CN114678508A - Carbon-based supported metal sulfide composite material and preparation method and application thereof - Google Patents

Carbon-based supported metal sulfide composite material and preparation method and application thereof Download PDF

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CN114678508A
CN114678508A CN202210388452.6A CN202210388452A CN114678508A CN 114678508 A CN114678508 A CN 114678508A CN 202210388452 A CN202210388452 A CN 202210388452A CN 114678508 A CN114678508 A CN 114678508A
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carbon
composite material
metal sulfide
metal
sulfide
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夏新辉
单心怡
张永起
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Yangtze River Delta Research Institute of UESTC Huzhou
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Yangtze River Delta Research Institute of UESTC Huzhou
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/027—Negative electrodes

Abstract

The invention discloses a carbon-based loaded metal sulfide composite material, and a preparation method and application thereof, wherein metal sulfide particles with the diameter of 10-100nm are uniformly distributed on the surface of a carbon-based material of the composite material. The nano metal sulfide in the composite material is uniformly distributed on the surface of the carbon-based material, the composite material is fused with molten metal lithium to obtain the lithium-carbon-based material/metal sulfide composite material, the metal lithium is uniformly distributed on the surface of the carbon-based material/metal sulfide, and the lithium-carbon-based material/metal sulfide composite material is applied to the negative electrode of a lithium metal battery.

Description

Carbon-based supported metal sulfide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of negative electrode materials of lithium metal batteries, in particular to a carbon-based loaded metal sulfide composite material and a preparation method and application thereof.
Background
In the past decades, the fast growing market for electric vehicles and small mobile communication devices has attracted extensive attention from consumers, manufacturers and researchers, and the demand for sustainable energy storage of electronic devices has increased, which has accelerated the development of high-energy power supply devices, especially lithium battery markets, toward low cost, long service life and high capacity worldwide. The lithium metal battery takes lithium metal as a negative electrode, can provide the most negative reduction potential (-3.4V compared with a standard hydrogen electrode) and higher theoretical specific capacity (3860mAh g)-1) Theoretical energy density can reach 600Wh kg-1Therefore, the energy storage device becomes the candidate with the best development and application prospect in the next generation of energy storage devices. However, there are some negative factors from the negative electrode in the lithium metal battery system, such as safety hazards caused by problems of lithium dendrite growth, volume expansion, etc., which greatly hinder the progress of commercial application thereof.
The lithium-carbon-based material composite structure can effectively alleviate the problems, the three-dimensional carbon-based framework structure can provide a larger specific surface area, the accommodating space of the metal lithium is enlarged, and then the problem of volume expansion is solved, and in addition, the three-dimensional conductive framework can effectively reduce the local current density distribution, conduct charges, adjust the charge distribution and inhibit the growth of dendritic crystals. However, general carbon-based materials cannot provide good lithium-philic property.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a carbon-based supported metal sulfide composite material, and a preparation method and an application thereof, so as to solve the problems that a carbon-based material in the prior art cannot provide good lithium affinity, the preparation of a metal sulfide has complicated steps, long time consumption, non-uniform particle size, poor binding force with a substrate, and the like.
The technical scheme for solving the technical problems is as follows: provides a carbon-based loaded metal sulfide composite material, wherein metal sulfide particles with the diameter of 10-100nm are uniformly distributed on the surface of a carbon-based material of the composite material.
The invention has the beneficial effects that: the nano metal sulfide in the composite material is uniformly distributed on the surface of the carbon-based material, and the lithium-carbon-based material/metal sulfide composite material is obtained by fusing the composite material and molten metal lithium, wherein the metal lithium is uniformly distributed on the surface of the carbon-based material/metal sulfide, so that the lithium-carbon-based material/metal sulfide composite material is applied to the negative electrode of a lithium metal battery, has long cycle life and stability, and has wide application prospects in the fields of electric automobiles, smart power grids, small-sized mobile communication equipment and the like.
