CN113206232B - Ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material and preparation method and application thereof - Google Patents

Ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material and preparation method and application thereof Download PDF

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CN113206232B
CN113206232B CN202110457400.5A CN202110457400A CN113206232B CN 113206232 B CN113206232 B CN 113206232B CN 202110457400 A CN202110457400 A CN 202110457400A CN 113206232 B CN113206232 B CN 113206232B
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ordered mesoporous
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doped carbon
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CN113206232A (en
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顾栋
张星
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Wuhan University WHU
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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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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
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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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    • 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
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    • 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
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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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Abstract

The invention discloses an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material and a preparation method and application thereof. The invention respectively fills metal salt and sulfur source into mesoporous silica (such as SBA-15, MCF, KIT-6, MCM-41, FDU-12 and SBA-16) which is not calcined to remove a template by a simple one-pot method, and prepares the layered metal sulfide nano composite material which has a plurality of characteristics of single layer, nitrogen doping, carbon compounding, ordered mesopores, high specific surface area and the like by high-temperature pyrolysis in-situ carbonization and vulcanization under the protection of inert atmosphere. The invention effectively solves the problems of poor conductivity, easy agglomeration, obvious volume effect and the like when the layered metal disulfide is applied to electrochemical energy storage. When the composite material is used as a negative electrode material of an alkali metal ion battery, good electrochemical performance is shown. Meanwhile, the invention provides a simple, effective, low-cost, safe and environment-friendly preparation method.

Description

Ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemistry and the field of micro-nano technology, and particularly relates to an ordered mesoporous single-layer nitrogen-doped metal sulfide composite material, and a preparation method and application thereof.
Background
The interlayer spacing of layered metal disulfides (e.g., molybdenum disulfide, tungsten disulfide, rhenium disulfide) is nearly twice that of graphite, which is an ideal alkali metal ion battery anode material. However, the metal sulfide alkali metal ion battery cathode material which can be practically applied still cannot be obtained at present due to the intrinsic defects of the metal sulfide. The main reasons are as follows: (1) compared with a graphite cathode, the metal sulfide has poor conductivity, low ionic or electronic conductivity and poor reaction reversibility; (2) most of the exposed active sites of the lamellar disulfide of the block are side sites, and the functions of the active sites of most basal planes are not well exerted; (3) during repeated charging and discharging, agglomeration is easy to occur between the lamellar metal sulfide layers, so that the exposed active sites are reduced; (4) during the intercalation and deintercalation of alkali metal ions, the volume of the negative electrode material may be expanded, and finally the electrode may be pulverized to lose contact with the current collector and fail. The preparation of a single layer of metal sulfide, heteroatom doping or carbon material compounding can effectively improve the problems. In the aspect of preparation method, Chinese patent CN202010074680.7 discloses a less-layer molybdenum disulfide/nitrogen-doped porous carbon nano composite catalyst for hydrogen production by water electrolysis, and the invention needs to be calcined at 1000 ℃, so that great potential safety hazard exists. CN 112473711A discloses a preparation method of a molybdenum disulfide/nitrogen and phosphorus co-doped coal-based carbon fiber composite material, which needs triethylene diamine and triphenylphosphine as additional nitrogen sources and phosphorus sources, and needs to prepare carbon fibers by electrostatic spinning and high-temperature calcination methods, and the composite material is prepared by a solvothermal method, so that the preparation process is complicated.
At present, a method which is efficient and environment-friendly and can prepare an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material is lacked.
Disclosure of Invention
Aiming at the technical problems, the invention provides an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material and a preparation method and application thereof.
The invention provides an effective, simple, low-cost and environment-friendly modification method, and the nanocomposite material which has multiple characteristics of single layer, nitrogen doping, carbon compounding, ordered mesopores, high specific surface area and the like is prepared by a one-pot method. The existence of the amorphous carbon skeleton can prevent the single-layer metal disulfide from being stacked again in the charging and discharging process, reduce the active sites and effectively relieve the volume expansion effect of the metal disulfide, thereby achieving the purpose of improving the performance of the metal sulfide applied to the aspect of electrochemical energy storage and conversion.
