CN112520763B - Method for preparing lithium sulfide by using lithium sulfate - Google Patents
Method for preparing lithium sulfide by using lithium sulfate Download PDFInfo
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- CN112520763B CN112520763B CN202010765264.1A CN202010765264A CN112520763B CN 112520763 B CN112520763 B CN 112520763B CN 202010765264 A CN202010765264 A CN 202010765264A CN 112520763 B CN112520763 B CN 112520763B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of material synthesis, and particularly relates to a method for preparing lithium sulfide by using lithium sulfate. Aiming at the defects that commercial lithium sulfide generally has higher price, difficult purity guarantee and the like, the invention discloses a method for preparing high-purity lithium sulfide by using a simple heating method.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a method for preparing lithium sulfide by using lithium sulfate.
Background
As a promising energy storage system, the lithium-sulfur battery is highly valued by researchers, and elemental sulfur in the conventional lithium-sulfur battery cathode material is being replaced by a new cathode material due to the defects of high volume effect, low conductivity and the like. The lithium sulfide anode has ideal pre-lithiation and high theoretical specific capacity (1166mA h g)-1) And is expected to become a new generation of lithium-sulfur battery anode material. Because lithium sulfide is in a fully lithiated state (unlike elemental sulfur), non-lithium metal negative electrode materials (e.g., silicon or tin) can be collocated, thereby circumventing the formation of metallic lithium dendrites and other safety issues. In addition to its compatibility with non-lithium metal cathodes, the use of lithium sulfide as the cathode material has the following advantages: (1) lithium sulfide is in a fully expanded state of sulfur, unlike sulfur which expands 80% in volume during lithiation. Thus, lithium sulfideDuring the initial delithiation process shrinks to create space to accommodate the volume expansion during subsequent lithiation. This not only helps to mitigate structural damage to the entire electrode, but also eliminates the need to intentionally create internal void spaces, thereby greatly simplifying the synthesis process. (2) Lithium sulfide (938 ℃) has a higher melting point than sulfur (115 ℃). Generally, the carbonization process occurs in a high temperature atmosphere, which makes the synthesis of the lithium sulfur-carbon composite material easier to handle.
However, the existing commercial lithium sulfide generally has the defects of high price, difficulty in ensuring purity and the like, which limits the development speed of scientific research institutions for the lithium-sulfur battery industry, so that the novel synthesis and preparation method capable of efficiently synthesizing the lithium sulfide with purity meeting the requirements of the scientific research institutions is of great significance.
Disclosure of Invention
The invention aims to solve the problems of complexity, higher price and the like of the existing lithium sulfide preparation method, and provides a novel method for synthesizing and preparing lithium sulfide which is high-efficiency and low-cost and meets the scientific research requirements.
The technical solution of the present invention is specifically described below.
The invention discloses a method for preparing lithium sulfide by using lithium sulfate, which comprises the following specific steps:
(1) uniformly mixing lithium hydride and lithium sulfate in a certain proportion under an inert atmosphere, and transferring the mixture into a closed reactor;
(2) heating the mixture to a set temperature at a certain rate and preserving the temperature for a certain time;
(3) after the reaction is finished and the temperature in the reactor is reduced to room temperature, collecting the gas in the reactor, and then taking out the reaction product under the inert atmosphere or vacuum condition;
(4) under inert atmosphere, dissolving the reaction product by using absolute ethyl alcohol, separating a solid phase and a liquid phase, and removing the solvent from the liquid phase to obtain the lithium sulfide powder.
In the invention, the lithium sulfate in the step (1) is anhydrous lithium sulfate.
In the invention, the molar ratio of lithium hydride to lithium sulfate in the step (1) is 8: (0.5-4).
In the invention, in the step (2), the heating rate is 1-10 ℃/min, the heating temperature is 100-.
In the present invention, the solvent removal conditions in the step (4) are as follows: and (3) keeping the temperature of 50-80 ℃ for 1-100h under the condition of dynamic vacuum, wherein the dynamic vacuum means that a vacuum pump always works in the process of heating and gasifying the solvent, so that the gasified solvent is pumped out.
In the present invention, the inert atmosphere is a gas that does not react with the reactant and the product, and specifically, is any one or more of argon, helium, or nitrogen.
In the present invention, the reaction equation is: li2SO4+8LiH→Li2S+4Li2O+4H2。
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials used in the synthesis method are lithium hydride and lithium sulfate, the raw materials required by the reaction are few, the purity of the reaction product can be ensured by ensuring the purity of the raw materials, and the purity of the product is not influenced by external factors such as the operation sequence and the like.
(2) The synthesis method is simple to operate, requires low reaction temperature, and has no treatment problems of waste water, waste gas, waste residues and the like.
(3) The reaction is triggered by solid-solid two-phase heating, can be easily controlled by controlling the reaction temperature and the reaction time, and is easy to realize industrialized large-scale production.
(4) The method has simple steps, simple process and low cost, and is suitable for continuous large-scale production.
Drawings
FIG. 1 is an X-ray diffraction pattern of lithium sulfide prepared in inventive example 1.