The carbon-based material in the composite material is used as a three-dimensional layered framework, a rapid electron transmission path, good flexibility and mechanical flexibility are provided, and the carbon-based material has a large specific surface area, so that the local current density can be reduced, more lithium metal can be accommodated, nucleation and growth of lithium dendrite can be inhibited, the volume expansion phenomenon can be effectively improved, and in addition, the three-dimensional layered framework provides a good electron diffusion channel, which is beneficial to the efficient and rapid implementation of electrochemical reaction; the metal sulfide can react with lithium metal to form Li2And S, a large number of active sites are provided for the uniform deposition of the lithium metal, the nucleation potential energy of the lithium metal is reduced, and the uniform deposition and growth of the lithium are guided, so that the metal sulfide uniformly dispersed on the surface of the carbon-based material provides a large number of adsorption sites for the deposition of the lithium metal, the uniform deposition of the lithium metal is promoted, and the stable and safe circulation of the battery is ensured. The carbon-based material and the metal sulfide can play a synergistic role in the two, and a high-performance lithium metal negative electrode is constructed.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the carbon-based material is carbon cloth, carbon nano tubes loaded on the carbon cloth or vertical graphene loaded on the carbon cloth.
The beneficial effect of adopting the further technical scheme is as follows: the carbon-based material selected by the invention has rich functional groups, so that the lithium affinity can be increased, the specific surface area of the substrate material can be greatly increased, and more lithium metal can be accommodated, so that the problem of volume expansion of a negative electrode structure of the lithium metal in the circulation process can be effectively solved, a more stable long circulation life can be obtained in a symmetrical battery, in addition, the large specific surface area can effectively reduce the local current density, and the polarization in the lithium metal de-intercalation process can be reduced, so that a smaller circulation overpotential can be provided.
Further, the size of the carbon-based material is (1-5) × (0.1-2) cm.
Further, the metal sulfide is at least one of nickel sulfide, cobalt sulfide, iron sulfide, chromium sulfide and manganese sulfide.
The invention also provides a preparation method of the carbon-based supported metal sulfide composite material, which comprises the following steps:
(1) mixing the ethanol solution of metal chloride with the same concentration and volume with the ethanol solution of thiourea to obtain a metal sulfide precursor solution;
(2) and soaking the carbon-based material in a metal sulfide precursor solution, drying, and heating by using instant high-temperature Joule heat to obtain the carbon-based loaded metal sulfide composite material.
For example, when the metal chloride is more than one kind, the concentration and volume of the ethanol solution of each metal chloride are the same as those of the ethanol solution of thiourea.
The beneficial effect of adopting the further technical scheme is as follows: the invention utilizes instantaneous high-temperature Joule heat to provide extremely fast heating rate in a short time, obtains metal sulfide nano-particles which are uniformly and evenly dispersed on a carbon-based material, and overcomes the problems of complex steps, long time consumption, non-uniform particle size, poor bonding force with a substrate and the like in the traditional method for preparing the metal sulfide by using a carbothermic method, the carbon-based material/metal sulfide composite material prepared by using the instantaneous high-temperature Joule heat method not only greatly improves the efficiency and the quality of synthesizing the metal sulfide, but also can be widely and efficiently applied to the preparation of various sulfides on different carbon-based materials, the uniformly loaded metal sulfide can provide rich nucleation sites and promote the uniform deposition of lithium metal, the composite material has the advantages of a high-conductivity framework and the metal sulfide, has excellent electrochemical performance, and the constructed lithium metal cathode has high specific capacity, the high cycle life and the low cycle overpotential have wide application prospect in the fields of electric vehicles, smart grids, small-sized mobile communication equipment and the like.
Further, the concentration of the ethanol solution of the metal chloride salt and the ethanol solution of the thiourea in the step (1) is 0.01-1 mol/L.
Further, in the step (1), the concentration of the ethanol solution of the metal chloride salt and the concentration of the ethanol solution of the thiourea are both 0.1 mol/L.
Further, the conditions of the instantaneous high-temperature joule heat in the step (2) are as follows: voltage is 10-60V, current is 2-20A, and pulse is 10-2000 ms.
