CN112018350A - Phosphorus-doped MoSe2/MXene composite material and preparation method thereof - Google Patents
Phosphorus-doped MoSe2/MXene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to phosphorus-doped MoSe2A method for preparing a/Mxene composite, said method comprising the steps of: dissolving a proper amount of molybdenum source material and selenium powder in a solvent, uniformly mixing to obtain a dispersion liquid, and adding MXene nanosheets, a phosphorus source material and ultrapure water into the dispersion liquid to obtain a mixed liquid; heating the mixed solution to 150 ℃ and 250 ℃, and reacting for 10-24 h; centrifuging, removing supernatant, washing and drying to obtain a primary product; calcining the primary product for 2-4h at the temperature of 600 ℃ in the protective atmosphere of 400-2the/MXene composite material. The phosphorus is doped with MoSe2MoSe utilized by/MXene composite negative electrode material2The material has good durability and low charge transfer resistance, and can inhibit agglomeration, increase active sites and specific surface area and buffer MoSe when compounded with MXene material2The volume change during potassium storage, and the doping of a small amount of heteroatom phosphorus increases the electronegativity of the composite material, so that vacancy defects are regulated and controlled to enhance the potassium ion adsorption capacity. The result shows that the composite material has excellent cycle performance and rate capability when used as a working electrode of a potassium ion battery.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to phosphorus-doped MoSe2a/MXene composite material and a preparation method thereof.
Background
Rechargeable lithium ion batteries have been widely used in portable electronic devices as popular energy storage devices for the past several decades. However, when the energy storage system is enlarged, the material cost becomes an important factor, and the cost thereof is increasing due to the scarcity of lithium resources, so that a potassium ion battery which has low material cost and abundant resources and is similar to a lithium ion battery attracts attention. The working voltage of the potassium ion battery is higher than that of the sodium ion battery, and the electrolyte transmission quantity and the mobility also have certain advantages in the rapid charging and discharging process. However, the larger particle size makes the material expand in volume and even crush in structure during repeated intercalation and deintercalation of potassium ions, which is a great challenge for realizing rapid charging and stable cycling of the potassium ion battery.
Compared with other negative electrode materials, the MXene material has a special accordion-shaped layered structure, shows an ultra-high specific surface area, plays roles of increasing active sites, inhibiting agglomeration, increasing ion contact area and stabilizing an overall structure, and has the advantages of good conductivity, material hydrophilicity and the like, but the interlayer spacing is small, and surface functional groups have certain adsorbability, so that an ideal ion rapid migration effect cannot be achieved when the MXene material is used alone.
Transition metal compounds based on Se are also receiving a great deal of attention as electrode materials. MoSe2The nano material has low charge transfer resistance and small overpotential value, and the working electrode modified by the nano material has good durability in controllable potential electrolysis under the acidic condition and has the advantages of band gap harmony, electronic multifunctionality and the like. But bulk MoSe2The larger particles can cause volume expansion in the potassium ion diffusion process, and the MoSe can be generated in the potassium ion insertion and extraction process2Layer receiverTo large internal stress, resulting in cracking of the material and poor electrochemical properties. Therefore, in order to improve the electrochemical performance, the conductivity and the material structure thereof must be improved.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a phosphorus-doped MoSe2the/MXene composite material. It is another object of the present invention to provide the phosphorus-doped MoSe2A preparation method of/MXene composite material. Further, the invention provides phosphorus-doped MoSe2Application of/MXene composite material, and phosphorus-doped MoSe2the/MXene composite material is applied to the negative electrode of the potassium ion battery.
