EV-GRADE HIGH-PURITY LITHIUM SULFIDE AND PREPARATION METHOD FOR THE SAME

Abstract

EV-grade high-purity lithium sulfide and a preparation method therefor, including: A. mixing and well grinding a lithium source and a sulfur source to obtain a mixture; B. primary reaction: mixing the mixture with hydrazine hydrate in an inert atmosphere and reacting to obtain an intermediate slurry; C. secondary reaction: performing secondary reaction on the intermediate slurry in the inert atmosphere and drying to obtain a crude lithium sulfide product; and D. calcining and ball milling the crude lithium sulfide product to obtain the EV-grade high-purity lithium sulfide. The purity of the EV-grade high-purity lithium sulfide prepared by the method is above 99.9%, the whiteness thereof is above 80, and D5015 m; the method is characterized by simple process operation, high safety, low energy consumption, low equipment requirements and low production cost; therefore, the method is suitable for industrial production.

Claims

1-12. (canceled)

13. A preparation method for EV-grade high-purity lithium sulfide, comprising: A. mixing and well grinding a lithium source and a sulfur source to obtain a mixture; B. primary reaction: mixing the mixture with hydrazine hydrate in an inert atmosphere and reacting to obtain an intermediate slurry; C. secondary reaction: performing secondary reaction on the intermediate slurry in the inert atmosphere and drying to obtain a crude lithium sulfide product, wherein in Step C, stage heating is performed, to be specific, first-stage heating is performed at 100 C.-150 C. for 2-4 hours, and second-stage heating is performed at 200 C.-400 C. for 4-6 hours; and D. calcining and ball milling the crude lithium sulfide product to obtain the EV-grade high-purity lithium sulfide, wherein in Step D, microwave calcination is employed, a calcining temperature is 450 C.-600 C., and a calcining time is 2-6 hours.

14. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein in Step A, the lithium source is at least one of lithium hydroxide monohydrate, lithium sulfite and lithium thiosulfate, and the sulfur source is at least one of sulfur powder, lithium sulfite and lithium thiosulfate.

15. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein in Step A, the lithium source and the sulfur source are added in a molar ratio of Li.sub.2O:S=1:1-2.

16. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein in Step B, the hydrazine hydrate is added in a molar ratio of Li.sub.2O:N.sub.2H.sub.2.Math.H.sub.2O=1:2-4.

17. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein the hydrazine hydrate is added in three batches, with an interval of 0.5-1 hour for each addition.

18. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein in Step B, the mixing and reaction comprises stirring at 30 C.-70 C. for 1-5 hours.

19. The preparation method for EV-grade high-purity lithium sulfide according to claim 18, wherein a stirring speed is 100-200 r/min.

20. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein a microwave generation frequency during the microwave calcination is 2.45 GHz.

21. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein in Step D, the ball milling indicates that the calcined lithium sulfide is subjected to ball milling 5-10 hours at a rotating speed of 100-500 r/min.

22. The preparation method for EV-grade high-purity lithium sulfide according to claim 13, wherein in Step B and Step C, inert gas is argon or nitrogen; in Step D, the calcination is performed in a nitrogen protective atmosphere, and the ball milling is performed in a closed condition protected by the inert atmosphere.

23. EV-grade high-purity lithium sulfide, wherein the EV-grade high-purity lithium sulfide is prepared by the preparation method for EV-grade high-purity lithium sulfide according to claim 21, and the mass purity of the EV-grade high-purity lithium sulfide is above 99.9%, and the whiteness thereof is above 80, and D5015 m.

24. The EV-grade high-purity lithium sulfide according to claim 23, wherein the mass purity of the EV-grade high-purity lithium sulfide is above 99.95%, and the whiteness thereof is above 82.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0027] In order to achieve the first purpose of the invention, the preparation method for EV-grade high-purity lithium sulfide includes:

[0028] A. mixing and well grinding a lithium source and a sulfur source to obtain a mixture;

[0029] B. primary reaction: mixing the mixture with hydrazine hydrate in an inert atmosphere and reacting to obtain an intermediate slurry;

[0030] C. secondary reaction: performing secondary reaction on the intermediate slurry in the inert atmosphere and drying to obtain a crude lithium sulfide product; and

[0031] D. calcining and ball milling the crude lithium sulfide product to obtain the EV-grade high-purity lithium sulfide.

[0032] In Step B and Step C, a reaction principle is as follows:

4LiOH.Math.H.sub.2O+2S+N.sub.2H.sub.4.Math.H.sub.2O=2Li.sub.2S+N.sub.2+9H.sub.2O.

[0033] Primary reaction is performed in Step B, where mixed raw materials are transferred to a reaction device protected by inert gas, and then hydrazine hydrate is added and stirred to obtain a lithium sulfide intermediate slurry. A large number of bubbles are generated during initial reaction, an addition rate of hydrazine hydrate is related to an amount of reactants. If the amount of reactants is large, the hydrazine hydrate is added too fast, and a large number of bubbles are generated due to violent reaction, which leads to the overflow of reaction materials. Therefore, the hydrazine hydrate needs to be added in batches, and the addition rate thereof is controlled mainly according to the reaction degree of the reactants; the hydrazine hydrate is preferably added in three batches, with an interval of 0.5-1 hour.