The technical scheme provided by the invention is as follows:
one of the purposes of the invention is to provide a preparation method of an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material, which comprises the following steps:
(1) adding tetraethyl orthosilicate (TEOS) into an amphiphilic block copolymer or a cationic surfactant solution, stirring and filtering;
(2) filtering the filtrate obtained in the step (1), keeping part of mother liquor for hydrothermal aging, and then filtering and drying to obtain a silicon dioxide template containing an amphiphilic block copolymer or a cationic surfactant;
(3) adding the silicon dioxide template obtained in the step (2) into a thiourea solution, stirring in a water bath, then adding a metal salt precursor, continuing stirring in the water bath to fully dissolve and disperse the metal salt precursor, and then evaporating the solvent to obtain powder;
(4) calcining the powder to obtain a crude product;
(5) removing the silicon dioxide template in the crude product, and freeze-drying to obtain the ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material.
Further, the amphiphilic block copolymer comprises P123, F127, and F108; the cationic surfactant comprises CTAB; the mesoporous silica template of the block copolymer or the cationic surfactant is selected from MCF-P123, KIT-6-P123, FDU-12-F127, SBA-16-F108, SBA-15-P123 or MCM-41-CTA+(ii) a The solution of the amphiphilic block copolymer or the cationic surfactant is selected to be dissolved in hydrochloric acid or sodium hydroxide solution, such as MCM-41-CTA+Templates were prepared under basic conditions, and other templates such as MCF-P123, KIT-6-P123, FDU-12-F127, SBA-16-F108, SBA-15-P123 were prepared under acidic conditions.
Further, the mass ratio of the mesoporous silica template containing the amphiphilic block compound or the cationic surfactant to tetraethyl orthosilicate in the step (1) is 1: 2-5; the reaction was carried out in a water bath at room temperature to 38 ℃ at 500 rpm.
Further, the step (2) may be omitted; the hydrothermal aging temperature in the step (2) is 90-130 ℃, and the aging time is 1-3 days.
Further, in the step (3), the mass ratio of the silicon dioxide template, the thiourea and the precursor is 1: 0.1-1.0; the precursor is selected from phosphomolybdic acid, phosphotungstic acid, ammonium perrhenate, ammonium vanadate, stannic chloride, sodium molybdate, ammonium thiomolybdate, sodium tungstate, ammonium thiotungstate, tetrabutyl ammonium tetrathiorhenate, stannic chloride or ammonium hexathiostannate.
Preferably, thiourea is used as a sulfur source, and when the metal salt precursor is phosphomolybdic acid, thiourea is used as the sulfur source, molybdenum disulfide can be completely sulfurized when the atomic ratio of Mo to S is 1: 2-8; when the metal salt precursor is phosphotungstic acid, the metal salt precursor can be completely vulcanized into tungsten disulfide when the atomic ratio of W to S is 1: 4-8; when the metal salt precursor is ammonium perrhenate, the metal salt precursor can be completely vulcanized into rhenium disulfide when the atomic ratio of Re to S is 1: 2-8; when the metal salt precursor is ammonium vanadate, the metal salt precursor can be completely sulfurized into vanadium disulfide when the atomic ratio of V to S is at least 1: 4-8; when the metal salt precursor is tin tetrachloride, the metal salt precursor can be completely vulcanized into tin disulfide when the atomic ratio of Sn to S is at least 1: 4-8.
Further, in the step (3), the water bath reaction temperature is between room temperature and 80 ℃, and the first water bath reaction time and the second water bath reaction time are both 1-2 h.
Further, in the step (4), calcination is carried out in Ar or N2Heating to 500-900 ℃ from room temperature at the heating rate of 2-10 ℃/min in the atmosphere, then preserving heat for 1-3 h, and naturally cooling to room temperature. Preferably, the calcining temperature is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h. Wherein the interlayer spacing, carbon content and graphitization degree of carbon of the layered metal disulfide can be adjusted by adjusting the calcination temperature and the loading amount (5-50 wt%).
