CN113346058A - Method for preparing bimetallic sulfide and carbon compound under ionic gel system - Google Patents

Method for preparing bimetallic sulfide and carbon compound under ionic gel system Download PDF

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CN113346058A
CN113346058A CN202110558120.3A CN202110558120A CN113346058A CN 113346058 A CN113346058 A CN 113346058A CN 202110558120 A CN202110558120 A CN 202110558120A CN 113346058 A CN113346058 A CN 113346058A
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trifluoromethanesulfonyl
carbon material
bis
methylimidazolium
butyl
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颜洋
李培权
刘稳
孙静
张颖
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Dalian University of Technology
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Dalian University of Technology
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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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing a bimetal sulfide and carbon compound under an ionic gel system, and belongs to the technical field of preparation of sodium ion battery electrode materials. The method firstly synthesizes ionic liquid and sp2Mixing hybrid carbon material with ion gel, and dissolving in water to prepare IL-sp2Dispersion of hybrid carbon material, bisThe metal source and the sulfur source are dispersed in sp under the electrostatic interaction with the ionic liquid cation or the oxygen-containing functional group2Around the hybrid carbon material, the equilibrium constant (K) is determined by the precipitation of metal sulfidesp) In the difference, the two metal sulfides are sequentially deposited on a GO lamellar under the ionic liquid assisted hydrothermal condition to obtain the bimetallic sulfide @ sp2A hybrid carbon material nanocomposite. The invention relieves the problems of poor conductivity of the metal sulfide, volume expansion and easy aggregation in the charging and discharging processes, and effectively improves the long cycle performance and high rate performance of the material.

Description

Method for preparing bimetallic sulfide and carbon compound under ionic gel system
Technical Field
The invention belongs to the technical field of preparation of sodium ion battery electrode materials, and particularly relates to a method for preparing a bimetallic sulfide and carbon compound under an ionic gel system.
Background
In the historical process of gradually realizing 'carbon peak reaching and carbon neutralization' in China, the use of fossil energy sources is reduced, and clean renewable energy sources mainly based on solar energy and wind energy are developed and utilized on a large scale. However, these clean renewable energy sources are unstable and non-persistent, difficult to directly utilize, and often store energy through an energy storage system before being utilized. Among energy storage systems with different modes, an electrochemical energy storage mode is a mature energy storage mode, a lithium ion battery with the advantages of high energy density, light weight and the like is one of the most concerned electric energy storage devices at present, and the application of the lithium ion battery in a large-scale energy storage system is fundamentally limited due to the characteristics of uneven regional distribution and annual price rise of lithium resources. And the sodium element in the same main group with the lithium element has the physical and chemical properties similar to the lithium element, and the sodium element has rich resources, wide distribution and low price, so that the sodium-ion battery is widely concerned and researched by people in a large-scale energy storage system.
In the negative electrode material of the sodium ion battery, the two-dimensional metal sulfide (such as SnS) with higher theoretical specific capacity2、SnS、MoS2、WS2、Bi2S3、FeS2、Cu2S, etc.) are receiving wide attention. The two-dimensional metal sulfide has the defects of low electron/ion conductivity, severe volume expansion in the sodium removal/sodium insertion process and easy mass aggregation, and leads to assembled electricityThe cell exhibits low cycling efficiency and poor rate performance, greatly limiting further commercial applications. In order to solve the problems, scientific research workers propose strategies such as structural design, size control, carbon composite material synthesis and the like, so that the conductivity of the material is improved, the problems of volume expansion and easy aggregation of the material are relieved, and the cycling stability and rate capability of the two-dimensional metal sulfide are improved to a certain extent.
Among the various carbon materials used in the carbon composite strategy, graphene (G), Graphene Oxide (GO), Carbon Nanotubes (CNTs) and their derivatives are widely used, and these materials are all sp2The hybrid carbon material has free pi bonds, is mostly composed of a single atomic layer, can be expanded to dozens of microns at any time in the transverse dimension, has the characteristics of light weight, high conductivity, good flexibility, large specific surface area and the like, and can be used as a substrate for growth of the bi-dimensional metal sulfide. The Ionic Liquid (IL) is a salt which is liquid at room temperature or near room temperature and consists of organic cations and anions, has the characteristics of non-volatility and no pollution, is called green solvent, and is sp2When the hybrid carbon materials are mixed, due to electrostatic interaction and pi-pi interaction between the hybrid carbon materials, a gel-like compound, called 'bucky gel', can be prepared, and has a very wide prospect in the field of nano composite material preparation.