Further, the conditions of the instantaneous high-temperature joule heat in the step (2) are as follows: voltage 40V, current 10A, pulse 100 ms.
Further, the instantaneous high-temperature Joule heating in the step (2) is to perform the heating reaction under the vacuum condition.
Further, the reaction gas of the instantaneous high-temperature joule heat in the step (2) is argon or nitrogen.
The invention also provides application of the carbon-based loaded metal sulfide composite material in preparation of a lithium metal battery cathode material.
The invention has the following beneficial effects:
1. the size, size uniformity, type and load density of sulfide particles can be controlled by adjusting the pulse time of the instantaneous high-temperature joule heat, the pulse voltage current, the precursor concentration, the reaction atmosphere and the current density.
2. The lithium-carbon-based material/metal sulfide composite material is obtained after the composite material is completely melted with lithium metal at high temperature, and can be used as a negative electrode material of a lithium metal battery, nano metal sulfides in the negative electrode material are uniformly distributed on the surface of a carbon-based material, and metal lithium is uniformly distributed on the surface of the carbon-based material/metal sulfide, so that the prepared lithium metal battery can be stably circulated for more than 500 circles, the coulombic efficiency is up to 99%, the lithium metal battery has high cycle life and stability, and the lithium metal battery has wide application prospects in the fields of electric automobiles, intelligent power grids, small mobile communication equipment and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon cloth loaded with metallic nickel sulfide prepared in example 1;
FIG. 2 is a scanning electron micrograph of the carbon cloth loaded metallic cobalt sulfide prepared in example 2;
FIG. 3 is a scanning electron micrograph of the carbon cloth loaded with metallic chromium sulfide prepared in example 3;
FIG. 4 is a scanning electron micrograph of the carbon cloth loaded with manganese sulfide prepared in example 4;
FIG. 5 is a scanning electron micrograph of the carbon cloth loaded with metallic iron sulfide-chromium sulfide obtained in example 5;
FIG. 6 is a scanning electron micrograph of the carbon cloth loaded perpendicular graphene/nickel sulfide prepared in example 6;
FIG. 7 is a scanning electron microscope image of the carbon cloth loaded carbon nanotube array/cobalt sulfide prepared in example 7;
fig. 8 is an element distribution diagram of the carbon cloth loaded with vertical graphene/nickel sulfide prepared in example 6 under a transmission electron microscope.
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. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving nickel chloride in ethanol, and obtaining 0.1mol/L ethanol solution of nickel chloride after complete dissolution; dissolving thiourea in ethanol, and obtaining 0.1mol/L ethanol solution of thiourea after complete dissolution;
(2) mixing 1mL of ethanol solution of nickel chloride and ethanol solution of thiourea to obtain metal nickel sulfide precursor solution;
(3) cutting carbon cloth into 2 x 0.5cm, soaking in metal nickel sulfide precursor solution, drying the soaked carbon cloth, fixing on a cavity bearing table in an instantaneous high-temperature joule heating device, then putting the bearing table into an inner cavity of the instantaneous high-temperature joule heating device, sealing flanges at two ends, switching on a power supply, vacuumizing the inner cavity, continuously introducing inert atmosphere (argon gas) with the flow of 200sccm, and setting the reaction parameters of the instantaneous high-temperature joule heating device as follows: voltage 40V, current 10A, pulse width 100ms, carry on the steady voltage pulse; and after the reaction is finished, obtaining the carbon-based loaded metal sulfide composite material, namely the carbon cloth/metal nickel sulfide composite material.
