CN109052488B - Cobalt disulfide material with high storage stability and preparation method and application thereof - Google Patents

Cobalt disulfide material with high storage stability and preparation method and application thereof Download PDF

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CN109052488B
CN109052488B CN201811029143.XA CN201811029143A CN109052488B CN 109052488 B CN109052488 B CN 109052488B CN 201811029143 A CN201811029143 A CN 201811029143A CN 109052488 B CN109052488 B CN 109052488B
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cobalt disulfide
storage stability
cobalt
high storage
acid
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CN109052488A (en
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曹勇
余天浪
刘效疆
余志勇
崔益秀
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Institute of Electronic Engineering of CAEP
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/30—Sulfides
    • 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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Abstract

The invention relates to the technical field of electrode material preparation, in particular to a cobalt disulfide material with high storage stability and a preparation method and application thereof; the method comprises the following steps: preparing a cobalt disulfide displacement reactant; mixing the cobalt disulfide displacement reactant and cobalt disulfide, placing at 120-600 ℃, and carrying out heat preservation reaction for 0.5-72 hours to obtain the catalyst. According to the invention, a protective layer structure is formed on the surface of cobalt disulfide by adopting a replacement mode under specific process conditions, so that the storage stability of cobalt disulfide is greatly improved, and when the cobalt disulfide is applied to products such as thermal batteries, lithium batteries and the like as an electrode material, the performance of the battery is greatly improved, and the battery has a huge application prospect.

Description

Cobalt disulfide material with high storage stability and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a cobalt disulfide material with high storage stability and a preparation method and application thereof.
Background
CoS2The sulfide with good conductivity has excellent electric, magnetic and catalytic performances, and can be widely applied to the fields of thermal batteries, lithium batteries, solar batteries, super capacitors and the like. At present, CoS2The preparation and synthesis of the catalyst mainly adopt a solid phase method and are prepared by the processes of high-temperature calcination of metal cobalt and excessive sulfur simple substance and desulfurization.
However, CoS synthesized by the solid phase method2In the presence of H2O、O2Easy decomposition in the environmental storage process to generate CoSO4·H2O obviously reduces the electric and magnetic catalytic performance of the catalyst, obviously influences the long-term stability of the catalyst and greatly limits the application of the catalyst.
Disclosure of Invention
The invention aims to provide a cobalt disulfide material with high storage stability and a preparation method thereof, the method solves the problem of easy decomposition by forming a shell structure on the surface of the cobalt disulfide material, greatly improves the storage stability of the cobalt disulfide material, and the cobalt disulfide material with high storage stability is applied to the aspects of thermal batteries, lithium batteries, solar batteries and super capacitors as an electrode material, so that the performance of the product is greatly improved, and the cobalt disulfide material has wide application prospect.
The technical scheme for solving the technical problems is as follows: the preparation method of the cobalt disulfide material with high storage stability is provided, and comprises the following steps:
(1) preparing a cobalt disulfide displacement reactant;
(2) mixing the cobalt disulfide displacement reactant and cobalt disulfide, placing at 120-600 ℃, and carrying out heat preservation reaction for 0.5-72 hours to obtain the catalyst.
The beneficial effects of adopting the above technical scheme are: according to the invention, a protective layer structure is formed on the surface of cobalt disulfide by adopting a replacement mode under specific process conditions, so that the storage stability of cobalt disulfide is greatly improved, and when the cobalt disulfide is applied to products such as thermal batteries, lithium batteries and the like as an electrode material, the performance of the battery is greatly improved, and the battery has a huge application prospect.
Further, in the step (1), the method for preparing the cobalt disulfide replacement reactant comprises the following steps:
adding acid and metal salt into at least one of water and alcohol as a solvent, and uniformly stirring to prepare a cobalt disulfide precursor displacement solution; wherein, the solvent can be water or alcohol, or a mixture of water and alcohol, when the solvent is a mixed solution of water and alcohol, the volume fraction of water is 50-90%, and the volume fraction of alcohol is 10-50%; the molar ratio of acid to metal salt is 0.5-3: 1; the metal salt is a soluble metal salt.
