CN112125283A - Method for preparing lithium sulfide by solid-liquid mixing and heating - Google Patents
Method for preparing lithium sulfide by solid-liquid mixing and heating Download PDFInfo
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- CN112125283A CN112125283A CN202010765234.0A CN202010765234A CN112125283A CN 112125283 A CN112125283 A CN 112125283A CN 202010765234 A CN202010765234 A CN 202010765234A CN 112125283 A CN112125283 A CN 112125283A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
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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
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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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- 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 solid-liquid mixing and heating. The invention discloses a method for preparing high-purity lithium sulfide, aiming at the defects of increasing the demand of a scientific research institution for lithium sulfide and the defects of complicated steps and harsh conditions of the existing preparation method. According to the method, the lithium sulfide powder with high purity can be obtained only by simply mixing and heating the raw materials and carrying out subsequent purification treatment.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a method for preparing lithium sulfide by solid-liquid mixing and heating.
Background
Lithium-sulfur batteries are considered to be one of the most promising next-generation batteries (Jiang, Li)2S-based Li-ion batteries: progress and features), and lithium sulfide Li2S is taken as a hotspot of the research of the lithium-sulfur battery, and compared with the traditional lithium-sulfur battery which takes sulfur as the battery anode, the lithium sulfide as the anode material has many advantages: (1) lithium sulfide is a final reactant of lithium and sulfur, and the volume expansion effect can not occur in the first charging process, so that the safety of the anode material is ensured; (2) the lithium sulfide has very high melting point (938 ℃), and the thermal stability also ensures that the lithium-sulfur battery can be safely used even at high temperature; (3) the lithium-containing quantity is high, and the lithium-containing battery can be combined with a negative electrode material without lithium to form a full battery, so that the safety of the whole battery is ensured. These advantages make lithium sulfide play an important role in future research.
However, the existing methods for preparing lithium sulfide are not many. Such as: (1) reducing lithium sulfate with carbon or hydrogen under heating condition; (2) reacting lithium with sulfur in liquid ammonia; (3) decomposing an ethanol mixture of lithium hydrosulfide with lithium ethoxide to prepare lithium sulfide; (4) lithium hydrosulfide is prepared by reacting pentoxy lithium with hydrogen sulfide, and then the lithium hydrosulfide is heated and decomposed in vacuum to prepare the lithium sulfide. The methods for preparing the lithium sulfide generally have the defects of complicated preparation process, complex and harsh preparation conditions, high price of reactants or impure products and the like, so that the high price of the lithium sulfide in the market is caused, and the research speed and the application of the lithium sulfide are limited. Therefore, it is of great significance to develop a method for preparing lithium sulfide which is efficient, cheap and has purity meeting the requirements of laboratories.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of lithium sulfide, which has the advantages of simple conditions, easiness in realization of industrial production, low preparation cost, high purity of the product lithium sulfide and the like.
The technical solution of the present invention is specifically described below.
The invention provides a method for preparing lithium sulfide by solid-liquid mixing and heating, which comprises the following specific steps:
(1) under inert atmosphere, uniformly mixing a lithium-containing substance and carbon disulfide according to a certain proportion, and transferring a solid-liquid mixture into a closed reactor;
(2) heating the mixture to a set temperature at a certain heating rate, and preserving heat for a certain time;
(3) after the reaction is finished and the temperature in the reactor is reduced to 100 ℃, collecting the gas in the reactor, and then taking out the 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 present invention, the lithium-containing material in the step (1) is any one of lithium hydroxide and lithium oxide or a mixture of both.
In the present invention, the lithium-containing material in step (1) needs to be dried in advance to contain no moisture.
In the invention, the molar ratio of the lithium-containing substance to the carbon disulfide in the step (1) is (0.1-6): 1.
in the invention, the heating rate in the step (2) is 1-10 ℃/min, the heating temperature is 200-.
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 nitrogen, argon, or helium.
In the invention, the chemical equation is as follows: 3Li2O+CS2→2Li2S+Li2CO3；6LiOH+2CS2→Li2S+2Li2CO3+3H2S。
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials used in the synthesis method are lithium-containing substances and carbon disulfide, the raw materials required by the reaction are few, the purity of the reaction product can be ensured as long as the purity of the raw materials is ensured, and the product purity is not influenced by external factors such as the operation sequence and the like.
(2) The synthetic method has no treatment problems of waste water, waste gas, waste residue and the like.
(3) The reaction is triggered by heating after solid-liquid mixing, and can be easily controlled by controlling the reaction temperature and the reaction time, so that the industrial large-scale production is easy to realize.
(4) The method has the advantages of few steps, simple process and low cost, and is suitable for 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
Uniformly mixing lithium hydroxide and carbon disulfide in a molar ratio of 1:1 in an argon atmosphere, transferring the mixture into a closed reactor, heating the mixture to 300 ℃ at a heating rate of 2 ℃/min, preserving the temperature for 5h, cooling the mixture to 100 ℃ after the reaction is finished, pumping gas in the reactor by using a vacuum pump, transferring the gas into an argon protection atmosphere, opening the reactor, taking out powder, pouring the powder into absolute ethyl alcohol, performing suction filtration after the powder is fully dissolved, and heating and evaporating filtrate to remove the absolute ethyl alcohol to obtain the lithium sulfide powder. FIG. 1 is a corresponding X-ray diffraction pattern for lithium sulfide as the product.
Example 2
Uniformly mixing lithium hydroxide and carbon disulfide according to a molar ratio of 6:1 in an argon and helium mixed atmosphere, transferring the mixture into a closed reactor, heating the mixture to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, cooling the mixture to 100 ℃ after the reaction is finished, pumping out gas in the reactor by using a vacuum pump, transferring the gas into a protective atmosphere of argon and helium mixed, opening the reactor, taking out powder, pouring the powder into absolute ethyl alcohol, performing suction filtration after the powder is fully dissolved, and heating and evaporating filtrate to obtain lithium sulfide powder.