Disclosure of Invention
The invention aims to provide a method for preparing a bimetallic sulfide and carbon composite under an ionic gel system. The preparation method is characterized in that the equilibrium constant (K) of the bimetallic sulfide due to precipitation under the induction of ionic liquid cations or oxygen-containing functional groups is prepared by the aid of an ionic gel systemsp) Different, but successively precipitated in sp2Stacked nanocomposites on hybrid carbon materials. The invention relieves the problems of poor conductivity of the metal sulfide, volume expansion and easy aggregation in the charging and discharging processes, and effectively improves the long cycle performance and high rate performance of the material.
The invention is realized by the following technical scheme:
a method for preparing a bimetallic sulfide and carbon composite under an ionic gel system comprises the following steps:
(1) mixing ionic liquids IL and sp2And adding the hybrid carbon material into an agate mortar or an ultrasonic cleaning machine, grinding or ultrasonically cleaning for a period of time, and fully mixing to obtain the ionic gel.
(2) Adding the obtained ionic gel into deionized water, and dispersing uniformly under ultrasound to obtain IL-sp2A hybrid carbon material dispersion solution; wherein sp2The concentration of the hybrid carbon material is 2-5 mg/ml-1。
(3) Adding a bimetallic source to IL-sp2Uniformly mixing the hybrid carbon material dispersion solution with stirring to obtain a mixed solution; then, adding a sulfur source into the mixed solution, and stirring and mixing uniformly under the same conditions to obtain a precursor solution with uniformly dispersed raw materials. Wherein the molar ratio of the bimetallic source to the sp is 0.25-42The mass ratio of the hybrid carbon material is 2-3: 1, and the molar ratio of the sulfur source to the bimetallic source is 3-4: 1.
(4) Transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction at the temperature of 180-220 ℃ for 12-24 h; and after the reaction is finished, washing, freezing and drying to obtain a solid product.
(5) Calcining the obtained solid product in a tubular furnace under the protection of inert atmosphere at the temperature of 500-800 ℃ for 2-6 h, and cooling to room temperature to obtain bimetallic sulfide and sp2A composite of hybrid carbon materials.
In the step (1), the ionic liquid is 1-butyl-3-methylimidazole dihydrogen phosphate ([ BMIM)]H2PO4) 1-butyl-3-methylimidazolium hydrogen sulfate ([ BMIM ]]HSO4) 1-butyl-3-methylimidazolium chloride ([ BMIM)]Cl), 1-butyl-3-methylimidazolium tetrafluoroborate ([ BMIM)]BF4) 1-butyl-3-methylimidazolium acetate ([ BMIM ]]Ac), 1-butyl-2, 3-dimethylimidazolium tetrafluoroborate ([ BMMIM)]BF4) 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ OMIM)][NTf2]) 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl)) Imide salt ([ HMIM)][NTf2]) 1-pentyl-3-methylimidazolium bromide ([ PMIM)]Br), N-hexylpyridinebis (trifluoromethanesulfonyl) imide salt ([ HPy)][NTf2]) N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt ([ BPy ]][NTf2]) 3-butylmethylammonium bis (trifluoromethanesulfonyl) imide salt ([ N ]1444][NTf2]) Tributylhexylphosphonium bis (trifluoromethanesulfonyl) imide salt ([ P ]4446][NTf2]) Tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt ([ P ]4444][NTf2]) N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt ([ P ]14][NTf2]) N-butyl-N-methylpiperidine bromide ([ PP)14]Br) in an amount of 0.6-1.5 ml.
In step (1), the sp2The hybrid carbon material is one or a combination of more than two of graphene (G), Graphene Oxide (GO), single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), carboxylated multi-walled carbon nanotubes and hydroxylated multi-walled carbon nanotubes.
