CN114275742A - Preparation method of lithium sulfide capable of realizing continuous production - Google Patents
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Abstract
The invention discloses a preparation method of lithium sulfide capable of continuous production, which adopts a lithium sulfide precursor and a carbon high-temperature pyrolysis reduction method to prepare lithium sulfide. The lithium sulfide precursor is coated with carbon to promote reaction, and meanwhile, a sulfur atmosphere in the furnace is provided in a sulfur powder evaporation mode, so that sulfur volatilization of the lithium sulfide precursor at high temperature is inhibited, and flowing nitrogen is used for atmosphere protection. The method does not need vacuum pumping or negative pressure protection, can be continuously carried out under normal pressure, and can realize continuous production by selectively using a roller kiln or a push plate furnace during amplification, thereby greatly reducing the production cost of the lithium sulfide.
Description
Technical Field
The invention belongs to the technical field of lithium sulfide production, and particularly relates to a preparation method of lithium sulfide capable of realizing continuous production.
Background
With the worldwide demand for "carbon peak and carbon neutralization", new energy vehicles are beginning to be favored by governments of various countries around the world. However, because the conventional lithium ion battery needs to be filled with electrolyte, the electrolyte is likely to leak when the battery is extruded by collision, and then the battery catches fire or even explodes. The electrolyte of the all-solid-state battery is in an all-solid-state form, so that the safety performance is greatly improved, and the all-solid-state battery is widely concerned by people.
Most of the anodes of the existing lithium ion batteries adopt a lithium iron phosphate system or a ternary system, and are matched with a graphite cathode. As the demand for energy density for lithium ion batteries has become higher, such batteries have been unable to meet the demand for energy density. The birth of lithium-sulfur batteries provides a solution to this problem.
Lithium sulfide has attracted attention as a lithium compound because of its use as a key material for sulfide solid electrolytes and as a positive electrode material for lithium-sulfur batteries. But the rapid rise of lithium metal price is caused by the fire heat of the current lithium ion battery market and the shortage and uneven distribution of global lithium ore resources. The current market price of lithium sulfide has risen to 1.2-1.5 ten thousand yuan/kg. Therefore, it is particularly important to develop a preparation method of lithium sulfide which is low in cost and can realize large-scale continuous production.
At first, the preparation method of lithium sulfide is relatively simple, and elemental sulfur and elemental lithium are promoted to perform a combination reaction by high temperature and high pressure, such as chinese patent CN 108190845A. The method has no waste gas, and greatly shortens the production flow. However, the method for preparing the lithium sulfide is high in cost, high in temperature and high in pressure in the production process, high in requirements for equipment type selection, difficult to control working conditions, and meanwhile, challenges are brought to subsequent treatment, and large-scale preparation is not easy to realize in the aspects of economy and process.
With the progress of science and technology, the preparation methods of lithium sulfide are mainly divided into a liquid phase reaction method and a solid phase sintering method. The liquid phase reaction method is as shown in Chinese patent CN105016310A, and the main idea of the patent is to mix lithium salt in an organic solvent, simultaneously introduce hydrogen sulfide gas, react under a heating state, and remove impurities to obtain high-purity lithium sulfide. The reaction avoids the sintering process at high temperature and reduces energy consumption. But the used organic solvent is a toxic solvent, hydrogen sulfide gas is also used in the reaction process, casualties on personnel are easily caused no matter the organic solvent or the hydrogen sulfide is leaked, and the difficulty of equipment type selection and subsequent recovery treatment is increased. Meanwhile, although the patent calls that high-purity lithium sulfide is prepared, no characterization or evidence can be shown in the patent specification, so that the purity and authenticity of the high-purity lithium sulfide are still required to be testified.
The main idea of the solid-phase sintering method is to mix a sulfur-containing lithium salt and a reducing agent and then sinter the mixture at a high temperature to prepare lithium sulfide, as shown in chinese patent CN 112678780A. This patent prepares lithium sulfide by a solid phase sintering method, and purifies the lithium sulfide by dissolution filtration. However, the method needs to be vacuumized to the pressure lower than 20Pa, large-scale continuous production cannot be realized, and the authenticity of an XRD pattern in a specification drawing is to be examined. Because of the air sensitivity of lithium sulfide, it is necessary to use an oxidation preventing film for covering when performing XRD test, or deterioration of lithium sulfide may occur. However, if an oxidation preventing film is used, a characteristic bulge of the oxidation preventing film occurs around 18 °. The figure has no characteristic bulge of the anti-oxidation film and no other impurity peaks, so the authenticity of the figure needs to be examined.
Disclosure of Invention
Aiming at the defects and shortcomings of the preparation method, the invention develops the preparation method of the lithium sulfide capable of realizing continuous production so as to realize the large-scale preparation of the lithium sulfide.
