CN112133892A - Sulfur-doped ReSe2Preparation method of/MXene composite material - Google Patents

Sulfur-doped ReSe2Preparation method of/MXene composite material Download PDF

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CN112133892A
CN112133892A CN202010795709.0A CN202010795709A CN112133892A CN 112133892 A CN112133892 A CN 112133892A CN 202010795709 A CN202010795709 A CN 202010795709A CN 112133892 A CN112133892 A CN 112133892A
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sulfur
mxene
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张业龙
周健文
徐晓丹
孙宏阳
李振瀚
宋伟东
郭月
温锦秀
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Wuyi University
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Abstract

The invention discloses sulfur-doped ReSe2The preparation method of the/MXene composite material takes MXene as a main substrate and synthesizes the ReSe2Loaded on MXene, and sulfur element is doped into ReSe2In the/MXene compound, the sulfur-doped ReSe is prepared by heat treatment reaction2the/MXene composite material. The sulfur-doped ReSe2/MXene composite material has good conductivity, increased interlayer spacing and large specific surface area. The special layered structure of MXene can effectively alleviate the problems of electrical property reduction, structure collapse and the like caused by the agglomeration or volume expansion of the negative electrode material in the cyclic charge-discharge process；ReSe2The load effectively improves the interlayer spacing and increases the specific surface area; further, doping of elemental sulfur renders the ReSe2the/MXene composite material exposes more active sites and vacancies and improves the potassium storage performance of the material. MXene, ReSe2The sulfur atoms are used for making up respective defects and deficiencies, the composite material has a synergistic effect, and the potassium storage performance, specific capacity, charge-discharge stability, electron transfer rate and other performances of the composite material are improved to the greatest extent. Meanwhile, the preparation process is simple and the performance is controllable.

Description

Sulfur-doped ReSe2Preparation method of/MXene composite material
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to sulfur-doped ReSe2A preparation method of/MXene composite material.
Background
Lithium ion batteries have been developed rapidly in the fields of portable electronic communication equipment, electric vehicles and the like, but at present, lithium resources are less in the earth, and the lithium resources are increasingly reduced along with the increase of battery requirements, so that the continuous development of battery technology is limited to a great extent. It is therefore desirable to develop a new battery to reduce the use of lithium ions. Potassium and lithium are both elements of the first main group, and have similar reserves and potentials, and potassium ions have higher potential platforms, energy densities and abundant reserves, so that the potassium ion has great development potential. In practical applications, however, potassium ion batteries still face significant challenges.
MXene is a compound composed of transition metal carbide and nitride or carbonitride, and the shape of the compound is similar to that of an accordion, and the surface of the material has abundant functional groups. The material has the following advantages when used as a battery material: the special structure of the catalyst shows an ultra-high specific surface area, and more contact areas of active sites and ions are increased; the good conductivity of the catalyst enables the ion movement resistance to be small, thereby reducing the reaction kinetics; ③ the surface functional group can increase the hydrophilicity of the material, etc. However, the electrochemical performance of MXene still has some defects, such as: small interlayer spacing, insufficient active sites, poor conductivity, and the like.
ReSe2Are typically two-dimensional transition metal chalcogenides (TMDCs) that exhibit a sandwich structure with weak interaction forces (van der waals forces) between each layer that can allow the insertion of ions without significant damage. As a negative electrode material, the material has excellent electrochemical performance, but the development of the material is severely limited by defects of poor conductivity, easy agglomeration and the like.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a sulfur-doped ReSe2the/MXene composite material. Another object of the present invention is to provide the above sulfur-doped ReSe2A preparation method of/MXene composite material. Further, the invention provides sulfur-doped ReSe2Application of/MXene composite material, and preparation method of sulfur-doped ReSe2the/MXene composite material is used for the negative electrode of the potassium ion battery.