In the step (1), the ionic gel is ionic liquid and sp2A homogeneous mixture of hybrid carbon materials.
In the steps (1) and (2), an ultrasonic cleaner is adopted for ultrasonic treatment, and the parameter conditions are as follows: and (3) carrying out ultrasonic treatment for 2-4 h at the temperature of 25-40 ℃.
In the step (2), the using amount of the deionized water is 10-30 ml.
In the step (3), the bimetal source is K2SnO3·3H2O、Na2MoO4·2H2O、Bi(NO3)3·9H2O、Na2WO4·2H2O、K2FeO4、SnCl4·5H2O、SnCl2·2H2O、FeSO4·7H2O、ZnCl2、CuSO4·5H2Any two of O in combination.
In the step (3), the sulfur source is one or a combination of more than two of L-cysteine, thiourea, thioacetamide, sodium sulfide, sodium thiosulfate and sulfur powder.
In the step (3), the magnetic stirrer for stirring has the parameter conditions that: stirring for 1.5-2 h at 15-25 ℃ and 300-500 r/min.
In the step (4), the washing is as follows: the preparation method comprises the following steps of taking one or more of water, ethanol, methanol, isobutanol, ethylene glycol, acetone, tetrahydrofuran, dimethyl sulfoxide, propylene carbonate, ethylene carbonate and N-methylpyrrolidone as a solvent, and performing centrifugation or vacuum filtration.
In the step (4), the freeze drying is as follows: and adding water into the wet solid product, uniformly mixing, freezing in a refrigerator for one night, transferring into a freeze dryer, and keeping at-50 to-40 ℃ for 18 to 24 hours.
In the step (5), the inert atmosphere is N2Atmosphere or Ar atmosphere.
The invention has the beneficial effects that: the invention provides a method for preparing a bimetal sulfide and carbon compound under an ionic gel system, which is carried out in IL-sp2Under the action of the hybrid carbon material gel-like compound, the bimetallic source and the sulfur source are dispersed in sp under the electrostatic interaction between the ionic liquid cation or the oxygen-containing functional group2Around the hybrid carbon material, the equilibrium constant (K) is determined by the precipitation of metal sulfidesp) In the difference, the two metal sulfides are sequentially deposited on a GO lamellar under the ionic liquid assisted hydrothermal condition to obtain the bimetallic sulfide @ sp2A hybrid carbon material nanocomposite. The nano composite material prepared and synthesized by the method has excellent cycle performance and rate capability when being used as a sodium ion battery cathode material, and has practical guiding significance for the design and preparation of metal sulfide materials.
Drawings
FIG. 1 shows SnS/MoS prepared in example 12XRD patterns of @ rGO nanocomposites.
FIG. 2 shows SnS/MoS prepared in example 12Raman plots of @ rGO nanocomposites.
FIG. 3 shows SnS/MoS prepared in example 12TEM images of @ rGO nanocomposites.
FIG. 4 shows SnS/MoS prepared in example 12@ rGO nano composite material at 0.1 A.g-1Lower, front three-ring chargerAnd (4) discharging a picture.
FIG. 5 shows SnS/MoS prepared in example 12@ rGO nano composite material at 1 A.g-1Long cycle performance plot under 200 cycles.
FIG. 6 shows SnS/MoS prepared in example 12Rate performance plot of @ rGO nanocomposite.
FIG. 7 shows Bi prepared in example 42S3/MoS2XRD patterns of @ rGO nanocomposites.
FIG. 8 shows Bi prepared in example 52S3/MoS2SEM images of @ rGO nanocomposites.
FIG. 9 shows Bi prepared in example 52S3/MoS2@ rGO nano composite material at 0.1 A.g-1And the first three circles of charge-discharge diagrams.
FIG. 10 shows Bi prepared in example 52S3/MoS2@ rGO nano composite material at 1 A.g-1Long cycle performance plot under 200 cycles.
FIG. 11 shows Bi prepared in example 52S3/MoS2Rate performance plot of @ rGO nanocomposite.
Detailed Description
The present invention will now be described in further detail by way of the following description of specific embodiments and the accompanying drawings, which are illustrative of the invention and not limiting.