[0034] In a specific embodiment, in Step A, the lithium source is at least one of lithium hydroxide monohydrate, lithium sulfite and lithium thiosulfate, and the sulfur source is at least one of sulfur powder, lithium sulfite and lithium thiosulfate.

[0035] In a specific embodiment, in Step A, the lithium source is lithium hydroxide monohydrate, and the sulfur source is sulfur powder.

[0036] The lithium hydroxide monohydrate and the sulfur powder are ground and mixed, so as to ensure that raw materials are well mixed and contacted; in the presence of hydrazine hydrate as a reducing agent, redox reaction occurs between the lithium hydroxide monohydrate and the sulfur powder to obtain a lithium sulfide intermediate slurry; the lithium sulfide intermediate slurry is subjected to secondary reaction and dried through heating to obtain a crude lithium sulfide product; the crude lithium sulfide product is calcined and subjected to ball milling to increase the whiteness thereof, so as to finally obtain an EV-grade lithium sulfide product.

[0037] In a specific embodiment, in Step A, the lithium source and the sulfur source are added in a molar ratio of Li.sub.2O:S=1:1-2.

[0038] The molar ratio of the invention refers to the ratio of the amount of substance. Lithium is calculated as Li.sub.2O and the sum of the molar weight of LizO in all raw materials, and S is also the sum of the molar weight of sulfur in all raw materials.

[0039] In a specific embodiment, in Step B, the hydrazine hydrate is added in a molar ratio of Li.sub.2O:N2H.sub.2.Math.H.sub.2O=1:2-4; preferably, the hydrazine hydrate is added in three batches, with an interval of 0.5-1 hour for each addition.

[0040] In a specific embodiment, in Step B, the mixing and reaction includes stirring at 30 C.-70 C. for 1-5 hours; and a stirring speed is preferably 100-200 r/min.

[0041] In a specific embodiment, in Step C, stage heating is performed, to be specific, first-stage heating is performed at 100 C.-150 C. for 2-4 hours, and second-stage heating is performed at 200 C.-400 C. for 4-6 hours.

[0042] Secondary reaction and drying are performed in Step C; the lithium sulfide intermediate slurry is transferred to a reaction vessel protected by inert gas and heated in stages for further reaction and drying to obtain the crude lithium sulfide product. In the invention, stage heating is performed to avoid too high heating temperature, bumping during liquid evaporation and slurry overflowing; if the temperature is too low, the raw materials are insufficiently reacted, and the product quality degrades.

[0043] In a specific embodiment, in Step D, a calcining temperature is 450 C.-600 C., and a calcining temperature is 2-6 hours.

[0044] In a specific embodiment, in Step D, microwave calcination is used, and a microwave generation frequency during the microwave calcination is preferably 2.45 GHz.

[0045] The microwave calcination is based on the penetrability of microwave and the targeted absorption effect of medium with high dielectric loss. Polar molecules are subjected to dipole turning and directional arrangement in the electromagnetic field by microwave, and the high-rate turning and arrangement intensifies the collision of molecules, thereby leading to the temperature rise of the system. For impurities in the crude lithium sulfide product, for example, sulfur, polysulfide and residual hydrazine hydrate, the boiling point of impurities can be quickly reached by heating, so as to achieve the effect of removing impurities and whitening. In addition, the high-frequency directional rotation of polar molecules under the action of microwave increases the effective collision between the molecules, so that the impurities such as sulfur coated inside lithium sulfide molecules can be dispersed. Compared with traditional calcination methods, microwave calcination feature in mild conditions, fast heating rate, heating uniformity, high efficiency, and ease of control.

[0046] In a specific embodiment, in Step D, the ball milling indicates that the calcined lithium sulfide is subjected to ball milling 5-10 hours at a stirring rate of 100-500 r/min.

[0047] In a specific embodiment, in Step B and Step C, inert gas is argon or nitrogen; in Step D, the calcination is performed in a nitrogen protective atmosphere, and the ball milling is performed in a closed condition protected by the inert atmosphere.

[0048] In order to achieve the second purpose of the invention, the EV-grade high-purity lithium sulfide is prepared by the preparation method for EV-grade high-purity lithium sulfide, where the mass purity of the EV-grade high-purity lithium sulfide is above 99.9%, and the whiteness thereof is above 80, and D5015 m.

[0049] In a specific embodiment, the mass purity of the EV-grade high-purity lithium sulfide is above 99.95%, and the whiteness thereof is above 82.5.

[0050] The following will make a further description for the specific embodiments of the invention with reference to examples, but this does not limit the invention to the scope of the embodiments.