The invention adopts the following technical scheme:
phosphorus-doped MoSe2A preparation method of/Mxene composite material belongs to a solvothermal method and comprises the following steps:
(1) weighing appropriate amount of MoSe2Adding a proper amount of chemical solvent into the material, fully stirring to obtain a dispersion liquid, and adding MXene nano-sheets and ultrapure water into the dispersion liquid, wherein the MXene nano-sheets and the MoSe are added2And a phosphorus source in a molar ratio of 1: 1: 0.05-0.5, treating for 1-5h in an ultrasonic cleaning instrument, stirring for 6-12h, and preparing into mixed solution with the concentration of 5-100 mg/ml;
(2) transferring the mixed solution into a reaction kettle, placing the reaction kettle into an oven, heating to 250 ℃ at 150-.
(3) Centrifuging the product obtained in the step (2) by using a detergent, and drying in a vacuum drying oven to obtain a primary product;
(4) placing the primary product into a corundum ark, calcining for 2-4h in a tubular furnace with protective atmosphere at 400-600 ℃, cooling to room temperature, and collecting to obtain phosphorus-doped MoSe2the/MXene composite material.
Further, the chemical solvent is selected from one or more of N, N-dimethylformamide, xylene and acetone, and N, N-dimethylformamide is preferably used.
Further, the detergent is at least one of ultrapure water and alcohol, and preferably, the detergent is washed 3 to 6 times with ultrapure water and then washed 3 to 6 times with alcohol.
Further, MXene is selected from Ti3C2Tx、V2CTx、Mo3N2Tx、Ta4C3TxOne or more of (A), e.g. Ti2CTx,Nb2CTxPreferably Ti3C2Tx。
Further, the phosphorus source material is one or more of triphenylphosphine, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
Further, the ultrasonic cleaning apparatus is sonicated for 2-5h, e.g., 2h, 3h, 5h, preferably 3h, at 25-40 deg.C, e.g., 25 deg.C, 28 deg.C, 30 deg.C, 35 deg.C, preferably 30 deg.C.
Further, the rotation speed set in the centrifugation in the step (3) is 5000-.
Further, the temperature of the vacuum drying is 60-100 ℃, preferably 80 ℃, and the drying time is 8-16h, such as 9h, 13h and 15 h.
Further, the protective gas in step (4) is one of argon, helium and nitrogen, preferably argon.
The potassium ion battery cathode comprises phosphorus-doped MoSe prepared by the preparation method2a/Mxene composite material.
A potassium ion battery comprises the battery cathode.
The invention has the beneficial effects that:
(1) compared with untreated MXene material, the phosphorus-doped MoSe prepared by the invention2the/MXene composite material increases the interlayer spacing of the material to accelerate the diffusion kinetics of potassium ions, and simultaneously stabilizes the structure to prevent larger volume expansion in the process of embedding and de-embedding the potassium ions; MoSe2Uniformly loaded on the surface of MXene material, effectively preventing MoSe2The agglomeration of the materials further improves the conductivity; a small amount of heteroatom phosphorus is doped to regulate vacancy so as to attract more potassium ions to be embedded, thereby obviously improving the electrochemical stability of the materialQualitative and potassium storage properties;
(2) the material of the invention has simple and efficient preparation operation, low cost and large-scale application.
Drawings
FIG. 1 is phosphorus-doped MoSe of example 12Scanning electron microscope images of the/MXene composite material;
FIG. 2 is phosphorus-doped MoSe of example 12A cycle performance diagram of the potassium ion battery assembled by the/MXene composite material under the current density of 100 mA/g;
FIG. 3 is a simple MoSe of comparative example 12A cycle performance diagram of the material assembled potassium ion battery under the current density of 100 mA/g;
FIG. 4 is a graph of the cycling performance of the potassium ion battery assembled with MXene material alone in comparative 2 at a current density of 100 mA/g;
FIG. 5 is an undoped MoSe in comparative example 32And the cycle performance of the/MXene composite material assembled potassium ion battery at the current density of 100mA/g is shown.
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.
Wherein the materials are commercially available unless otherwise specified;
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 MoSe2 material is available from Yokoka metals materials, Inc., CAS number 12058-18-3, size: 10-100nm, purity: 99. 99%, color: gray, packaging: vacuum bottles or bags.
