CN110943217A - Bimetallic sulfide/sulfur particle composite material converted from metal organic framework, preparation method and application thereof - Google Patents
Bimetallic sulfide/sulfur particle composite material converted from metal organic framework, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a bimetallic sulfide/sulfur particle composite material converted by a metal organic framework, a preparation method and application thereof, wherein the preparation method comprises the following steps: carrying out vulcanization treatment on the prepared Zn-Co-MOFs/carbon cloth composite material by using a sodium sulfide solution to obtain ZnCo2S4Soaking the/carbon cloth composite material in a sulfur carbon disulfide solution, drying, and then carrying out sulfur fumigation to obtain ZnCo2S4Carbon cloth/S composite materialAnd (5) feeding. Compared with the prior art, the ZnCo prepared by the invention2S4Inherits the porous characteristics of MOF materials, the open porous surface is beneficial to the massive loading of sulfur particles and provides physical limitation for the volume expansion of sulfur, and ZnCo2S4The compound has strong adsorption effect on polysulfide, can obviously inhibit the shuttle effect of the lithium-sulfur battery, and improves the cycle performance and rate capability of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery composite materials, and particularly relates to a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, a preparation method and application thereof, which are used for a lithium-sulfur battery anode and a lithium-sulfur battery.
Background
The great consumption of fossil fuels and the consequent environmental pollution problems are at the back of the economic flight of today's society, and the development of clean energy storage and conversion facilities is therefore at an urgent pace. The lithium ion battery has the advantages of good stability, wide temperature range, long cycle life, low self-discharge rate and the like, and is widely favored and applied in the new energy market.
However, the low capacity density of lithium ion batteries limits their further large-scale applications, and in recent years, lithium sulfur batteries have been used at their high capacity density (1675mAh g)-1) Is intensively studied by academia. In addition, the positive active material sulfur of the lithium sulfur battery is non-toxic and widely distributed in nature, so the lithium sulfur battery becomes the most potential battery system.
Currently, there are several problems to be solved in lithium sulfur batteries: (1) sulfur itself has very poor conductivity, only 5X 10-30S cm-1There is a large impedance during battery cycling, resulting in slower electron transfer; (2) there is a volume expansion of about 80%, and a large volume change of sulfur during charge and discharge easily leads to pulverization and collapse of the positive electrode structure, resulting inA sharp decay in capacity; (3) "shuttle effect" of lithium-sulfur batteries, discharge product Li2Sx(x ═ 4,6,8) can dissolve in the electrolyte, pass through the separator to reach the negative electrode, react with lithium metal, causing low sulfur utilization and irreversible loss of capacity.
Since the practical application of the lithium-sulfur battery is limited by the above problems, researchers generally increase the conductivity of the whole positive electrode by loading sulfur particles on a material with better conductivity, such as a carbon-based material (graphene, carbon nanotubes, carbon microspheres, etc.), so as to accelerate the electron transport. In addition, the specific structure of the carbon-based material may also physically limit the volume expansion of sulfur. The "shuttle effect" of lithium-sulfur batteries has been a problem that has plagued researchers, and metal oxides, sulfides, phosphides, etc. have a large chemisorption on their discharge products, and the "shuttle effect" is suppressed by forming a polar bond with Li or S in polysulfides.
Currently, improving the conductivity of the positive electrode of lithium-sulfur batteries, inhibiting the volume expansion of sulfur and the "shuttling effect" of the discharge products has become a common consensus to improve the cycle performance and service life of batteries.
The lithium-sulfur battery with high capacity density and low cost is provided, and the lithium-sulfur battery is beneficial to the realization of industrial application as soon as possible.
Disclosure of Invention
The invention aims to provide a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework and a preparation method thereof2S4Soaking the carbon cloth composite material in a sulfur carbon disulfide solution, drying and then fumigating to obtain the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework.
The invention also provides the use of the bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, in particular the use as a positive electrode of a lithium sulfur battery.