Example 1:
(1) 0.6ml of [ BMIM ]]H2PO4And 45mg of Graphene Oxide (GO) are added into an agate mortar and ground for 10min to obtain [ BMIM ]]H2PO4-GO ion gel.
(2) Will obtain [ BMIM]H2PO4adding-GO ionic gel into 15ml of deionized water, and dispersing uniformly under ultrasound to obtain [ BMIM ]]H2PO4-GO dispersed solution, GO concentration 3 mg-ml-1。
(3) 0.2437mmol K2SnO3·3H2O and 0.2437mmol Na2MoO4·2H2Addition of O to [ BMIM]H2PO4-GO in a dispersion solution at 21 ℃ and 300r/minStirring for 1.5h to obtain a mixed solution; then, 1.9496mmol of L-cysteine was added to the mixed solution, and the mixture was stirred and mixed under the same conditions to obtain a precursor solution in which the raw material was uniformly dispersed.
(4) Transferring the precursor solution into a stainless steel reaction kettle with 25ml of polytetrafluoroethylene as a lining for hydrothermal reaction at the reaction temperature of 200 ℃ for 24 hours; and after the reaction is finished, washing and freeze drying are carried out to obtain a solid product.
(5) The obtained solid product is carried out at 5 ℃ for min under the protection of argon-1The heating rate is increased from room temperature to 600 ℃, kept for 2 hours and naturally reduced to room temperature to obtain the product SnS/MoS2@ rGO nanocomposites.
Example 2:
(1) 1ml of [ BMIM ]]HSO4Adding 50mg of Graphene Oxide (GO) into an agate mortar, and grinding for 10min to obtain [ BMIM ]]HPO4-GO ion gel.
(2) Will obtain [ BMIM]HSO4Adding GO ion gel into 10ml deionized water, and dispersing uniformly under ultrasound to obtain [ BMIM ]]HSO4-a GO dispersion solution, GO concentration 5 mg-ml-1。
(3) 0.2437mmol K2SnO3·3H2O and 0.2437mmol Na2MoO4·2H2Addition of O to [ BMIM]HSO4Stirring the GO dispersed solution for 1.5 hours at 21 ℃ under the condition of 300r/min to obtain a mixed solution; then, 1.7059mmol of thioacetamide was added to the mixed solution, and the mixture was stirred and mixed under the same conditions to obtain a precursor solution in which the raw material was uniformly dispersed.
(4) Transferring the precursor solution into a stainless steel reaction kettle with 25ml of polytetrafluoroethylene as a lining for hydrothermal reaction at the reaction temperature of 200 ℃ for 24 hours; and after the reaction is finished, washing and freeze drying are carried out to obtain a solid product.
(5) The obtained solid product is carried out at 5 ℃ for min under the protection of argon-1The heating rate is increased from room temperature to 600 ℃, kept for 6 hours and naturally reduced to room temperature to obtain the product SnS/MoS2@ rGO nanocomposites.
Example 3:
(1) 1.5ml of [ OMIM ]][NTf2]And 60mg of single-walled carbon nanotubes (SWCNTs) were added to an agate mortar and ground for 10min to obtain [ OMIM ]][NTf2]-CNTs ionic gels.
(2) The obtained [ OMIM][NTf2]Adding the-CNTs ionic gel into 30ml of deionized water, and uniformly dispersing under ultrasound to obtain [ OMIM][NTf2]CNTs dispersion, CNTs concentration 2mg ml-1。
(3) 0.2437mmol K2SnO3·3H2O and 0.2437mmol Na2MoO4·2H2Addition of O to [ OMIM][NTf2]Stirring the CNTs dispersion solution for 1.5h at 25 ℃ at 500r/min to obtain a mixed solution; then, 1.9496mmol of sodium thiosulfate was added to the mixed solution, and the mixture was stirred and mixed uniformly under the same conditions to obtain a precursor solution in which the raw material was uniformly dispersed.
(4) Transferring the precursor solution into a stainless steel reaction kettle with 50ml of polytetrafluoroethylene as a lining for hydrothermal reaction at the reaction temperature of 200 ℃ for 24 hours; and after the reaction is finished, washing and freeze drying are carried out to obtain a solid product.
