CN107256956B - Nitrogen-doped carbon-coated vanadium nitride electrode material and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated vanadium nitride electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen-doped carbon-coated vanadium nitride electrode material and a preparation method and application thereof. The electrode material is prepared by taking vanadium pentoxide as a main raw material to obtain a vanadium pentoxide nanowire precursor; then, taking a pyrrole monomer as a main raw material to coat polypyrrole on the surface of the vanadium pentoxide nanowire precursor; finally, the catalyst is prepared by calcining. The preparation method is simple, has high repeatability and has lower requirements on equipment and medicines; the prepared electrode material can be applied to a lithium-sulfur battery anode material, can also be used as a lithium ion battery cathode material, can be compounded with graphene, and shows excellent electrochemical performance.
Description
Technical Field
The invention relates to a nitrogen-doped carbon-coated vanadium nitride electrode material and a preparation method and application thereof, belonging to the technical field of lithium ion batteries.
Background
With the increasing energy demand, lithium ion batteries are widely used in modern society as a clean energy storage device. At present, the commercial lithium ion battery has low energy density and can not meet the requirements of high-power electrical appliances, so that the development of a novel lithium battery material with high specific capacity becomes the key for solving the problems. Lithium sulfur batteries have received much attention because of their unique advantages in application due to their ultra-high energy density. In addition, the sulfur reserves on the earth are abundant, the price is low, and the environment is friendly, so that the lithium-sulfur battery system has a good commercial application prospect.
However, in practical applications, the lithium-sulfur battery still has many problems to be solved urgently, such as poor conductivity of elemental sulfur and extremely low conductivity of sulfur at room temperature, which affects rate performance of the battery; the dissolution of polysulfide as an intermediate product of the battery can cause the loss of active substances, thereby influencing the coulombic efficiency and reducing the battery capacity; in addition, the density difference between sulfur and lithium sulfide is large, which causes volume expansion, thereby destroying the shape and structure of the material and causing capacity attenuation. In order to solve the above problems, researchers have made a series of optimizations on lithium sulfur battery systems in recent years, and porous materials such as carbon, conductive polymers, etc. are used as a support material for sulfur in lithium sulfur batteries to solve the problems of sulfur non-conductivity and volume expansion. For example, chinese patent document CN104466183A discloses a polypyrrole lithium sulfur battery positive electrode material and a preparation method thereof, the positive electrode material of the lithium sulfur battery is formed by compounding a polypyrrole film with lotus leaf-shaped and/or hollow microspherical and/or granular polypyrrole bodies growing on the surface and elemental sulfur; the preparation method comprises the steps of taking an aqueous solution containing a dopant and a pyrrole monomer as an electrolyte, preparing a polypyrrole film by adopting an electrochemical three-electrode method, and fusing and compounding the polypyrrole film with elemental sulfur under a vacuum condition to obtain the polypyrrole/sulfur composite material; the method has simple steps and convenient and fast operation, and the prepared cathode material can be used for preparing the lithium-sulfur battery; but the polypyrrole in the material has poor conductivity, the problem of poor sulfur conductivity cannot be well solved, and the electrical property of the positive electrode material applied to the lithium-sulfur battery is poor. For another example, chinese patent document CN 105161722a discloses a porous carbon nanofiber membrane for a lithium-sulfur battery positive electrode material and a preparation method thereof, the preparation method includes precursor fiber preparation, low-temperature pretreatment and high-temperature carbonization treatment; the porous carbon nanofiber membrane has continuous through holes and an ultra-large specific surface area, can be applied to lithium-sulfur batteries after being filled with elemental sulfur, and can also be widely applied to the fields of supercapacitors, adsorption and the like; however, the carbon material in the material prepared by the invention has the advantages that a large amount of sulfur is dissolved out due to the limited domain effect, the loss of sulfur is caused, the electrical property of the material is poor, and the material needs to be subjected to heat treatment at a high temperature in the preparation process, so that the cost is high.
