CN113967483A - Application of bimetallic two-dimensional MOF series catalyst to lithium-sulfur battery - Google Patents

Application of bimetallic two-dimensional MOF series catalyst to lithium-sulfur battery Download PDF

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CN113967483A
CN113967483A CN202111230575.9A CN202111230575A CN113967483A CN 113967483 A CN113967483 A CN 113967483A CN 202111230575 A CN202111230575 A CN 202111230575A CN 113967483 A CN113967483 A CN 113967483A
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梁宵
孟瑞晋
陈萱萱
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Hunan University
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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Abstract

The invention relates to a preparation method of a bimetallic two-dimensional Metal Organic Framework (MOF) series catalyst and a partitioned series catalysis of the MOF series catalyst on a sulfur reduction process in a lithium sulfur battery, belonging to the technical field of development and research of new energy materials. A small amount of conductive carbon is added in the synthesis process of the MOF, sulfur is loaded, then the conductive carbon is coated on a current collector to serve as a working electrode of a battery, a metal lithium sheet serves as a counter electrode and a reference electrode, a polypropylene film serves as a diaphragm, an organic solution serves as electrolyte, and the button battery is assembled in a glove box filled with high-purity argon. Compared with the prior art, the catalyst can be used as a zoned series catalyst in the electrochemical reduction process of sulfur, is widely applied to the energy field of lithium-sulfur batteries and the like, and has excellent charge/discharge performance.

Description

Application of bimetallic two-dimensional MOF series catalyst to lithium-sulfur battery
Technical Field
The invention relates to a preparation method and application of an electrode material, in particular to a preparation method and application of a bimetallic two-dimensional MOF series catalyst, and belongs to the technical field of development and research of new energy materials.
Background
Lithium sulfur batteries have become a powerful candidate for the next generation of high performance energy storage technologies due to their high theoretical energy density and cost effectiveness. However, the electrochemical process of the lithium-sulfur battery is a multi-step conversion reaction, and soluble polysulfide (LiPS) intermediates shuttle between the positive electrode and the negative electrode and react with the lithium negative electrode to generate short-chain polysulfide, so that the active substances of the positive electrode are continuously lost. The shuttling effect ultimately leads to high self-discharge rates, low coulombic efficiencies and poor cycle performance. In addition, the reaction kinetics of the interconversion process of these polysulfide intermediates is slow, resulting in lower power and energy densities of the battery. Based on the challenges, researchers at home and abroad mainly develop a proper anode carrier material, and physical and chemical limitation and chemical adsorption are carried out on the LiPS according to the physicochemical characteristics of the sulfur-carrying material so as to reduce the shuttle effect influence. However, in practical applications, the use of a porous support material or intermediate coating material increases the amount of electrolyte and the volume of the electrode, resulting in a significant decrease in the mass-to-volume ratio and the volumetric energy of the lithium-sulfur battery. Unlike polysulfide adsorption strategies to suppress its diffusion, methods have recently been proposed to accelerate polysulfide conversion using catalyst materials to reduce the effects of shuttling effects. The catalyst material can reduce the energy barrier of the conversion reaction of the LiPS and accelerate the conversion of soluble polysulfide to insoluble end products, thereby solving the problem of enrichment of the soluble LiPS in the electrolyte.
Metal organic framework MOFs have exposed metal sites and open pore structures, which are widely used for storage, catalysis, separation and release of guest molecules. The MOFs are crystal materials formed by metal ion nodes and ligand molecular frameworks through coordination bonds and have periodic structures. Due to the limitation of edge growth, coordinately unsaturated metal sites will reversibly bind to solvent/reactant molecules, which can accelerate polysulfide conversion reactions in lithium sulfur cells. Based on the framework structure of the semiconductor MOF, the metal/nitrogen doped carbon materials obtained by heat treatment and carbonization have been studied more deeply, and the materials (MOF derivatives) have good electronic conductivity, and metal elements keep a monoatomic dispersion or clustering state in a carbon matrix, so the metal/nitrogen doped carbon materials are catalyst materials with excellent performance. The MOF derivative has a plurality of typical applications in the aspect of catalytic conversion of a lithium-sulfur battery, and the utilization rate of active substance sulfur and the energy density of the battery are improved. Although effective, the metal/nitrogen-doped carbon materials prepared by the above-mentioned high-temperature carbonization methods not only require high-temperature (600 ℃ or higher) operation under an inert atmosphere, but also require precise control of synthesis conditions to prevent the growth of metal atom aggregates, thereby being disadvantageous for large-scale utilization.