The invention adopts the following technical scheme:
sulfur-doped ReSe2The preparation method of the/MXene composite material belongs to a solvothermal method and specifically comprises the following steps:
(1) reacting with ReSe2Fully and uniformly mixing the nano particles, a proper amount of solvent and water to obtain a dispersion liquid;
(2) mixing MXene nanosheets, dispersion liquid, a sulfur source and water, performing ultrasonic treatment for 0.5-1 h at the temperature of 20-50 ℃ to prepare mixed liquid with the concentration of 1-100mg/ml, and then stirring for 1-5 h;
(3) transferring the stirred mixed solution into a reaction kettle in a microwave heating box, heating to 150-;
(4) grinding the crude product obtained in the step (3) to ensure that the crude product is uniformly distributed, putting the crude product into a corundum ark, heating the crude product to 200-300 ℃ in a tubular furnace filled with protective gas, calcining the crude product for 2-4h, naturally cooling the crude product to room temperature, and collecting the calcined product to obtain the sulfur-doped ReSe2the/MXene composite material.
Further, the solvent is at least one of N, N-dimethylformamide, cyclohexane and xylene, preferably N, N-dimethylformamide; the cleaning agent is at least one of water and ethanol, and preferably is alternately cleaned for 2-10 times by deionized water and absolute ethyl alcohol.
Further, the MXene nano-sheet and the ReSe2The molar ratio of the nanoparticles to the sulfur source is 1: 1: 0.01-0.9.
Further, MXene is Ti3C2Tx、Ti2CTx、Nb2CTx、Ta4C3Tx、Ti3CNTXOne or more of; such as Ti2CTxIs like Nb2CTx(ii) a Preferably, Ti3C2TxAnd Ti3CNTXThe mass ratio of (1): 5 to 10, wherein TxIs a surface functional group-O, -OH or-F.
Further, the calcination can increase the crystallinity, and can make the sulfur atom doping more sufficient, and the sulfur atom partially replaces the selenium atom.
Further, the sulfur source is one or more of sulfur powder, thiourea and thioacetamide.
Further, the particle size of the sulfur source is 50 to 150 mesh, for example 120 mesh; the particle size of the ReSe2 nanoparticles is 10nm to 100nm, preferably 20nm to 50nm, such as 10nm, 20nm, 50nm, 100 nm; the MXene nanosheets have a size of 1-5 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm.
Further, the sulfur-doped ReSe2The sulfur doping amount of the/MXene composite material is 1-20 wt%, such as 1-10 wt%, 3-12 wt% and 6-15 wt%.
Further, the mixed solution in the step (3) is moved into a reaction kettle and heated to 150-250 ℃ in a microwave heating box, preferably 120-180 ℃, for example, 140 ℃, 160 ℃, 180 ℃; the reaction time is 10-18h, such as 12h, 15h and 18 h.
Further, the rotation speed of the centrifugation in the step (3) is 6000-; centrifuging for 5-10min, preferably 6-8min, such as 5min, 6min, 7min, 8min, 9min, and 10 min; the vacuum drying temperature is 50-70 deg.C, preferably 60 deg.C, and the drying time is 8-12h, such as 10h, 11h, and 12 h.
Further, the protective gas in step (4) is one of argon, helium and nitrogen, preferably argon.
The sulfur-doped ReSe2Sulfur-doped ReSe prepared by preparation method of/MXene composite material2the/MXene composite material.
A potassium ion battery cathode comprising the sulfur-doped ReSe2the/MXene composite material.
The invention has the beneficial effects that:
(1) sulfur doped ReSe of the invention2The preparation method of the/MXene composite material takes MXene as a main substrate and takes the Re as2Loaded on MXene, and sulfur element is doped into ReSe2In the/MXene compound, the sulfur-doped ReSe is prepared by heat treatment reaction2MXene composite material, MXene, ReSe2The sulfur atoms are used for making up respective defects and deficiencies, so that the composite material has a synergistic effect, and the potassium storage performance, specific capacity, charge-discharge stability, electron transfer rate and other performances of the composite material are improved to the greatest extent;
(2) the special layered structure of MXene in the sulfur-doped ReSe2/MXene composite material effectively alleviates the problems of electrical property reduction, structure collapse and the like caused by agglomeration or volume expansion of a negative electrode material in the cyclic charge-discharge process; ReSe2The load effectively improves the interlayer spacing and increases the specific surface area; further, doping of elemental sulfur renders the ReSe2the/MXene composite material exposes more active sites and vacancies and improves the potassium storage performance of the material.