The method is a conventional method unless otherwise specified.
The invention provides phosphorus-doped MoSe2Preparation of/MXene composite materialThe synthesis method of MoSe2 is shown in the following:
synthesis of carbon-based transition metal sulfur/selenide composite material in Tang-Cai and application thereof in lithium ion battery [ D ]. Yangzhou university, 2019 ] "
Example 1
Phosphorus-doped MoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.1mmol of MoSe was weighed2Adding 10ml of N, N-dimethylformamide as a chemical solvent, mixing, fully stirring to obtain a dispersion solution, adding 0.1mmol of MXene nanosheets, 0.01mmol of triphenylphosphine and 20ml of ultrapure water into the dispersion solution, treating for 3 hours in an ultrasonic cleaning instrument at 30 ℃, and stirring for 10 hours by using a magnetic stirrer to prepare a mixed solution;
(2) transferring the mixed solution into a reaction kettle, clamping and sealing the reaction kettle, and putting the reaction kettle into a drying oven to be heated to 200 ℃ for reaction for 16 hours;
(3) centrifuging the product obtained in the step (2) for 5min at 8000r/min, discarding the supernatant, washing the filter residue with ultrapure water for 5 times, washing the filter residue with alcohol for 5 times, setting the drying temperature of the product in a vacuum drying oven at 80 ℃, and drying for 12h to obtain an initial product;
(4) putting the primary product into a corundum ark, calcining for 4 hours at 450 ℃ in a tubular furnace with argon protective atmosphere, cooling to room temperature, and collecting to obtain phosphorus-doped MoSe2the/MXene composite material.
Doping phosphorus with MoSe2Mixing the/MXene composite material, the super P and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing to obtain a working electrode of the potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling the working electrode of the potassium ion battery into a 2032 type button battery; all assembly was performed in an inert atmosphere glove box.
This example phosphorus doped MoSe2The potassium ion battery assembled by the MXene composite negative electrode material still has high specific capacity of 360.5mA h/g after being cycled for 100 circles under the current density of 100mA/g, and the material of the embodiment has good cycle performance and charge-discharge capacity.
Example 2
Phosphorus-doped MoSe2The preparation method of the/MXene composite material comprises the following steps:
((1) weigh 0.2mmol of MoSe2Adding 10ml of N, N-dimethylformamide as a chemical solvent, mixing, fully stirring to obtain a dispersion liquid, adding 0.2mmol of MXene nanosheets, 0.015mmol of triphenylphosphine and 20ml of ultrapure water into the dispersion liquid, treating for 3 hours in an ultrasonic cleaning instrument at 30 ℃, and stirring for 10 hours by using a magnetic stirrer to prepare a mixed liquid;
(2) transferring the stirred mixed solution into a reaction kettle, clamping and sealing the reaction kettle, and putting the reaction kettle into a drying oven to be heated to 230 ℃ for reaction for 18 hours;
(3) centrifuging the product obtained in the step (2) for 5min under the condition of 9000r/min, discarding the supernatant, washing the filter residue with ultrapure water for 5 times, washing the filter residue with alcohol for 5 times, setting the drying temperature of the product in a vacuum drying oven at 80 ℃, and drying for 12h to obtain an initial product;
(4) putting the primary product into a corundum ark, calcining for 4 hours at 450 ℃ in a tubular furnace with argon protective atmosphere, cooling to room temperature, and collecting to obtain phosphorus-doped MoSe2the/MXene composite material.
Doping phosphorus with MoSe2Mixing the/MXene composite material, the super P and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing to obtain a working electrode of the potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling the working electrode of the potassium ion battery into a 2032 type button battery; all assembly was performed in an inert atmosphere glove box.
This example phosphorus doped MoSe2The potassium ion battery assembled by the/MXene composite negative electrode material still has high specific capacity of 375.3mA h/g after being cycled for 100 circles under the current density of 100mA/g, and the material of the embodiment has good cycle performance and charge-discharge capacity.