Lithium sulfur batteries involve solid-liquid-solid heterogeneous conversion, and a single catalytic active center is difficult to meet the requirements of multi-species catalytic conversion in a real battery environment, so that the design of a lithium sulfur battery catalyst has a great challenge. According to the invention, trace conductive carbon is added into the prepared bimetallic two-dimensional MOF, the bimetallic two-dimensional MOF can be used as a lithium-sulfur battery catalyst, and the two-dimensional MOFs has a larger specific surface area and a large number of unsaturated metal sites, so that the bimetallic two-dimensional MOF is an ideal sulfur-carrying catalyst for improving the electrocatalytic performance, and the mass and load transfer process can be accelerated; the bimetal active sites can be connected in series with catalytic liquid-liquid (Li) through strong coupling synergistic effect2S8→Li2S4) And liquid-solid (Li)2S4→Li2S) two areas, which accelerate polysulfide conversion efficiency, inhibit shuttle effect, improve the utilization rate of active substances of conversion reaction, and improve the electrochemical performance of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bimetallic two-dimensional MOF tandem catalyst, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a bimetal two-dimensional MOF series catalyst and a preparation method thereof adopt the following steps:
(1) ultrasonically dispersing Co salt hexahydrate, Ni salt hexahydrate, terephthalic acid and trace conductive carbon in a mixed solvent of distilled water, ethanol and DMF (dimethyl formamide);
(2) adding triethylamine into the solution obtained in the step (1), and uniformly stirring;
(3) and (3) carrying out ultrasonic treatment on the solution obtained in the step (2) at room temperature for a long time, or preparing the bimetal two-dimensional MOF under the microwave action of a microwave reactor, washing the bimetal two-dimensional MOF for a plurality of times by DMF (dimethyl formamide) and ethanol, and drying in vacuum to obtain a bimetal two-dimensional MOF powder sample.
The Co salt hydrate in the step (1) is cobalt nitrate hexahydrate or cobalt chloride hexahydrate, and the Ni salt hydrate is nickel nitrate hexahydrate or nickel chloride hexahydrate; the conductive carbon is mesoporous carbon CMK-3, Ketjen black KB or carbon black Super P; the molar ratio of the Co salt hexahydrate, the Ni salt hexahydrate, the terephthalic acid and the trace conductive carbon is 1:1:2: 2-1: 1:3: 10; the volume ratio of water, ethanol and DMF in the mixed solvent is 1:1: 10-1: 1: 20.
The mole number of the added triethylamine in the step (2) is 5-10 times of that of the terephthalic acid.
The ultrasonic power range in the step (3) is 100-400W, and the ultrasonic time is 5-20 h; or the microwave temperature is 30-40 ℃ and the time is 0.5-2 h.
The application of the bimetallic two-dimensional MOF series catalyst comprises the steps of coating the bimetallic two-dimensional MOF series catalyst on a current collector after sulfur loading to serve as a working electrode of a battery, taking a metal lithium sheet as a counter electrode and a reference electrode, taking a polypropylene membrane as a diaphragm, taking an organic solution as an electrolyte, and assembling the bimetallic two-dimensional MOF series catalyst into the lithium sulfur battery in a glove box filled with high-purity argon.
The sulfur carrying amount of the bimetallic two-dimensional MOF series catalyst is 30-90% by mass; dissolving sulfur in diethylamine, mixing with MOF ethanol dispersion, dropwise adding dilute nitric acid for neutralization, and stirring for 0.5-3 h; the current collector can be an aluminum foil, a carbon-coated aluminum foil, carbon paper or a titanium foil; the electrolyte applied to the lithium-sulfur battery is selected from a mixed solution of 1-6 mol/LLITFSI DME and DOL, wherein the volume of the DME is 1-5 times that of the DOL; the series catalyst refers to bimetallic Ni and Co sites respectively corresponding to lithium-sulfur batteries
Figure BDA0003315743950000033
And
Figure BDA0003315743950000034
Figure BDA0003315743950000035
catalysis of the conversion reaction.