Further, the method of claim 1, wherein: in the step (5), 5-20 wt% of HF or 0.2-2.0 mol/L NaOH is used for removing the silicon dioxide template from the crude product; the freeze drying temperature is-45 to-85 ℃, and the drying time is 12 to 48 hours.
The template used in the preparation method is a silicon dioxide template which is not subjected to high-temperature calcination after hydrothermal aging. Due to the surfactants in the channels, such as: in the presence of P123, CTAB, F127 and F108, the surfactant is carbonized in situ and inserted into the molybdenum disulfide layer to form a monolayer of molybdenum disulfide while vulcanizing at high temperature. When the silica template is removed, the product perfectly replicates the ordered mesoporous structure of the template. And because the thiourea contains heteroatoms such as nitrogen, sulfur and the like, the heteroatoms are doped into crystal lattices of amorphous carbon and metal sulfide in situ in the carbonization and vulcanization processes. In the step (2), the template pore channels are simultaneously arrangedFilling metal salt and thiourea precursor, decomposing thiourea at high temperature to obtain H2S, vulcanizing the metal salt precursor, thereby avoiding the need of additionally using H2S gas and thiourea are used, so that the preparation process is simpler, safer and more environment-friendly.
The second purpose of the invention is to provide the ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material prepared by the method.
The invention also aims to provide application of the ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material as a negative electrode material of an alkali metal ion battery.
The invention has the beneficial effects that:
1) the method mainly utilizes the surfactant which is still present in the pore canal of the silicon dioxide template as an organic carbon source, fills a sulfur source and a metal salt precursor into the pore canal, and forms the ordered mesoporous nitrogen-doped single-layer metal sulfide in situ under the protection of inert gas, thereby realizing the controllable preparation of the ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material.
2) The invention is also suitable for different types of mesoporous silica templates, such as MCF-P123, KIT-6-P123, FDU-12-F127, SBA-16-F108 and SBA-15-P123.
3) The material prepared by the invention shows excellent cycling stability and higher specific capacity in the aspect of electrochemical performance.
4) The invention has the advantages of environmental protection, low cost, high safety, high yield and the like in the preparation process.
Drawings
FIG. 1 ordered mesoporous monolayer MoS2HRTEM of/nitrogen doped carbon composite.
FIG. 2 ordered mesoporous monolayer MoS2Wide angle XRD pattern of/nitrogen doped carbon composite.
FIG. 3 ordered mesoporous monolayer MoS2Small-angle XRD pattern of/N-doped carbon composite material
FIG. 4 is a view of an ordered mesoporous monolayer WS2Wide angle XRD pattern of/nitrogen doped carbon composite.
FIG. 5 ordered mesoporous monolayer ReS2Nitrogen doped carbon compositeWide angle XRD pattern of material.
FIG. 6 ordered mesoporous single layer MoS2When the/nitrogen-doped carbon composite material is applied to a sodium ion battery, the content of the Ag is 0.05 Ag-1The current density of (a) is lower than the charge-discharge curve of the first three circles.
FIG. 7 ordered mesoporous single layer MoS2When the/nitrogen-doped carbon composite material is applied to a sodium ion battery, the content is 1.0A g-1Current density lower cycle curve.
FIG. 8 ordered mesoporous monolayer MoS2When the/nitrogen-doped carbon composite material is applied to a potassium ion battery, the content of the Ag is 0.05 Ag-1The current density of (a) is lower than the charge-discharge curve of the first three circles.
FIG. 9 ordered mesoporous monolayer MoS2When the/nitrogen-doped carbon composite material is applied to the potassium ion battery, the content is 1.0A g-1Current density lower cycle curve of (a).
Detailed Description
The following further describes the specific implementation steps of the present invention with reference to the drawings, and the present invention is not limited thereto at all.
A preparation method of an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material comprises the following steps:
1) preparing a template: compared with the traditional mesoporous silica template, such as SBA-15, the amphiphilic block copolymer P123 is usually used as a surfactant, TEOS is used as a silicon source, and after the gel sol and aging process, calcination in air is usually required to remove the surfactant P123. In the invention, the block copolymer P123 existing in the aged pore channel of the silicon dioxide template is used as a carbon source, so that the step of intermediate high-temperature calcination or nitric acid extraction is omitted, and an organic carbon source is reserved, so that the subsequent preparation process of the ordered mesoporous single-layer metal sulfide is simpler and more effective, and is safe and environment-friendly.