In the prior art, carbon and a porous material thereof are used as a carrier material of sulfur in a lithium-sulfur battery, and due to the confinement effect of a common carbon material, a large amount of sulfur can be dissolved out, so that the loss of sulfur is caused, the charge and discharge performance of the lithium-sulfur battery is not facilitated, and the preparation method of the porous carbon substrate is complicated, has high cost and cannot meet the actual requirements.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-doped carbon-coated vanadium nitride electrode material, which aims to inhibit the dissolution rate of polysulfide in the charging and discharging process and reduce the capacity attenuation rate of a lithium sulfur battery when being applied to a lithium sulfur battery positive electrode material.
The invention also provides a preparation method and application of the nitrogen-doped carbon-coated vanadium nitride electrode material, and the preparation method is simple, high in repeatability and low in requirements on equipment and medicines; the prepared electrode material can be applied to a lithium-sulfur battery anode material, can also be used as a lithium ion battery cathode material, and shows excellent electrochemical performance.
The technical scheme of the invention is as follows:
a nitrogen-doped carbon-coated vanadium nitride electrode material is characterized in that the microscopic morphology of the electrode material is as follows: the surface of the vanadium nitride nanowire is coated with a nitrogen-doped carbon material; the diameter of the vanadium nitride nanowire is 30-150nm, the length of the vanadium nitride nanowire is 0.5-3 mu m, and the thickness of the nitrogen-doped carbon layer is 10-40 nm.
According to the invention, the mass content of vanadium nitride in the electrode material is preferably 65-80%, and the mass content of carbon is preferably 20-35%.
According to the optimization of the invention, the electrode material is prepared by taking vanadium pentoxide as a main raw material to obtain a vanadium pentoxide nanowire precursor; then, taking a pyrrole monomer as a main raw material to coat polypyrrole on the surface of the vanadium pentoxide nanowire precursor; finally, the catalyst is prepared by calcining.
Preferably, the mass ratio of the vanadium pentoxide nanowire precursor to the pyrrole is 0.1-0.2: 0.03-0.12.
The preparation method of the nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps:
(1) dissolving vanadium pentoxide in deionized water, adding aqueous hydrogen peroxide, and stirring at room temperature for 1-3h to obtain a mixed solution; carrying out hydrothermal reaction at 180 ℃ and 220 ℃ for 3-5 days; washing and drying to obtain a vanadium pentoxide nanowire precursor;
(2) dissolving a surfactant in deionized water, adding the vanadium pentoxide nanowire precursor obtained in the step (1) and a pyrrole monomer, fully mixing and uniformly dispersing, and stirring at-5-5 ℃ for 0.5-3h to obtain a reaction solution; adding an aqueous solution of an initiator under the stirring condition, and reacting for 3-7h at-5-5 ℃; and (3) calcining for 1-3h at the temperature of 600 ℃ in the atmosphere of ammonia gas after washing and drying to obtain the nitrogen-doped carbon-coated vanadium nitride electrode material.
According to the invention, the mass concentration of the vanadium pentoxide in the mixed liquor in the step (1) is preferably 0.1-1.5%, and the mass concentration of the hydrogen peroxide is preferably 2-6%.
Preferably according to the invention, the concentration by mass of hydrogen peroxide in the aqueous hydrogen peroxide solution in step (1) is between 20 and 30%.
Preferably, according to the invention, the hydrothermal reaction temperature in step (1) is 200-205 ℃.
Preferably, the hydrothermal reaction temperature in the step (1) is 205 ℃ and the hydrothermal reaction time is 4 days.
According to the invention, the washing modes in the step (1) and the step (2) are both: washing with deionized water and absolute ethyl alcohol alternately.
Preferably, according to the present invention, the drying conditions in step (1) are: drying at 50-80 deg.C for 3-6 h.
According to the preferable selection of the invention, the mass ratio of the vanadium pentoxide nanowire precursor, the surfactant and the pyrrole monomer in the reaction solution in the step (2) is 0.1-0.2: 0.3-0.6: 0.03-0.12.
Preferably, in the reaction solution in the step (2), the mass ratio of the vanadium pentoxide nanowire precursor to the surfactant to the pyrrole monomer is 0.1-0.14: 0.4-0.5: 0.05-0.1.