Lithium sulfur batteries involve solid-liquid-solid heterogeneous conversion, and a single catalytic active center is difficult to meet the requirements of multi-species catalytic conversion in a real battery environment, so that the design of a lithium sulfur battery catalyst has a great challenge. Compared with the prior artCompared with the prior art, the bimetallic two-dimensional MOF series catalyst does not need a high-temperature carbonization step, and the preparation process is simple. According to the invention, trace conductive carbon is added into the bimetal two-dimensional MOF, and the bimetal two-dimensional MOF is prepared by adopting an ultrasonic method or a microwave method and can be used as a series catalyst for chemical reaction of the lithium-sulfur battery sulfur. Wherein the conductive carbon can improve the electronic conductivity of the sulfur electrode, and the bimetallic two-dimensional MOF provides a catalytic active center for polysulfide. The two-dimensional MOFs have larger specific surface area and a large number of unsaturated metal sites, are ideal sulfur-carrying catalysts for improving the electrocatalytic performance, and can accelerate the mass and load transfer process; the bimetal active sites can be connected in series with catalytic liquid-liquid (Li) through strong coupling synergistic effect2S8→Li2S4) And liquid-solid (Li)2S4→Li2S) two areas, which accelerate polysulfide conversion efficiency, inhibit shuttle effect, improve the utilization rate of active substances of conversion reaction, and improve the electrochemical performance of the lithium-sulfur battery. For example, bimetallic two-dimensional MOF catalysts are at 0.1C (1C 1675mAg ═ m ag-1) Under the current density, the specific discharge capacity of the first circle is 1450mAh g-1Is obviously higher than that of a single-metal two-dimensional MOF catalyst.
Drawings
FIG. 1 is a scanning electron microscope photograph of bimetallic two-dimensional MOF nanosheets prepared in example 1;
FIG. 2 is a TEM micrograph of the bimetallic two-dimensional MOF catalyst prepared in example 2 after sulfur loading;
FIG. 3 is an X-ray diffraction pattern of a bimetallic two-dimensional MOF catalyst and sulfur-loaded sample prepared in example 3;
FIG. 4 is a graph of the infrared absorption spectra of the single and bimetallic two-dimensional MOF catalysts prepared in example 4;
FIG. 5 is a linear sweep curve and a Tafel slope curve corresponding to the reduction peak position for the bimetallic two-dimensional MOF catalyst sulfur-loaded anode and the single-metal two-dimensional MOF catalyst sulfur-loaded anode, respectively, prepared in example 5;
fig. 6 is a first charge-discharge curve of the bimetallic two-dimensional MOF catalyst sulfur-loaded anode and the single-metal two-dimensional MOF catalyst sulfur-loaded anode prepared in example 6 at a current density of 0.1C.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The preparation method of the bimetallic two-dimensional MOF series catalyst and the application of the bimetallic two-dimensional MOF series catalyst in the lithium-sulfur battery comprises the following steps:
(1) 0.3mmol of CoCl2·6H2O，0.3mmol NiCl2·6H2O, 0.78mmol of terephthalic acid and 2.5mmol (namely 30mg) of CMK-3 are ultrasonically dispersed in 4mL of distilled water, 4mL of ethanol and 62mL of DMF, 6mmol of triethylamine is added to be uniformly stirred, the mixture is ultrasonically treated for 10h under the power of 200W, DMF and ethanol are respectively subjected to centrifugal washing and vacuum drying at 60 ℃ to obtain a bimetallic MOF two-dimensional powder sample, a scanning electron microscope picture of the sample is shown in figure 1, and the nanosheet prepared by the method is thin and uniform and is transparent.
(2) Carrying sulfur by using a bimetallic two-dimensional MOF series catalyst, wherein the mass percent of the carried sulfur is 30%, dissolving the sulfur in diethylamine, mixing with MOF ethanol dispersion, dropwise adding dilute nitric acid for neutralization, and stirring for 1 h; then coating the carbon paper as a working electrode of the battery, taking a metal lithium sheet as a counter electrode and a reference electrode, taking a polypropylene membrane as a diaphragm, taking a mixed solution of DME and DOL (the volume ratio of DME to DOL is 1:1) of 1mol/LLITFSI as an electrolyte, and assembling the lithium-sulfur battery in a glove box filled with high-purity argon.
Example 2
The preparation method of the bimetallic two-dimensional MOF series catalyst and the application of the bimetallic two-dimensional MOF series catalyst in the lithium-sulfur battery comprises the following steps:
(1) 0.3mmol of CoCl2·6H2O，0.3mmol NiCl2·6H2O, 0.6mmol of terephthalic acid, 0.6mmol of KB in 4mL of distilled water, 4mL of ethanol and 40mL of DMF, ultrasonically dispersing, adding 3mmol of triethylamine, uniformly stirring, ultrasonically treating for 6h at 400W, and respectively passing through DAnd (3) performing centrifugal washing on MF and ethanol, and drying at 60 ℃ in vacuum to obtain a bimetallic two-dimensional MOF powder sample.
