CN115472810A - Vanadium-based carbon nanofiber composite negative electrode material of potassium ion battery and preparation method and application thereof - Google Patents

Vanadium-based carbon nanofiber composite negative electrode material of potassium ion battery and preparation method and application thereof Download PDF

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CN115472810A
CN115472810A CN202211328588.4A CN202211328588A CN115472810A CN 115472810 A CN115472810 A CN 115472810A CN 202211328588 A CN202211328588 A CN 202211328588A CN 115472810 A CN115472810 A CN 115472810A
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carbon nanofiber
vanadium
ion battery
potassium ion
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李林林
周启超
彭生杰
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Nanjing University of Aeronautics and Astronautics
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Abstract

The invention belongs to the research field of electrode materials of potassium ion batteries, and particularly discloses a vanadium-based carbon nanofiber composite anode material of a potassium ion battery, and a preparation method and application thereof. The method comprises the steps of preparing an electrostatic spinning membrane by using polyacrylonitrile as a precursor, obtaining a carbon nanofiber membrane by pre-oxidizing in air and activating in inert gas, growing vanadium oxide in situ by using solvothermal reaction, and vulcanizing in the inert gas atmosphere to obtain the vanadium-based carbon nanofiber composite material with a stable structure. The potassium ion battery cathode material synthesized by the method has higher specific capacity and good cycling stability. Under the current density of 0.05A/g, the specific capacity of 350 mAh/g can be kept; when the current density is increased to 0.2A/g, the specific capacity can reach 300 mAh/g.

Description

Vanadium-based carbon nanofiber composite negative electrode material of potassium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of potassium ion batteries, and particularly relates to a vanadium-based carbon nanofiber composite cathode material of a potassium ion battery, and a preparation method and application thereof.
Background
With the exhaustion of fossil fuels and the increasingly prominent environmental problems, the development of green and environment-friendly renewable energy sources has become a necessary requirement for sustainable development. However, renewable energy sources such as solar energy, wind energy, tidal energy, geothermal energy and the like are affected by unstable factors such as regions, seasons and the like, cannot be directly incorporated into a power grid, and can be effectively utilized only by energy storage, conversion, storage and release. Therefore, the research on efficient and stable electrochemical energy storage devices is the key point for developing green energy.
At present, lithium ion batteries have enjoyed great success in the fields of portable power supplies, electric vehicles, partial power grid energy storage technologies and the like. However, further development of lithium ion batteries is limited by scarcity of their resource reserves. The chemical property of potassium in the same main group is similar to that of lithium, the potassium has standard electrode potential similar to that of lithium, the energy density is high, the storage amount in the crust is rich, and the cost is relatively low. In terms of energy density and reserve, potassium ion batteries have broad prospects in large-scale energy applications.
Since potassium ions have a larger atomic radius than lithium ions, potassium ions cause a large volume change and structural damage when they are intercalated into/deintercalated from an electrode material, resulting in a sharp decrease in energy density thereof. Therefore, the search for an electrode material suitable for reversible intercalation and deintercalation of potassium ions has a very important significance for the application of potassium ion batteries. The vanadium-based electrode material has the characteristics of high theoretical specific capacity, rich resources, low price and the like, but the vanadium-based electrode material has low self conductivity and large volume change in the charging and discharging processes, so that the energy density is sharply reduced. The invention uses a crosslinked carbon nanofiber network as a conductive substrate and composites ultrathin VS on the substrate 2 Nano-sheet flower cluster is used for constructing nano-scale vanadium-based carbon nanofiber composite material, which not onlyThe problem of structural rupture caused by volume expansion in the circulation process is relieved, and the surface compounded nano flower cluster structure provides a large number of active sites and active areas, so that potassium ions are better embedded and separated, and the material has excellent potassium storage performance.
Disclosure of Invention
The invention provides a vanadium-based carbon nanofiber composite negative electrode material for a potassium ion battery, which aims to solve the problems of low specific capacity, short cycle life, poor stability and the like of the negative electrode material for the potassium ion battery in the prior art.