According to the preferable selection of the invention, the mass concentration of the vanadium pentoxide nanowire precursor in the reaction liquid in the step (2) is 0.1-0.3%.
Preferably, in step (2), the surfactant is one of sodium dodecylbenzene sulfonate, cetyl trimethyl ammonium bromide or sodium dodecyl sulfonate.
Preferably, according to the invention, in the preparation of the reaction solution in the step (2), the reaction solution is stirred for 1h at 0 ℃; the reaction conditions in the step (2) are as follows: the reaction is carried out for 5h at 0 ℃.
Preferably, in step (2), the initiator is one of ammonium persulfate and ferric trichloride.
According to the invention, the mass concentration of the initiator in the aqueous solution of the initiator in the step (2) is preferably 2 to 5%.
Preferably, according to the invention, the molar ratio of the initiator to the pyrrole monomer in step (2) is 1: 1.
According to the invention, the drying method in the step (2) is preferably as follows: vacuum degree of 1.3-10Pa, and freeze drying at-90- -80 deg.C for 4-6 hr.
According to the invention, the calcining temperature in the step (2) is 550 ℃, the calcining time is 2.5h, and the heating rate is 3-4 ℃/min.
The application of the nitrogen-doped carbon-coated vanadium nitride electrode material is applied to preparing a lithium-sulfur battery anode material or serving as a lithium ion battery cathode material.
According to the invention, the method for preparing the positive electrode material of the lithium-sulfur battery by applying the nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps: mixing the nitrogen-doped carbon-coated vanadium nitride electrode material with elemental sulfur according to the mass ratio of 2-4:6-8, and heating at the temperature of 150-.
The application of the nitrogen-doped carbon-coated vanadium nitride electrode material in the preparation of the nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material comprises the following steps: dispersing the nitrogen-doped carbon-coated vanadium nitride electrode material into N, N-dimethylformamide, adding graphene powder, and ultrasonically dispersing for 2-4h at room temperature to obtain a dispersion liquid; filtering, washing and drying to obtain the product.
When the nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material is used as a lithium battery cathode, the process of preparing an electrode by a traditional coating method is not needed, and a binder and a conductive agent are not needed to be added, so that the nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material can be directly used, and excellent electrochemical performance is shown.
According to the invention, the mass ratio of the nitrogen-doped carbon-coated vanadium nitride electrode material to the graphene powder is preferably 10-30: 5-15; the mass concentration of the graphene powder in the dispersion liquid is 0.003-0.02%.
The graphene powder according to the present invention is commercially available.
The invention has the following beneficial effects:
(1) the preparation method is simple, has low energy consumption and high repeatability, has low requirements on equipment and medicines, and can be used for mass production; the raw materials are simple and easy to obtain, and the cost is low; the preparation process is environment-friendly and safe, no toxic and harmful substances are generated, the final product can be obtained by calcining at a lower temperature after one-time hydrothermal reaction, and the product does not need to be subjected to subsequent treatment.
(2) The nitrogen-doped carbon-coated vanadium nitride electrode material prepared by the invention is applied to the positive electrode material of the lithium-sulfur battery, and the vanadium nitride and sulfur have stronger interaction to form a V-S bond, so that polysulfide is adsorbed, the dissolution of the polysulfide is inhibited, the coulomb efficiency of the battery is improved, the cycle stability of the battery is improved, and the multiplying power performance of the battery is also improved. The lithium-sulfur battery positive electrode material is applied to a lithium-sulfur battery positive electrode material, the capacity is 751.9mAh/g after 100 cycles when the voltage is within a range of 1.6-3.0V and the current density is 0.2C, the capacity maintenance rate is 78%, and the coulomb efficiency is more than 95%.
(3) The nitrogen-doped carbon-coated vanadium nitride electrode material prepared by the invention can also be applied to a lithium ion battery cathode material and shows excellent electrochemical performance; in the voltage range of 0.01-3.0V and the current density of 100mA/g, the capacity after 90 cycles is 556.1mAh/g, and the capacity maintenance rate is 76%.