(2) Sulfur is carried by a bimetallic two-dimensional MOF series catalyst, the mass percent of the carried sulfur is 90%, the sulfur is dissolved in diethylamine and mixed with MOF ethanol dispersion liquid, stirring time is 3h after dropwise adding dilute nitric acid for neutralization, a transmission electron microscope photo is shown in figure 2, and the sulfur is uniformly distributed on the surface of lamellar bimetallic MOF. Then coating sulfur-loaded bimetallic two-dimensional MOF on a titanium foil to serve as a working electrode of the battery, taking a metal lithium sheet as a counter electrode and a reference electrode, taking a polypropylene membrane as a diaphragm, taking a mixture of DME and DOL (DME and DOL in a volume ratio of 5:1) of 6mol/L LiTFSI as electrolyte, and assembling the lithium-sulfur battery in a glove box filled with high-purity argon.
Example 3
(1) 0.3mmol of Co (NO)3)2·6H2O，0.3mmol Ni(NO3)2·6H2And ultrasonically dispersing 0.9mmol of terephthalic acid and 0.9mmol of Super P in 4mL of distilled water, 4mL of ethanol and 80mL of DMF, adding 3mmol of triethylamine, uniformly stirring, transferring the uniformly mixed solution into a microwave tube, reacting for 0.5h in a microwave reactor at 40 ℃, respectively centrifugally washing by DMF and ethanol, and drying at 60 ℃ in vacuum to obtain a bimetallic two-dimensional MOF powder sample.
(2) The sulfur is carried by a bimetallic two-dimensional MOF series catalyst, the mass percentage of the carried sulfur is 80%, the sulfur is dissolved in diethylamine and mixed with MOF ethanol dispersion liquid, the stirring time is 0.5h after the dropwise addition of dilute nitric acid for neutralization, the X-ray diffraction patterns of the bimetallic two-dimensional MOF before and after the sulfur carrying are shown in figure 3, the fact that the bimetallic MOF is a crystal can be known, and the XRD diffraction peak of the MOF is covered after the high sulfur carrying. Then coating the sulfur-loaded bimetallic two-dimensional MOF on a titanium foil to serve as a working electrode of the battery, taking a metal lithium sheet as a counter electrode and a reference electrode, taking a polypropylene membrane as a diaphragm, taking a mixture of DME and DOL (DME and DOL in a volume ratio of 5:1) of 6mol/LLITFSI as electrolyte, and assembling the lithium-sulfur battery in a glove box filled with high-purity argon.
Example 4
(1) 0.3mmol of Co (NO)3)2·6H2O，0.3mmol Ni(NO3)2·6H2And ultrasonically dispersing 0.7mmol of terephthalic acid and 1.5mmol of Super P in 4mL of distilled water, 4mL of ethanol and 62mL of DMF, adding 7mmol of triethylamine, uniformly stirring, transferring the uniformly mixed solution into a microwave tube, reacting for 2h in a microwave reactor at 30 ℃, respectively centrifugally washing by DMF and ethanol, and drying at 60 ℃ in vacuum to obtain a bimetallic two-dimensional MOF powder sample.
(2) The method comprises the steps of loading sulfur on a bimetallic two-dimensional MOF series catalyst by 60 mass percent, dissolving the sulfur in diethylamine, mixing the sulfur with MOF ethanol dispersion liquid, dropwise adding dilute nitric acid for neutralization, stirring for 2 hours, coating the sulfur-loaded bimetallic two-dimensional MOF on a carbon-coated aluminum foil to serve as a working electrode of a battery, taking a metal lithium sheet as a counter electrode and a reference electrode, taking a polypropylene membrane as a diaphragm, taking a 2mol/L mixture (the volume ratio of DME to DOL is 2:1) of DME and DOL of LiTFSI as electrolyte, and assembling the lithium-sulfur battery in a glove box filled with high-purity argon.
The infrared absorption spectra of the single metal Ni-MOF, the single metal Co-MOF and the double metal two-dimensional MOF catalysts are shown in figure 4, and the single metal MOF and the double metal MOF have the same absorption peaks, which shows that the single metal MOF and the double metal MOF have similar structural frameworks.
