CN110797514A - Molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, preparation method thereof and application of composite material in positive electrode of lithium-sulfur battery - Google Patents
Molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, preparation method thereof and application of composite material in positive electrode of lithium-sulfur battery Download PDFInfo
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Abstract
The invention discloses a molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, a preparation method thereof and application thereof in a lithium-sulfur battery anode. The composite material is made into an electrode and applied to the positive electrode of a lithium-sulfur secondary battery. According to the invention, molybdenum and nitrogen are doped into the carbon nanoflower framework in a covalent bond form to serve as a sulfur framework material, a small amount of molybdenum and nitrogen are doped to increase the chemical adsorption of polysulfide ions, the high specific surface area is maintained, the carbon polarity is increased, the effective physical adsorption of the polysulfide ions is ensured, moreover, the flower-shaped structure is favorable for the rapid electron transfer and the rapid electrolyte ion diffusion, the utilization rate of sulfur is increased, and finally the comprehensive performance of the lithium-sulfur battery is synergistically improved.
Description
Technical Field
The invention belongs to the field of nano materials and lithium-sulfur batteries, and particularly relates to a molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, a preparation method thereof and application thereof in a lithium-sulfur battery anode.
Background
The lithium-sulfur battery as the second-generation lithium ion battery has the advantages that the sulfur is rich in natural content, wide in source, non-toxic and harmless, and the ultrahigh theoretical specific capacity (1675mAh/g) of the sulfur is multiple times of that of the lithium ion battery, but the conductivity of the sulfur is low (10)-5S), volume expansion (300%) occurs in the battery charging and discharging process, a shuttle effect is also accompanied in the battery circulation process, polysulfide ions are dissolved in electrolyte to generate loss of active substances, and simultaneously generated precipitates are enriched in a lithium cathode to cause irreversible attenuation and even damage of the battery performance. This series of reasons is the major difficulty in the current research on lithium sulfur batteries.
The carbon is used as a framework to load sulfur as the positive electrode of the lithium-sulfur battery, so that the conductivity of the sulfur positive electrode can be improved to a certain extent, and the absorption of polysulfide ions is enhanced, thereby improving the performance of the lithium-sulfur battery. For example, patent CN106340632 discloses a carbon nanosphere/sulfur composite material and a preparation method and application thereof, mesoporous channels in the carbon nanospheres with flower-shaped structures are used for facilitating diffusion and ion transport of electrolyte ions, the carbon nanospheres with abundant micropores, mesopores and large specific surface areas can load more sulfur active substances and inhibit dissolution of polysulfide, thin petal-shaped carbon nanosheets are convenient for electron rapid transfer, and nitrogen doping improves electrical activity and enhances physical adsorption effect on sulfur, thereby improving performance of the lithium-sulfur battery. However, the non-polar carbon material does not physically adsorb the polar polysulfide ions so far, which is detrimental to the cycle life of the battery, and the patent discloses that the optimized battery is cycled for only 200 cycles. Transition metal sulfide, oxide, nitride, phosphide and the like can form covalent interaction with sulfur in polysulfide ions so as to realize chemical adsorption on the polysulfide ions and reduce loss of the polysulfide ions, so that the transition metal sulfide, oxide, nitride, phosphide and the like are regarded as promising polysulfide ion adsorbents. However, since the conductivity of the transition metal compound is not particularly good, it is more preferable to use a metal compound as a host for sulfur on a carbon material. For example, CN109378459 discloses a positive electrode material of a lithium-sulfur battery and a preparation method thereof, and the patent uses basic manganese oxide to perform in-situ modification on graphene to obtain a graphene-basic manganese oxide compound. The hydroxyl functional group (OH) in the graphene composite basic metal oxide (manganese oxide) has a hydrogen bonding effect with an intermediate of a lithium-sulfur battery reaction, and the dissolution of polysulfide in an electrolyte is favorably relieved. In the invention, the growth mode of the basic oxide is changed due to the interface effect of the graphene, the basic oxide is not rod-shaped but sheet-shaped, and clusters, nano particles and a porous nano layer are formed on the surface of the graphene, so that the graphene has strong adsorption and lithium-sulfur compound ion performance. In fact, however, effective chemisorption occurs only on the surface of these metal compounds. In order to increase the adsorption effect, the similar invention must increase the loading of the metal compound with poor conductivity, which inevitably reduces the electron migration rate and simultaneously reduces the surface area and pore volume of the corresponding composite material, and the performance of the lithium-sulfur battery is greatly reduced.
Thus, the rational incorporation of a small number of metal atoms into the carbon skeleton via covalent bonds and the use of the composite as a sulfur host not only changes the polarity of the carbon to enhance physisorption, but also ensures that surface sites are effectively exposed to suppress polysulfide loss via chemisorption without reducing the specific surface area and pore volume of the material, and is expected to exhibit high overall performance.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention aims to provide a molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, a preparation method thereof and application thereof in a lithium-sulfur battery anode.
The invention discloses a molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, which comprises a molybdenum and nitrogen co-doped flower-shaped carbon nanosphere and amorphous sulfur which are compounded with each other, wherein the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere is formed by doping molybdenum and nitrogen into a flower-shaped carbon nanosphere framework in a covalent bond mode, the flower-shaped carbon nanosphere framework is formed by arranging a plurality of petal-shaped porous carbon sheets in a petal-shaped unfolding mode with one end serving as a common base point and the other end serving as a petal-shaped base point, and the covalent bond comprises a C-Mo bond and a C-N bond.