The invention also provides a vanadium-based carbon nanofiber composite negative electrode material for the potassium ion battery prepared by the preparation method and the potassium ion battery using the composite negative electrode material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1) Dissolving polyacrylonitrile by using dimethyl formamide formate, and stirring for 10-12 h at 60-70 ℃ to obtain electrostatic spinning solution; carrying out electrostatic spinning by using the spinning solution to obtain an electrostatic spinning film; cutting the obtained electrostatic spinning membrane, pre-oxidizing for 1-2 hours at 250-300 ℃, then placing the electrostatic spinning membrane into an inert gas atmosphere, and activating for 1-2 hours at 250-300 ℃ to obtain an electro-spun carbon nanofiber membrane material;
2) Dissolving triisopropoxyl vanadium oxide in isopropanol to prepare a homogeneous phase transfer solution, adding the electrospun carbon nanofiber membrane material obtained in the step (1), performing a solvent thermal reaction at 150-200 ℃ for 10-12 h, performing vacuum drying at 80 ℃ for 10h after cleaning, and performing further oxidation at 300-350 ℃ for 1-2 h to obtain an in-situ grown vanadium oxide carbon nanofiber composite membrane material;
3) And (3) respectively placing the vanadium oxide carbon nanofiber composite membrane material prepared in the step (2) and a sulfur source reagent into a lower air opening and an upper air opening of a ceramic boat, then placing the ceramic boat in an inert gas atmosphere, and heating for 4-6 h at 500-700 ℃, so as to obtain the vanadium-based carbon nanofiber composite material. .
In the step (1), the mass fraction of the polyacrylonitrile is 8-12%.
The electrostatic spinning voltage in the step (1) is 18-24 kV, the liquid flow is 0.8-1.0 mL/h, and the distance from the needle to the collector is 20-25 cm.
In the step (2), the volume ratio of the triisopropoxytriantivaquoxide to the isopropanol is (0.1-0.5): 30.
In the step (2), the cleaning process comprises three times of deionized water washing and one time of ethanol washing.
The sulfur source reagent in the step (3) is any one of sulfur powder and thioacetamide, and the mass ratio of the vanadium oxide carbon nanofiber composite membrane material to the sulfur source reagent is 1: (5-10).
An application of a vanadium-based carbon nanofiber composite cathode material of a potassium ion battery in preparation of the potassium ion battery.
A potassium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein a negative electrode material layer comprises a negative electrode active substance, a conductive agent and a binder, and the negative electrode active substance is the vanadium-based carbon nanofiber composite material.
The invention has the beneficial effects that:
in the vanadium-based carbon nanofiber composite cathode material, the VS is ultrathin 2 The nano-sheet layer clusters are evenly anchored on the staggered carbon nano-fiber network to form VS 2 the/ECF composite anode material. The carbon nanofiber network structure which is crosslinked mutually is used as a carrier, so that electron and ion transmission is promoted, and the volume change caused by the insertion and the extraction of potassium ions is relieved; VS anchored at the surface of carbon nanofibers 2 The ultrathin nanosheet cluster provides rich reactive active sites and active areas while maintaining ultrahigh theoretical specific capacity, increases active potassium storage sites, and improves diffusion rate of potassium ions. The two components are mutually promoted while keeping respective advantages, and the problems of low specific capacity and short cycle life of the potassium ion battery anode material in the prior art are solved.
The vanadium-based carbon nanofiber composite cathode material prepared by electrostatic spinning, a solvothermal method and gas-phase vulcanization keeps the diameter of carbon nanofibers at 500-800 nm and the thickness of a single piece of a uniformly anchored nanosheet layer cluster at 5-10 nm. By adopting the preparation method of the invention, the recovery is reducedThe size of the nano particles of the negative electrode is combined, so that the particle agglomeration phenomenon in the circulation process is avoided, and the structural fracture caused by volume expansion is effectively relieved. At the same time, the small fiber diameter can load more VS per unit area 2 The ultrathin nanosheet layer clusters have larger specific surface area and more active sites, and are more beneficial to the infiltration of the electrolyte of the potassium ion battery and the embedding and the extraction of potassium ions. Therefore, when the vanadium-based carbon nanofiber composite material is used as a potassium ion battery cathode, the specific capacity of 350 mAh/g can be kept under the current density of 0.05A/g; when the current density is increased to 0.2A/g, the specific capacity of more than 300 mAh/g still exists; in the circulation process, the coulombic efficiency is stabilized at 100%, and the electrochemical performance and the rate capability are good.