(5) The obtained solid product is carried out at 5 ℃ for min under the protection of argon-1Heating the mixture for 4 hours from room temperature to 750 ℃, and naturally cooling the mixture to the room temperature to obtain the product SnS/MoS2@ SWCNTs nanocomposites.
Example 4:
(1) 0.6ml of [ BMIM ]]H2PO4And 45mg of Graphene Oxide (GO) are added into an agate mortar and ground for 10min to obtain [ BMIM ]]H2PO4-GO ion gel.
(2) Will obtain [ BMIM]H2PO4adding-GO ionic gel into 15ml of deionized water, and dispersing uniformly under ultrasound to obtain [ BMIM ]]H2PO4-GO dispersed solution, GO concentration 3 mg-ml-1。
(3) 0.2002mmol of Bi (NO)3)3·9H2O and 0.2002mmol Na2MoO4·2H2Adding O to the [ 2 ], [BMIM]H2PO4Stirring the GO dispersed solution for 2 hours at the temperature of 25 ℃ and at the speed of 400r/min to obtain a mixed solution; then, 1.6016mmol of L-cysteine was added to the mixed solution, and the mixture was stirred and mixed under the same conditions to obtain a precursor solution in which the raw material was uniformly dispersed.
(4) Transferring the precursor solution into a stainless steel reaction kettle with 25ml of polytetrafluoroethylene as a lining for hydrothermal reaction at the reaction temperature of 200 ℃ for 24 hours; and after the reaction is finished, washing and freeze drying are carried out to obtain a solid product.
(5) The obtained solid product is carried out at 5 ℃ for min under the protection of argon-1Heating the mixture from room temperature to 500 ℃ for 2 hours, and naturally cooling the mixture to room temperature to obtain a product Bi2S3/MoS2@ rGO nanocomposites.
Example 5:
(1) 0.6ml of [ BMIM ]]H2PO4And 45mg of Graphene Oxide (GO) are added into an agate mortar and ground for 10min to obtain [ BMIM ]]H2PO4-GO ion gel.
(2) Will obtain [ BMIM]H2PO4adding-GO ionic gel into 15ml of deionized water, and dispersing uniformly under ultrasound to obtain [ BMIM ]]H2PO4-GO dispersed solution, GO concentration 3 mg-ml-1。
(3) 0.0931mmol of Bi (NO)3)3·9H2O and 0.3724mmol Na2MoO4·2H2Addition of O to [ BMIM]H2PO4Stirring the GO dispersed solution for 2 hours at the temperature of 25 ℃ and at the speed of 400r/min to obtain a mixed solution; then, 1.8620mmol of L-cysteine was added to the mixed solution, and the mixture was stirred and mixed under the same conditions to obtain a precursor solution in which the raw material was uniformly dispersed.
(4) Transferring the precursor solution into a stainless steel reaction kettle with 25ml of polytetrafluoroethylene as a lining for hydrothermal reaction at the reaction temperature of 200 ℃ for 24 hours; and after the reaction is finished, washing and freeze drying are carried out to obtain a solid product.
(5) The solid product obtained is treated at 5 ℃ mi under the protection of argonn-1Heating the mixture from room temperature to 500 ℃ for 2 hours, and naturally cooling the mixture to room temperature to obtain a product Bi2S3/MoS2@ rGO nanocomposites.
Example 6:
(1) 1ml of [ HMIM ]][NTf2]And 60mg of graphene (G) were put in an agate mortar and ground for 10min to obtain [ HMIM ]][NTf2]-G ion gel.
(2) Will obtain [ HMIM][NTf2]Adding the-G ionic gel into 15ml of deionized water, and uniformly dispersing under ultrasound to obtain [ HMIM ]][NTf2]-G dispersed solution, GO concentration 4 mg-ml-1。
(3) 0.0931mmol of Na2WO4·2H2O and 0.3724mmol Na2MoO4·2H2Addition of O to [ HMIM][NTf2]Stirring the dispersed solution G for 1.5 hours at the temperature of 25 ℃ and at the speed of 400r/min to obtain a mixed solution; then, 1.3965mmol of thiourea was added to the mixed solution, and the mixture was stirred and mixed uniformly under the same conditions to obtain a precursor solution in which the raw material was uniformly dispersed.