The specific technical scheme of the invention is as follows:
a method for preparing a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, comprising the steps of:
1) dissolving cobalt salt and zinc salt in water to obtain a solution A;
2) dissolving 2-methylimidazole in water to obtain a solution B;
3) adding the solution B into the solution A, stirring and mixing, adding carbon cloth, standing for reaction, taking out the carbon cloth, washing and drying to obtain the Zn-Co-MOFs/carbon cloth composite material;
4) putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step 3) into a sodium sulfide solution for hydrothermal reaction, taking out the product, washing and drying to obtain a self-supporting transition metal sulfide composite material ZnCo2S4A carbon cloth composite material;
5) soaking the self-supporting transition metal sulfide composite material prepared in the step 4) in a carbon disulfide solution of sulfur for reaction, then taking out, drying, and then carrying out sulfur fumigation to obtain the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework.
In the step 1), the concentration of the zinc salt in the solution A is 0.01-0.025 mol/L, preferably 0.015-0.02 mol/L; the zinc salt is one or two of zinc sulfate heptahydrate or zinc nitrate hexahydrate.
In the step 1), the concentration of the cobalt salt in the solution A is 0.02-0.05 mol/L, preferably 0.03-0.04 mol/L; the cobalt salt is one or two of cobalt sulfate heptahydrate or cobalt nitrate hexahydrate.
In the step 2), the concentration of the 2-methylimidazole in the solution B is 0.2-0.5 mol/L, preferably 0.35-0.4 mol/L.
In the step 3), the carbon cloth is respectively ultrasonically cleaned for 10min by using acetone, ethanol and water before use.
In the step 3), the volume ratio of the solution A to the solution B is 1: 1.
in the step 3), the stirring time is 1 min.
The standing reaction in the step 3) is carried out at the temperature of 20-28 ℃, preferably 25 ℃, and the standing reaction time is 4-12 hours, preferably 5-8 hours. In the standing process, the organic ligand provided by the 2-methylimidazole fully reacts with zinc ions and cobalt ions in the solution A and grows on the carbon cloth.
In the step 3), the washing refers to rinsing with deionized water for three times; the drying refers to drying at 60 ℃ for 12 h.
In the step 4), the sodium sulfide solution is prepared by dissolving sodium sulfide nonahydrate in water.
In the step 4), the concentration of the sodium sulfide solution is 0.05-0.5mol/L, preferably 0.1-0.3 mol/L.
In the step 4), the hydrothermal reaction temperature is 90-150 ℃, and preferably 100-120 ℃; the hydrothermal reaction time is 5 to 12 hours, preferably 6 to 9 hours. The hydrothermal reaction temperature is low, and the low-temperature vulcanization is realized.
In step 4), the washing is rinsing with deionized water three times, and the drying is drying at 60 ℃ for 12 hours.
In the step 5), the concentration of the carbon disulfide solution of sulfur is 1-3 mol/L, preferably 1.25-2 mol/L.
In the step 4), sulfur is dissolved in carbon disulfide to form a solution, when the self-supporting transition metal sulfide composite material is soaked in the sulfur carbon disulfide solution, the solution can uniformly and fully infiltrate the carbon cloth and the composite material growing on the carbon cloth, and then the carbon disulfide is dried and volatilized, so that the sulfur can be uniformly loaded on the composite material.
In the step 5), the soaking time is 3-10 min, preferably 5-8 min.
In the step 5), drying is carried out for 12 hours at the drying temperature of 45 ℃.
In the step 5), the sulfuration temperature is 145-160 ℃, the sulfuration time is 12-16h, and the sulfuration atmosphere is argon. The sulfur already loaded on the composite material is subjected to the sulfur fumigation treatment under the above conditions, so that the sulfur can be more firmly loaded on the composite material.
The bimetallic sulfide/sulfur particle composite material converted from the metal organic framework is prepared by the method. The prepared composite material has excellent conductivity and flexibility, sulfur particles with the size of 200 plus 300 nanometers are loaded on the transition metal sulfide after sulfur fumigation, the preparation method is simple, the requirement on instruments and equipment is low, and the composite material can be used for assembling flexible lithium-sulfur batteries. The growth of MOFs at room temperature and the subsequent low-temperature vulcanization can greatly save the use of energy and reduce the preparation cost.
The application of the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework provided by the invention is particularly used for manufacturing the positive electrode of the lithium-sulfur battery and is used for the lithium-sulfur battery.