Example 2:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving cobalt chloride in ethanol, and obtaining 0.01mol/L ethanol solution of cobalt chloride after complete dissolution; dissolving thiourea in ethanol, and obtaining 0.01mol/L ethanol solution of thiourea after complete dissolution;
(2) mixing an ethanol solution of cobalt chloride and an ethanol solution of thiourea, wherein the volumes of the ethanol solutions are all 1mL, so as to obtain a precursor solution of metal cobalt sulfide;
(3) cutting carbon cloth into a size of 1 multiplied by 0.1cm, soaking the carbon cloth in a metal sulfide precursor solution, drying the soaked carbon cloth, fixing the carbon cloth on a cavity bearing table in an instantaneous high-temperature joule heating device, then putting the bearing table into an inner cavity of the instantaneous high-temperature joule heating device, sealing flanges at two ends, switching on a power supply, vacuumizing the inner cavity, continuously introducing an inert atmosphere (argon gas) with the flow of 200sccm, and setting the reaction parameters of the instantaneous high-temperature joule heating device as follows: voltage is 10V, current is 2A, pulse width is 10ms, and voltage-stabilizing pulse is carried out; and after the reaction is finished, obtaining the carbon-based loaded metal sulfide composite material, namely the carbon cloth/metal cobalt sulfide composite material.
Example 3:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving chromium chloride in ethanol, and obtaining 1mol/L ethanol solution of the chromium chloride after the chromium chloride is completely dissolved; dissolving thiourea in ethanol, and obtaining 1mol/L ethanol solution of thiourea after the thiourea is completely dissolved;
(2) mixing the ethanol solution of chromium chloride and the ethanol solution of thiourea with the volumes of 3mL to obtain a precursor solution of the metal chromium sulfide;
(3) cutting carbon cloth into 5 multiplied by 2cm, soaking in metal chromium sulfide precursor solution, drying the soaked carbon cloth, fixing on a cavity bearing table in an instantaneous high-temperature joule heating device, then putting the bearing table into an inner cavity of the instantaneous high-temperature joule heating device, sealing flanges at two ends, switching on a power supply, vacuumizing the inner cavity, continuously introducing inert atmosphere (argon gas) with the flow of 2000sccm, and setting the reaction parameters of the instantaneous high-temperature joule heating device as follows: voltage 60V, current 20A, pulse width 2000ms, to perform voltage-stabilizing pulse; and after the reaction is finished, obtaining the carbon-based loaded metal sulfide composite material, namely the carbon cloth/metal chromium sulfide composite material.
Example 4:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving manganese chloride in ethanol, and obtaining 0.1mol/L ethanol solution of manganese chloride after completely dissolving the manganese chloride; dissolving thiourea in ethanol to obtain 0.1mol/L ethanol solution of thiourea after the thiourea is completely dissolved;
(2) mixing an ethanol solution of manganese chloride and an ethanol solution of thiourea, wherein the volumes of the ethanol solutions are all 1mL, so as to obtain a precursor solution of metal manganese sulfide;
(3) cutting carbon cloth into 2 x 0.5cm, soaking in metal manganese sulfide precursor solution, drying the soaked carbon cloth, fixing on a cavity bearing table in an instantaneous high-temperature joule heating device, then putting the bearing table into an inner cavity of the instantaneous high-temperature joule heating device, sealing flanges at two ends, switching on a power supply, vacuumizing the inner cavity, continuously introducing inert atmosphere (argon gas) with the flow of 200sccm, and setting the reaction parameters of the instantaneous high-temperature joule heating device as follows: voltage 40V, current 10A, pulse width 100ms, carry on the steady voltage pulse; and after the reaction is finished, obtaining the carbon-based loaded metal sulfide composite material, namely the carbon cloth/metal manganese sulfide composite material.
Example 5:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving ferric chloride in ethanol to obtain 0.1mol/L ethanol solution of ferric chloride after complete dissolution; dissolving chromium chloride in ethanol to obtain 0.1mol/L ethanol solution of chromium chloride; dissolving thiourea in ethanol to obtain 0.1mol/L ethanol solution of thiourea after the thiourea is completely dissolved;
(2) mixing 1mL of ethanol solution of ferric chloride, 1mL of ethanol solution of chromium chloride and 1mL of ethanol solution of thiourea to obtain a metal ferric sulfide-chromium sulfide precursor solution;
(3) cutting carbon cloth into 2 multiplied by 0.5cm, soaking the carbon cloth in metal ferric sulfide-chromium sulfide precursor solution, drying the soaked carbon cloth, fixing the carbon cloth on a cavity bearing table in an instantaneous high-temperature joule heating device, then putting the bearing table into an inner cavity of the instantaneous high-temperature joule heating device, sealing flanges at two ends, switching on a power supply, vacuumizing the inner cavity, continuously introducing inert atmosphere (nitrogen) with the flow of 200sccm, and setting the reaction parameters of the instantaneous high-temperature joule heating device as follows: voltage 40V, current 10A, pulse width 100ms, carry on the steady voltage pulse; after the reaction is finished, the carbon-based supported metal sulfide composite material, namely the carbon cloth/metal iron sulfide-chromium sulfide composite material is obtained.