Drawings
FIG. 1 is an X-ray diffraction diagram of the product obtained in example 2 of the present invention.
FIG. 2 is a scanning electron micrograph (lower magnification and higher magnification) of the product obtained in example 2 of the present invention.
FIG. 3 is a graph showing the cycle profile of the product obtained in example 2 of the present invention.
FIG. 4 is a graph showing the cycle profile of the product obtained in example 2 of the present invention.
Detailed Description
In order to make the technical solution and advantages of the present invention clearer, the present invention will be described in detail with reference to the accompanying drawings and examples, which are only used for explaining the present invention and are not used for limiting the present invention.
Example 1
The vanadium-based carbon nanofiber composite negative electrode material for the potassium ion battery in the embodiment comprises a staggered carbon nanofiber network and nanosheet clusters which are uniformly anchored on the outer surface of carbon nanofibers, wherein the nanosheet clusters are formed by VS2 nanosheets. Specifically, the preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery comprises the following steps:
1) Dissolving 1.0 g of polyacrylonitrile by using 10 mL of formic acid dimethylamide, and stirring at constant temperature of 60 ℃ for 10h in an oil bath kettle to obtain the clear and transparent electrostatic spinning solution. The solution was then transferred to a 10 mL syringe, attached to a latex tube and a 0.6 mm diameter needle, and mounted on an electro-spinning machine. The machine voltage is set to be 20 kV, the liquid flow is 0.8 mL/min, the distance from the needle to the aluminum foil collector is 20 cm, and the white electrostatic spinning film can be obtained. Taking the electrostatic spinning film off the aluminum foil, and placing the electrostatic spinning film in a muffle furnace to heat up to 280 ℃ at a speed of 1 ℃/min for heat preservation for 1h for pre-oxidation; and then heating to 280 ℃ at a speed of 10 ℃/min under the argon atmosphere of a tube furnace, and preserving heat for 1h for activation to obtain the electrospun carbon nanofiber membrane material.
2) Dissolving 0.15 mL of triisopropoxyl vanadium oxide in 30 mL of isopropanol to prepare a homogeneous phase transfer solution, taking an electrospun carbon nanofiber membrane material with the size of 2 x 4 cm and the homogeneous phase transfer solution, placing the electrospun carbon nanofiber membrane material and the homogeneous phase transfer solution in a 50 mL reaction kettle, sealing, and carrying out a solvothermal reaction for 10 hours in a 200 ℃ oven. Washing the reacted fiber sheet with water and ethanol, drying the fiber sheet for 10h in a vacuum drying oven at 80 ℃, and then calcining the fiber sheet for 1h in a muffle furnace at the temperature of 2 ℃/min to 320 ℃ to obtain the in-situ growth vanadium oxide carbon nanofiber composite membrane material.
3) And (3) respectively placing the obtained vanadium oxide carbon nanofiber membrane composite material and sulfur powder in a mass ratio of 1: 5 into a lower air port and an upper air port of a porcelain boat, and heating to 600 ℃ for 5 hours at a speed of 1 ℃/min in a tube furnace argon atmosphere to obtain the vanadium-based carbon nanofiber composite material.
Uniformly mixing the obtained vanadium-based carbon nanofiber composite material, conductive agent Keqin black and adhesive CMC according to the mass ratio of 7: 2: 1, adding a proper amount of deionized water to prepare slurry, uniformly coating the slurry on copper foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the potassium ion battery negative electrode piece. Finally, in a glove box, the potassium ion battery is obtained by sequentially combining the positive electrode shell, the positive electrode sheet (potassium sheet), the diaphragm (Whatmann GF/C), the electrolyte (KFSIEC: DC =1: 1), the negative electrode sheet, the elastic sheet and the negative electrode shell, and then the test is carried out.
