CN111261854A - Elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber and preparation method and application thereof - Google Patents
Elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber and a preparation method and application thereof, and belongs to the field of ion batteries. According to the invention, the nitrogen-doped carbon nanofiber flexible film is prepared by electrostatic spinning and heat treatment and used as a matrix, elm-shaped molybdenum diselenide nanosheets are coated on the nitrogen-doped carbon nanofiber in situ through hydrothermal reaction to form a core-shell structure, the special nanostructure of molybdenum diselenide has a high active specific surface area, the aluminum storage efficiency can be improved, high specific capacity is obtained, the nitrogen-doped carbon nanofiber forms a three-dimensional conductive network, the capability of rapidly transferring electrons is provided for high-rate charging and discharging, high-power discharging and rapid charging are realized, the stress generated in the charging and discharging cycle process can be buffered by the three-dimensional porous nitrogen-doped carbon nanofiber, the deformation of an active material is reduced, the structural stability of the active material is maintained, and the cycle stability of a battery is improved.
Description
Technical Field
The invention relates to the technical field of ion batteries, in particular to elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber and a preparation method and application thereof.
Background
With the economic development and the improvement of living standards, the demand for electric vehicles and portable electronic devices has increased. At present, electric automobiles and portable electronic devices mainly rely on lithium ion batteries as power sources. However, as the limited price of lithium resources rises, on the one hand the cost of lithium ion batteries increases and on the other hand the sustainability of their supply is also alarming. Therefore, development of low-cost, high-reserve metal-ion batteries as a replacement or supplement for lithium-ion batteries has been a hot point of research. Aluminum has a high storage capacity and a low price, and is an ideal material for replacing lithium as a negative electrode of a metal ion battery from the viewpoint of sustainable development. However, the aluminum ion has three positive charges, so that the surface charge density of the aluminum ion is much higher than that of the lithium ion, and therefore, the aluminum ion can generate strong electrostatic interaction with the matrix of the positive electrode energy storage material, the energy storage efficiency of the aluminum ion is far lower than that of the lithium ion, and the defect is also a main problem limiting the practical application of the aluminum ion battery. In order to overcome the disadvantage of the aluminum ion battery, a positive electrode structure with high electron and ion transmission capability needs to be constructed, so that the energy storage efficiency of the aluminum ion battery is improved. Compared with molybdenum disulfide, molybdenum diselenide has two obvious advantages as an aluminum storage electrode material: 1) the interlayer distance (0.65nm) is larger than that of molybdenum disulfide (0.62nm), and the intercalation/deintercalation resistance of aluminum ions is small if the interlayer distance is large. 2) The conductivity of molybdenum diselenide is stronger than that of molybdenum disulfide, so that the diffusion capacity of aluminum ions between molybdenum diselenide layers is stronger. The specific performances of the two points in the battery performance are the improvement of the rate performance. Therefore, molybdenum diselenide has great development potential as the anode material of the aluminum ion battery.
In the prior art, the problem of low specific capacity exists when molybdenum diselenide is used as the anode material of the aluminum ion battery.
Disclosure of Invention
In view of the above, the present invention provides an elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber, and a preparation method and an application thereof. In the invention, the elm-shaped molybdenum diselenide is uniformly coated on the surface of the nitrogen-doped carbon nanofiber, so that the contact area of the electrode active material and the electrolyte is increased, the effective aluminum storage sites are increased, the utilization rate of the electrode active material is improved, and the specific capacity of the battery is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber, which comprises the following steps:
mixing polyacrylonitrile and N, N-dimethylformamide to obtain a precursor solution;
carrying out electrostatic spinning on the precursor solution to obtain a flexible film;
carrying out heat treatment on the flexible film to obtain nitrogen-doped carbon nanofibers;
mixing the nitrogen-doped carbon nanofiber, a molybdenum source precursor and a selenium source precursor, and then carrying out hydrothermal reaction to obtain a hydrothermal product;
and carrying out heat treatment on the hydrothermal product in nitrogen to obtain the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber.
Preferably, the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.5-0.8: 5-8.
Preferably, the voltage of the electrostatic spinning is 18-20 KV, the distance between the needle head and the receiving plate is 15-20 cm, the propelling speed is 10-15 mu L/min, the temperature is 35-40 ℃, and the humidity is 40-45%.