(3) The preparation method has simple and safe preparation process and low cost, and is favorable for popularizing sulfur-doped ReSe2The application of the/MXene composite material as the negative electrode material of the potassium ion battery.
Drawings
Fig. 1 is a scanning electron micrograph of the MXene material alone in comparative example 1;
FIG. 2 Sulfur doped ReSe in example 12Scanning electron microscope images of the/MXene composite material;
FIG. 3 Sulfur doped ReSe in example 12And the cycle performance of the/MXene composite material assembled potassium ion battery is measured at the current density of 100 mA/g.
FIG. 4 is a graph of the cycle performance of the MXene anode material alone assembled potassium ion battery of comparative example 1 at a current density of 100 mA/g;
FIG. 5 shows the ReSe alone in comparative example 22And (3) a cycle performance graph of the assembled potassium ion battery with the negative electrode material under the current density of 100 mA/g.
FIG. 6 shows the ReSe in comparative example 32The cycle performance of the/MXene material assembled potassium ion battery is measured under the current density of 100 mA/g.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.
Wherein the materials are commercially available unless otherwise specified;
the ReSe2Nanoparticles are purchased from Shenzhen Liu carbon science and technology Limited, model: ReSe2Crystal size 20-50nm, purity: high purity 99.999%, lattice type: semiconductor material, anisotropic material.
The Ti3C2TxNanoparticles were purchased from beijing beike science and technology ltd, code BK2020011814, size: 1-5 μm, purity: 99%, product application field: energy storage, catalysis, analytical chemistry, and the like.
The method is a conventional method unless otherwise specified.
Example 1
Sulfur-doped ReSe2The preparation method of the/MXene composite material comprises the following steps:
(1) adding 0.1mmol of ReSe2Fully stirring and uniformly mixing the nano particles, 10ml of N, N-Dimethylformamide (DMF) and 5ml of ultrapure water to obtain a suspension;
(2) 0.1mmol of MXene (Ti)3C2Tx) Nanosheet, suspension, 0.06mmol of sulfur powder andmixing 15ml of ultrapure water, treating in an ultrasonic cleaning instrument with the ultrasonic frequency of 50W for 0.5h at 25 ℃, and then magnetically stirring for 4h to obtain a mixed solution;
(3) transferring the stirred mixed solution into a reaction kettle with the capacity of 60ml, heating the mixed solution to 150 ℃ in a microwave heating box, reacting for 10 hours, and naturally cooling the mixed solution to room temperature; transferring the product into a centrifuge tube, centrifuging for 5min under the condition of 7000r/min, respectively washing filter residue from which supernatant is removed with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven to obtain a crude product, wherein the drying temperature is 65 ℃ and the drying time is 10 h;
(4) grinding the crude product obtained in the step (3) until the crude product is uniformly distributed, putting the crude product into a corundum ark, heating the corundum ark to 250 ℃ in a tube furnace filled with argon, calcining the corundum ark for 3 hours, naturally cooling the corundum ark to room temperature, and collecting the product to obtain the sulfur-doped ReSe2the/MXene composite material.
Doping sulphur with ReSe2The preparation method comprises the following steps of uniformly mixing a/MXene composite material, a conductive agent super P carbon and a polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on copper foil, drying and cutting into pieces to be used as a working electrode of the potassium ion battery, and assembling a 2032 type button half-cell by using 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as an electrolyte, a metal potassium sheet as a counter electrode and glass fiber as a diaphragm; all assembly was performed in an inert atmosphere glove box.