Example 6:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving nickel chloride in ethanol, and obtaining 0.1mol/L ethanol solution of nickel chloride after complete dissolution; dissolving thiourea in ethanol to obtain 0.1mol/L ethanol solution of thiourea after the thiourea is completely dissolved;
(2) mixing ethanol solution of nickel chloride and ethanol solution of thiourea with the volume of 1mL to obtain metal nickel sulfide precursor solution;
(3) cut into 2 x 1 cm's size with the perpendicular graphite alkene of carbon cloth load, soak in metal nickel sulfide precursor solution, after the carbon cloth drying after will soaking, be fixed in on the chamber plummer in the instantaneous high temperature joule heat device, then put into the inner chamber of instantaneous high temperature joule heat device with the plummer, seal both ends flange, the switch on power supply carries out evacuation treatment to the inner chamber, later continuously lets in the inert atmosphere (argon gas) of 200sccm flow, the reaction parameter who sets up instantaneous high temperature joule heat device is: voltage 45V, current 15A, pulse width 100ms, carry on the steady voltage pulse; and after the reaction is finished, obtaining the carbon-based supported metal sulfide composite material, namely the carbon cloth supported vertical graphene/metal nickel sulfide composite material.
Example 7:
a preparation method of the carbon-based supported metal sulfide composite material comprises the following steps:
(1) dissolving cobalt chloride in ethanol, and obtaining 0.1mol/L ethanol solution of cobalt chloride after the cobalt chloride is completely dissolved; dissolving thiourea in ethanol to obtain 0.1mol/L ethanol solution of thiourea after the thiourea is completely dissolved;
(2) mixing an ethanol solution of cobalt chloride and an ethanol solution of thiourea, wherein the volumes of the ethanol solutions are all 1mL, so as to obtain a precursor solution of metal cobalt sulfide;
(3) cutting carbon cloth loaded carbon nanotubes into a size of 2 multiplied by 0.5cm, soaking in a metal cobalt sulfide precursor solution, drying the soaked carbon cloth, fixing the carbon cloth on a cavity bearing table in an instantaneous high-temperature joule heating device, then putting the bearing table into an inner cavity of the instantaneous high-temperature joule heating device, sealing flanges at two ends, switching on a power supply, vacuumizing the inner cavity, continuously introducing an inert atmosphere (argon gas) with the flow of 200sccm, and setting the reaction parameters of the instantaneous high-temperature joule heating device as follows: voltage is 50V, current is 10A, pulse width is 100ms, and voltage stabilization pulse is carried out; after the reaction is finished, the carbon-based loaded metal sulfide composite material, namely the carbon cloth loaded carbon nano tube/metal cobalt sulfide composite material is obtained.
Test examples
First, characterization detection
Scanning electron microscope examination was performed on the carbon-based supported metal sulfide composite materials prepared in examples 1 to 7, and the results are shown in fig. 1 to 7. As can be seen from fig. 1 to 7, the nano-sized metal sulfide particles in the composite material prepared by the present invention are uniformly distributed on the surface of the carbon-based material.
The carbon-based metal sulfide-loaded composite material prepared in example 6 was analyzed by transmission electron microscopy, and the results are shown in fig. 8. As can be seen from FIG. 8, the sulfur and nickel elements in the composite material prepared by the present invention are uniformly distributed in the metal sulfide particles.