(4) Transferring the precursor solution into a stainless steel reaction kettle with 25ml of polytetrafluoroethylene as a lining for hydrothermal reaction at the temperature of 180 ℃ for 20 hours; and after the reaction is finished, washing and freeze drying are carried out to obtain a solid product.
(5) The obtained solid product is carried out at 5 ℃ for min under the protection of argon-1Heating at room temperature to 800 deg.C for 2h, and naturally cooling to room temperature to obtain product WS2/MoS2@ G nanocomposite.
SnS/MoS as shown in FIG. 12The diffraction peak of XRD of @ rGO corresponds to the standard card of SnS, and MoS is not found2Characteristic peak of (002), indicating MoS2There are few layers in the (002) direction.
SnS/MoS as shown in FIG. 22MoS is represented in Raman diagram of @ rGO2Characteristic peak of (2), proving MoS2The strength ratio of the D peak to the G peak of the rGO is more than 1, which indicates that the material has more defects, namely Na+Has better storageAnd (4) storage performance.
SnS/MoS as shown in FIG. 32The TEM image of @ rGO shows that the addition of IL well maintains the two-dimensional lamellar structure of rGO, SnS/MoS2On which the dispersion is stacked.
SnS/MoS as shown in FIG. 42@ rGO at 0.1 A.g-1The first three circles of charge-discharge curves below can be seen, SnS and MoS2With Na+The voltage plateaus of the charging and discharging of the reaction are both present.
SnS/MoS as shown in FIG. 52@ rGO at 1A. g-1Under the long circulation of 200 circles, the yarn still has 379.4mAh g-1The high specific capacity and the capacity retention rate of 82.1 percent show extremely excellent cycle performance.
SnS/MoS as shown in FIG. 62@ rGO is 0.1-10 A.g-1In the rate test under the condition, 10 A.g-1The lower surface still has 239.0mAh g-1The high specific capacity proves that the material synthesized by the method has excellent rate capability.
As shown in FIG. 7, Bi2S3/MoS2Diffraction peaks of XRD of @ rGO and Bi2S3The standard cards correspond to each other and do not show MoS2Characteristic peak of (002), indicating MoS2There are few layers in the (002) direction.
As shown in FIG. 8, Bi2S3/MoS2The SEM image of @ rGO illustrates that the addition of IL well maintains the two-dimensional lamellar structure of rGO, Bi2S3/MoS2Growing on the surface thereof.
As shown in FIG. 9, Bi2S3/MoS2@ rGO at 0.1 A.g-1MoS can be seen from the first three circles of charge-discharge curves2With Na+The voltage plateau of the charging and discharging of the reaction is significant, and Bi2S3Is weaker due to Bi2S3The content is low.
As shown in FIG. 10, Bi2S3/MoS2@ rGO at 1A. g-1And under the long circulation of 200 circles, the capacity retention rate of 79.2 percent is still achieved, and the excellent long circulation performance is shown.
As shown in FIG. 11, Bi2S3/MoS2@ rGO is 0.1-10 A.g-1After the multiplying power test under the condition, the reaction returns to 0.1 A.g-1Still has 514.1mAh g-1The high specific capacity proves that the material synthesized by the method has excellent rate capability and rate stability.

