier gas.

3. The lithium sulfide powder according to claim 1, characterized in that transition metal cations of iron, nickel and/or chromium are present in a concentration range of 0.01-10 ppm, and carbonate, sulfate, sulfite, thiosulfate, chloride, bromide and/or iodide anions are present in a concentration range of 1-1,000 ppm.

4. The lithium sulfide powder according to claim 1, characterized in that it is free-flowing, whereby when charging a metal hopper with a body diameter of 45 mm, a neck diameter of 5 mm, a neck length of 3 mm and an opening angle of 55° with 3.5 grams of said lithium sulfide powder, said lithium sulfide powder emerges from the metal hopper leaving a residual amount of not more than 0.0005 grams, after opening the outlet.

5. The process according to claim 2, characterized in that the lithium sulfide powder is converted to sulfidic solid electrolytes, wherein at least 90% by weight of the lithium sulfide powder is converted to sulfidic solid electrolytes.

6. The process according to claim 2, characterized in that the reaction temperature in step 1 is between 200° C. and 400° C.

7. The process according to claim 6, characterized in that the reaction temperature in step 1 is between 300° C. and 400° C.

8. The process according to claim 2, characterized in that in step 2, a constant hydrogen sulfide stream consisting of a mixture of H.sub.2S and an inert carrier gas is introduced into the reactor filled with the lithium hydroxide formed in step 1, wherein the mixing ratio is between 0 vol. % of inert gas in 100 vol. % of H.sub.2S and 99 vol. % of inert gas and 1 vol. % of H.sub.2S.

9. The process according to claim 8, characterized in that argon or nitrogen is used as a carrier gas.

10. Lithium hydroxide obtained according to the process of claim 2, characterized in that the particles formed in step 1 have an average particle size between 250 and 1,500 μm and BET surfaces areas between 1 and 100 m.sup.2/g.

11. The process according to claim 2, characterized in that a heating rate of 1-100° C./min is applied in order to reach the reaction temperature.

12. The process according to claim 2, characterized in that the reaction temperature of step 2 is between 20° C. and 450° C.

13. The process according to claim 2, characterized in that the reaction temperature of step 2 is between 200° C. and 400° C.

Description

EXAMPLES

(1) Step 1—Preparation of a Highly Reactive, Free-Flowing LiOH Powder for Use in Step 2

(2) TABLE-US-00001 Drying conditions* Product characteristics Inert gas BET volume Heating Temper- Absence surface Conver- flow rate rate ature Time d.sub.50 of area Pore sion to Example [l/h] [° C./min] [° C.] [min] Fluidity** [μm] dust*** [m.sup.2/g] structure**** Li.sub.2S***** [%] LiOH•H.sub.2O — — — — medium 450 No 0.7 None 0 raw material 1 400 4 150 180 medium 246 Yes 1.5 coarse; irregular 50 2 400 4 250 180 high 310 Yes 9.2 coarse & fine; 60 regular 3 400 4 350 180 high 359 Yes 7.3 coarse & fine; 90 regular 4 400 4 450 180 high 359 Yes 4.8 coarse; irregular 92 5 400 60 150 180 medium 265 Yes 5.1 coarse & fine, 50 irregular 6 400 60 250 180 high 319 Yes 7.1 coarse & fine; 70 regular 7 400 60 350 180 high 327 Yes 7.6 coarse & fine; 90 regular 8 400 60 450 180 high 321 Yes 3.8 coarse & fine; 90 regular *Drying in 4 cm diam. quartz glass reactor and 0.1 kg LiOH•H.sub.2O initial weight *Solid residue in hopper <0.0005 g ***no particles <150 μm ****derived from scanning electron micrographs *****Conversion determined by X-ray powder diffraction of the samples after stoichiometric H.sub.2S dosage

(3) Step 2—Preparation of a highly reactive, free-flowing Li.sub.2S powder from the products of step 1

(4) TABLE-US-00002 Reaction conditions* Volume flow Volume flow Product characteristics rate of rate of BET inert reactive Heating Temper- Absence surface Conver- gas N2 gas H2S rate ature Time D50 of area Pore sion to Example [l/h] [l/h] [° C./min] [° C.] [min] Fluidity** [μm] dust*** [m2/g] structure**** Li.sub.6PS.sub.5Br***** 09 300 100 4 150 60 high 267 Yes 4.4 coarse; irregular 0 10 300 100 4 250 60 high 375 Yes 8.6 coarse & fine; 93 regular 11 300 100 4 350 60 high 341 Yes 14.3 coarse & fine; ND regular 12 300 100 4 450 60 high 438 Yes 7.4 coarse; irregular ND 13 300 100 60 150 60 high 367 Yes 5.4 coarse & fine, ND irregular 14 300 100 60 250 60 high 392 Yes 15.01 coarse & fine; ND regular 15 300 100 60 350 60 high 311 Yes 14.6 coarse & fine; 94 regular 16 300 100 60 450 60 high 361 Yes 6.6 coarse & fine; 100 regular 17 Commercial Li.sub.2S None 15 No 3.6 None 48 18 Commercial Li.sub.2S None <75 No 3.7 None 37 *Reaction in 4 cm diam. quartz glass reactor and 0.1 kg LiOH•H.sub.2O initial weight **Solid residue in hopper <0.0005 g ***no particles <150 μm ****derived from scanning electron micrographs *****determined by X-ray powder diffraction of the samples according to the synthesis route known from the literature

(5) Influence of Impurities on Reactivity

(6) TABLE-US-00003 Reaction conditions for drying* Volume Reactivity w.sub.i Heating Temper- flow rate of Conversion of (Li.sub.2CO.sub.3) rate ature Time Inert gas LiOH to Li.sub.2S** Example [Wt %] [° C./min] [° C.] [min] [l/h] [%] 19 1 60 350 180 400 51 20 5 60 350 180 400 50 21 10 60 350 180 400 44 Reaction conditions for sulfidation* Volume Reactivity Volume flow rate of Conversion of flow rate of reactive gas Heating Temper- Li.sub.2S to Inert gas Reaktivgas rate ature Time Li.sub.6PS.sub.5Br*** Example N2 [l/h] H2S [l/h] [° C./min] [° C.] [min] [%] 19 300 100 60 350 60 97 20 300 100 60 350 60 82 21 300 100 60 350 60 80 *Reaction in 4 cm diam. quartz glass reactor, 0.1 kg LiOH•H.sub.2O initial weight, drying conditions as in Example 7, reaction conditions as in Example 15 **Conversion determined by X-ray powder diffraction of the samples after stoichiometric H.sub.2S dosage ***Conversion determined by X-ray powder diffraction of the samples according to the synthesis route known from the literature