(4) The nitrogen-doped carbon-coated vanadium nitride electrode material prepared by the invention adopts polypyrrole as a carbon source, and the polypyrrole has rich nitrogen content, so that the nitrogen-doped carbon material is obtained after carbonization, thereby improving the conductivity of the material on one hand, being beneficial to adsorbing polysulfide on the other hand, and further improving the electrochemical performance.
(5) When the nitrogen-doped carbon-coated vanadium nitride material is used for preparing the nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material, the obtained composite material can be directly used without the process of preparing an electrode by a traditional coating method and the addition of a binder and a conductive agent, so that the composite material has excellent electrochemical performance.
Drawings
Fig. 1 is an XRD pattern of the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in example 1.
Fig. 2 is an SEM photograph of the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in example 1.
Fig. 3 is a TEM photograph of the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in example 1.
Fig. 4 is an SEM photograph of the nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material prepared in application example 1.
Fig. 5 is a graph of cycle performance in application example 2.
Fig. 6 is a graph of rate capability in application example 2.
Fig. 7 is a graph of cycle performance in application example 3.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the examples, graphene powder is commercially available and available from Deyang alkene carbon technology Inc.
Example 1
A nitrogen-doped carbon-coated vanadium nitride electrode material is characterized in that the microscopic morphology of the electrode material is as follows: the surface of the vanadium nitride nanowire is coated with a nitrogen-doped carbon material; the average diameter of the vanadium nitride nanowire is 40nm, the average length of the vanadium nitride nanowire is 1.5 mu m, and the average thickness of the nitrogen-doped carbon layer is 10 nm;
the mass content of vanadium nitride in the electrode material is 75.9%, and the mass content of carbon in the electrode material is 24.1%.
The preparation method of the nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps:
(1) dissolving 0.364g of vanadium pentoxide in 30ml of deionized water, adding 5ml of 30% aqueous hydrogen peroxide, and stirring at room temperature for 2 hours to obtain a mixed solution; carrying out hydrothermal reaction for 4 days at 205 ℃; respectively and alternately washing for 3 times by centrifugation, deionized water and absolute ethyl alcohol, and drying for 5 hours at 60 ℃ to obtain a vanadium pentoxide nanowire precursor;
(2) dissolving 0.5g of sodium dodecyl sulfate in 50mL of deionized water, adding 0.1g of the vanadium pentoxide nanowire precursor obtained in the step (1) and 100 mu L of pyrrole monomer, fully mixing and dispersing uniformly, and stirring at 0 ℃ for 1h to obtain a reaction solution; adding 15mL of aqueous solution of ammonium persulfate with the mass concentration of 2.2% under the condition of stirring, and reacting for 5h at the temperature of 0 ℃; filtering, alternately washing with deionized water and anhydrous alcohol for 3 times respectively, vacuum degree of 1.5Pa, freeze drying at-80 deg.C for 5h, calcining at 550 deg.C for 2.5h in ammonia atmosphere, and heating at 3 deg.C/min.
The XRD pattern of the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the prepared electrode material contains carbon and vanadium nitride.
SEM and TEM photographs of the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in this example are shown in fig. 2 and 3, and it can be seen from fig. 2 and 3 that the micro-morphology of the prepared electrode material is: nanowires with an average diameter of 50nm and an average length of 1.5 μm.
Example 2
A method for preparing a nitrogen-doped carbon-coated vanadium nitride electrode material, which comprises the following preparation steps of example 1, except that the pyrrole monomer is added in an amount of 60 μ L in the step (2); 15mL of an aqueous solution of ammonium persulfate having a mass concentration of 1.3% was added, and the other steps were identical to those in example 1.