Preferably, the heat treatment of the flexible film sequentially comprises the steps of preoxidation for 2-3 hours in an air atmosphere, carbonization and in-situ nitrogen doping in nitrogen, wherein the preoxidation temperature is 230-240 ℃, the carbonization and in-situ nitrogen doping temperature is 850-860 ℃ independently, and the total heat preservation time of the carbonization and in-situ nitrogen doping is 6-8 hours.
Preferably, the heating rate of the temperature rise from the pre-oxidation temperature to the carbonization and in-situ nitrogen doping temperature is 3-5 ℃/min.
Preferably, the temperature of the hydrothermal reaction is 200-220 ℃ and the time is 10-12 h.
Preferably, the temperature for heat treatment in nitrogen is 450-480 ℃ and the time is 2-3 h.
The invention also provides the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber prepared by the preparation method in the technical scheme, the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber takes elm-shaped molybdenum diselenide as a shell, nitrogen-doped carbon nanofiber as a core, and the elm-shaped molybdenum diselenide is of a sheet structure.
Preferably, the content of the elm-shaped molybdenum diselenide is 75-80 wt%.
The invention also provides application of the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber as an aluminum ion battery anode material.
The invention provides a preparation method of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber, which comprises the following steps: mixing polyacrylonitrile and N, N-dimethylformamide to obtain a precursor solution; carrying out electrostatic spinning on the precursor solution to obtain a flexible film; carrying out heat treatment on the flexible film to obtain nitrogen-doped carbon nanofibers; mixing the nitrogen-doped carbon nanofiber, a molybdenum source precursor and a selenium source precursor, and then carrying out hydrothermal reaction to obtain a hydrothermal product; and carrying out heat treatment on the hydrothermal product in nitrogen to obtain the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber.
According to the invention, the nitrogen-doped carbon nanofiber flexible film is prepared by electrostatic spinning and heat treatment and used as a matrix, elm-shaped molybdenum diselenide nanosheets are coated on the nitrogen-doped carbon nanofiber in situ through hydrothermal reaction to form a core-shell structure, the special nanostructure of molybdenum diselenide has a high active specific surface area, the aluminum storage efficiency can be improved, high specific capacity is obtained, the nitrogen-doped carbon nanofiber forms a three-dimensional conductive network, the capability of rapidly transferring electrons is provided for high-rate charging and discharging, high-power discharging and rapid charging are realized, the stress generated in the charging and discharging cycle process can be buffered by the three-dimensional porous nitrogen-doped carbon nanofiber, the deformation of an active material is reduced, the structural stability of the active material is maintained, and the cycle stability of a battery is improved. The material applied to the aluminum ion battery as the anode material has the following advantages:
1) the nitrogen-doped carbon nanofiber flexible thin film is used as a growth substrate to obtain a flexible composite structure material, can be directly used as an anode of an aluminum ion battery to obtain a flexible battery, and can be applied to flexible power consumption equipment needing bending or other deformation modes. In addition, since a current collector, a binder and a conductive agent are not required, the overall weight of the battery is reduced, and the energy density of the battery system is improved.
2) In the nitrogen-doped carbon nanofiber, single carbon nanofibers with one-dimensional electron transmission characteristics are overlapped in a disordered mode to form a three-dimensional conductive network, and electron transfer and ion diffusion can be promoted. In addition, the conductivity of the carbon nano fiber can be further improved by nitrogen doping, so that the rate capability of the battery is improved, and the defect of the transition metal chalcogenide in the aspect of conductivity is overcome.
3) The nitrogen-doped carbon nanofibers with the ultrahigh length-diameter ratio are interwoven to form a porous three-dimensional structure, so that stress changes caused by repeated embedding and de-embedding processes of aluminum ions with high charge density in the charging and discharging processes can be well buffered, the deformation of an electrode active material is reduced, and the cycling stability of a battery is improved.
4) The elm-shaped molybdenum diselenide is uniformly coated on the surface of the carbon nanofiber, so that the contact area of the electrode active material and the electrolyte is increased, the effective aluminum storage sites are increased, the utilization rate of the electrode active material is improved, and the specific capacity of the battery is improved.