Example 2
The vanadium-based carbon nanofiber composite cathode material for the potassium ion battery in the embodiment comprises a staggered carbon nanofiber network and nanosheet layer clusters uniformly anchored on the outer surface of carbon nanofibers, wherein the nanosheet layer clusters are formed by VS2 nanosheets. Specifically, the preparation method of the vanadium-based carbon nanofiber composite anode material of the potassium ion battery comprises the following steps:
1) Dissolving 1.0 g of polyacrylonitrile by using 10 mL of formic acid dimethylamide, and stirring for 10h at a constant temperature in a 60 ℃ oil bath kettle to obtain a clear and transparent electrostatic spinning solution. The solution was then transferred to a 10 mL syringe, attached to a latex tube and a 0.6 mm diameter needle, and mounted on an electro-spinning machine. The machine voltage is set to be 20 kV, the liquid flow is 0.8 mL/min, the distance from the needle to the aluminum foil collector is 20 cm, and the white electrostatic spinning film can be obtained. Taking the electrostatic spinning membrane off the aluminum foil, and placing the electrostatic spinning membrane in a muffle furnace to heat to 280 ℃ at a rate of 1 ℃/min for heat preservation for 1h for pre-oxidation; and then heating to 280 ℃ at a speed of 10 ℃/min under the argon atmosphere of a tube furnace, and preserving heat for 1h for activation to obtain the electrospun carbon nanofiber membrane material.
2) Dissolving 0.2 mL of triisopropoxyl vanadium oxide in 30 mL of isopropanol to prepare a homogeneous phase transfer solution, taking an electrospun carbon nanofiber membrane material with the size of 2 x 4 cm and the homogeneous phase transfer solution, placing the electrospun carbon nanofiber membrane material and the homogeneous phase transfer solution in a 50 mL reaction kettle, sealing, and carrying out a solvothermal reaction for 10 hours in a 200 ℃ oven. Washing the reacted fiber sheet with water and ethanol, drying the fiber sheet in a vacuum drying oven at 80 ℃ for 10h, and then, heating to 320 ℃ at 2 ℃/min in a muffle furnace for 1h, thereby obtaining the in-situ growth vanadium oxide carbon nanofiber composite membrane material.
3) And (3) respectively placing the obtained vanadium oxide carbon nanofiber membrane composite material and sulfur powder into a lower air inlet and an upper air inlet of a porcelain boat according to a mass ratio of 1: 5, and heating to 600 ℃ for 5 hours at a speed of 1 ℃/min in an argon atmosphere of a tube furnace to obtain the vanadium-based carbon nanofiber composite material.
Uniformly mixing the obtained vanadium-based carbon nanofiber composite material, conductive agent Keqin black and adhesive CMC according to the mass ratio of 7: 2: 1, adding a proper amount of deionized water to prepare slurry, uniformly coating the slurry on copper foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the potassium ion battery negative electrode piece. Finally, in a glove box, the potassium ion battery is obtained by sequentially combining the positive electrode shell, the positive electrode sheet (potassium sheet), the diaphragm (Whatman GF/C), the electrolyte (KFSI EC: DC =1: 1), the negative electrode sheet, the elastic sheet and the negative electrode shell, and then the test is carried out.