Sulfur doped ReSe of this example2Under the current density of 100mA/g, the reversible capacity of the potassium ion battery assembled by the MXene composite negative electrode material after 100 cycles is 326.6mA h/g, which is 5.3 times of the reversible capacity (61.1mA h/g) of the potassium ion battery assembled by the undoped MXene negative electrode material, and is simple ReSe23.18 times of the negative electrode material (102.4mA h/g) is ReSe21.14 times of/MXene negative electrode material (286.2mA h/g), sulfur doped ReSe of this example2the/MXene composite negative electrode material has good potassium storage performance and charge-discharge cycle performance.
Example 2
Sulfur-doped ReSe2The preparation method of the/MXene composite material comprises the following steps：
(1) Adding 0.1mmol of ReSe2Fully stirring and uniformly mixing the nano particles, 15ml of N, N-Dimethylformamide (DMF) and 10ml of ultrapure water to obtain a suspension;
(2) 0.1mmol of MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 0.07mmol of sulfur powder and 20ml of ultrapure water, treating for 0.5h in an ultrasonic cleaning instrument with ultrasonic frequency of 50W at 27 ℃, and then magnetically stirring for 5h to obtain a mixed solution;
(3) transferring the mixed solution into a reaction kettle with the capacity of 60ml, heating the mixed solution to 180 ℃ in a microwave heating box, reacting for 12h, naturally cooling the mixed solution to room temperature, transferring the product to a centrifugal tube, centrifuging the product for 5min by using a centrifugal machine under the condition of 7500r/min, washing filter residues for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the filter residues in a vacuum drying box to obtain a crude product, wherein the drying temperature is 60 ℃ and the drying time is 10 h;
(4) grinding the crude product obtained in the step (3) until the crude product is uniformly distributed, putting the crude product into a corundum ark, heating the corundum ark in a tube furnace filled with argon to 280 ℃, calcining the corundum ark for 3 hours, naturally cooling the corundum ark to room temperature, collecting the product to obtain the sulfur-doped ReSe2the/MXene composite material.
Doping sulphur with ReSe2The preparation method comprises the following steps of uniformly mixing a/MXene composite material, a conductive agent super P carbon and a polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on copper foil, drying and cutting into pieces to be used as a working electrode of the potassium ion battery, and assembling a 2032 type button half-cell by using 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as an electrolyte, a metal potassium sheet as a counter electrode and glass fiber as a diaphragm; all assembly was performed in an inert atmosphere glove box.
Sulfur doped ReSe of this example2Under the current density of 100mA/g, the reversible capacity of the potassium ion battery assembled by the MXene composite negative electrode material after 100 cycles is 335.2mA h/g, which is 5.4 times of the reversible capacity (61.1mA h/g) of the potassium ion battery assembled by the undoped MXene negative electrode material, and is simple ReSe23.27 times of the negative electrode material (102.4mA h/g) is ReSe2of/MXene negative electrode Material (286.2mA h/g)1.17 times, sulfur doped ReSe of this example2the/MXene composite negative electrode material has good potassium storage performance and charge-discharge cycle performance.
Example 3
Sulfur-doped ReSe2The preparation method of the/MXene composite material comprises the following steps:
(1) adding 0.2mmol of ReSe2Fully stirring and uniformly mixing the nano particles, 15ml of N, N-Dimethylformamide (DMF) and 10ml of ultrapure water to obtain a suspension;
(2) 0.2mmol of MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 0.13mmol of thiourea and 20ml of ultrapure water, treating in an ultrasonic cleaning instrument at 27 ℃ for 0.5h at the ultrasonic frequency of 50W, and magnetically stirring for 4h to obtain a mixed solution;
(3) transferring the mixed solution into a reaction kettle with the capacity of 60ml, heating the mixed solution to 180 ℃ in a microwave heating box, reacting for 12h, naturally cooling the mixed solution to room temperature, transferring the product to a centrifugal tube, centrifuging the product for 5min by using a centrifugal machine under the condition of 7500r/min, washing filter residues for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the filter residues in a vacuum drying box to obtain a crude product, wherein the drying temperature is 60 ℃ and the drying time is 10 h;
(4) grinding the crude product obtained in the step (3) until the crude product is uniformly distributed, putting the crude product into a corundum ark, heating the corundum ark to 280 ℃ in a tube furnace filled with argon, calcining the corundum ark for 3 hours, naturally cooling the corundum ark to room temperature, and collecting the product to obtain the sulfur-doped ReSe2the/MXene composite material.