The preparation method comprises the steps of growing Zn-Co-MOFs material on carbon cloth at room temperature (20-28 ℃), and then carrying out vulcanization treatment by using sodium sulfide solution to obtain ZnCo2S4A/carbon cloth composite material. Finally, the prepared composite material is soaked in a carbon disulfide solution of sulfur, the sulfur is fumigated after the composite material is dried, and sulfur particles are loaded on the prepared composite material to obtain ZnCo2S4A/carbon cloth/S composite material.
In order to improve the conductivity of the positive electrode of the lithium-sulfur battery, inhibit the volume expansion of sulfur and inhibit the shuttle effect of discharge products, which have become the requirements of improving the cycle performance and the service life of the battery, the sulfur-loaded substrate material needs to have excellent conductivity, stronger chemical adsorption and a special physical structure to limit the pulverization of sulfur and avoid the collapse of the positive electrode structure, so as to realize the high stability and high cycle capacity of the lithium-sulfur battery. The carbon cloth substrate improves the conductivity of the whole lithium-sulfur battery anode, and the bendable performance of the carbon cloth enables the whole anode material to have the potential of assembling flexible batteries. In the preparation process, the organic ligand provided by 2-methylimidazole reacts with zinc ions and cobalt ions to coordinate with each other to form MOFs material which grows on the carbon cloth tightly and presents the inherent porous characteristic of the MOF material, and the vulcanized ZnCo material2S4The nanosheets have a height of 1-2 microns, form a cross-linked three-dimensional network structure, are favorably and fully infiltrated by electrolyte, and improve the reaction kinetics in the charging and discharging process of the battery. By dissolving sulfur powder in CS2In the solution, sulfur can be more uniformly loaded on the carbon cloth overgrown with the material by soaking in the solution, the open porous surface is also favorable for the large-scale loading of sulfur particles and provides physical limitation for the volume expansion of the sulfur,and ZnCo2S4Polar bonds can be formed between the lithium sulfur battery and polysulfide, so that polysulfide can be well adsorbed, the shuttle effect of the lithium sulfur battery can be obviously inhibited, and the cycle performance and the rate capability of the battery are improved.
Compared with the prior art, the invention has the following advantages: the shuttle effect of the lithium-sulfur battery can be obviously inhibited, the cycle performance and the rate capability of the battery are improved, and the prepared composite material can be directly used as the positive electrode of the lithium-sulfur battery without additional binder and conductive additive, so that the assembly cost of the battery is further reduced. In addition, the preparation method is simple, can be finished at room temperature, does not need high energy consumption, has low requirements on instruments and equipment and the like, and can be used for large-scale batch preparation. The lithium-sulfur battery anode prepared by the composite material has flexibility, can be bent, and has excellent conductivity.
Drawings
FIG. 1 is an SEM image of a bimetallic sulfide converted from a metal organic framework prepared in step 4) of example 1;
FIG. 2 is an SEM image of a bimetallic sulfide/sulfur particle composite converted from a metal organic framework prepared in example 1;
FIG. 3 is an SEM image of a bimetallic sulfide/sulfur particle composite converted from a metal organic framework prepared in example 2;
FIG. 4 is an SEM image of a bimetallic sulfide/sulfur particle composite converted from a metal organic framework prepared in example 3;
FIG. 5 is an SEM image of a bimetallic sulfide/sulfur particle composite converted from a metal organic framework prepared in example 4;
FIG. 6 is an SEM image of a bimetallic sulfide/sulfur particle composite converted from a metal organic framework prepared in example 5;
FIG. 7 is an XRD pattern of a bimetallic sulfide/sulfur particle composite converted from a metal organic framework prepared in example 3;
fig. 8 is a graph showing the cycle stability test of the bi-metal sulfide/sulfur particle composite material converted from a metal-organic framework, prepared in example 2, as a positive electrode material of a lithium sulfur battery at a current density of 0.2C;
fig. 9 is a charge and discharge curve of the bi-metal sulfide/sulfur particle composite material converted from a metal organic framework prepared in example 2 as a positive electrode material of a lithium sulfur battery at a current density of 0.2C;
fig. 10 is a graph showing the cycle stability test of the bi-metal sulfide/sulfur particle composite material converted from a metal-organic framework, prepared in example 5, as a positive electrode material of a lithium sulfur battery at a current density of 0.2C;
fig. 11 is a charge and discharge curve of the bimetal sulfide/sulfur particle composite material converted from the metal organic framework and prepared in example 5 as a positive electrode material of a lithium sulfur battery at a current density of 0.2C.