2) Preparing an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material: simultaneously filling a sulfur source and a metal salt precursor into a mesoporous silica template with a pore channel containing a surfactant or a segmented copolymer, and filling the precursor into the pore channel of the template through a solvent volatilization process. Then passes through high temperature inertSex (Ar or N)2) Calcining in the atmosphere to obtain the ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material.
3) Removing the silicon dioxide template by using a certain amount of 5-20 wt% of HF or 0.2-2.0 mol/L NaOH, and then carrying out freeze drying at-45 to-85 ℃ to obtain a final product.
Example 1
1) Preparation of SBA-15-P123: 20.0 g P123 was added to a mixture of 650 mL of water and 100 mL of concentrated hydrochloric acid (37 wt%), stirred at 38 ℃ for 2 hours, then 41.6 g of TEOS was added, stirred at 500 rpm for 24 hours, the solution was filtered, transferred to a hydrothermal kettle, and hydrothermal at 110 ℃ for 24 hours. And finally, after the hydrothermal reaction is finished, reducing the temperature of the hydrothermal kettle to room temperature, carrying out suction filtration on the solution, and drying the template in a 50 ℃ oven for later use.
2) Ordered mesoporous single-layer MoS2Preparing a nitrogen-doped carbon composite material: 0.2212 g of thiourea was added into a beaker (50 mL) containing 10 mL of water, and the mixture was mechanically stirred in a 50 ℃ water bath, after fully dissolved and dispersed, 0.5 g of SBA-15-P123 was added, stirred for 1 hour, 0.2232 g of phosphomolybdic acid was added, and after stirring for 1 hour, the mixture was stirred in an oven at 70 ℃ (the oven temperature cannot be higher than the melting point of the precursor) until all the water was evaporated. And transferring the dried powdery precursor into a tube furnace, and calcining for 2 hours at 600 ℃ in Ar atmosphere at the temperature rising speed of 5 ℃/min. After cooling to room temperature, the SiO solution was cooled with 20 mL of 10 wt% HF2After the template is removed, freezing and drying at-85 ℃ to obtain the final ordered mesoporous single-layer MoS2A nitrogen-doped carbon composite material. FIGS. 1-3 show the prepared ordered mesoporous single-layer MoS2TEM image, wide-angle XRD and small-angle XRD image of/nitrogen-doped carbon composite material. As shown in FIG. 1, MoS2The nitrogen-doped carbon composite material mainly comprises a single layer of molybdenum disulfide. Meanwhile, the (002) characteristic peak of the multilayer molybdenum disulfide which is positioned at about 14.4 degrees disappears obviously in wide-angle XRD (figure 2), which is an important characteristic of the monolayer molybdenum disulfide, and the result is consistent with the TEM image result. FIG. 3 is an ordered mesoporous single layer MoS2The small angle XRD pattern of the/N-doped carbon composite material is clearly observed as shown in the figureThe four peaks (100), (110), (200) and (210) correspond to a two-dimensional hexagonal structure, consistent with the small angle XRD results of SBA-15. In conclusion, the invention can be proved to be capable of preparing ordered mesoporous single-layer MoS2A nitrogen-doped carbon composite material.
Example 2
Preparation of ordered mesoporous monolayer WS according to the procedure of example 12A nitrogen-doped carbon composite material.
0.6354 g of thiourea was added into a beaker (50 mL) containing 10 mL of water, and the mixture was mechanically stirred in a 50 ℃ water bath, after fully dissolved and dispersed, 0.5 g of SBA-15-P123 was added, stirred for 1 hour, 0.2254 g of phosphotungstic acid was added, and after stirring for 1 hour, the mixture was stirred in an oven at 70 ℃ (the oven temperature could not be higher than the melting point of the precursor) until the water was completely volatilized. And transferring the dried mixed precursor into a tubular furnace, and calcining for 2 h at 600 ℃ in Ar atmosphere at the heating speed of 5 ℃/min. After cooling to room temperature, the SiO solution was cooled with 20 mL of 10 wt% HF2After the template is removed, freeze-drying at-85 ℃ is carried out, and the final ordered mesoporous monolayer WS is obtained as shown in figure 42A nitrogen-doped carbon composite material.