Example 5
(1) 0.4mmol of Co (NO)3)2·6H2O，0.4mmol Ni(NO3)2·6H2And ultrasonically dispersing 0.8mmol of terephthalic acid and 4mmol of Super P in 5mL of distilled water, 5mL of ethanol and 60mL of DMF, adding 8mmol of triethylamine, uniformly stirring, transferring the uniformly mixed solution into a microwave tube, reacting for 1h in a microwave reactor at 30 ℃, respectively centrifugally washing by DMF and ethanol, and drying at 60 ℃ in vacuum to obtain a bimetallic two-dimensional MOF powder sample.
(2) Sulfur is carried by a bimetallic two-dimensional MOF series catalyst, the mass percent of the carried sulfur is 70%, the sulfur is dissolved in diethylamine and mixed with MOF ethanol dispersion liquid, diluted nitric acid is dripped for neutralization, the stirring time is 1.5h, then the sulfur-carried bimetallic two-dimensional MOF is coated on aluminum foil to be used as a working electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, a polypropylene membrane is used as a diaphragm, a 3mol/L mixture (the volume ratio of DME to DOL is 1:1) of DME and DOL of LiTFSI is used as electrolyte, and the lithium-sulfur battery is assembled in a glove box filled with high-purity argon.
The linear sweep rate curve (figure 5a) and tafel slope curve (figures 5b and 5c) of corresponding peak positions after sulfur loading of the single metal Ni-MOF, single metal Co-MOF and bimetallic two-dimensional MOF catalysts and the single metal salt (the sum of the mole numbers of Co and Ni) are added into the catalyst (1) and other experimental steps are invariable. As can be seen from FIG. 5, the comparison of the single metal MOF catalyst, Ni-MOF
Figure BDA0003315743950000068
Has smaller Tafel slope in the conversion process, and Co-MOF is in the process of neutralization
Figure BDA0003315743950000069
The conversion reaction has a smaller tafel slope. Namely that bimetallic Ni and Co in bimetallic two-dimensional MOF series catalyst are respectively applied to lithium-sulfur batteries
Figure BDA0003315743950000065
Figure BDA0003315743950000066
And
Figure BDA0003315743950000067
plays a role in obvious catalytic conversion.
Example 6
(1) 0.4mmol of Co (NO)3)2·6H2O，0.4mmol Ni(NO3)2·6H2And ultrasonically dispersing 1mmol of terephthalic acid and 1.2mmol of CMK-3 in 5mL of distilled water, 5mL of ethanol and 70mL of DMF, adding 10mmol of triethylamine, uniformly stirring, transferring the uniformly mixed solution into a microwave tube, reacting for 1h at 40 ℃ in a microwave reactor, respectively centrifugally washing with DMF and ethanol, and drying at 60 ℃ in vacuum to obtain a bimetallic two-dimensional MOF powder sample.
(2) Sulfur is carried by a bimetallic two-dimensional MOF series catalyst, the mass percent of the carried sulfur is 60%, the sulfur is dissolved in diethylamine and mixed with MOF ethanol dispersion liquid, diluted nitric acid is dripped for neutralization, the stirring time is 2 hours, then the sulfur-carried bimetallic two-dimensional MOF is coated on carbon paper to be used as a working electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, a polypropylene membrane is used as a diaphragm, a 2mol/L mixture (the volume ratio of DME to DOL) of LiTFSI and DOL is used as electrolyte, and the lithium sulfur battery is assembled in a glove box filled with high-purity argon.
The single metal salt (the sum of the mole numbers of Co and Ni) is added in the step (1), and the other experimental steps are not changed to prepare the single metal two-dimensional MOF catalyst. After the sulfur is loaded on the single metal Ni-MOF, the single metal Co-MOF and the bimetallic two-dimensional MOF catalyst, when the current density is 0.1C, the first charge-discharge curve is shown in figure 6, and the specific discharge capacity of the first circle of the bimetallic two-dimensional MOF catalyst is 1450mAh g according to figure 6-1Significantly higher than the single metal two-dimensional MOF catalyst.
Example 7
(1) 0.2mmol of Co (NO)3)2·6H2O，0.2mmol Ni(NO3)2·6H2And ultrasonically dispersing 0.6mmol of terephthalic acid and 0.6mmol of KB in 5mL of distilled water, 5mL of ethanol and 60mL of DMF, adding 3mmol of triethylamine, uniformly stirring, ultrasonically treating for 20h at 100W of power, respectively centrifugally washing by DMF and ethanol, and drying at 60 ℃ in vacuum to obtain a bimetallic two-dimensional MOF powder sample.