Example 3
Phosphorus-doped MoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.3mmol of MoSe was weighed2Adding 10ml of N, N-dimethylformamide as a chemical solvent, mixing, fully stirring to obtain a dispersion liquid, adding 0.3mmol of MXene nanosheets, 0.12mmol of triphenylphosphine and 20ml of ultrapure water into the dispersion liquid, treating for 3 hours in an ultrasonic cleaning instrument at 30 ℃, and stirring for 10 hours by using a magnetic stirrer to prepare a mixed liquid;
(2) transferring the mixed solution into a reaction kettle, clamping and sealing the reaction kettle, and putting the reaction kettle into a drying oven to be heated to 220 ℃ for reaction for 16 hours;
(3) centrifuging the product obtained in the step (2) for 5min at 8000r/min, discarding the supernatant, washing the filter residue with ultrapure water for 5 times, washing the filter residue with alcohol for 5 times, setting the drying temperature of the product in a vacuum drying oven at 80 ℃, and drying for 12h to obtain an initial product;
(4) putting the primary product into a corundum ark, calcining for 4 hours at 450 ℃ in a tubular furnace with argon protective atmosphere, cooling to room temperature, and collecting to obtain phosphorus-doped MoSe2the/MXene composite material.
Doping phosphorus with MoSe2Mixing the/MXene composite material, the super P and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing to obtain a working electrode of the potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling into a 2032 type button half-battery; all assembly was performed in an inert atmosphere glove box.
This example phosphorus doped MoSe2The potassium ion battery assembled by the MXene composite negative electrode material still has high specific capacity of 388.6mA h/g after being cycled for 100 circles under the current density of 100mA/g, and the material of the embodiment has good cycle performance and charge-discharge capacity.
Example 4
Phosphorus-doped MoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.5mmol of MoSe was weighed2Adding 10ml of chemical solvent N, N-dimethylformamide, fully stirring to obtain a dispersion liquid, adding 0.5mmol of MXene nanosheet, 0.25mmol of triphenylphosphine and 20ml of ultrapure water into the dispersion liquid,treating in 30 deg.C ultrasonic cleaning instrument for 3 hr, and stirring with magnetic stirrer for 10 hr to obtain mixed solution;
(2) transferring the mixed solution into a reaction kettle, clamping and sealing the reaction kettle, and putting the reaction kettle into a drying oven to be heated to 250 ℃ for reaction for 16 hours;
(3) centrifuging the product obtained in the step (2) for 5min at 8000r/min, discarding the supernatant, washing the filter residue with ultrapure water for 5 times, washing the filter residue with alcohol for 5 times, setting the drying temperature of the product in a vacuum drying oven at 80 ℃, and drying for 12h to obtain an initial product;
(4) putting the primary product into a corundum ark, calcining for 4 hours at 450 ℃ in a tubular furnace with argon protective atmosphere, cooling to room temperature, and collecting to obtain phosphorus-doped MoSe2the/MXene composite material.
Doping phosphorus with MoSe2Mixing the/MXene composite material, the super P and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing to obtain a working electrode of the potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling into a 2032 type button half-battery; all assembly was performed in an inert atmosphere glove box.
This example phosphorus doped MoSe2The potassium ion battery assembled by the MXene composite negative electrode material still has high specific capacity of 371.6mA h/g after being cycled for 100 circles under the current density of 100mA/g, and the material of the embodiment has good cycle performance and charge-discharge capacity.