The beneficial effects of adopting the above technical scheme are: the cobalt disulfide precursor displacement solution is composed of water or alcohol or a solution of water and alcohol in a certain proportion, so that the pressure of a reaction system is improved, displaced ions and cobalt disulfide are uniformly coated, and the next displacement reaction can be effectively promoted.
Further, the specific process of the step (2) is as follows:
placing cobalt disulfide in a cobalt disulfide precursor displacement solution to prepare a suspension, placing the suspension at 120-240 ℃ and 10-60Mpa, carrying out heat preservation reaction for 24-48 hours, and then cooling to obtain a cobalt disulfide material with high storage stability; wherein the concentration of the cobalt disulfide is 20-100 g/L.
The beneficial effects of adopting the above technical scheme are: the invention is characterized in that cobalt disulfide precursor displacement solution and cobalt disulfide are in oneThe replacement reaction is carried out under the conditions of fixed proportion, temperature and pressure, a shell layer with the thickness of 3-30nm can be effectively generated on the surface of the cobalt disulfide, and the cobalt disulfide and H are avoided2O and O2Thereby increasing the CoS2Storage stability of (1).
Further, placing cobalt disulfide in a cobalt disulfide precursor displacement solution to prepare a suspension, placing the suspension at 180 ℃ and 10Mpa, carrying out heat preservation reaction for 48 hours, and then cooling to obtain a cobalt disulfide material with high storage stability; wherein the concentration of the cobalt disulfide is 20-100 g/L.
The soluble metal salt is soluble metal salt such as chloride, sulfate, oxalate, acetate, nitrate, cyanide and the like of Fe, Ni, Mn, Zr or Ti; fe can be FeSO4、FeCl2、Fe(CN)2Ferrous oxalate, and the like.
The acid is at least one of hydrochloric acid, acetic acid, nitric acid, citric acid and sulfuric acid.
Further, in the step (1), the method for preparing the cobalt disulfide replacement reactant comprises the following steps:
mixing at least one of lithium halide, sodium halide and potassium halide to obtain a mixture, adding metal salt into the mixture, and uniformly mixing to obtain a cobalt disulfide replacement molten salt carrier; for example, lithium halide, sodium halide and potassium halide may be mixed, wherein the mass ratio of lithium halide in the mixture is 20 to 50%, the mass ratio of sodium halide in the mixture is 20 to 50%, and the mass ratio of potassium halide in the mixture is 30 to 60%;
the lithium halide comprises at least one of LiF, LiCl and LiBr;
the sodium halide comprises at least one of NaF, NaCl and NaBr;
the potassium halide comprises at least one of KF, KCl and KBr;
wherein the lithium halide, the sodium halide and the potassium halide are contained in the mixture in an amount of +/-5 wt% of the lowest eutectic component of the mixture; wherein, the component content of the lowest eutectic point is obtained by querying a database (website: http:// www.crct.polymtl.ca/FACT/documentation /).
The beneficial effects of adopting the above technical scheme are: the invention provides a liquid environment by taking a molten salt carrier of halide as a replacement reactant, thereby promoting the replacement of CoS ion pair2The uniform coating can effectively promote the next displacement reaction, make the displacement layer uniform and avoid insufficient displacement effect or performance reduction caused by over-thinness or over-thicknessness.
Further, the specific process in the step (2) is as follows:
placing the cobalt disulfide replacement molten salt carrier in a non-oxidizing atmosphere environment at 240-600 ℃, preserving heat, reacting for 0.5-12 hours, cooling, and reacting to obtain a cobalt disulfide material with a shell structure; wherein the mass ratio of the cobalt disulfide to the cobalt disulfide replacement molten salt carrier is 1: 1-5.
The cobalt disulfide material with high storage stability prepared by the method has a protective layer on the surface, and CoS can be avoided2During storage with H2O and O2Direct contact, thereby significantly increasing CoS2Storage stability of (C), thereby avoiding CoS2The electric, magnetic and catalytic performances are reduced due to decomposition.