Example 3
A preparation method of a nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps:
(1) dissolving 0.364g of vanadium pentoxide in 30ml of deionized water, adding 5ml of 30% aqueous hydrogen peroxide, and stirring at room temperature for 2 hours to obtain a mixed solution; carrying out hydrothermal reaction at 200 ℃ for 3 days; respectively and alternately washing for 3 times by centrifugation, deionized water and absolute ethyl alcohol, and drying for 4 hours at 70 ℃ to obtain a vanadium pentoxide nanowire precursor;
(2) dissolving 0.4g of sodium dodecyl sulfate in 50mL of deionized water, adding 0.1g of the vanadium pentoxide nanowire precursor obtained in the step (1) and 80 mu L of pyrrole monomer, fully mixing and dispersing uniformly, and stirring at 0 ℃ for 1h to obtain a reaction solution; adding 10mL of aqueous solution of ammonium persulfate with the mass concentration of 2.6% under the condition of stirring, and reacting for 5h at the temperature of 0 ℃; filtering, alternately washing with deionized water and anhydrous alcohol for 3 times respectively, vacuum degree of 1.5Pa, freeze drying at-80 deg.C for 5h, calcining at 400 deg.C for 3h in ammonia atmosphere, and heating at 4 deg.C/min.
Example 4
A preparation method of a nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps:
(1) dissolving 0.364g of vanadium pentoxide in 30ml of deionized water, adding 5ml of 30% aqueous hydrogen peroxide, and stirring at room temperature for 2 hours to obtain a mixed solution; carrying out hydrothermal reaction for 4 days at 205 ℃; respectively and alternately washing for 3 times by centrifugation, deionized water and absolute ethyl alcohol, and drying for 6 hours at 60 ℃ to obtain a vanadium pentoxide nanowire precursor;
(2) dissolving 0.3g of sodium dodecyl benzene sulfonate in 50mL of deionized water, adding 0.1g of the vanadium pentoxide nanowire precursor obtained in the step (1) and 40 mu L of pyrrole monomer, fully mixing and dispersing uniformly, and stirring at 0 ℃ for 1h to obtain a reaction solution; adding 10mL of aqueous solution of ammonium persulfate with the mass concentration of 1.3% under the condition of stirring, and reacting for 5h at the temperature of 0 ℃; filtering, alternately washing with deionized water and anhydrous alcohol for 3 times respectively, vacuum degree of 1.5Pa, freeze drying at-80 deg.C for 5h, calcining at 600 deg.C for 1h in ammonia atmosphere, and heating at 4 deg.C/min.
Example 5
A preparation method of a nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps:
(1) dissolving 0.364g of vanadium pentoxide in 30ml of deionized water, adding 5ml of 30% aqueous hydrogen peroxide, and stirring at room temperature for 2 hours to obtain a mixed solution; carrying out hydrothermal reaction for 4 days at 205 ℃; respectively and alternately washing for 3 times by centrifugation, deionized water and absolute ethyl alcohol, and drying for 5 hours at 70 ℃ to obtain a vanadium pentoxide nanowire precursor;
(2) dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 50mL of deionized water, adding 0.1g of the vanadium pentoxide nanowire precursor obtained in the step (1) and 120 mu L of pyrrole monomer, fully mixing and uniformly dispersing, and stirring at 0 ℃ for 1h to obtain a reaction solution; adding 20mL of aqueous solution of ammonium persulfate with the mass concentration of 2% under the stirring condition, and reacting for 5h at the temperature of 0 ℃; filtering, alternately washing with deionized water and anhydrous alcohol for 3 times respectively, vacuum degree of 1.5Pa, freeze drying at-80 deg.C for 5h, calcining at 550 deg.C for 2.5h in ammonia atmosphere, and heating at 3 deg.C/min.
Application example 1
An application of a nitrogen-doped carbon-coated vanadium nitride electrode material in preparing a nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material comprises the following steps: dispersing 20mg of the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in the example 1 into 200mL of N, N-dimethylformamide, adding 7mg of graphene powder, performing ultrasonic dispersion at room temperature for 3 hours to obtain a dispersion solution, performing suction filtration to form a sheet, and drying at 120 ℃ for 2.5 hours to obtain the nitrogen-doped carbon-coated vanadium nitride electrode material.
The graphene powder was purchased from de yang ene carbon technologies ltd.
The SEM photograph of the flexible material prepared in this application example is shown in fig. 4, and it can be seen from fig. 4 that the micro-morphology of the flexible material is: the graphene sheet is loaded with a nanowire with the diameter of 50nm and the length of 1.5 mu m, and the nanowire is a nitrogen-doped carbon-coated vanadium nitride composite material.