Example 3
The vanadium-based carbon nanofiber composite cathode material for the potassium ion battery in the embodiment comprises a staggered carbon nanofiber network and nanosheet layer clusters uniformly anchored on the outer surface of carbon nanofibers, wherein the nanosheet layer clusters are formed by VS2 nanosheets. Specifically, the preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery comprises the following steps:
1) Dissolving 1.0 g of polyacrylonitrile by using 10 mL of formic acid dimethylamide, and stirring for 10h at a constant temperature in a 60 ℃ oil bath kettle to obtain a clear and transparent electrostatic spinning solution. The solution was then transferred to a 10 mL syringe, attached to a latex tube and a 0.6 mm diameter needle, and mounted on an electro-spinning machine. The machine voltage is set to be 20 kV, the liquid flow is 0.8 mL/min, the distance from the needle to the aluminum foil collector is 20 cm, and the white electrostatic spinning film can be obtained. Taking the electrostatic spinning membrane off the aluminum foil, and placing the electrostatic spinning membrane in a muffle furnace to heat to 280 ℃ at a rate of 1 ℃/min for heat preservation for 1h for pre-oxidation; and then heating to 280 ℃ at a speed of 10 ℃/min under the argon atmosphere of a tube furnace, and preserving heat for 1h for activation to obtain the electrospun carbon nanofiber membrane material.
2) Dissolving 0.15 mL of triisopropoxyl vanadium oxide in 30 mL of isopropanol to prepare a homogeneous phase transfer solution, taking an electrospun carbon nanofiber membrane material with the size of 2 x 4 cm and the homogeneous phase transfer solution, placing the electrospun carbon nanofiber membrane material and the homogeneous phase transfer solution in a 50 mL reaction kettle, sealing, and carrying out a solvothermal reaction for 10 hours in a 200 ℃ oven. Washing the reacted fiber sheet with water and ethanol, drying the fiber sheet in a vacuum drying oven at 80 ℃ for 10h, and then, heating to 320 ℃ at 2 ℃/min in a muffle furnace for 1h, thereby obtaining the in-situ growth vanadium oxide carbon nanofiber composite membrane material.
3) And (2) respectively placing the obtained vanadium oxide carbon nanofiber membrane composite material and thioacetamide into a lower air port and an upper air port of a porcelain boat according to a mass ratio of 1: 5, and heating to 600 ℃ for 5 hours at 1 ℃/min in the argon atmosphere of a tube furnace to obtain the vanadium-based carbon nanofiber composite material.
Uniformly mixing the obtained vanadium-based carbon nanofiber composite material, conductive agent Keqin black and adhesive CMC according to the mass ratio of 7: 2: 1, adding a proper amount of deionized water to prepare slurry, uniformly coating the slurry on copper foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the potassium ion battery negative electrode piece. Finally, the potassium ion battery was obtained by combining the positive electrode case, the positive electrode sheet (potassium sheet), the separator (Whatman GF/C), the electrolyte (KFSI EC: DC =1: 1), the negative electrode sheet, the elastic sheet, and the negative electrode case in this order in a glove box and tested.
Example 4
The vanadium-based carbon nanofiber composite cathode material for the potassium ion battery in the embodiment comprises a staggered carbon nanofiber network and nanosheet layer clusters uniformly anchored on the outer surface of carbon nanofibers, wherein the nanosheet layer clusters are formed by VS2 nanosheets. Specifically, the preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery comprises the following steps:
1) Dissolving 1.0 g of polyacrylonitrile by using 10 mL of formic acid dimethylamide, and stirring for 10h at a constant temperature in a 60 ℃ oil bath kettle to obtain a clear and transparent electrostatic spinning solution. The solution was then transferred to a 10 mL syringe, attached to a latex tube and a 0.6 mm diameter needle, and mounted on an electro-spinning machine. The machine voltage is set to be 20 kV, the liquid flow is 0.8 mL/min, the distance from the needle to the aluminum foil collector is 20 cm, and the white electrostatic spinning film can be obtained. Taking the electrostatic spinning membrane off the aluminum foil, and placing the electrostatic spinning membrane in a muffle furnace to heat to 280 ℃ at a rate of 1 ℃/min for heat preservation for 1h for pre-oxidation; and then heating to 280 ℃ at a speed of 10 ℃/min under the argon atmosphere of a tube furnace, and preserving heat for 1h for activation to obtain the electrospun carbon nanofiber membrane material.