Claims (10)

1. A method for preparing a bimetallic sulfide and carbon composite under an ionic gel system is characterized by comprising the following steps:
(1) mixing ionic liquids IL and sp2Grinding or ultrasonically treating the hybrid carbon material, and fully mixing to obtain ionic gel;
(2) adding the obtained ionic gel into deionized water, and dispersing uniformly under ultrasound to obtain IL-sp2A hybrid carbon material dispersion solution; wherein sp2The concentration of the hybrid carbon material is 2-5 mg/ml-1；
(3) Adding a bimetallic source to IL-sp2Uniformly mixing the hybrid carbon material dispersion solution with stirring to obtain a mixed solution; then, adding a sulfur source into the mixed solution, and stirring and mixing uniformly under the same condition to obtain a precursor solution with uniformly dispersed raw materials; wherein the molar ratio of the bimetallic source to the sp is 0.25-42The mass ratio of the hybrid carbon material is 2-3: 1, and the molar ratio of the sulfur source to the bimetallic source is 3-4: 1;
(4) transferring the precursor solution into a reaction kettle for hydrothermal reaction at the temperature of 180-220 ℃ for 12-24 h; after the reaction is finished, washing, freezing and drying to obtain a solid product;
(5) calcining the obtained solid product under the protection of inert atmosphere at the temperature of 500-800 ℃ for 2-6 h, and cooling to room temperature to obtain bimetallic sulfide and sp2A composite of hybrid carbon materials.
2. The method of claim 1, wherein the ionic liquid is 1-butyl-3-methylimidazolium dihydrogen phosphate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium acetate, 1-butyl-2, 3-dimethylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-pentyl-3-methylimidazolium bromide, N-hexylpyridinium bis (trifluoromethanesulfonyl) imide, N-butylpyridinium bis (trifluoromethanesulfonyl) imide, N-butylimidazolium bromide, N-butyllithium chloride, N-2-methylimidazolium tetrafluoroborate, N-1-butyllithium bromide, N-3-lithium bromide, N-lithium chloride, and N-lithium chloride, One of N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt, 3-butylmethylammonium bis (trifluoromethanesulfonyl) imide salt, tributylhexylphosphonium bis (trifluoromethanesulfonyl) imide salt, tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, and N-butyl-N-methylpiperidinium bromide salt.
3. Method according to claim 1 or 2, characterized in that said sp is2The hybrid carbon material is one or the combination of more than two of graphene, graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, carboxylated multi-walled carbon nanotubes and hydroxylated multi-walled carbon nanotubes.
4. The method of claim 1 or 2, wherein the bimetallic source is K2SnO3·3H2O、Na2MoO4·2H2O、Bi(NO3)3·9H2O、Na2WO4·2H2O、K2FeO4、SnCl4·5H2O、SnCl2·2H2O、FeSO4·7H2O、ZnCl2、CuSO4·5H2Any two of O in combination.
5. The method of claim 3, wherein the bimetallic source is K2SnO3·3H2O、Na2MoO4·2H2O、Bi(NO3)3·9H2O、Na2WO4·2H2O、K2FeO4、SnCl4·5H2O、SnCl2·2H2O、FeSO4·7H2O、ZnCl2、CuSO4·5H2Any two of O in combination.
6. The method of claim 1, 2 or 5, wherein the sulfur source is one or a combination of two or more of L-cysteine, thiourea, thioacetamide, sodium sulfide, sodium thiosulfate and sulfur powder.
7. The method of claim 3, wherein the sulfur source is one or a combination of more than two of L-cysteine, thiourea, thioacetamide, sodium sulfide, sodium thiosulfate and sulfur powder.
8. The method according to claim 1, 2, 5 or 7, wherein in step (1), the ionic liquid is used in an amount of 0.6-1.5 ml; in the step (2), the amount of deionized water is 10-30 ml.
9. The method according to claim 1, 2, 5 or 7, wherein in steps (1) and (2), the ultrasound is performed by using an ultrasonic cleaner, and the parameter conditions are as follows: carrying out ultrasonic treatment for 2-4 h at the temperature of 25-40 ℃; in the step (3), the magnetic stirrer for stirring has the parameter conditions that: stirring for 1.5-2 h at 15-25 ℃ and 300-500 r/min; in the step (4), the washing is as follows: using one or more of water, ethanol, methanol, isobutanol, ethylene glycol, acetone, tetrahydrofuran, dimethyl sulfoxide, propylene carbonate, ethylene carbonate and N-methylpyrrolidone as a solvent, and performing centrifugal or vacuum filtration; the freeze drying is carried out by using a freeze dryer at the temperature of between 50 ℃ below zero and 40 ℃ below zero for 18 to 24 hours.
10. The method of claim 1, 2, 5 or 7, wherein in step (5), the inert atmosphere is N2Atmosphere or Ar atmosphere.
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