5) Simple preparation and low cost. Compared with CVD growth of molybdenum selenide nanosheets, the hydrothermal reaction is easier to operate, the cost is low, batch production can be realized, and the yield is high.
Drawings
Fig. 1 is a flow chart of the present invention for preparing elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers;
FIG. 2 shows the results of the measurement of the temperature of the aluminum ion battery prepared in example 1 at 100mA · g-1Constant current cycle charge-discharge specific volume and coulombic efficiency chart;
fig. 3 is a first charge and discharge voltage-capacity curve of the aluminum ion battery prepared in example 1;
FIG. 4 is a cyclic voltammetry scan test chart of the aluminum ion battery prepared in example 1;
FIG. 5 is a graph of rate capability tests of the aluminum-ion battery prepared in example 1 at different current densities;
fig. 6 is a scanning electron microscope image of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers;
FIG. 7 is a transmission electron microscope image of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers;
fig. 8 is an EDS energy spectrum of C, N, W, S elements in elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber;
fig. 9 is an XRD spectrum of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber;
fig. 10 is a TGA plot of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers;
fig. 11 is a constant current charge and discharge cycle test chart of the respective use of molybdenum diselenide and the elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber composite structure prepared in example 1 as the positive electrode material of an aluminum ion battery;
fig. 12 is a constant current cycle test chart of the aluminum ion battery obtained in example 2.
Detailed Description
The invention provides a preparation method of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber, which comprises the following steps:
mixing polyacrylonitrile and N, N-dimethylformamide to obtain a precursor solution;
carrying out electrostatic spinning on the precursor solution to obtain a flexible film;
carrying out heat treatment on the flexible film to obtain nitrogen-doped carbon nanofibers;
mixing the nitrogen-doped carbon nanofiber, a molybdenum source precursor and a selenium source precursor, and then carrying out hydrothermal reaction to obtain a hydrothermal product;
and carrying out heat treatment on the hydrothermal product in nitrogen to obtain the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber.
The invention mixes polyacrylonitrile and N, N-dimethylformamide to obtain precursor solution. In the invention, the mass ratio of polyacrylonitrile to N, N-dimethylformamide is preferably 0.5-0.8: 5-8. In the invention, the Mw of the polyacrylonitrile is preferably 130,000-150,000. In the invention, the mixing is preferably carried out for 8-10 hours at 40-50 ℃ by magnetic stirring.
After the precursor solution is obtained, the invention carries out electrostatic spinning on the precursor solution to obtain the flexible film.
In the invention, the voltage of electrostatic spinning is preferably 18-20 KV, the distance between a needle head and a receiving plate is preferably 15-20 cm, the advancing speed is preferably 10-15 muL/min, the temperature is preferably 35-40 ℃, and the humidity is preferably 40-45%.
After the flexible film is obtained, the invention carries out heat treatment on the flexible film to obtain the nitrogen-doped carbon nanofiber.
In the invention, the heat treatment of the flexible film preferably comprises the steps of preoxidation for 2-3 hours in an air atmosphere, carbonization and in-situ nitrogen doping in nitrogen, wherein the preoxidation temperature is preferably 230-240 ℃, the carbonization and in-situ nitrogen doping temperature is preferably 850-860 ℃ independently, and the total heat preservation time of the carbonization and in-situ nitrogen doping is preferably 6-8 hours. In the present invention, the pre-oxidation serves as a stabilizing function.
In the invention, the heating rate from the pre-oxidation temperature to the carbonization and in-situ nitrogen doping temperature is preferably 3-5 ℃/min.
After the heat treatment is finished, the nitrogen-doped carbon nanofiber is preferably naturally cooled to room temperature in a nitrogen atmosphere to obtain the nitrogen-doped carbon nanofiber.
After the nitrogen-doped carbon nanofiber is obtained, the nitrogen-doped carbon nanofiber, the molybdenum source precursor and the selenium source precursor are mixed and then subjected to hydrothermal reaction to obtain a hydrothermal product. In the invention, the nitrogen-doped carbon nanofiber is used as a growth substrate of molybdenum diselenide in hydrothermal reaction.