Example 3
An ordered mesoporous monolayer, ReS, was prepared according to the method of example 12A nitrogen-doped carbon composite material.
0.2212 g of thiourea was added into a beaker (50 mL) containing 10 mL of water, and the mixture was mechanically stirred in a 50 ℃ water bath to dissolve and disperse the thiourea sufficiently, then 0.5 g of SBA-15-P123 was added, the mixture was stirred for 1 hour, 0.3215 g of ammonium perrhenate was added, the mixture was stirred for 1 hour, and the mixture was dried in an oven at 70 ℃ (the temperature of the oven could not be higher than the melting point of the precursor) until the water was completely volatilized. And transferring the dried mixed precursor into a tubular furnace, and calcining for 2 h at 600 ℃ in Ar atmosphere at the heating speed of 5 ℃/min. After cooling to room temperature, the SiO solution was cooled down to room temperature with 20 mL of 10 wt% HF2After the template is removed, freeze-drying at-85 ℃ is carried out, as shown in figure 5, and the final ordered mesoporous monolayer ReS is obtained2A nitrogen-doped carbon composite material.
Example 4
Using MCF-P123 as a template to prepareMoS with ordered mesoporous monolayers2A nitrogen-doped carbon composite material.
1) Preparation of MCF-P123: 20.0 g P123 g, 0.23 g NH4F. 20.0 g of Trimethylbenzene (TMB) was added to a mixed solution of 650 mL of water and 100 mL of concentrated hydrochloric acid (37 wt%), and after stirring at 38 ℃ for 2 hours at a rotation speed of 500 rpm, 41.6 g of TEOS was added, and after stirring for 24 hours, the solution was filtered with suction, transferred to a hydrothermal reactor, and hydrothermal at 110 ℃ for 24 hours. And finally, after the hydrothermal process is finished, reducing the temperature of the hydrothermal kettle to room temperature, carrying out suction filtration, and drying at 50 ℃ for later use.
2) Ordered mesoporous single-layer MoS2Preparing a nitrogen-doped carbon composite material: 0.2212 g of thiourea was added into a beaker (50 mL) containing 10 mL of water, and the mixture was mechanically stirred in a 50 ℃ water bath, after fully dissolving and dispersing, 0.5 g of MCF-P123 was added, and the mixture was stirred for 1 hour, 0.2232 g of phosphomolybdic acid was added, and after stirring for 1 hour, the mixture was stirred in an oven at 70 ℃ (the oven temperature could not be higher than the melting point of the precursor) until the water was completely volatilized. And transferring the dried mixed precursor into a tubular furnace, and calcining for 2 h at 600 ℃ in Ar atmosphere at the heating speed of 5 ℃/min. After cooling to room temperature, the SiO solution was cooled with 20 mL of 10 wt% HF2After the template is removed, freezing and drying at-85 ℃ to obtain the final ordered mesoporous single-layer MoS2A nitrogen-doped carbon composite material.
Example 5
The prepared composite material is subjected to electrochemical performance tests, such as cycle life, coulombic efficiency, alternating current impedance and the like under different current densities, and the reason for the excellent electrochemical performance is analyzed.