The cobalt disulfide material has high storage stability, and is applied to the preparation of electrode materials of thermal batteries, lithium batteries, solar batteries and super capacitors, so that the CoS content is greatly improved2The material is the performance of thermal batteries, lithium batteries, solar batteries, super capacitors and the like of electrode materials, and has wide application prospect and practical significance.
Drawings
Figure 1 is an XRD pattern of cobalt disulphide material according to the invention, which has not been treated by the process according to the invention, before and after storage in air (100% humidity) for 170h, respectively, with cobalt disulphide material treated according to example 1 according to the invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1:
a method for preparing a cobalt disulfide material with high storage stability comprises the following steps:
preparing a cobalt disulfide precursor replacement solution: adding 0.05mol of citric acid and 0.05mol of FeCl2Dissolving the cobalt disulfide precursor into 100ml of deionized water, and uniformly stirring to obtain a cobalt disulfide precursor replacement solution;
0.05mol CoS2Adding the cobalt disulfide precursor into the replacement solution, and uniformly stirring to prepare a suspension;
pouring the suspension into a high-pressure reaction kettle, and carrying out heat preservation reaction at 200 ℃ and 40Mpa for 24 hours;
cleaning and centrifugally filtering the cooled mixture in the high-pressure reaction kettle, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain CoS with a shell structure2A material.
Example 2:
a method for preparing a cobalt disulfide material with high storage stability comprises the following steps:
preparing a cobalt disulfide precursor replacement solution: citric acid (0.2mol), sulfuric acid (0.01mol) and MnCl2(0.1mol) is dissolved in 100ml of mixed solvent of ethylene glycol, glycerol and tetrol, and the mixture is stirred evenly to obtain cobalt disulfide precursor displacement solution; wherein the volume ratio of the ethylene glycol to the glycerol to the erythritol is 2:1: 1;
0.1mol CoS2Adding the cobalt disulfide precursor into the replacement solution, and uniformly stirring to prepare a suspension;
pouring the suspension into a high-pressure reaction kettle, and carrying out heat preservation reaction at 180 ℃ and 60Mpa for 30 hours;
cleaning and centrifugally filtering the cooled mixture in the high-pressure reaction kettle, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain CoS with a shell structure2A material.
Example 3:
a method for preparing a cobalt disulfide material with high storage stability comprises the following steps:
preparing a cobalt disulfide precursor replacement solution: citric acid (0.1mol) and sulfuric acid (0.02 mo)l)、Ni 2SO4(0.1mol) is dissolved in 100ml of mixed solvent of glycol, glycerol, erythritol and water, and the mixture is stirred evenly to obtain cobalt disulfide precursor displacement solution; the volume of the ethylene glycol, the glycerol, the erythritol and the water is 1:1:1: 3;
0.15mol CoS2Adding the cobalt disulfide precursor into the replacement solution, and uniformly stirring to prepare a suspension;
pouring the suspension into a high-pressure reaction kettle, and carrying out heat preservation reaction at 240 ℃ and 10Mpa for 48 hours;
cleaning and centrifugally filtering the cooled mixture in the high-pressure reaction kettle, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain CoS with a shell structure2A material.
Example 4:
a method for preparing a cobalt disulfide material with high storage stability comprises the following steps:
preparing a cobalt disulfide replacement molten salt carrier: 0.4g of FeCl21g of LiCl (45 wt%) -KCl (55 wt%) was uniformly mixed to obtain a mixture;
1gCoS2Placing the mixture and the mixture in argon, preserving the heat for 3 hours at 400 ℃, and cooling;
dissolving the mixture, filtering, and drying in a vacuum oven at 80 ℃ for 24h to obtain the CoS with a shell structure2A material.
Example 5:
a method for preparing a cobalt disulfide material with high storage stability comprises the following steps:
preparing a cobalt disulfide replacement molten salt carrier: 0.4g of NiCl21g of LiCl (22 wt%) -LiBr (68.4 wt%) -LiF (9.6 wt%) was uniformly mixed to obtain a mixture;
0.5g of CoS2Placing the mixture and the mixture in argon, preserving the temperature for 10 hours at 460 ℃, and cooling;
dissolving the mixture, filtering, and drying in a vacuum oven at 80 ℃ for 24h to obtain the CoS with a shell structure2A material.