In the present invention, the molybdenum source precursor is preferably prepared by a method comprising the steps of: dissolving 2-3 mmol of sodium molybdate dihydrate in 50-60 mL of deionized water; the selenium source precursor is preferably prepared by a method comprising the following steps: dissolving 4-6 mmol of selenium powder in 10-15 mL of hydrazine hydrate.
In the invention, the dosage ratio of the molybdenum element in the molybdenum source precursor, the selenium in the selenium source precursor and the nitrogen-doped carbon nanofiber is preferably 2-3 mmol: 4-6 mmol: 0.1 to 0.2 g.
In the invention, the temperature of the hydrothermal reaction is preferably 200-220 ℃, and the time is preferably 10-12 h.
In the invention, the hydrothermal reaction is preferably carried out in a polytetrafluoroethylene reaction kettle, after the hydrothermal reaction is finished, the polytetrafluoroethylene reaction kettle is preferably cooled to room temperature, and a hydrothermal product is obtained by filtering and alternately washing with deionized water/absolute ethyl alcohol, wherein the hydrothermal product is a composite film structure of molybdenum diselenide and nitrogen-doped carbon nanofiber.
After a hydrothermal product is obtained, the hydrothermal product is subjected to heat treatment in nitrogen to obtain the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber.
In the invention, the temperature of the heat treatment in the nitrogen is preferably 450-480 ℃, and the time is preferably 2-3 h. In the invention, the heat treatment in nitrogen can further improve the crystallinity of the molybdenum diselenide nanosheets coated on the surface of the nitrogen-doped carbon nanofiber to form the elm-shaped molybdenum diselenide nanosheets.
The invention also provides the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber prepared by the preparation method in the technical scheme, the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber takes elm-shaped molybdenum diselenide as a shell, nitrogen-doped carbon nanofiber as a core, and the elm-shaped molybdenum diselenide is of a sheet structure.
In the invention, the content of the elm-shaped molybdenum diselenide is preferably 75-80 wt%, and the doping amount of nitrogen in the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber is preferably 3-5 wt%.
The invention also provides application of the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber as an aluminum ion battery anode material.
In a specific embodiment of the present invention, the assembly of the aluminum-ion battery preferably comprises the steps of: and (3) preparing electrolyte and assembling the battery in a glove box with a high-purity argon atmosphere, and packaging the soft-package battery by adopting an aluminum-plastic film. The high-purity aluminum foil is used as a negative electrode, the thickness of the aluminum foil is 0.2mm, and the purity is 99.999%. Before use, the aluminum foil is polished and then cleaned by absolute ethyl alcohol. Whatman (GF/D) was used as a battery separator, and a double-layer separator was used to prevent short circuit due to membrane puncture. The elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber prepared by the method is a flexible self-supporting film, can be directly used as the anode of an aluminum ion battery, does not need additional binder and conductive agent, and does not need the process steps of pulping, coating, drying and the like required by the traditional electrode preparation. The electrolyte adopts room-temperature ionic liquid, and the weight ratio of anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride is 1.3-1.5: 1, and mixing the components in a molar ratio of 1.
To further illustrate the present invention, the elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber provided by the present invention, and the preparation method and application thereof, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Fig. 1 is a flow chart of the preparation of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers according to the present invention, in which polyacrylonitrile and N, N-dimethylformamide are mixed to obtain a precursor solution, then electrostatic spinning is performed to obtain a flexible thin film (polyacrylonitrile nanofiber thin film), the flexible thin film is subjected to heat treatment to obtain nitrogen-doped carbon nanofibers, the nitrogen-doped carbon nanofibers, a molybdenum source precursor, and a selenium source precursor are mixed, then hydrothermal reaction is performed, and then heat treatment is performed in nitrogen to obtain the elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers.