Detailed Description
Example 1
A method for preparing a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, comprising the steps of:
(1) 0.1927g of zinc sulfate heptahydrate and 0.3880g of cobalt nitrate hexahydrate are dissolved in 40mL of water to obtain a solution A;
(2) dissolving 1.13g of 2-methylimidazole in 40mL of water to obtain a solution B;
(3) respectively ultrasonically cleaning the carbon cloth with acetone, ethanol and water for 10min before use, quickly pouring the solution B into the solution A, stirring for 1min, adding the cleaned carbon cloth, standing for 4h at 25 ℃, taking out the carbon cloth, washing with deionized water for three times, and drying for 12h at 60 ℃ to obtain the Zn-Co-MOFs/carbon cloth composite material;
(4) dissolving 0.95g of sodium sulfide nonahydrate in 35mL of water to obtain a sodium sulfide solution, then putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step (3) into the sodium sulfide solution, carrying out hydrothermal reaction at 100 ℃ for 6h, taking out a product, washing with deionized water for three times, and drying at 60 ℃ for 12h to obtain a self-supporting transition metal sulfide composite material, namely ZnCo2S4A carbon cloth composite material; the SEM image is shown in FIG. 1.
(5) Dissolving 0.4g of sulfur powder in 10mL of carbon disulfide, soaking the composite material prepared in the step (4) in a sulfur carbon disulfide solution for 4min, taking out, and drying at 45 DEG CDrying for 12h, and then fumigating at 145 ℃ for 12h in argon atmosphere to obtain the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework, namely ZnCo2S4A/carbon cloth/S composite material. The SEM image is shown in FIG. 2.
Example 2
A method for preparing a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, comprising the steps of:
(1) 0.2070g of zinc sulfate heptahydrate and 0.4049g of cobalt sulfate heptahydrate are dissolved in 40mL of water to obtain a solution A;
(2) dissolving 1.31g of 2-methylimidazole in 40mL of water to obtain a solution B;
(3) respectively ultrasonically cleaning the carbon cloth with acetone, ethanol and water for 10min before use, quickly pouring the solution B into the solution A, stirring for 1min, adding the cleaned carbon cloth, standing for 6h at 22 ℃, taking out the carbon cloth, washing with deionized water for three times, and drying for 12h at 60 ℃ to obtain the Zn-Co-MOFs/carbon cloth composite material;
(4) dissolving 1.82g of sodium sulfide nonahydrate in 35mL of water to obtain a sodium sulfide solution, then putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step (3) into the sodium sulfide solution, carrying out hydrothermal reaction at 120 ℃ for 8h, taking out a product, washing the product with deionized water for three times, and drying the product at 60 ℃ for 12h to obtain a self-supporting transition metal sulfide composite material; namely ZnCo2S4A carbon cloth composite material;
(5) dissolving 0.6g of sulfur powder in 10mL of carbon disulfide, soaking the composite material prepared in the step (4) in a sulfur carbon disulfide solution for 4min, taking out, drying at 45 ℃ for 12h, and then fumigating at 155 ℃ for 12h in an argon atmosphere to obtain the bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, namely ZnCo2S4A/carbon cloth/S composite material. The SEM image is shown in FIG. 3.