The nitrogen-doped carbon-coated vanadium nitride composite graphene flexible material prepared by the application example can be directly used as a lithium battery cathode, and the current density is 100mA g-1The first turn had a capacitance of 757.2mAh g-1The capacity after 100 cycles is 467.9mAh g-1。
Application example 2
The application of the nitrogen-doped carbon-coated vanadium nitride electrode material in preparing the lithium-sulfur battery anode material comprises the following steps: and mixing the nitrogen-doped carbon-coated vanadium nitride electrode material prepared in the embodiment 1 with elemental sulfur according to the mass ratio of 3:7, and heating at 155 ℃ for 12 hours to obtain the carbon-coated vanadium nitride electrode material.
The electrical property test method is as follows:
the raw materials are mixed according to the active substance: super P: the mass ratio of PVDF is 7: 2: 1 proportion, taking NMP as a solvent to prepare slurry, coating the slurry on aluminum foil, fully drying and tabletting to obtain the positive plate. A lithium sheet for a negative electrode of a battery. Adding 0.4mol/L LiNO into a glove box protected by inert gas3And 1moL/L LiTFSI, LiNO3 and LiTFSI with the volume ratio of 1:1 as electrolyte and Celgerd2500 as diaphragm, and assembling the cell into a 2320 type button cell. And carrying out charge and discharge tests in a voltage range of 1.6-3.0V on a blue tester.
The cycle performance of the positive electrode material for lithium-sulfur battery prepared in example 1 of this application is shown in FIG. 5. from FIG. 5, it can be seen that the first cycle capacity is 963.8mAh g at a current density of 0.2C-1Capacity of 751.9mAhg after 100 cycles of circulation-1The capacity maintenance rate is 78%, and the coulomb efficiency is maintained above 95%; the rate capability of the lithium-sulfur battery positive electrode material prepared in this application example is shown in fig. 6, and it can be seen from fig. 6 that the capacities at current densities of 0.1C, 0.2C, 0.5C and 1C were 869.3, 722.3, 623.2 and 532.2mAh g, respectively-1When the current density returns to 0.1C, the capacity returns to 804mAh g-1The method has good rate performance.
Application example 3
An application of a nitrogen-doped carbon-coated vanadium nitride electrode material as a lithium ion battery cathode material.
The performance test method comprises the following steps:
a nitrogen doped carbon coated vanadium nitride electrode material prepared as in example 1: acetylene black: the mass ratio of PVDF is 7: 2: 1 proportion, taking NMP as a solvent to prepare slurry, coating the slurry on copper foil, fully drying and tabletting to obtain the negative plate. A lithium sheet for a negative electrode of a battery. In a glove box protected by inert gas, 1mol/L LiPF6/EC/DMC/DEC (volume ratio: 1:1:1) is used as electrolyte, Celgerd2300 is used as diaphragm, and a 2320 type button cell is assembled. And performing charge and discharge test in a voltage range of 0.01-3.0V on a blue tester.
The cycle performance chart of this application example is shown in FIG. 7, and it can be seen from FIG. 7 that when the current density is 100mA/g, the capacity after 90 cycles is 556.1mAhg-1The first-turn capacitance is 725.3mAhg-1The capacity maintenance rate is 76%, and the coulomb efficiency is maintained above 90%.