In order to achieve the above purpose, the invention provides a preparation method of lithium sulfide capable of realizing continuous production, which comprises the following steps:
a. mixing a sulfur-containing lithium salt, an organic carbon source and a carbon material in proportion, and dispersing in an organic solvent for wet mixing, wherein the organic carbon source is an organic carbon-based adhesive which can be carbonized at high temperature;
b. pressing the obtained material into blocks in a die after filter pressing, putting the pressed materials into a crucible, and sintering at high temperature under the protection of flowing nitrogen by using a tubular furnace, wherein sulfur powder is placed in a low-temperature area, and materials are placed in a high-temperature area;
c. and crushing the sintered material, dissolving the crushed material in an alcohol solvent, and drying the crushed material in a vacuum oven to remove the solvent to obtain the lithium sulfide.
Preferably, the organic carbon source comprises at least one of polydopamine, resorcinol-formaldehyde resin, glucose, sucrose, polyvinylpyrrolidone, pitch, lithium carboxymethylcellulose.
Preferably, the organic solvent in step a comprises at least one of ethanol, methanol, isopropanol, ethylene glycol, n-butanol.
Preferably, the carbon material in step a is any one of hard carbon and soft carbon graphite.
Preferably, the wet mixing apparatus in step a comprises at least one of a planetary ball mill, a high-speed mixer, and a stirred ball mill.
Preferably, the sintering mode of the high temperature section in the step b is three-section calcination, the temperature is maintained at 400 ℃ for 1-12h in 200-one, 650 ℃ for 1-12h in 500-one and 950 ℃ for 1-24h in 700-one.
Preferably, the low-temperature section is synchronously insulated at 200-400 ℃ when the high-temperature section enters the insulation zone at 700-950 ℃ in the step b.
Preferably, the nitrogen gas inlet rate in step b is 100mL/min to 100L/min.
Preferably, the alcoholic solvent in step c is one or more of anhydrous grade methanol, ethanol, ethylene glycol and isopropanol.
Preferably, the drying temperature of the vacuum oven in the step c is 40-60 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the method comprises the steps of mixing a sulfur-containing lithium salt, an organic carbon source and a carbon material, carrying out high-temperature sintering reaction to prepare lithium sulfide, dissolving the lithium sulfide in anhydrous alcohol, stirring, filtering and drying the crushed lithium sulfide to obtain the lithium sulfide powder with the purity of more than 99.9%.
(1) The method firstly uses a solvent for dispersion and then carries out filter pressing and sintering, and aims to shorten the process route, enhance the solid-solid contact of the lithium salt containing sulfur, the organic carbon source and the carbon material, promote the kinetic effect of the reaction and reduce the activation energy required by the reaction.
(2) The sintering material is placed in a high-temperature area in the high-temperature sintering process to ensure that enough temperature can be provided to promote the reaction to be complete, the sulfur powder is placed in a low-temperature area to supplement sulfur elements, the reduction of the purity of the generated material caused by the volatilization of sulfur in the reaction process is avoided, the method does not need to maintain the vacuum degree any more, but adopts flowing atmosphere protection, and continuous production can be realized by using an atmosphere roller kiln or an atmosphere push plate furnace in the subsequent amplification process, so that the traditional batch production mode is changed, and the production cost is greatly reduced.
(3) And (3) crushing, dissolving, filtering and drying the sintered product, wherein the raw materials required for production and the intermediate product generated in the production process are not dissolved in an alcohol solvent, so that the effective separation of lithium sulfide and impurities can be realized, and the purity of the lithium sulfide is improved to more than 99.9%.
Drawings
FIG. 1 is an XRD pattern of a sintered material, a recrystallized material after purification and drying, and a lithium sulfide standard card of example 1.
Detailed Description
The invention discloses a preparation method of lithium sulfide capable of realizing continuous production, which mainly comprises the following steps:
(1) mixing a sulfur-containing lithium salt, an organic carbon source and a carbon material in proportion, and dispersing in an organic solvent for wet mixing;
(2) pressing the obtained material into blocks in a die after filter pressing, putting the pressed materials into a crucible, and sintering at high temperature under the protection of flowing nitrogen by using a tubular furnace, wherein sulfur powder is placed in a low-temperature area, and materials are placed in a high-temperature area;
(3) and crushing the sintered material, dissolving the crushed material in an alcohol solvent, and removing the solvent through a vacuum oven to obtain the lithium sulfide.
The step (1) is a material mixing process, and lithium salt containing sulfur, an organic carbon source and a carbon material are mixed in proportion and dispersed in an organic solvent for wet mixing. The reason for using wet mixing is as follows: a. wetting the surfaces of the raw materials by using an organic solvent to ensure that the raw materials have stronger bonding strength; b. the dynamic effect of the mixed material is enhanced, so that the mixed material is more uniform; c. when ball milling and mixing are used, the particle size of the raw materials can be reduced, and the reaction is promoted to be easier to occur. Meanwhile, the ball milling can be used for reducing the particle size of the raw materials, and then the high-speed mixer is used for mixing the materials, so that the same material mixing effect can be achieved.