Example 5
Phosphorus-doped MoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 0.62mmol of MoSe was weighed2Adding 10ml of N, N-dimethylformamide as a chemical solvent, mixing, fully stirring to obtain a dispersion liquid, adding 0.62mmol of MXene nanosheets, 0.28mmol of triphenylphosphine and 20ml of ultrapure water into the dispersion liquid, treating for 3 hours in an ultrasonic cleaner at 30 ℃, and stirring for 10 hours by using a magnetic stirrer to prepare a mixed liquid;
(2) transferring the stirred mixed solution into a reaction kettle, clamping and sealing the reaction kettle, and putting the reaction kettle into a drying oven to be heated to 200 ℃ for reaction for 16 hours;
(3) centrifuging the product obtained in the step (2) for 5min under the condition of 8500r/min, discarding the supernatant, washing the filter residue with ultrapure water for 5 times, washing the filter residue with alcohol for 5 times, setting the drying temperature of the product in a vacuum drying oven at 80 ℃, and drying for 12h to obtain an initial product;
(4) placing the primary product into a corundum ark, calcining for 4 hours at 550 ℃ in a tubular furnace with argon protective atmosphere, cooling to room temperature, and collecting to obtain phosphorus-doped MoSe2the/MXene composite material.
Doping phosphorus with MoSe2Mixing the/MXene composite material, the super P and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing to obtain a working electrode of the potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling into a 2032 type button half-battery; all assembly was performed in an inert atmosphere glove box.
This example phosphorus doped MoSe2The potassium ion battery assembled by the MXene composite negative electrode material still has high specific capacity of 381.7mA h/g after being cycled for 100 circles under the current density of 100mA/g, and the material of the embodiment has good cycle performance and charge-discharge capacity.
Comparative example 1
Simple MoSe2The preparation method of the material comprises the following steps:
adding MoSe2Mixing the materials, super P and a polyvinylidene fluoride binder according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing the black slurry to be used as a working electrode of a potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling the 2032 type button half-cell; all assembly was performed in an inert atmosphere glove box.
This example is MoSe2The capacity of the potassium ion battery assembled by the negative electrode material under the current density of 100mA/g is 163.7 mAh/g.
Comparative example 2
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.
FIG. 5 is a graph of the cycle performance of MXene material assembled potassium ion batteries measured at a current density of 100 mA/g.
As can be seen from the figure, the MXene material assembled potassium ion battery has good cycling stability in the charging and discharging processes under the current density of 100mA/g, but the specific capacity is smaller and is 101.1mA h/g.
Comparative example 3
1) 0.5mmol of MoSe was weighed2Adding 10ml of N, N-dimethylformamide as a chemical solvent, mixing, fully stirring to obtain a dispersion liquid, adding 0.5mmol of MXene nanosheets and 20ml of ultrapure water into the dispersion liquid, treating for 3 hours in an ultrasonic cleaning instrument at 30 ℃, and stirring for 10 hours by using a magnetic stirrer to prepare a mixed liquid;
(2) transferring the mixed solution into a reaction kettle, clamping and sealing the reaction kettle, and putting the reaction kettle into a drying oven to be heated to 250 ℃ for reaction for 16 hours;
(3) centrifuging the product obtained in the step (2) for 5min at 8000r/min, discarding the supernatant, washing the filter residue with ultrapure water for 5 times, washing the filter residue with alcohol for 5 times, setting the drying temperature of the product in a vacuum drying oven at 80 ℃, and drying for 12h to obtain an initial product;
(4) placing the primary product into a corundum ark, calcining for 4 hours at 450 ℃ in a tubular furnace with argon protective atmosphere, cooling to room temperature, and collecting to obtain MoSe2the/MXene composite material.
Adding MoSe2Mixing the/MXene composite material, the super P and the polyvinylidene fluoride binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, magnetically stirring to form black slurry, coating the black slurry on copper foil, drying and slicing to obtain a working electrode of the potassium ion battery, taking a metal potassium sheet as a counter electrode and taking glass fiber as a diaphragm, and assembling into a 2032 type button half-battery; all assembled in an inert atmosphere glove boxIs carried out in (1).
This example is MoSe2The specific capacity of 294.3mA h/g is obtained when the potassium ion battery assembled by the/MXene composite material is cycled for 100 circles under the current density of 100 mA/g.