Example 1

[0051] Lithium hydroxide monohydrate, sulfur powder and hydrazine hydrate were taken in a molar ratio of Li.sub.2O:S:N.sub.2H.sub.4.Math.H.sub.2O=1:1:3, and the lithium hydroxide monohydrate and the sulfur powder were mixed and ground in a grinder. Ground raw materials were placed into a reaction device protected by argon, hydrazine hydrate was added in batches, and reaction between the ground raw materials and the hydrazine hydrate was made for 1 hour at a stirring rate of 100 r/min and a temperature of 30 C. A lithium sulfide intermediate slurry was transferred to a reaction vessel protected by argon, subjected to reaction at 100 C. for 2 hours in a first stage, and then dried at 300 C. for 4 hours through heating to obtain the crude lithium sulfide product. Then, the crude lithium sulfide product was transferred to a microwave calcining furnace, and calcined at 450 C. for 2 hours in a nitrogen protective atmosphere to obtain high-whiteness lithium sulfide. The calcined lithium sulfide was placed a sealed ball milling tank and subjected to ball milling for 5 hours at room temperature at a stirring rate of 100 r/min to obtain a lithium sulfide product Li.sub.2S-1. The purity, whiteness, particle size and other parameters of the obtained product are as shown in Table 1.

Example 2

[0052] Lithium hydroxide monohydrate, sulfur powder and hydrazine hydrate were taken in a molar ratio of Li.sub.2O:S:N.sub.2H.sub.4.Math.H.sub.2O=1:2:3.5, and the lithium hydroxide monohydrate and the sulfur powder were mixed and ground in a grinder. Ground raw materials were placed into a reaction device protected by argon, hydrazine hydrate was added in batches, and reaction between the ground raw materials and the hydrazine hydrate was made for 3 hours at a stirring rate of 150 r/min and a temperature of 30 C. A lithium sulfide intermediate slurry was transferred to a reaction vessel protected by argon, subjected to reaction at 120 C. for 3 hours in a first stage, and dried at 350 C. for 5 hours through heating to obtain the crude lithium sulfide product. Then, the crude lithium sulfide product was transferred to a microwave calcining furnace, and calcined at 500 C. for 4 hours in a nitrogen protective atmosphere to obtain high-whiteness lithium sulfide. The calcined lithium sulfide was placed a sealed ball milling tank and subjected to ball milling for 8 hours at room temperature at a stirring rate of 300 r/min to obtain a lithium sulfide product Li.sub.2S-2. The purity, whiteness, particle size and other parameters of the obtained product are as shown in Table 1.

Example 3

[0053] Lithium hydroxide monohydrate, sulfur powder and hydrazine hydrate were taken in a molar ratio of Li.sub.2O:S:N.sub.2H.sub.4.Math.H.sub.2O=1:2:4, and the lithium hydroxide monohydrate and the sulfur powder were mixed and ground in a grinder. Ground raw materials were placed into a reaction device protected by argon, hydrazine hydrate was added in batches, and reaction between the ground raw materials and the hydrazine hydrate was made for 5 hours at a stirring rate of 200 r/min and a temperature of 30 C. A lithium sulfide intermediate slurry was transferred to a reaction vessel protected by argon, subjected to reaction at 150 C. for 4 hours in a first stage, and dried at 400 C. for 6 hours through heating to obtain the crude lithium sulfide product. Then, the crude lithium sulfide product was transferred to a microwave calcining furnace, and calcined at 600 C. for 6 hours in a nitrogen protective atmosphere to obtain high-whiteness lithium sulfide. The calcined lithium sulfide was placed a sealed ball milling tank and subjected to ball milling for 10 hours at room temperature at a stirring rate of 500 r/min to obtain a lithium sulfide product Li.sub.2S-3. The purity, whiteness, particle size and other parameters of the obtained product are as shown in Table 1.

Comparative Example 1

[0054] The comparative example provides a preparation method for lithium sulfide, where the method is similar to the method in Example 3, except that the lithium sulfide product is obtained directly after Step C, without subsequent calcining and ball milling steps. The lithium sulfide obtained in the comparative example has low purity and whiteness because a small amount of impurities such as sulfur powder, polysulfide and hydrazine hydrate remain in the dried product. The purity, whiteness, particle size and other parameters of the obtained product are as shown in Table 1.

TABLE-US-00001 TABLE 1 Purity, whiteness and particle sizes in examples and comparative example Product number Li.sub.2S-1 Li.sub.2S-2 Li.sub.2S-3 Li.sub.2S-4 Chemical Main content 99.96 99.95 99.98 98.72 composition (%) Impurity Na 0.0058 0.0085 0.0037 0.014 K 0.00051 0.00066 0.00032 0.0021 Ca 0.00086 0.00086 0.0022 0.0051 Mg 0.00033 0.00022 0.000021 0.0045 Si 0.0049 0.0043 0.0047 0.012 Al 0.0001 0.00052 0.00037 0.0092 Fe 0.00003 0.00063 0.00016 0.0016 Zn 0.00018 0.0002 0.0043 Ni 0.00002 0.00001 0.00008 Cr 0.00004 0.00002 0.00012 Mn 0.00002 0.00001 0.00007 Co 0.00023 Pb 0.000012 0.00028 Ti 0.0007 0.00036 0.00045 0.00013 Whiteness 81.81 82.6 83.2 73.2 D.sub.50 (m) 20.472 14.356 10.091 63.568