2) Dissolving 0.4 mL of triisopropoxyl vanadium oxide in 30 mL of isopropanol to prepare a homogeneous phase transfer solution, placing an electrospun carbon nanofiber membrane material with the size of 2 x 4 cm and the homogeneous phase transfer solution in a 50 mL reaction kettle, sealing, and carrying out a solvothermal reaction for 10h in a 200 ℃ oven. Washing the reacted fiber sheet with water and ethanol, drying the fiber sheet in a vacuum drying oven at 80 ℃ for 10h, and then, heating to 320 ℃ at 2 ℃/min in a muffle furnace for 1h, thereby obtaining the in-situ growth vanadium oxide carbon nanofiber composite membrane material.
3) Respectively placing the obtained vanadium oxide carbon nanofiber membrane composite material and thioacetamide in a mass ratio of 1: 5 at a lower air inlet and an upper air inlet of a porcelain boat, and heating to 600 ℃ for 5 h at 1 ℃/min under the argon atmosphere of a tube furnace to obtain the vanadium-based carbon nanofiber composite material.
Uniformly mixing the obtained vanadium-based carbon nanofiber composite material, conductive agent Keqin black and adhesive CMC according to the mass ratio of 7: 2: 1, adding a proper amount of deionized water to prepare slurry, uniformly coating the slurry on copper foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the potassium ion battery negative electrode piece. Finally, the potassium ion battery was obtained by combining the positive electrode case, the positive electrode sheet (potassium sheet), the separator (Whatman GF/C), the electrolyte (KFSI EC: DC =1: 1), the negative electrode sheet, the elastic sheet, and the negative electrode case in this order in a glove box and tested.
Example 5
The vanadium-based carbon nanofiber composite cathode material for the potassium ion battery in the embodiment comprises a staggered carbon nanofiber network and nanosheet layer clusters uniformly anchored on the outer surface of carbon nanofibers, wherein the nanosheet layer clusters are formed by VS2 nanosheets. Specifically, the preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery comprises the following steps:
1) Dissolving 1.0 g of polyacrylonitrile by using 10 mL of formic acid dimethylamide, and stirring for 10h at a constant temperature in a 60 ℃ oil bath kettle to obtain a clear and transparent electrostatic spinning solution. The solution was then transferred to a 10 mL syringe, attached to a latex tube and a 0.6 mm diameter needle, and mounted on an electro-spinning machine. The machine voltage is set to be 20 kV, the liquid flow is 0.8 mL/min, the distance from the needle to the aluminum foil collector is 20 cm, and the white electrostatic spinning film can be obtained. Taking the electrostatic spinning membrane off the aluminum foil, and placing the electrostatic spinning membrane in a muffle furnace to heat to 280 ℃ at a rate of 1 ℃/min for heat preservation for 1h for pre-oxidation; and then heating to 280 ℃ at a speed of 10 ℃/min under the argon atmosphere of a tubular furnace, and carrying out heat preservation for 1h for activation, thus obtaining the electrospun carbon nanofiber membrane material.
2) Dissolving 0.2 mL of triisopropoxyl vanadium oxide in 30 mL of isopropanol to prepare a homogeneous phase transfer solution, placing an electrospun carbon nanofiber membrane material with the size of 2 x 4 cm and the homogeneous phase transfer solution in a 50 mL reaction kettle, sealing, and carrying out a solvothermal reaction for 10h in a 200 ℃ oven. Washing the reacted fiber sheet with water and ethanol, drying the fiber sheet in a vacuum drying oven at 80 ℃ for 10h, and then, heating to 320 ℃ at 2 ℃/min in a muffle furnace for 1h, thereby obtaining the in-situ growth vanadium oxide carbon nanofiber composite membrane material.
3) Respectively placing the obtained vanadium oxide carbon nanofiber membrane composite material and thioacetamide in a mass ratio of 1: 5 at a lower air inlet and an upper air inlet of a porcelain boat, and heating to 700 ℃ for 5 h at 1 ℃/min under the argon atmosphere of a tube furnace to obtain the vanadium-based carbon nanofiber composite material.