Example 3
A method for preparing a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, comprising the steps of:
(1) 0.2261g of zinc nitrate hexahydrate and 0.4424g of cobalt nitrate hexahydrate are dissolved in 40mL of water to obtain a solution A;
(2) dissolving 1.24g of 2-methylimidazole in 40mL of water to obtain a solution B;
(3) respectively ultrasonically cleaning the carbon cloth with acetone, ethanol and water for 10min before use, quickly pouring the solution B into the solution A, stirring for 1min, adding the cleaned carbon cloth, standing for 5h at 28 ℃, taking out the carbon cloth, washing with deionized water for three times, and drying for 12h at 60 ℃ to obtain the Zn-Co-MOFs/carbon cloth composite material;
(4) dissolving 1.45g of sodium sulfide nonahydrate in 35mL of water to obtain a sodium sulfide solution, then putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step (3) into the sodium sulfide solution, carrying out hydrothermal reaction at 100 ℃ for 7h, taking out a product, washing the product with deionized water for three times, and drying the product at 60 ℃ for 12h to obtain a self-supporting transition metal sulfide composite material; namely ZnCo2S4A carbon cloth composite material;
(5) dissolving 0.4g of sulfur powder in 10mL of carbon disulfide, soaking the composite material prepared in the step (4) in a sulfur carbon disulfide solution for 4min, taking out, drying at 45 ℃ for 12h, and then fumigating at 160 ℃ for 14h in an argon atmosphere to obtain the bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, namely ZnCo2S4A/carbon cloth/S composite material. The SEM image is shown in FIG. 4, and the XRD image is shown in FIG. 7.
Example 4
A method for preparing a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, comprising the steps of:
(1) 0.2300g of zinc sulfate heptahydrate and 0.4657g of cobalt nitrate hexahydrate are dissolved in 40mL of water to obtain a solution A;
(2) dissolving 1.18g of 2-methylimidazole in 40mL of water to obtain a solution B;
(3) respectively ultrasonically cleaning the carbon cloth with acetone, ethanol and water for 10min before use, quickly pouring the solution B into the solution A, stirring for 1min, adding the cleaned carbon cloth, standing for 7h at 20 ℃, taking out the carbon cloth, washing with deionized water for three times, and drying for 12h at 60 ℃ to obtain the Zn-Co-MOFs/carbon cloth composite material;
(4) dissolving 1.24g of sodium sulfide nonahydrate in 35mL of water to obtain a sodium sulfide solution, then putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step (3) into the sodium sulfide solution, carrying out hydrothermal reaction at 110 ℃ for 6h, taking out a product, washing the product with deionized water for three times, and drying the product at 60 ℃ for 12h to obtain a self-supporting transition metal sulfide composite material; namely ZnCo2S4A carbon cloth composite material;
(5) dissolving 0.5g of sulfur powder in 10mL of carbon disulfide, soaking the composite material prepared in the step (4) in a sulfur carbon disulfide solution for 4min, taking out, drying at 45 ℃ for 12h, and then fumigating at 155 ℃ for 15h in an argon atmosphere to obtain the bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, namely ZnCo2S4A/carbon cloth/S composite material. The SEM image is shown in FIG. 5.
Example 5
A method for preparing a bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, comprising the steps of:
(1) 0.1190g of zinc nitrate hexahydrate and 0.2250g of cobalt sulfate heptahydrate are dissolved in 40mL of water to obtain a solution A;
(2) dissolving 1.45g of 2-methylimidazole in 40mL of water to obtain a solution B;
(3) respectively ultrasonically cleaning the carbon cloth with acetone, ethanol and water for 10min before use, quickly pouring the solution B into the solution A, stirring for 1min, adding the cleaned carbon cloth, standing for 10h at room temperature, taking out the carbon cloth, washing with deionized water for three times, and drying at 60 ℃ for 12h to obtain the Zn-Co-MOFs/carbon cloth composite material;
(4) dissolving 2.55g of sodium sulfide nonahydrate in 35mL of water to obtain a sodium sulfide solution, then putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step (3) into the sodium sulfide solution, carrying out hydrothermal reaction at 95 ℃ for 8h, taking out a product, washing the product with deionized water for three times, and drying the product at 60 ℃ for 12h to obtain a self-supporting transition metal sulfide composite material; namely ZnCo2S4Carbon cloth composite material
(5) 0.6g of sulfur powder is dissolved in 10mL of carbon disulfide, and the composite material prepared in the step (4) is soaked in a sulfur carbon disulfide solutionTaking out for 8min, drying at 45 deg.C for 12h, and fumigating at 160 deg.C for 16h in argon atmosphere to obtain bimetallic sulfide/sulfur particle composite material converted from metal-organic framework, i.e. ZnCo2S4A/carbon cloth/S composite material. The SEM image is shown in FIG. 6.