Example 3
Uniformly mixing lithium oxide and carbon disulfide in a molar ratio of 1:1 in a helium atmosphere, transferring the mixture into a closed reactor, heating the mixture to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 hours, cooling the mixture to 100 ℃ after the reaction is finished, pumping gas in the reactor by using a vacuum pump, transferring the gas into a helium protective atmosphere, opening the reactor, taking out powder, pouring the powder into absolute ethyl alcohol, fully dissolving the powder, carrying out suction filtration, and heating and evaporating filtrate to obtain lithium sulfide powder.
Example 4
Uniformly mixing lithium oxide and carbon disulfide at a molar ratio of 0.1:1 in an argon and helium mixed atmosphere, transferring the mixture into a closed reactor, heating the mixture to 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, cooling the mixture to 100 ℃ after the reaction is finished, pumping gas in the reactor by using a vacuum pump, transferring the gas into a mixed protective atmosphere of argon and helium, opening the reactor, taking out powder, pouring the powder into absolute ethyl alcohol, performing suction filtration after full dissolution, and heating and evaporating filtrate to obtain lithium sulfide powder.
Example 5
Uniformly mixing lithium hydroxide and carbon disulfide in a molar ratio of 3:1 in a nitrogen atmosphere, transferring the mixture into a closed reactor, heating the mixture to 200 ℃ at a heating rate of 1 ℃/min, preserving the temperature for 100 hours, cooling the mixture to 100 ℃ after the reaction is finished, pumping gas in the reactor by using a vacuum pump, transferring the gas into a nitrogen protection atmosphere, opening the reactor, taking out powder, pouring the powder into absolute ethyl alcohol, fully dissolving the powder, carrying out suction filtration, and heating and evaporating filtrate to obtain the lithium sulfide powder.
Example 6
Uniformly mixing lithium hydroxide, lithium oxide and carbon disulfide in a molar ratio of 1:1:2 in an argon atmosphere, transferring the mixture into a closed reactor, heating the mixture to 400 ℃ at a heating rate of 2 ℃/min, preserving the heat for 12 hours, cooling the mixture to 100 ℃ after the reaction is finished, pumping out gas in the reactor by using a vacuum pump, transferring the gas into an argon protection atmosphere, opening the reactor, taking out powder, pouring the powder into absolute ethyl alcohol, fully dissolving, carrying out suction filtration, and heating and evaporating filtrate to obtain 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 (7)
1. A method for preparing lithium sulfide by solid-liquid mixing and heating is characterized by comprising the following steps:
(1) under inert atmosphere, uniformly mixing a lithium-containing substance and carbon disulfide according to a certain proportion, and transferring a solid-liquid mixture into a closed reactor;
(2) heating the mixture to a set temperature at a certain heating rate, and preserving heat for a certain time;
(3) after the reaction is finished and the temperature in the reactor is reduced to 100 ℃, collecting the gas in the reactor, and then taking out the 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.
2. The method for preparing lithium sulfide by solid-liquid mixing and heating according to claim 1, wherein: the lithium-containing substance is any one of lithium hydroxide and lithium oxide or a mixture of the lithium hydroxide and the lithium oxide.
3. The method for preparing lithium sulfide by solid-liquid mixing and heating according to claim 1, wherein: the lithium-containing substance is dried and does not contain moisture.
4. The method for preparing lithium sulfide by solid-liquid mixing and heating according to claim 1, wherein: the molar ratio of the lithium-containing substance to the carbon disulfide in the step (1) is (0.1-6): 1.
5. the method for preparing lithium sulfide by solid-liquid mixing and heating according to claim 1, wherein: the heating temperature in the step (2) is 200-.
6. The method for preparing lithium sulfide by solid-liquid mixing and heating according to claim 1, wherein: the inert atmosphere is any one or more of nitrogen, argon or helium.
7. The method for preparing lithium sulfide by solid-liquid mixing and heating according to claim 1, wherein: the chemical equation involved in the synthesis method is as follows: 3Li2O+CS2→2Li2S+Li2CO3；6LiOH+2CS2→Li2S+2Li2CO3+3H2S。
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010765234.0A CN112125283A (en) | 2020-08-03 | 2020-08-03 | Method for preparing lithium sulfide by solid-liquid mixing and heating |
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| CN202010765234.0A CN112125283A (en) | 2020-08-03 | 2020-08-03 | Method for preparing lithium sulfide by solid-liquid mixing and heating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195103A (en) * | 2021-12-30 | 2022-03-18 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
| WO2023032701A1 (en) * | 2021-09-02 | 2023-03-09 | Ａｇｃ株式会社 | Method for producing lithium sulfide |
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| JPH09278423A (en) * | 1996-04-16 | 1997-10-28 | Furukawa Co Ltd | Production of lithium sulfide |
| FR2977722A1 (en) * | 2011-07-05 | 2013-01-11 | Commissariat Energie Atomique | ELECTRODES SEPARATOR FOR LITHIUM / SULFUR ACCUMULATOR |
| CN103107318A (en) * | 2013-02-04 | 2013-05-15 | 中南大学深圳研究院 | Preparation method of composite positive pole material for lithium sulphur battery |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023032701A1 (en) * | 2021-09-02 | 2023-03-09 | Ａｇｃ株式会社 | Method for producing lithium sulfide |
| CN114195103A (en) * | 2021-12-30 | 2022-03-18 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
| CN114195103B (en) * | 2021-12-30 | 2022-08-30 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
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