Claims (5)
1. An application of a nitrogen-doped carbon-coated vanadium nitride electrode material is applied to preparation of a lithium-sulfur battery anode material or a nitrogen-doped carbon-coated vanadium nitride composite graphene lithium ion battery cathode flexible material;
the method for preparing the positive electrode material of the lithium-sulfur battery by applying the nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps: mixing the nitrogen-doped carbon-coated vanadium nitride electrode material with elemental sulfur according to the mass ratio of 2-4:6-8, and heating at the temperature of 150-;
the method for preparing the nitrogen-doped carbon-coated vanadium nitride composite graphene lithium ion battery cathode flexible material by applying the nitrogen-doped carbon-coated vanadium nitride electrode material comprises the following steps: dispersing the nitrogen-doped carbon-coated vanadium nitride electrode material into N, N-dimethylformamide, adding graphene powder, and ultrasonically dispersing for 2-4h at room temperature to obtain a dispersion liquid; filtering, washing and drying to obtain the product; the mass ratio of the nitrogen-doped carbon-coated vanadium nitride electrode material to the graphene powder is 10-30: 5-15; the mass concentration of the graphene powder in the dispersion liquid is 0.003-0.01%;
the micro-morphology of the nitrogen-doped carbon-coated vanadium nitride electrode material is as follows: the surface of the vanadium nitride nanowire is coated with a nitrogen-doped carbon material; the diameter of the vanadium nitride nanowire is 30-150nm, the length of the vanadium nitride nanowire is 0.5-3 mu m, and the thickness of the nitrogen-doped carbon layer is 10-40 nm; the mass content of vanadium nitride in the electrode material is 65-80%, and the mass content of carbon is 20-35%;
the nitrogen-doped carbon-coated vanadium nitride electrode material is prepared by the following preparation method:
(1) dissolving vanadium pentoxide in deionized water, adding aqueous hydrogen peroxide, and stirring at room temperature for 1-3h to obtain a mixed solution; carrying out hydrothermal reaction at 200-; washing and drying to obtain a vanadium pentoxide nanowire precursor;
the mass concentration of the vanadium pentoxide and the hydrogen peroxide in the mixed solution is 0.5-1.5% and 2-6%; the mass concentration of the hydrogen peroxide in the aqueous hydrogen peroxide solution is 20-30%;
(2) dissolving a surfactant in deionized water, adding the vanadium pentoxide nanowire precursor obtained in the step (1) and a pyrrole monomer, fully mixing and uniformly dispersing, and stirring at-5-5 ℃ for 0.5-3h to obtain a reaction solution; adding an aqueous solution of an initiator under the stirring condition, and reacting for 3-7h at-5-5 ℃; after washing and drying, calcining for 1-3h at the temperature of 400-600 ℃ in the atmosphere of ammonia gas to obtain the nitrogen-doped carbon-coated vanadium nitride electrode material;
the mass ratio of the vanadium pentoxide nanowire precursor to the surfactant to the pyrrole monomer in the reaction solution is 0.1-0.2: 0.3-0.6: 0.03-0.12; the surfactant is one of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide or sodium dodecyl sulfonate.
2. The use of the nitrogen-doped carbon-coated vanadium nitride electrode material according to claim 1, wherein the hydrothermal reaction temperature in the step (1) is 205 ℃ and the hydrothermal reaction time is 4 days.
3. The application of the nitrogen-doped carbon-coated vanadium nitride electrode material as claimed in claim 1, wherein in the reaction solution in the step (2), the mass ratio of the vanadium pentoxide nanowire precursor to the surfactant to the pyrrole monomer is 0.1-0.14: 0.4-0.5: 0.05-0.1;
the mass concentration of the vanadium pentoxide nanowire precursor in the reaction liquid in the step (2) is 0.1-0.3%;
the mass concentration of the initiator in the aqueous solution of the initiator in the step (2) is 2-5%; the molar ratio of the initiator to the pyrrole monomer is 1: 1.
4. The application of the nitrogen-doped carbon-coated vanadium nitride electrode material as claimed in claim 1, wherein the initiator in the step (2) is one of ammonium persulfate or ferric trichloride.
5. The application of the nitrogen-doped carbon-coated vanadium nitride electrode material as claimed in claim 1, wherein in the preparation of the reaction solution in the step (2), the reaction solution is stirred for 1 hour at 0 ℃; the reaction conditions in the step (2) are as follows: reacting for 5 hours at 0 ℃;
in the step (2), the calcining temperature is 550 ℃, the calcining time is 2.5h, and the heating rate is 3-4 ℃/min.
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| CN107256956B (en) * | 2017-06-28 | 2020-04-17 | 山东大学 | Nitrogen-doped carbon-coated vanadium nitride electrode material and preparation method and application thereof |
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| CN115020723A (en) * | 2022-06-20 | 2022-09-06 | 巢湖学院 | Ultrathin vanadium nitride/nitrogen-doped carbon composite material and preparation method thereof |
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