Example 1
Step 1: sample preparation
Preparing nitrogen-doped carbon nanofibers:
0.5g of polyacrylonitrile (Mw: 130,000 to 150,000) was dissolved in a solvent of 5g N, N-dimethylformamide, and magnetically stirred at 40 ℃ for 10 hours to form a uniform and transparent solution, which was used as a precursor solution of nitrogen-doped carbon nanofibers for electrostatic spinning. In the electrostatic spinning process, the specific experimental parameter ranges are as follows: the voltage is 18KV, the distance between the needle and the receiving plate is 15cm, the propelling speed is 10 muL/min, the temperature is 35 ℃, and the humidity is 40%. And after electrostatic spinning is finished, the white flexible film is taken off from the receiving plate, heat treatment is carried out, and the steps of pre-oxidation stabilization, carbonization and nitrogen doping are finished in the heat treatment process. First, the film obtained by electrostatic spinning was subjected to pre-oxidation stabilization for 2 hours in an air atmosphere at a heat treatment temperature of 230 ℃. And after the pre-oxidation is stable, introducing high-purity nitrogen into the tubular furnace, raising the furnace temperature from 230 ℃ to 850 ℃, raising the temperature at the rate of 3 ℃/min, and preserving the temperature for 8 hours to carry out carbonization and in-situ nitrogen doping. And naturally cooling to room temperature in a high-purity nitrogen atmosphere to obtain the nitrogen-doped carbon nanofiber. The nitrogen-doped carbon nanofiber is used as a growth substrate of molybdenum diselenide in hydrothermal reaction. The precursor of the hydrothermal reaction is the mixture of two solutions of a molybdenum source and a selenium source. The molybdenum source precursor is 2mmol of sodium molybdate dihydrate dissolved in 50mL of deionized water, and the selenium source precursor is 4mmol of selenium powder dissolved in 10mL of hydrazine hydrate. 0.1g of nitrogen-doped carbon nanofiber is mixed with the molybdenum selenide precursor solution, and the mixture and the nitrogen-doped carbon nanofiber cut into small blocks are transferred into a polytetrafluoroethylene reaction kettle together, and hydrothermal reaction is carried out for 12 hours at 200 ℃. And after the reaction is finished, cooling the reaction kettle to room temperature, and alternately washing the reaction kettle by filtering and deionized water/absolute ethyl alcohol to obtain the composite film structure of the molybdenum diselenide and the nitrogen-doped carbon nanofiber. And carrying out heat treatment on the film for 3h at 450 ℃ in a high-purity nitrogen atmosphere, further improving the crystallinity of the molybdenum diselenide nanosheets coated on the surfaces of the carbon nanofibers, forming elm-shaped molybdenum diselenide nanosheets, and obtaining the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofibers.
Step 2: battery assembly
And preparing electrolyte and assembling the battery in a glove box in a high-purity argon atmosphere. And packaging the soft package battery by adopting an aluminum plastic film. The high-purity aluminum foil is used as a negative electrode, the thickness of the aluminum foil is 0.2mm, and the purity is 99.999%. Before use, the aluminum foil is polished and then cleaned by absolute ethyl alcohol. Whatman (GF/D) was used as a battery separator, and a double-layer separator was used to prevent short circuit due to membrane puncture. The molybdenum diselenide @ nitrogen-doped carbon nanofiber prepared by the method is a flexible self-supporting film, so that the molybdenum diselenide @ nitrogen-doped carbon nanofiber can be directly used as the anode of an aluminum ion battery, and does not need additional binder and conductive agent, and does not need the process steps of pulping, coating, drying and the like required by the traditional electrode preparation. The electrolyte adopts room temperature ionic liquid, and the weight ratio of anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride is 1.3: 1, and mixing the components in a molar ratio of 1.
And step 3: electrochemical testing
1) Constant current cycling test
Constant current cycling tests were performed with the LAND CT2001A battery test system. The current value was 100mA · g-1The voltage range is 0.1V-2V. The number of cycles was 200.
FIG. 2 shows 100mA · g-1The constant current circulation charge-discharge specific volume and coulombic efficiency chart is shown in figure 2, the first specific capacity can reach 296.3 mAh.g-1After 200 cycles, the specific discharge capacity can still be kept at 169.9 mAh.g-1Coulombic efficiency was higher than 95%. The high specific capacity and good cycling stability are derived from the synergistic effect generated by the excellent composite structure of the molybdenum diselenide @ nitrogen-doped carbon nanofiber. The molybdenum diselenide is evenly coated on the surface of the carbon nanofiber in an elm shape, so that the active specific surface area is improved, the aluminum storage efficiency of the active material is increased, and the specific capacity is improved. In addition, the nitrogen-doped carbon nanofiber is a three-dimensional porous network structure, so that stress change caused by repeated embedding and de-embedding of aluminum ions in the circulating process can be well buffered, the deformation of the active material is reduced, the structural stability of the active material is kept, the structure of the active material is prevented from being collapsed, and good circulating stability is obtained.