Doping sulphur with ReSe2The preparation method comprises the following steps of uniformly mixing a/MXene composite material, a conductive agent super P carbon and a polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on copper foil, drying and cutting into pieces to be used as a working electrode of the potassium ion battery, and assembling a 2032 type button half-cell by using 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as an electrolyte, a metal potassium sheet as a counter electrode and glass fiber as a diaphragm; all assembly was performed in an inert atmosphere glove box.
Sulfur doped ReSe of this example2/MXene composite anode material assemblyUnder the current density of 100mA/g, the reversible capacity of the potassium ion battery after 100 cycles is 313.4mA h/g, which is 5.1 times of the reversible capacity (61.1mA h/g) of the cathode of the potassium ion battery without MXene, and is simple ReSe23.06 times of the negative electrode material (102.4mA h/g) is the ReSe21.09 times of/MXene negative electrode material (286.2mA h/g), and the sulfur-doped ReSe of the embodiment2the/MXene composite negative electrode material has very stable charge-discharge cycle performance.
Example 4
Sulfur-doped ReSe2The preparation method of the/MXene composite material comprises the following steps:
(1) adding 0.2mmol of ReSe2Fully stirring and uniformly mixing the nano particles, 15ml of N, N-Dimethylformamide (DMF) and 10ml of ultrapure water to obtain a suspension;
(2) 0.2mmol of MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 0.16mmol of thiourea and 20ml of ultrapure water, treating in an ultrasonic cleaning instrument with ultrasonic frequency of 50W for 0.5h at 27 ℃, and then magnetically stirring for 4h to obtain a mixed solution;
(3) transferring the mixed solution into a reaction kettle with the capacity of 60ml, heating the mixed solution to 180 ℃ in a microwave heating box, reacting for 12h, naturally cooling the mixed solution to room temperature, transferring the product to a centrifugal tube, centrifuging the product for 5min by using a centrifugal machine under the condition of 7500r/min, washing filter residues for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the filter residues in a vacuum drying box to obtain a crude product, wherein the drying temperature is 60 ℃ and the drying time is 10 h;
(4) grinding the crude product obtained in the step (3) until the crude product is uniformly distributed, putting the crude product into a corundum ark, heating the corundum ark to 300 ℃ in a tube furnace filled with argon, calcining the corundum ark for 3 hours, naturally cooling the corundum ark to room temperature, and collecting the product to obtain the sulfur-doped ReSe2the/MXene composite material.
Doping sulphur with ReSe2The preparation method comprises the steps of uniformly mixing the MXene composite material, the conductive agent super P-carbon and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on copper foil, drying and cutting into pieces to be used as the working electrode of the potassium ion battery, and mixing 1M KFSI EC (ethylene carbonate)) PC (propylene carbonate) (1:1) is used as electrolyte, a metal potassium sheet is used as a counter electrode and glass fiber is used as a diaphragm, and a 2032 type button half-cell is assembled; all assembly was performed in an inert atmosphere glove box.
Sulfur doped ReSe of this example2Under the current density of 100mA/g, the reversible capacity of the potassium ion battery assembled by the MXene composite negative electrode material after 100 cycles is 344.1mA h/g, which is 5.6 times of the reversible capacity (61.1mA h/g) of the negative electrode of the undoped MXene potassium ion battery, and is simple ReSe23.36 times of the negative electrode material (102.4mA h/g) is the ReSe21.2 times of/MXene negative electrode material (286.2mA h/g), and the sulfur-doped ReSe of the embodiment2the/MXene composite negative electrode material has very stable charge-discharge cycle performance.