As can be seen from FIG. 1, the material prepared by the method of the present invention contains phosphorus and MoSe2The material is uniformly loaded on MXene material, no agglomeration phenomenon exists, and the interlayer spacing is caused by phosphorus and MoSe2The loading of the material increases. As can be seen from FIGS. 2-5, pure MoSe2The material cycle stability is very poor due to the massive MoSe2The larger particles can cause volume expansion in the potassium ion diffusion process, and the MoSe can be generated in the potassium ion insertion and extraction process2The layer is subjected to large internal stress, resulting in cracking of the material; although the simple MXene material has good stability, the specific capacity is very small, namely only 101.1mA h/g, because the interlayer spacing is small and the surface functional group has certain adsorbability, the ideal quick ion migration effect cannot be achieved when the single MXene material is used alone; MoSe2The cycle stability and the specific capacity of the/MXene composite material are improved to a certain extent, but the specific capacity of the/MXene composite material cannot meet the requirement on the expanded application of the potassium ion battery cathode, and the electrochemical performance of the MXene composite material is still to be improved; phosphorus-doped MoSe prepared by the invention2The specific capacity of the/MXene composite material is remarkably improved, the cycling stability performance is excellent, a small amount of heteroatom phosphorus doping regulation vacancies can attract more potassium ions to be embedded, and the electrochemical stability and the potassium storage performance of the material are further improved.
In summary, the above cases do not limit the scope of the patent application, and the listed cases have good electrochemical performance, and any modification or idea made by the patent is within the protection and coverage scope of the present invention.
Claims (10)
1. Phosphorus-doped MoSe2The preparation method of the/Mxene composite material is characterized by comprising the following steps:
(1) adding appropriate amount of MoSe2Dissolving in a solvent to obtain a dispersion liquid, adding MXene nanosheets, a phosphorus source material and water into the dispersion liquid, and preparing into a mixed liquid with the concentration of 5-100 mg/ml;
(2) heating the mixed solution to 150 ℃ and 250 ℃, and reacting for 10-24 h;
(3) centrifuging the product obtained in the step (2), removing supernatant, washing and drying to obtain a primary product;
(4) calcining the primary product for 2-4h at the temperature of 600 ℃ in the protective atmosphere of 400-2the/MXene composite material.
2. The phosphorus doped MoSe of claim 12The preparation method of the/MXene composite material is characterized in that the MXene nanosheets and MoSe2And the molar ratio of the phosphorus source material to the phosphorus source material is 1: 1: 0.05-0.5.
3. The phosphorus doped MoSe of claim 12The preparation method of the/MXene composite material is characterized in that the chemical solvent is selected from one or more of N, N-dimethylformamide, xylene and acetone.
4. The phosphorus doped MoSe of claim 12The preparation method of the/MXene composite material is characterized in that the MXene is Ti3C2Tx、V2CTx、Mo3N2Tx、Ta4C3TxOne or more of (a).
5. The phosphorus doped MoSe of claim 12The preparation method of the/MXene composite material is characterized in that the phosphorus source material is one or more of sodium dihydrogen phosphate, triphenylphosphine and potassium dihydrogen phosphate.
6. The phosphorus doped MoSe of claim 12The preparation method of the/MXene composite material is characterized in that the centrifugal rotating speed in the step (3) is 5000-10000r/min, and the centrifugal time is 5-20 min.
7. The phosphorus doped MoSe of claim 12/MXene composite materialThe preparation method is characterized in that the temperature of vacuum drying in the step (3) is 60-100 ℃, and the drying time is 8-16 h.
8. The phosphorus doped MoSe of claim 12The preparation method of the/MXene composite material is characterized in that the protective atmosphere in the step (4) is one of argon, helium and nitrogen.
9. A potassium ion battery negative electrode, characterized in that it comprises phosphorus-doped MoSe prepared by the preparation method of any one of claims 1 to 82the/MXene composite material.
10. A potassium ion battery comprising the battery negative electrode of claim 9.
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