(2) Sulfur is carried by a bimetallic two-dimensional MOF series catalyst, the mass percent of the carried sulfur is 40%, the sulfur is dissolved in diethylamine and mixed with MOF ethanol dispersion liquid, dilute nitric acid is dripped for neutralization, the stirring time is 1.5h, then the sulfur-carried bimetallic two-dimensional MOF is coated on aluminum foil to be used as a working electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, a polypropylene membrane is used as a diaphragm, a mixed solution of DME and DOL (DME-DOL volume ratio of 4mol/L LiTFSI) is used as electrolyte, and the lithium-sulfur battery is assembled in a glove box filled with high-purity argon.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (12)

1. A preparation method of a bimetallic two-dimensional MOF tandem catalyst is characterized by comprising the following steps:
(1) ultrasonically dispersing Co salt hexahydrate, Ni salt hexahydrate, terephthalic acid and trace conductive carbon in a mixed solvent of distilled water, ethanol and dimethyl formamide (DMF);
(2) adding triethylamine into the solution obtained in the step (1), and uniformly stirring;
(3) and (3) carrying out ultrasonic treatment on the solution obtained in the step (2) at room temperature for a long time, or preparing the bimetal two-dimensional MOF under the microwave action of a microwave reactor, washing the bimetal two-dimensional MOF for a plurality of times by DMF (dimethyl formamide) and ethanol, and drying in vacuum to obtain a bimetal two-dimensional MOF powder sample.
2. The method for preparing the bimetallic two-dimensional MOF tandem catalyst according to claim 1, wherein the Co salt hydrate in the step (1) is cobalt nitrate hexahydrate or cobalt chloride hexahydrate, and the Ni salt hydrate is nickel nitrate hexahydrate or nickel chloride hexahydrate.
3. The method for preparing the bimetallic two-dimensional MOF tandem catalyst according to claim 1, wherein the conductive carbon in the step (1) is mesoporous carbon CMK-3, Ketjen black KB or carbon black Super P.
4. The preparation method of the bimetallic two-dimensional MOF series catalyst according to claim 1, wherein the molar ratio of Co salt hexahydrate, Ni salt hexahydrate, terephthalic acid and trace conductive carbon in the step (1) is 1:1:2: 2-1: 1:3: 10.
5. The preparation method of the bimetallic two-dimensional MOF series catalyst according to claim 1, wherein the volume ratio of distilled water, ethanol and DMF in the mixed solvent in the step (1) is 1:1: 10-1: 1: 20.
6. The preparation method of the bimetallic two-dimensional MOF tandem catalyst according to claim 1, wherein the molar number of the added triethylamine in the step (2) is 5-10 times that of terephthalic acid.
7. The preparation method of the bimetallic two-dimensional MOF series catalyst according to claim 1, wherein in the step (3), the ultrasonic power is 100-400W, and the ultrasonic time is 5-20 h; or the microwave temperature is 30-40 ℃ and the time is 0.5-2 h.
8. The application of the bimetallic two-dimensional MOF series catalyst as claimed in any one of claims 1 to 7, wherein the bimetallic two-dimensional MOF series catalyst is coated on a current collector as a working electrode of a battery after being carried with sulfur, a metal lithium sheet is a counter electrode and a reference electrode, a polypropylene film is a diaphragm, an organic solution is an electrolyte, and the lithium-sulfur battery is assembled under a high-purity argon atmosphere.
9. The application of the bimetallic two-dimensional MOF series catalyst is characterized in that the sulfur content of the bimetallic two-dimensional MOF series catalyst is 30-90% by mass, the sulfur is dissolved in diethylamine and mixed with MOF ethanol dispersion liquid, and the stirring sulfur-carrying time is 0.5-3 h after the dropwise addition of dilute nitric acid for neutralization.
10. Use of a bimetallic two-dimensional MOF series catalyst according to claim 8, wherein the current collector can be an aluminum foil, a carbon-coated aluminum foil, a carbon paper or a titanium foil.
11. The application of the bimetallic two-dimensional MOF tandem catalyst is characterized in that the organic solvent is selected from a mixed solution of 1-6 mol/L of bis (trifluoromethyl) sulfimide Lithium (LiTFSI) ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL), wherein the volume of the DME is 1-5 times of the DOL.
12. The bi-metal two-dimensional of claim 8The application of MOF tandem catalyst is characterized in that the tandem catalyst refers to the bimetallic Ni and Co which are respectively applied to lithium-sulfur batteries
Figure FDA0003315743940000021
And
Figure FDA0003315743940000022
Figure FDA0003315743940000023
catalysis of the conversion reaction.
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