Detailed description of the invention
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the embodiments described below are only a part of the embodiments of the present invention, and do not represent all the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Weighing lithium hydride and lithium sulfate according to a molar ratio of 8:1 under the protection of argon atmosphere, pouring the lithium hydride and the lithium sulfate into an agate mortar, fully grinding and mixing, transferring the mixture into a reactor, heating the mixture to 500 ℃ at a heating rate of 2 ℃/min, preserving the heat for 2h, cooling the mixture to room temperature after the reaction is finished, pumping out gas in the reactor to reach a vacuum state, transferring the gas to an argon protection atmosphere, opening the reactor, and taking out powder to obtain the powder containing the lithium sulfide. And dissolving the powder by using absolute ethyl alcohol, filtering, heating the filtrate at 50 ℃ for 10h, and evaporating to obtain the lithium sulfide powder. FIG. 1 is the corresponding X-ray diffraction pattern, and the resulting product is a single phase of lithium sulfide.
Example 2
Weighing lithium hydride and lithium sulfate according to a molar ratio of 8:2 under the protection of argon atmosphere, pouring the lithium hydride and the lithium sulfate into an agate mortar, fully grinding and mixing, transferring the mixture into a reactor, heating the mixture to 200 ℃ at a heating rate of 1 ℃/min, preserving the temperature for 100h, cooling the mixture to room temperature after the reaction is finished, pumping gas in the reactor out to reach a vacuum state, transferring the reactor into an argon protection atmosphere, opening the reactor, and taking out powder to obtain the powder containing the lithium sulfide. And dissolving the powder by using absolute ethyl alcohol, filtering, heating the filtrate at 80 ℃ for 1h, and evaporating to obtain the lithium sulfide powder.
Example 3
Under the protection of helium atmosphere, weighing lithium hydride and lithium sulfate according to a molar ratio of 8:0.5, pouring the lithium hydride and the lithium sulfate into an agate mortar, fully grinding and mixing, transferring the mixture into a reactor, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, cooling to room temperature after the reaction is finished, pumping gas in the reactor out to reach a vacuum state, transferring the reactor into helium protective atmosphere, opening the reactor, and taking out powder to obtain the powder containing lithium sulfide. And dissolving the powder by using absolute ethyl alcohol, filtering, heating the filtrate at 60 ℃ for 5h, and evaporating to obtain the lithium sulfide powder.
Example 4
Weighing lithium hydride and lithium sulfate according to a molar ratio of 8:4 under the protection of nitrogen atmosphere, pouring the lithium hydride and the lithium sulfate into an agate mortar, fully grinding and mixing, transferring the mixture into a reactor, heating the mixture to 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 50h, cooling the mixture to room temperature after the reaction is finished, pumping gas in the reactor out to reach a vacuum state, transferring the mixture into the nitrogen atmosphere, opening the reactor, and taking out powder to obtain the powder containing lithium sulfide. And dissolving the powder by using absolute ethyl alcohol, filtering, heating the filtrate at 50 ℃ for 100h, and evaporating to obtain the lithium sulfide powder.
Example 5
Under the protection of a mixed atmosphere of argon and helium, weighing lithium hydride and lithium sulfate according to a molar ratio of 8:0.5, pouring the lithium hydride and lithium sulfate into an agate mortar, fully grinding and mixing, transferring the mixture into a reactor, heating to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 10 hours, cooling to room temperature after the reaction is finished, pumping out gas in the reactor to reach a vacuum state, transferring the reactor into a mixed protection atmosphere of argon and helium, opening the reactor, and taking out powder to obtain the powder containing lithium sulfide. And dissolving the powder by using absolute ethyl alcohol, filtering, heating the filtrate at 60 ℃ for 8h, and evaporating to obtain the lithium sulfide powder.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A method for preparing lithium sulfide by using lithium sulfate is characterized by comprising the following steps:
(1) uniformly mixing lithium hydride and lithium sulfate in a certain proportion under an inert atmosphere, and transferring the mixture into a closed reactor;
(2) heating the mixture to a set temperature at a certain rate and preserving the temperature for a certain time;
(3) after the reaction is finished and the temperature is reduced to room temperature, collecting the gas in the reactor, and then taking out the reaction product under the inert atmosphere or vacuum condition;
(4) under inert atmosphere, dissolving the reaction product by using absolute ethyl alcohol, separating a solid phase and a liquid phase, and removing the solvent from the liquid phase to obtain lithium sulfide powder;
wherein, in the step (2), the heating rate is 1-10 ℃/min, the heating temperature is 100-;
the solvent removing conditions in the step (4) are as follows: keeping the temperature of 50-80 ℃ for 1-100h under the dynamic vacuum condition.
2. The method for preparing lithium sulfide from lithium sulfate according to claim 1, wherein: the lithium sulfate in the step (1) is anhydrous lithium sulfate.
3. The method for preparing lithium sulfide from lithium sulfate according to claim 1, wherein: the molar ratio of lithium hydride to lithium sulfate in the step (1) is 8: (0.5-4).
4. The method for preparing lithium sulfide from lithium sulfate according to claim 1, wherein: the inert atmosphere is any one or more of argon, helium or nitrogen.
5. The method for preparing lithium sulfide from lithium sulfate according to claim 1, wherein: the chemical equation involved in the synthesis method is as follows: li2SO4+8LiH→Li2S+4Li2O+4H2。
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| CN113793933B (en) * | 2021-09-10 | 2023-05-30 | 深圳市研一新材料有限责任公司 | Lithium sulfide for solid electrolyte and preparation method and application thereof |
| CN115231527B (en) * | 2022-07-29 | 2024-02-27 | 深圳博粤新材料科技有限公司 | Method for preparing lithium sulfide by reducing lithium sulfate through organic gas pyrolysis |
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