Fig. 3 is a first charge-discharge voltage-capacity curve, and as can be seen from fig. 3, the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber serving as the anode material of the aluminum ion battery has an obvious charge-discharge voltage platform in the charge-discharge process. The discharge voltage plateau is about 0.72V and the charge voltage plateau is about 1.2V.
And (3) taking the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber aluminum ion battery anode as a working electrode to perform cyclic voltammetry scanning test. The voltage value of the charge-discharge reaction voltage platform is consistent with that of the cyclic voltammetry scanning curve peak, and the cyclic voltammetry scanning curves are highly overlapped, so that the electrochemical redox reaction generated at the anode has good reversibility as shown in fig. 4.
2) Multiplying power performance test under different current densities
In practical applications, there are many application requirements that require large current high power discharge and large current fast charge. Rate performance of the battery at different current densities is critical. Therefore, rate performance tests under different current densities are designed. The current density is from 100mA g-1The initial increase is carried out, and the initial increase is sequentially increased to 150mA g-1，200mA·g-1，250mA·g-1Finally return to 100mA g-1Dwell for 10 cycles at each current density. When the current density is increased, it becomes a control step of the entire electrode reaction because the diffusion rate of the reactive particles in the electrode active material is limited.
If the electrode material has strong electron transport capability, when the current density is increased, the specific capacity of the battery can be reduced to a certain degree, but the specific capacity of the battery can not be greatly reduced. As can be seen from FIG. 5, the specific discharge capacity increased from 247mAh g with an increase in current density-1Sequentially reducing to 217.8mAh g-1,195.3mAh·g-1,159mAh·g-1. The elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber prepared by the method has good rate capability and can keep certain specific capacity under higher charge-discharge rate. Finally, when the current density returns to 100mA g-1The specific discharge capacity is correspondingly recovered to 243mAh g-1It is explained that the structure of the electrode active material is not destroyed after undergoing a series of high-rate charge and discharge. The battery has good rate performance, and is derived from the good electron transport capability and the structural stability of the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber composite material.
Step 4 topography characterization
1) Scanning Electron microscope testing (SEM)
Fig. 6 is a scanning electron microscope image of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers, and it can be seen from fig. 6 that elm-like sheet structures formed by molybdenum diselenide nanosheets are coated on the surface of the carbon nanofibers to form core-shell composite structures. The uniformly dispersed flaky nano structure can increase the active specific surface area, increase the contact area of molybdenum diselenide and electrolyte and increase the aluminum storage efficiency of the electrode active material, thereby improving the charge-discharge specific capacity of the battery.
2) Transmission electron microscope Test (TEM)
Fig. 7 is a transmission electron microscope image of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber, and it can be seen from fig. 7 that since molybdenum diselenide has a lamellar structure and is not stacked, the edge of the carbon nanofiber is clearly visible and no black agglomeration morphology occurs. The thin layer coating structure is beneficial to improving the effective specific surface area of the electrode active material, thereby improving the charge-discharge specific capacity of the battery.
3) Auger electron spectroscopy test (EDS)
Fig. 8 is an EDS energy spectrum diagram of C, N, W, S elements in elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofibers, and element distributions of C, N, Se, and Mo can be obtained by energy spectrum analysis, and it can be seen that Mo and Se are uniformly distributed in the carbon nanofibers, and the N elements are uniformly doped in the carbon nanofibers, which proves that molybdenum diselenide is uniformly coated on the surface of the carbon nanofibers, and the nitrogen elements are uniformly doped in the carbon nanofibers, forming a uniform molybdenum diselenide @ nitrogen-doped carbon nanofiber composite structure. According to the EDS scan, the nitrogen doping atomic percentage is 4.11%.