Comparative example 1
Weighing 80mg of MXene material, 10mg of super P and 10mg of polyvinylidene fluoride binder, mixing, adding a small amount of N-methylpyrrolidone, stirring, coating on a copper foil, drying at 90 ℃ for 3 hours, cutting the copper foil into a round shape by using a slicing machine to serve as a working electrode, drying, putting the round shape into an inert atmosphere glove box with oxygen and water contents lower than 0.4ppm, and assembling into a 2032 type button battery by using a metal potassium sheet as a counter electrode and glass fiber as a diaphragm.
Comparative example 2
80mg of ReSe are weighed2Mixing the materials, 10mg of super P and 10mg of polyvinylidene fluoride binder, adding a small amount of N-methyl pyrrolidone, stirring, coating on a copper foil, drying at 90 ℃ for 3 hours, cutting the copper foil into a round shape by a slicer to be used as a working electrode, drying, putting into an inert atmosphere glove box with oxygen and water contents lower than 0.4ppm, and assembling into a 2032 type button battery by using a metal potassium sheet as a counter electrode and using glass fiber as a diaphragm.
Comparative example 3
(1) Adding 0.1mmol of ReSe2Fully stirring and uniformly mixing the nano particles, 15ml of N, N-Dimethylformamide (DMF) and 10ml of ultrapure water to obtain a suspension;
(2) 0.1mmol of MXene (Ti)3C2Tx) Mixing the nano-sheets, the suspension and 20ml of ultrapure water, and carrying out ultrasonic treatment at 27 ℃ and the ultrasonic frequency of 50WTreating in a cleaning instrument for 0.5h, and then magnetically stirring for 5h to obtain a mixed solution;
(3) transferring the mixed solution into a reaction kettle with the capacity of 60ml, heating the mixed solution to 180 ℃ in a microwave heating box, reacting for 12h, naturally cooling the mixed solution to room temperature, transferring the product to a centrifugal tube, centrifuging the product for 5min by using a centrifugal machine under the condition of 7500r/min, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the product in a vacuum drying box to obtain a crude product, wherein the drying temperature is 60 ℃ and the drying time is 10 h;
(4) grinding the crude product obtained in the step (3) until the crude product is uniformly distributed, putting the crude product into a corundum ark, heating the corundum ark in a tube furnace filled with argon to 280 ℃, calcining the corundum ark for 3 hours, naturally cooling the corundum ark to room temperature, and collecting the product to obtain ReSe2the/MXene composite material.
Reacting with ReSe2The preparation method comprises the following steps of uniformly mixing a/MXene composite material, a conductive agent super P carbon and a polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on copper foil, drying and cutting into pieces to be used as a working electrode of the potassium ion battery, and assembling a 2032 type button half-cell by using 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as an electrolyte, a metal potassium sheet as a counter electrode and glass fiber as a diaphragm; all assembly was performed in an inert atmosphere glove box.
FIG. 1 is a scanning electron micrograph of MXene material alone in comparative example 1, and FIG. 2 is a sulfur-doped ReSe in example 12Scanning electron microscope images of the/MXene composite material. As can be seen from FIGS. 1-2, the MXene material used in the invention has a multi-layer structure, no impurities are on the surface, but the interlayer distance is small, the doped MXene composite material still keeps the original accordion-shaped layer structure, the interlayer distance is obviously increased, and the surface of the MXene material has no agglomeration phenomenon, which indicates that the sulfur-doped ReSe is successfully prepared in the embodiment2the/MXene composite material.