The alcohol organic solvent is used for mixing the materials in the step (1) because the raw materials are not dissolved in the alcohol solvent, a good dispersing effect can be achieved, and the solvent is easy to recover and convenient to recycle.
In the step (2), the mixed slurry is directly pressed into blocks in a die after being subjected to filter pressing, so that the steps of drying and transporting materials are avoided, and the process route is shortened. Meanwhile, solid-solid contact of the sulfur-containing lithium salt, the organic carbon source and the carbon material is enhanced, the dynamic effect of the reaction is promoted, and the activation energy required by the reaction is reduced.
The sintering mode of the high temperature section in the step (2) is three-section calcination, and the temperature is kept for 1-12h at the temperature of 200-400 ℃, 1-12h at the temperature of 500-650 ℃ and 1-24h at the temperature of 700-950 ℃ under the protection of nitrogen atmosphere. The first stage of heat preservation is to remove residual organic solvent and crystal water carried by lithium salt containing sulfur during material mixing, and meanwhile, the organic carbon source is in a molten state, so that the raw materials are mixed more uniformly. And the second stage of heat preservation promotes the carbonization of the organic carbon source, and at the moment, the raw materials only contain lithium salt containing sulfur and a carbon material and have no other impurities. Third stage heat preservation generation Li2SO4+2C＝Li2S+2CO2By carbothermal reduction to form lithium sulfide and CO2Is carried away by flowing nitrogen gas to prevent Li formation2O and Li2CO3. When the temperature reaches the third-stage heat-preservation temperature zone, sulfur vapor is carried out along with the flowing atmosphere, so that the purity is prevented from being reduced due to loss of sulfur, the temperature of the low-temperature zone is increased to 200-400 ℃, sulfur powder is volatilized and is carried to the high-temperature zone by the flowing atmosphere to carry out a supplementary reaction, and the lost sulfur is involved.
The sintering process in the step (2) does not need to maintain the vacuum degree like other methods, but adopts flowing atmosphere protection, provides sulfur vapor to supplement a sulfur source, can realize continuous production by using an atmosphere roller kiln or an atmosphere push plate furnace in the subsequent amplification process, changes the traditional batch production mode, and greatly reduces the production cost.
Preferably, the nitrogen gas inlet speed in the step (2) is 100mL/min to 100L/min.
In the step (3), the material is broken and then is more easily dissolved in an anhydrous alcohol solvent. Raw materials required by production and intermediate products generated in the production process are not dissolved in alcohol solvents, so that effective separation of lithium sulfide and impurities can be realized, and the purity of the lithium sulfide is improved to more than 99.9%.
Preferably, the material is crushed to 200-400 mesh and the temperature of the vacuum oven is set to 40-60 ℃.
The invention can realize the continuous production of high-purity lithium sulfide, change the traditional batch production mode and greatly reduce the production cost.
The invention is further illustrated by the following examples without restricting it to the described embodiments.
Example 1
Taking 40g of lithium sulfate monohydrate, 5g of polyvinylpyrrolidone and 5g of conductive carbon black, dispersing in isopropanol, and mixing for 15min at 1400rpm by using a high-speed mixer;
filtering the suspension, recovering filtrate, pressing the filter cake into square blocks in a mold, placing the square blocks into a crucible, placing the crucible in a right temperature area of the tubular furnace, and placing the crucible containing a small amount of sulfur powder in a left temperature area;
introducing nitrogen from the left end of the tubular furnace until the oxygen content in the tubular furnace is less than 30ppm, the nitrogen flow rate is 100mL/min, heating the high-temperature zone, and keeping the nitrogen flow rate unchanged from the process of heating to the process of cooling the tubular furnace to room temperature;
heating the high-temperature area to 250 ℃ and preserving heat for 6 hours;
heating the high-temperature area to 600 ℃, and preserving heat for 5 hours;
heating the high-temperature area to 900 ℃, and preserving heat for 8 hours;
and when the sample is cooled to the room temperature along with the furnace, covering the sample, transferring the sample into a glove box filled with argon, grinding and crushing the sample, adding the sample into anhydrous glycol, stirring and dissolving the sample for three hours at the normal temperature, and filtering the mixture.
The filtrate was placed in a vacuum oven set at 50 ℃ for 24h to dry.