Example 6:
a method for preparing a cobalt disulfide material with high storage stability comprises the following steps:
preparing a cobalt disulfide replacement molten salt carrier: 0.4g of NiCl21g LiF (0.67 wt%) -LiBr (53.5 wt%) -KBr (45.83 wt%) was uniformly mixed to obtain a mixture;
1.4gCoS2Placing the mixture and the mixture in nitrogen, preserving heat for 1h at 600 ℃, and cooling;
dissolving the mixture, filtering, and drying in a vacuum oven at 80 ℃ for 24h to obtain the CoS with a shell structure2A material.
Test example:
the cobalt disulfide material which is not treated by the method of the invention and the cobalt disulfide material which is treated by the method of the invention and has storage stability are respectively stored in the air (100 percent of humidity) for 170h, and the materials before and after the materials are respectively stored in the air are respectively subjected to XRD analysis, and the structures are shown in figure 1;
as can be seen in FIG. 1, the untreated CoS2After storage, the CoS prepared in example 1 of the present invention undergoes a large amount of decomposition2After storage, the original crystal structure can be still maintained, which shows that after the treatment of the method of the invention, CoS2The storage stability of the product is obviously improved, and the product has a great application prospect.
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. The preparation method of the cobalt disulfide material with high storage stability is characterized by comprising the following steps:
(1) the displacement reactants were formulated as follows:
taking at least one of water and alcohol as a solvent, adding acid and metal salt into the solvent, and uniformly stirring to prepare a cobalt disulfide precursor displacement solution; the concentration of the acid is 0.05-1 mol/L;
the molar ratio of the acid to the metal salt is 0.5-3: 1;
the metal salt is soluble metal salt;
(2) placing cobalt disulfide in a cobalt disulfide precursor displacement solution to prepare a suspension, placing the suspension at 120-240 ℃ under the condition of 10-60MP a, carrying out heat preservation reaction for 24-48 hours, and then cooling to obtain a cobalt disulfide material with high storage stability; wherein the concentration of the cobalt disulfide is 20-100 g/L;
alternatively, (1) the metathesis reaction was formulated as follows:
mixing at least one of lithium halide, sodium halide and potassium halide to obtain a mixture, adding metal salt into the mixture, and uniformly mixing to obtain a cobalt disulfide replacement molten salt carrier;
the lithium halide comprises at least one of LiF, LiCl and LiBr; the sodium halide comprises at least one of NaF, NaCl and NaBr;
the potassium halide comprises at least one of KF, KCl and KBr;
the lithium halide, the sodium halide and the potassium halide are contained in the mixture in a content of +/-5 wt% of the lowest eutectic point component of the mixture;
(2) mixing cobalt disulfide and a cobalt disulfide replacement molten salt carrier, placing the mixture in a non-oxidizing atmosphere environment at the temperature of 240-600 ℃, carrying out heat preservation reaction for 0.5-12 hours, cooling, and reacting to obtain a cobalt disulfide material with a shell structure; wherein the mass ratio of the cobalt disulfide to the cobalt disulfide replacement molten salt carrier is 1: 1-5.
2. The method for preparing cobalt disulfide material with high storage stability as claimed in claim 1, wherein cobalt disulfide is placed in a cobalt disulfide precursor displacement solution to prepare a suspension, and the suspension is placed at 180 ℃ and 10MP a for heat preservation reaction for 48 hours and then cooled to obtain the cobalt disulfide material with high storage stability;
wherein the concentration of the cobalt disulfide is 20-100 g/L.
3. The method for preparing cobalt disulfide material with high storage stability as claimed in claim 1, wherein:
the acid is at least one of hydrochloric acid, acetic acid, nitric acid, citric acid and sulfuric acid;
the soluble metal salt is soluble metal salt of Fe, Ni, Mn, Zr or Ti.
4. The cobalt disulfide material with high storage stability prepared by the method for preparing a cobalt disulfide material with high storage stability of any one of claims 1 to 3.
5. Use of the cobalt disulfide material with high storage stability of claim 4 in the preparation of electrode materials for thermal batteries, lithium batteries, solar cells, supercapacitors.
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