Second, performance test
300mg of lithium pieces were weighed in a glove box filled with argon, heated to 350 ℃ to be melted, and the carbon-based supported metal sulfide composite material and the commercial lithium pieces prepared in examples 1 to 7 were brought close to the melted metal lithium, respectively, and the melted metal lithium was absorbed into the composite material, and after cooling, a lithium-carbon-based material/metal sulfide composite material was obtained.
The obtained lithium-carbon-based material/metal sulfide composite material is used as a positive electrode and a negative electrode to form a symmetrical battery, and the specific battery forming method comprises the following steps: the electrolyte is prepared by the following method: lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in a solvent at a volume ratio of 1: 1 mixed solution of ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) in which the concentration of LiTFSI is 1mol/L, and then 2 wt% of lithium nitrate (LiNO) is added3) Preparing electrolyte, and dripping 35 mu L of electrolyte into each battery; the diaphragm is Celgard 2400 type polypropylene microporous membrane; the assembly of the CR2025 type button cell is completed in a glove box taking argon as protective gas, and the water-oxygen partial pressure of the glove box is less than 0.1 ppm.
After the above-mentioned battery was allowed to stand for 24 hours, the cycle stability was measured at 25. + -. 1 ℃ using an electrochemical workstation, and the results are shown in Table 1. As can be seen from table 1, the negative electrode of the lithium metal battery constructed with the composite material prepared according to the present invention has a high cycle life and stability.
TABLE 1 Performance of a Battery comprising a carbon-based Metal sulphide-loaded composite
Figure BDA0003594662760000091
Figure BDA0003594662760000101
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 (10)

1. The carbon-based loaded metal sulfide composite material is characterized in that metal sulfide particles with the diameter of 10-100nm are uniformly distributed on the surface of a carbon-based material of the composite material.
2. The carbon-based supported metal sulfide composite material according to claim 1, wherein the carbon-based material is carbon cloth, carbon nanotube supported by carbon cloth, or vertical graphene supported by carbon cloth.
3. The carbon-based supported metal sulfide composite material according to claim 1, wherein the metal sulfide is at least one of nickel sulfide, cobalt sulfide, iron sulfide, chromium sulfide, and manganese sulfide.
4. The method for preparing a carbon-based supported metal sulfide composite material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing ethanol solutions of metal chloride and thiourea with the same concentration and volume to obtain a metal sulfide precursor solution;
(2) and soaking the carbon-based material in a metal sulfide precursor solution, drying, and heating by using instant high-temperature Joule heat to obtain the carbon-based loaded metal sulfide composite material.
5. The method for preparing a carbon-based supported metal sulfide composite material according to claim 4, wherein the concentrations of the ethanol solution of the metal chloride salt and the ethanol solution of thiourea in the step (1) are both 0.01 to 1 mol/L.
6. The method for preparing a carbon-based supported metal sulfide composite material according to claim 4 or 5, wherein the concentrations of the ethanol solution of the metal chloride salt and the ethanol solution of thiourea in the step (1) are both 0.1 mol/L.
7. The method for preparing the carbon-based supported metal sulfide composite material according to claim 4, wherein the conditions of the instantaneous high-temperature Joule heat in the step (2) are as follows: voltage is 10-60V, current is 2-20A, and pulse is 10-2000 ms.
8. The method for preparing a carbon-based supported metal sulfide composite material according to claim 4 or 7, wherein the conditions of the instantaneous high-temperature Joule heat in the step (2) are as follows: voltage 40V, current 10A, pulse 100 ms.
9. The method for preparing the carbon-based supported metal sulfide composite material according to claim 4, wherein the reaction gas of the instantaneous high-temperature Joule heat in the step (2) is argon or nitrogen.
10. Use of the carbon-based supported metal sulfide composite material according to any one of claims 1 to 3 for preparing a negative electrode material for a lithium metal battery.
CN202210388452.6A 2022-04-13 2022-04-13 Carbon-based supported metal sulfide composite material and preparation method and application thereof Pending CN114678508A (en)

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