1) Ordered mesoporous monolayer MoS prepared in example 1 was used2The preparation method of the CR2025 button type sodium ion battery prepared from the nitrogen-doped carbon composite material comprises the following steps:
uniformly mixing an active substance, acetylene black and 5% by mass of polytetrafluoroethylene aqueous dispersion emulsion together to obtain a mixture; dropwise adding N-methyl pyrrolidone into the mixture to obtain a mixture for coating;
the active Material described in step (i) was prepared in example 1Prepared ordered mesoporous single-layer MoS2A nitrogen-doped carbon composite;
the mass fraction of active substances in the mixture in the step I is 70%, the mass fraction of acetylene black is 20%, and the mass fraction of polytetrafluoroethylene is 10%;
the mass ratio of the volume of the N-methylpyrrolidone to the active substance in the step I is (1-2 mL): (5-10 mg);
uniformly coating the mixture for coating obtained in the step I on a copper box with the diameter of 14 mm, and then carrying out vacuum drying for 12 hours at the temperature of 80 ℃ to obtain a pole piece with the surface containing active substances; obtaining the mass of the active substance on the pole piece by using a difference method;
and thirdly, transferring the pole piece with the surface containing the active substance into a vacuum glove box to complete the assembly of the button cell, wherein a glass fiber diaphragm (GD/Whatman) is a cell diaphragm, a sodium piece is a counter electrode, the pole piece with the surface containing the active substance is a working electrode, assembling the working electrode, the diaphragm, the counter electrode, a gasket and a cell shell into the CR2025 button cell in the glove box, sealing the button cell by using a sealing machine, and finally standing the prepared button cell at normal temperature for 12 h to activate the cell, namely completing the preparation of the CR2025 button cell.
2) Ordered mesoporous monolayer MoS prepared in example 1 was used2The preparation method of the CR2025 button type potassium ion battery by the nitrogen-doped carbon composite material comprises the following steps:
uniformly mixing an active substance, acetylene black and 5% by mass of polytetrafluoroethylene aqueous dispersion emulsion together to obtain a mixture; dropwise adding N-methyl pyrrolidone into the mixture to obtain a mixture for coating;
the active substance in the step (I) is the ordered mesoporous single-layer MoS prepared in the step (2)2A nitrogen-doped carbon composite;
the mass fraction of active substances in the mixture in the step I is 70%, the mass fraction of acetylene black is 20%, and the mass fraction of polytetrafluoroethylene is 10%;
the mass ratio of the volume of the N-methylpyrrolidone to the active substance in the step I is (1-2 mL): (5-10 mg);
uniformly coating the mixture for coating obtained in the step I on a copper box with the diameter of 14 mm, and then carrying out vacuum drying for 12 hours at the temperature of 80 ℃ to obtain a pole piece with the surface containing active substances; then obtaining the mass of the active substance on the pole piece by using a differential method;
and thirdly, transferring the pole piece with the surface containing the active substance into a vacuum glove box to complete the assembly of the button cell, wherein a glass fiber diaphragm (GD/Whatman) is a cell diaphragm, a potassium sheet is a counter electrode, the pole piece with the surface containing the active substance is a working electrode, assembling the working electrode, the diaphragm, the counter electrode, a gasket and a cell shell into the CR2025 button cell in the glove box, sealing the button cell by using a sealing machine, and finally standing the prepared button cell at normal temperature for 12 h to activate the cell, thus completing the preparation of the CR2025 button type potassium ion cell.
3) The battery is subjected to cycle life test and electrochemical performance analysis.
Fig. 6 and 7 are a charge and discharge curve of the sodium ion battery prepared in example 5 at a current density of 0.1A/g for the first three cycles and a cycle curve at a current density of 1.0A/g, respectively. As shown in FIG. 6, the ordered mesoporous monolayer MoS2When the nitrogen-doped carbon composite material is applied to a sodium ion battery cathode, the charge and discharge capacity of the first ring is 750 mAh/g and 1380 mAh/g respectively, and the coulombic efficiency of the first ring is 55%. There was little decay in the capacity over the subsequent two cycles, showing good cycling stability. When the current density is 1.0A/g, the reversible specific capacity is still kept about 450 mAh/g after 200 cycles, and the high reversible specific capacity is shown.
Fig. 8 and 9 are a charge and discharge curve of the potassium ion battery prepared in example 5 at a current density of 0.1A/g for the first three rounds and a cycle curve at a current density of 1.0A/g, respectively. As shown in FIG. 8, the ordered mesoporous monolayer MoS2When the/nitrogen-doped carbon composite material is applied to a potassium ion battery cathode, the charge and discharge capacities of the first circle are 550 mAh/g and 1210 mAh/g respectively, and the coulombic efficiency of the first circle is 45%. The charging and discharging curve is heavy in the following two circlesAnd (3) the obtained product has good cycle stability. When the current density is 1.0A/g, the reversible specific capacity is still kept about 220 mAh/g after 100 cycles of circulation.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.