4) X-ray diffraction test (XRD)
Fig. 9 is an XRD spectrum of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber, which shows that the XRD spectrum of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber is consistent with the PDF standard card of molybdenum diselenide (JCPDS 29-0914). The diffraction peak corresponding to graphitized carbon of the carbon nanofiber is about 26 degrees and is superposed with the diffraction peak of the (004) crystal face of the molybdenum diselenide. XRD results prove that in the composite structure synthesized by the experimental scheme of the patent, the elm-shaped nano-sheet coated on the surface of the carbon nano-fiber is molybdenum diselenide.
5) Thermal analysis Test (TGA)
Fig. 10 is a TGA plot of elm-like molybdenum diselenide @ nitrogen-doped carbon nanofibers. The thermal analysis test is carried out in air atmosphere, the test temperature range is from room temperature to 800 ℃, and the heating rate is 5 ℃ min-1. It is known that the thermogravimetric curve is slightly increased at the initial stage of temperature rise because molybdenum diselenide is oxidatively decomposed into trioxidesMolybdenum and molybdenum diselenide. Subsequently, as the temperature rises, the molybdenum diselenide sublimes, the carbon nanofibers are oxidized into carbon dioxide to volatilize, and the remaining substance at the end of the 800 ℃ experiment is molybdenum trioxide, the mass percent of which is 44.46%. According to the mass fraction of the molybdenum trioxide, the mass percentage content of the molybdenum diselenide in the molybdenum diselenide @ nitrogen-doped carbon nanofiber is 78.42%.
The core-shell composite structure of the elm-shaped molybdenum diselenide nanosheet coated on the surface of the nitrogen-doped carbon nanofiber is prepared, and in the material, the special nanostructure of the molybdenum diselenide has high active specific surface area, so that the aluminum storage efficiency can be improved, and high specific capacity can be obtained. The nitrogen-doped carbon nanofiber forms a three-dimensional conductive network, provides the capability of rapidly transferring electrons for high-rate charge and discharge, and realizes high-power discharge and rapid charge. The three-dimensional porous nitrogen-doped carbon nanofiber can buffer stress generated in the charge-discharge cycle process, reduce the deformation of an active material, keep the structure stable and improve the cycle stability of the battery.
Compared with pure molybdenum diselenide without nitrogen-doped carbon nanofiber as a growth base, the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber composite material prepared by the method has higher specific capacity and more stable cycle performance. At 100mA · g-1Under the current density of the aluminum ion battery, the composite structures of molybdenum diselenide and elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber are respectively used as anode materials of the aluminum ion battery to carry out constant-current charge-discharge cycle tests. The test results are shown in fig. 11. The cycle stability and the charging and discharging capacity of the molybdenum diselenide which is not compounded with the nitrogen-doped carbon nanofiber are obviously lower than those of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber. The initial discharge specific capacities of the two were 226.1mAh g-1And 296.3mAh · g-1The discharge specific capacity of the molybdenum diselenide is obviously lower than that of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber. After two hundred cycles, the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber can keep 169.9 mAh.g-1The specific discharge capacity of the molybdenum diselenide is reduced to 94.8 mAh.g-1. The difference of the two cyclic performances is derived from the different shapes of the molybdenum diselenide on one hand, if notThe nitrogen-doped carbon nanofiber is used as a substrate, so that molybdenum diselenide is uniformly dispersed and coated on the substrate, the molybdenum diselenide can form a stacking structure, the contact between an active material and electrolyte is not facilitated, the effective specific surface area of the active material is reduced, and the specific capacity is reduced. On the other hand, in the repeated charge-discharge cycle process, stress action is generated due to repeated insertion and extraction of aluminum ions, so that the molybdenum diselenide structure is damaged. At h.g-1In the molybdenum diselenide @ nitrogen-doped carbon nanofiber, the three-dimensional porous nitrogen-doped carbon nanofiber network can buffer the stress effect, protect the structural stability of the molybdenum diselenide in the composite material, and improve the cycle stability.