FIGS. 3-6 are respectively sulfur-doped ReSe in example 12The composite material of/MXene, the simple MXene negative electrode material in the comparative example 1 and the independent ReSe in the comparative example 22Negative electrode Material, ReSe in comparative example 32The current of the potassium ion battery assembled by the/MXene material is 100mA/gMeasured cycling performance plot at density. As can be seen from FIGS. 3-6, the sulfur-doped ReSe of the present invention2The specific capacity, potassium storage performance and cycle performance of the/MXene composite material after 100 cycles are far superior to those of the materials in comparative examples 1-3. Referring to fig. 4, the reversible capacity of the simple MXene negative electrode material in comparative example 1 is very low, and is only 61.1mA h/g; see FIG. 5, ReSe alone in comparative example 22The specific capacity of the negative electrode material declined after 10 cycles due to the ReSe alone2The cathode material is easy to agglomerate, the structure is unstable, and the charge and discharge performance is poor; see FIG. 6, ReSe in comparative example 32the/MXene material has good potassium storage performance in the charge and discharge processes, higher specific capacity and stable charge and discharge performance, the battery performance is still not ideal, and the electrochemical performance of the battery needs to be further improved.
Referring to FIG. 3, the invention takes MXene as a main substrate to synthesize the ReSe2Loaded on MXene and doping sulfur element to ReSe2In the/MXene compound, the sulfur-doped ReSe is prepared by heat treatment reaction2the/MXene composite material. The obtained sulfur-doped ReSe2/MXene composite material has good conductivity, increased interlayer spacing and large specific surface area, and the special layered structure of MXene can effectively alleviate the problems of electrical property reduction, structure collapse and the like caused by the agglomeration or volume expansion of a negative electrode material in the cyclic charge-discharge process; ReSe2The load effectively improves the interlayer spacing and increases the specific surface area; further, doping of elemental sulfur renders the ReSe2the/MXene composite material exposes more active sites and vacancies, thereby improving the potassium storage performance of the material. Thus, MXene, ReSe2The sulfur atoms can make up respective defects and deficiencies, have a synergistic effect, and improve the performances of the composite material such as potassium storage performance, specific capacity, charge-discharge stability, electron transfer rate and the like to the maximum extent. Meanwhile, the preparation process is simple and the performance is controllable.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.

Claims (10)

1. Sulfur-doped ReSe2The preparation method of the/MXene composite material is characterized by comprising the following steps:
(1) reacting with ReSe2Fully mixing the nano particles, the solvent and water to obtain a dispersion liquid;
(2) mixing MXene nanosheets, dispersion liquid, a sulfur source and water, and performing ultrasonic treatment to prepare mixed liquid with the concentration of 1-100 mg/ml;
(3) heating the stirred mixed solution to 150 ℃ and 250 ℃, reacting for 10-24h to obtain suspension, centrifuging, washing and drying to obtain a crude product;
(4) heating the crude product obtained in the step (3) to 200-300 ℃ in a protective atmosphere, calcining for 2-4h, cooling and collecting to obtain the sulfur-doped ReSe2the/MXene composite material.
2. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that the solvent is at least one of N, N-dimethylformamide, cyclohexane and xylene; preferably, the cleaning agent is at least one of water and ethanol.
3. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that the MXene is Ti3C2Tx、Ti2CTx、Nb2CTx、Ta4C3Tx、Ti3CNTXOne or more of (a).
4. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that the sulfur source is one or more of sulfur powder, thiourea and thioacetamide.
5. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that the sulfur-doped ReSe2The sulfur doping amount in the/MXene composite material is 1-20 wt%.
6. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that MXene nanosheets and ReSe2The mole of nanoparticles and sulfur source was 1: 1: 0.01-0.9.
7. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that the centrifugal rotating speed in the step (3) is 6000-; preferably, the drying temperature in the step (3) is 50-70 ℃, and the drying time is 8-12 h.
8. The sulfur-doped ReSe of claim 12The preparation method of the/MXene composite material is characterized in that the protective gas in the step (4) is one or more of argon, helium and nitrogen.
9. A potassium ion battery negative electrode, characterized in that it comprises sulfur-doped ReSe prepared by the preparation method of any one of claims 1 to 82the/MXene composite material.
10. A potassium ion battery comprising the potassium ion battery negative electrode according to claim 9.
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