Example 6
The application of the bimetallic sulfide/sulfur particle composite material converted by the metal organic framework is used for manufacturing the positive electrode of the lithium-sulfur battery, and the lithium-sulfur battery is assembled by using the manufactured positive electrode of the lithium-sulfur battery.
The method specifically comprises the following steps: the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework and prepared in the example 2 is used as a positive electrode, a lithium sheet is used as a negative electrode, and a commercially available 1mol/L LiTFSI/DME + DOL solution is adopted as an electrolyte to assemble the lithium-sulfur battery. The result of the cycle stability test at a current density of 0.2C using a battery tester for the charge and discharge performance test is shown in fig. 8. As can be seen from FIG. 8, the cycling stability of the battery is good, and the specific discharge capacity of the battery is still stable at 539.8mAh/g after 50 times of cycling. The charge and discharge curves at a current density of 0.2C are shown in fig. 9.
Example 7
The application of the bimetallic sulfide/sulfur particle composite material converted by the metal organic framework is used for manufacturing the positive electrode of the lithium-sulfur battery, and the lithium-sulfur battery is assembled by using the manufactured positive electrode of the lithium-sulfur battery.
The method specifically comprises the following steps: the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework and prepared in example 5 is used as a positive electrode, a lithium sheet is used as a negative electrode, and a commercially available 1mol/L LiTFSI/DME + DOL solution is adopted as an electrolyte to assemble the lithium-sulfur battery. The results of the cycle stability test at a current density of 0.2C using a battery tester for the charge and discharge performance test are shown in fig. 10. As can be seen from FIG. 10, the cycling stability of the battery is good, and the specific discharge capacity of the battery is still stable at 625.3mAh/g after 50 times of cycling. The charge and discharge curves at a current density of 0.2C are shown in FIG. 11.
Claims (10)
1. A process for the preparation of a bimetallic sulphide/sulphur particle composite transformed with a metal organic framework, characterized in that it comprises the following steps:
1) dissolving cobalt salt and zinc salt in water to obtain a solution A;
2) dissolving 2-methylimidazole in water to obtain a solution B;
3) adding the solution B into the solution A, stirring and mixing, adding carbon cloth, standing for reaction, taking out the carbon cloth, washing and drying to obtain the Zn-Co-MOFs/carbon cloth composite material;
4) putting the Zn-Co-MOFs/carbon cloth composite material prepared in the step 3) into a sodium sulfide solution for hydrothermal reaction, taking out the product, washing and drying to obtain a self-supporting transition metal sulfide composite material ZnCo2S4A carbon cloth composite material;
5) soaking the self-supporting transition metal sulfide composite material prepared in the step 4) in a carbon disulfide solution of sulfur for reaction, then taking out, drying, and then carrying out sulfur fumigation to obtain the bimetallic sulfide/sulfur particle composite material converted from the metal organic framework.
2. The preparation method according to claim 1, wherein in step 1), the concentration of the zinc salt in the solution A is 0.01-0.025 mol/L.
3. The method according to claim 1 or 2, wherein in step 1), the concentration of the cobalt salt in the solution A in step 1) is 0.02-0.05 mol/L.
4. The preparation method according to claim 1, wherein in the step 2), the concentration of the 2-methylimidazole in the solution B is 0.2-0.5 mol/L.
5. The method according to claim 1, wherein in the step 3), the standing reaction in the step 3) is carried out at 20 to 28 ℃ for 4 to 12 hours.
6. The method according to claim 1, wherein in the step 4), the concentration of the sodium sulfide solution is 0.05 to 0.5 mol/L.
7. The preparation method according to claim 1, wherein in the step 4), the hydrothermal reaction temperature is 90-150 ℃ and the hydrothermal reaction time is 5-12 h.
8. The preparation method according to claim 1, wherein in the step 5), the concentration of the carbon disulfide solution of sulfur is 1-3 mol/L.
9. A bimetallic sulfide/sulfur particle composite material converted from a metal organic framework, prepared by the preparation method as set forth in any one of claims 1 to 8.
10. Use of a bimetallic sulphide/sulphur particle composite transformed with a metal-organic framework, prepared by a method according to any one of claims 1 to 8, in a lithium-sulphur battery.
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