Claims (8)

1. A preparation method of an ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material for an alkali metal ion battery is characterized in that a surfactant which is still present in a pore channel of a silicon dioxide template is used as an organic carbon source, a sulfur source and a metal salt precursor are filled into the pore channel, and the ordered mesoporous nitrogen-doped single-layer metal sulfide is formed in situ under the protection of inert gas; the surfactant is selected from an amphiphilic block copolymer or a cationic surfactant;
the method comprises the following steps:
(1) adding tetraethyl orthosilicate (TEOS) into an amphiphilic block copolymer or a cationic surfactant solution, stirring in a water bath, and performing suction filtration; the amphiphilic block copolymer is selected from P123, F127 or F108; the cationic surfactant is selected from CTAB;
(2) filtering the filtrate obtained in the step (1), reserving part of mother liquor for hydrothermal aging at 90-130 ℃, wherein the aging time is 1-3 days, and then filtering and drying to obtain a silicon dioxide template containing an amphiphilic block copolymer or a cationic surfactant; the mesoporous silica template containing the amphiphilic block copolymer or the cationic surfactant is selected from MCF-P123, KIT-6-P123, FDU-12-F127, SBA-16-F108, SBA-15-P123 or MCM-41-CTA+；
(3) Adding the silicon dioxide template obtained in the step (2) into a thiourea solution, stirring in a water bath, then adding a metal salt precursor, continuing stirring in the water bath to fully dissolve and disperse the metal salt precursor, and then evaporating the solvent to obtain powder; the mass ratio of the silicon dioxide template to the thiourea to the precursor is 1: 0.1-1.0;
(4) placing the powder in Ar or N2Calcining under the atmosphere to obtain a crude product, heating at the speed of 2-10 ℃/min, heating from room temperature to 500-900 ℃, then preserving heat for 1-3 h, and naturally cooling to room temperature; adjusting the interlayer spacing, the carbon content and the graphitization degree of the carbon of the layered metal disulfide by adjusting the calcination temperature and the filling amount;
(5) removing the silicon dioxide template in the crude product, and freeze-drying to obtain the ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material.
2. The method of claim 1, wherein: according to the solubility characteristics of the amphiphilic block copolymer or the cationic surfactant, hydrochloric acid or sodium hydroxide solution is selected to be dissolved.
3. The method of claim 1, wherein: the mass ratio of the mesoporous silica template of the amphiphilic block copolymer or the cationic surfactant to the tetraethyl orthosilicate in the step (1) is 1: 2-5; the reaction temperature is between room temperature and 38 ℃, and the stirring is carried out for 24 hours at the rotating speed of 500 revolutions per minute.
4. The method of claim 1, wherein: in the step (3), the metal salt precursor is selected from phosphomolybdic acid, phosphotungstic acid, ammonium perrhenate, ammonium vanadate, tin chloride, sodium molybdate, ammonium thiomolybdate, sodium tungstate, ammonium thiotungstate, tetrabutylammonium tetrathiorhenate, tin tetrachloride or ammonium hexathiostannate.
5. The method of claim 1, wherein: in the step (3), the water bath reaction temperature is 50-80 ℃, and the first water bath reaction time and the second water bath reaction time are both 1-2 hours.
6. The method of claim 1, wherein: the method of claim 1, wherein: in the step (5), 5-10 wt% of HF or 0.2-1.0 mol/L NaOH is used for removing the silicon dioxide template from the crude product; the freeze drying temperature is-45 to-85 ℃, and the drying time is 12 to 48 hours.
7. An ordered mesoporous single-layer metal sulfide/nitrogen-doped carbon composite material for an alkali metal ion battery, which is characterized in that: prepared by the method of any one of claims 1 to 6.
8. Use of the ordered mesoporous single layer metal sulfide/nitrogen doped carbon composite of claim 7 for an alkali metal ion battery as a negative electrode material for an alkali metal ion battery.
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