Uniformly mixing the obtained vanadium-based carbon nanofiber composite material, conductive agent Keqin black and adhesive CMC according to the mass ratio of 7: 2: 1, adding a proper amount of deionized water to prepare slurry, uniformly coating the slurry on copper foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the potassium ion battery negative electrode piece. Finally, the potassium ion battery was obtained by combining the positive electrode case, the positive electrode sheet (potassium sheet), the separator (Whatman GF/C), the electrolyte (KFSI EC: DC =1: 1), the negative electrode sheet, the elastic sheet, and the negative electrode case in this order in a glove box and tested.

Claims (10)

1. A vanadium-based carbon nanofiber composite anode material of a potassium ion battery is characterized in that: the composite anode material comprises a staggered carbon nanofiber network and a nanosheet pattern cluster uniformly anchored on the outer surface of the carbon nanofiber, wherein the nanosheet pattern cluster is clustered by VS 2 A nanosheet.
2. The vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 1, wherein: the diameter of the carbon nanofiber is 500-800 nm, and the thickness of a single piece of the nanosheet layer cluster is 5-10 nm.
3. The preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 1 or 2, is characterized by comprising the following steps of:
1) Dissolving polyacrylonitrile by using dimethyl formamide, and stirring for 10-12 hours at 60-70 ℃ to obtain electrostatic spinning solution; carrying out electrostatic spinning by using the spinning solution to obtain an electrostatic spinning film; cutting the obtained electrostatic spinning membrane, pre-oxidizing for 1-2 h at 250-300 ℃, then, placing the electrostatic spinning membrane in an inert gas atmosphere, and activating for 1-2 h at 250-300 ℃ to obtain an electrospun carbon nanofiber membrane material;
2) Dissolving triisopropoxyl vanadium oxide in isopropanol to prepare a homogeneous phase transfer solution, adding the electrospun carbon nanofiber membrane material obtained in the step 1), performing solvent thermal reaction for 10-12 h at 150-200 ℃, performing vacuum drying for 10h at 80 ℃ after cleaning, and performing further oxidation for 1-2 h at 300-350 ℃ to obtain a vanadium oxide carbon nanofiber composite membrane material;
3) Respectively placing the vanadium oxide carbon nanofiber composite membrane material prepared in the step 2) and a sulfur source in a lower air port and an upper air port of a porcelain boat, then placing the porcelain boat in an inert gas atmosphere, and heating for 4-6 h at 500-700 ℃ to obtain the vanadium oxide carbon nanofiber composite membrane material.
4. The preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 1), the mass fraction of polyacrylonitrile in the spinning solution is 8-12%.
5. The preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 3, wherein the preparation method comprises the following steps: the voltage of the electrostatic spinning in the step 1) is 18-24 kV, the liquid flow is 0.8-1.0 mL/h, and the distance from a needle head of an injector to a collector used in the electrostatic spinning is 20-25 cm.
6. The preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 3, wherein the preparation method comprises the following steps: the volume ratio of the triisopropoxytriantivanadia to the isopropanol in the step 2) is (0.1-0.5): 30.
7. The preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 2), the cleaning process comprises three times of deionized water cleaning and one time of ethanol cleaning.
8. The preparation method of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 3), the sulfur source is any one of sulfur powder and thioacetamide, and the mass ratio of the vanadium oxide carbon nanofiber composite membrane material to the sulfur source is 1: (5-10).
9. The application of the vanadium-based carbon nanofiber composite anode material for the potassium ion battery prepared by the preparation method of any one of claims 3 to 8 in preparing the potassium ion battery.
10. The use of claim 9, wherein: the potassium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode material layer comprises a negative electrode active material, a conductive agent and a binder, and the negative electrode active material is the vanadium-based carbon nanofiber composite negative electrode material of the potassium ion battery prepared by the preparation method of any one of claims 3-8.
CN202211328588.4A 2022-10-27 2022-10-27 Vanadium-based carbon nanofiber composite negative electrode material of potassium ion battery and preparation method and application thereof Pending CN115472810A (en)

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