Example 2
Step 1: sample preparation
The nitrogen-doped carbon nanofibers were prepared as the substrate for hydrothermal growth of molybdenum diselenide using the same procedure as in example 1. And mixing 0.05g of nitrogen-doped carbon nanofiber with a molybdenum diselenide precursor, wherein the molybdenum diselenide precursor is a mixed solution of 2mmol of sodium molybdate dihydrate dissolved in 50mL of deionized water and 4mmol of selenium powder dissolved in 10mL of hydrazine hydrate. The amount of nitrogen-doped carbon nanofiber substrate used in example 2 was halved compared to example 1. In the hydrothermal growth process of molybdenum diselenide, because the carbon nanofibers are used as the growth substrate of the molybdenum diselenide, the molybdenum diselenide can be uniformly loaded on the carbon substrate, and the loading effect can be influenced by the dosage of the substrate, so that the electrochemical performance is influenced. In example 2, the mass fraction of molybdenum diselenide was 91.27%, and the atomic percentage of nitrogen was 2.06%.
The sample obtained in example 2 was used as a positive electrode material of an aluminum ion battery, and an aluminum ion battery was assembled by the same procedure as in example 1 to perform a constant current cycle test. The current value was 100mA · g-1The voltage range is 0.1V-2V, and the cycle number is 200 times. As shown in fig. 12. The first discharge specific capacity is 211.7 mAh.g-1After 200 cycles, the specific discharge capacity is 153.5mAh g-1. It can be seen that the specific capacity in example 2 is lower than that in example 1. This is because an excessively high molybdenum diselenide loading causes the accumulation of molybdenum diselenide nanosheets, a decrease in the effective contact area of the electrolyte and the active material, a decrease in the active sites for aluminum storage, and the resulting active materialThe utilization rate is reduced and the specific capacity is reduced. Thus, when compounding nitrogen-doped carbon nanofibers with molybdenum diselenide, the ratio of the carbon substrate to molybdenum diselenide should be selected to be such that the molybdenum diselenide is uniformly loaded without stacking. Too high loading can result in stacking of molybdenum diselenide nanosheets, reducing the utilization rate of the active material, while too low loading of molybdenum diselenide can result in insufficient specific capacity.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber is characterized by comprising the following steps of:
mixing polyacrylonitrile and N, N-dimethylformamide to obtain a precursor solution;
carrying out electrostatic spinning on the precursor solution to obtain a flexible film;
carrying out heat treatment on the flexible film to obtain nitrogen-doped carbon nanofibers;
mixing the nitrogen-doped carbon nanofiber, a molybdenum source precursor and a selenium source precursor, and then carrying out hydrothermal reaction to obtain a hydrothermal product;
and carrying out heat treatment on the hydrothermal product in nitrogen to obtain the elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber.
2. The preparation method according to claim 1, wherein the mass ratio of polyacrylonitrile to N, N-dimethylformamide is 0.5-0.8: 5-8.
3. The preparation method according to claim 1, wherein the electrostatic spinning voltage is 18-20 KV, the distance between the needle and the receiving plate is 15-20 cm, the advancing speed is 10-15 μ L/min, the temperature is 35-40 ℃, and the humidity is 40-45%.
4. The preparation method according to claim 1, wherein the heat treatment of the flexible film comprises pre-oxidation in an air atmosphere for 2-3 hours, and then carbonization and in-situ nitrogen doping in nitrogen gas, wherein the pre-oxidation temperature is 230-240 ℃, the carbonization and in-situ nitrogen doping temperature is 850-860 ℃ independently, and the total holding time of the carbonization and in-situ nitrogen doping is 6-8 hours.
5. The method according to claim 4, wherein the temperature increase rate from the pre-oxidation temperature to the carbonization and in-situ nitrogen doping temperature is 3-5 ℃/min.
6. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 200-220 ℃ for 10-12 hours.
7. The method according to claim 1, wherein the heat treatment in nitrogen is carried out at a temperature of 450 to 480 ℃ for 2 to 3 hours.
8. The elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber prepared by the preparation method of any one of claims 1-7, wherein the elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber takes elm-like molybdenum diselenide as a shell, nitrogen-doped carbon nanofiber as a core, and the elm-like molybdenum diselenide is in a sheet structure.
9. The elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber as claimed in claim 8, wherein the content of the elm-like molybdenum diselenide is 75-80 wt%.
10. Use of the elm-like molybdenum diselenide @ nitrogen-doped carbon nanofiber as claimed in claim 8 or 9 as an aluminum ion battery positive electrode material.
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