The dried material is high-purity lithium sulfide, and the sintered material, the purified and dried material and the PDF standard card are shown in figure 1, wherein the purified and dried material is in an amorphous state, and is subjected to XRD test after being subjected to heat preservation for 2 hours at 500 ℃. It can be seen from fig. 1 that the purity of the material after purification is improved. The ICP test results are shown in attached table 1 and also illustrate the purity of the material.
TABLE 1
| Impurity element | Content/ppm | Impurity element | Content/ppm |
| Ag | - | Mn | - |
| Al | 10.4503 | Mo | - |
| As | - | Na | 7.4905 |
| Au | - | Ni | - |
| B | - | P | - |
| Ba | - | Pb | - |
| Be | - | Pd | - |
| Bi | - | Pt | - |
| Ca | 5.5921 | Sb | - |
| Cr | - | Se | - |
| Cd | - | Si | - |
| Co | - | Sn | - |
| Cu | 0.5877 | Sr | - |
| Fe | - | Ti | - |
| Ga | - | Tl | - |
| Ge | - | V | - |
| Hf | - | W | - |
| Hg | - | Zn | - |
| K | 7.8644 | Zr | - |
| Mg | 1.5562 |
Example 2
Taking 70g of lithium sulfate monohydrate, 15g of polydopamine and 4g of conductive carbon black, dispersing in ethanol, and mixing for 30min at 400rpm by using a ball mill;
filtering the suspension, recovering filtrate, pressing the filter cake into square blocks in a mold, placing the square blocks into a crucible, placing the crucible in a right temperature area of the tubular furnace, and placing the crucible containing a small amount of sulfur powder in a left temperature area;
introducing nitrogen from the left end of the tubular furnace until the oxygen content in the tubular furnace is less than 30ppm, the nitrogen flow rate is 300mL/min, heating the high-temperature zone, and keeping the nitrogen flow rate unchanged from the process of heating to the process of cooling the tubular furnace to room temperature;
heating the high-temperature area to 280 ℃ and preserving heat for 7 hours;
heating the high-temperature area to 650 ℃, and preserving heat for 7 hours;
heating the high-temperature zone to 880 ℃, and preserving heat for 4 hours;
and when the sample is cooled to the room temperature along with the furnace, covering the sample, transferring the sample into a glove box filled with argon, grinding and crushing the sample, adding the sample into anhydrous glycol, stirring and dissolving the sample for five hours at the normal temperature, and filtering the mixture.
The filtrate was placed in a vacuum oven set at 55 ℃ for 20h to dry.
The material obtained after drying was highly pure lithium sulfide and the test results were similar to example 1.
Claims (10)
1. A preparation method of lithium sulfide capable of realizing continuous production is characterized by comprising the following steps:
a. mixing a sulfur-containing lithium salt, an organic carbon source and a carbon material in proportion, and dispersing in an organic solvent for wet mixing, wherein the organic carbon source is an organic carbon-based adhesive which can be carbonized at high temperature;
b. pressing the obtained material into blocks in a die after filter pressing, putting the pressed materials into a crucible, and sintering at high temperature under the protection of flowing nitrogen by using a tubular furnace, wherein sulfur powder is placed in a low-temperature area, and materials are placed in a high-temperature area;
c. and crushing the sintered material, dissolving the crushed material in an alcohol solvent, and drying the crushed material in a vacuum oven to remove the solvent to obtain the lithium sulfide.
2. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: the organic carbon source comprises at least one of polydopamine, resorcinol-formaldehyde resin, glucose, sucrose, polyvinylpyrrolidone, asphalt and lithium carboxymethyl cellulose.
3. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: the organic solvent in step a comprises at least one of ethanol, methanol, isopropanol, ethylene glycol and n-butanol.
4. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: the carbon material in step a is any one of hard carbon and soft carbon graphite.
5. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: the wet mixing equipment in the step a comprises at least one of a planetary ball mill, a high-speed mixer and a stirring ball mill.
6. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: in the step b, the sintering mode of the high temperature section is three-section calcination, the temperature is kept for 1-12h at the temperature of 200-plus-one-material 400 ℃, the temperature is kept for 1-12h at the temperature of 500-plus-one-material 650 ℃, and the temperature is kept for 1-24h at the temperature of 700-plus-one-material 950 ℃.
7. The method for preparing lithium sulfide capable of realizing continuous production according to claim 5, wherein the method comprises the following steps: and (c) synchronously preserving the heat of the low-temperature section at 200-400 ℃ when the high-temperature section enters the heat preservation area at 700-950 ℃.
8. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: the nitrogen gas inlet speed in the step b is 100mL/min to 100L/min.
9. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: in the step c, the alcohol solvent is one or more of anhydrous methanol, ethanol, glycol and isopropanol.
10. The method for preparing lithium sulfide capable of realizing continuous production according to claim 1, wherein the method comprises the following steps: in the step c, the drying temperature of the vacuum oven is 40-60 ℃.
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