The molybdenum-nitrogen co-doped flower-type carbon nanospheres are further arranged to have the diameter of 220-250nm, the thickness of the petal-type porous carbon sheets is 4-20nm, the gaps between the petal-type carbon walls are 10-30nm, and the overall specific surface area of the material is 400-600 m-2g-1The pore volume is 1.1-1.8cm3g-1Left and right.
The mass fraction of the molybdenum atoms in the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres is 4-10%, the mass fraction of the nitrogen in the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres is 4-8%, and the mass fraction of the molybdenum atoms in the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres is preferably 9.47%.
The further setting is that nitrogen in the composite material is derived from the use of precursor chitosan and the introduction of ammonia gas in the annealing process, and molybdenum is derived from the introduction of molybdate in the hydrothermal process.
And further setting that the amorphous sulfur enters a pore structure of the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres through the capillary action after being melted by sulfur, and uniformly dispersing on the petal-shaped porous carbon sheets, wherein the mass fraction of the amorphous sulfur accounts for 65-75 wt%.
As a second aspect of the present invention, the present invention provides a method for preparing a preferred molybdenum-nitrogen co-doped flower-type carbon nanoball/sulfur composite, comprising the steps of:
(1) synthesis of hard template silicon dioxide nanospheres
Adding 2g of cetyl pyridine bromide and 1.2g of urea into 60ml of deionized water, ultrasonically dissolving to form a homogeneous mixed solution of the cetyl pyridine bromide and the urea, preparing a mixed solution of 60 cyclohexane, 5ml of n-amyl alcohol and 5g of tetraethyl orthosilicate, mixing the two solutions into a three-neck flask with a proper volume, mechanically stirring for 1h at room temperature, wherein the stirring speed is between 500 and 2500rmp, then transferring the mixed solution into a reaction kettle, reacting for 6h at 120 ℃, then sequentially filtering, washing and drying to obtain a light yellow or white solid, and calcining for 6h at 550 ℃ in a muffle furnace to obtain silicon dioxide nanospheres;
(2) preparation of flower-shaped nanospheres
Taking 0.5g of the silicon dioxide nanospheres prepared in the step (1), mixing 1g of chitosan, ultrasonically dissolving and dispersing in 75ml of deionized water to form a uniform mixed solution, transferring the mixed solution to a reaction kettle, reacting in a 180 ℃ oven for 12 hours, carrying out suction filtration, washing and drying once to obtain coffee powder, annealing in an argon atmosphere of a 800 ℃ tube furnace for 2 hours, and etching away a silicon dioxide nanosphere hard template by using 20 wt% of HF solution to obtain flower-shaped carbon nanospheres;
(3) preparation of molybdenum-nitrogen co-doped flower-type carbon nanospheres
Weighing 100mg of the flower-type carbon nanosphere obtained in the step (2) and 100mg of cetyl trimethyl ammonium bromide serving as a surfactant in 30ml of water, ultrasonically dispersing, then adding 12-50 mg of molybdate into the solution for further ultrasonic dispersion, pouring the solution with uniform ultrasonic dispersion into a reaction kettle, carrying out hydrothermal reaction in a drying oven at 200 ℃ for 10 hours, carrying out suction filtration, drying and collecting powder; annealing the powder at the high temperature of 800 ℃ for 2h in the mixed gas atmosphere of argon and ammonia gas to obtain a target product molybdenum-nitrogen co-doped flower-shaped carbon nanosphere;
(4) preparation of molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material
And (3) ball-milling and uniformly mixing the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres prepared in the step (3) and elemental sulfur according to the mass ratio of 3:7, putting the mixture into a volumetric flask, reacting in an oven at 165 ℃ for 12 hours, and cooling to room temperature after the reaction is finished to obtain the nitrogen-doped barbed carbon nanosphere/sulfur composite material.
Further setting the volume ratio of argon to ammonia in the annealing atmosphere in the step (3) to be 9:1-7: 3.
Further setting that the method for removing the silicon dioxide template in the step (2) is a NaOH etching template, a HF etching template or HNO3One of the templates is etched.
The further setting is that the NaOH etching method for removing the silicon dioxide template in the step (2) specifically comprises the following steps: at a concentration of 2mol L-1Reacting in NaOH solution at 10-100 deg.C for 6-10 h.
Further setting that the HF etching method for removing the silicon dioxide template in the step (2) specifically comprises the following steps: reacting in HF solution with the concentration of 20% at room temperature for 6-10 h.
Further setting the carbonization treatment condition in the step (2) to be 1-10 ℃ for min-1The temperature is raised to 900 ℃ at the rate of 700-.
Further setting the mass ratio of the molybdate to the flower-shaped carbon nanosphere in the step (3) to be 12:100, 25:100 and 50: 100.
The molybdate in the step (3) is further set to be one or a combination of ammonium molybdate, sodium molybdate and potassium molybdate.
In addition, as a third aspect of the invention, the invention also provides a method for applying the molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material to a positive electrode of a lithium-sulfur battery, wherein the molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, conductive carbon and polyvinylidene fluoride are uniformly mixed according to the mass ratio of 8:1:1, coated on an aluminum foil current collector, subjected to vacuum drying at 60 ℃, rolled and sliced to obtain the positive electrode of the lithium-sulfur battery.
As a fourth aspect of the invention, the invention also provides a lithium-sulfur battery, which comprises a negative electrode, an electrolyte, a diaphragm and a shell, and further comprises a positive electrode of the lithium-sulfur battery prepared by the method of claim 8, wherein the negative electrode is a lithium sheet, and the electrolyte is a mixed solution of lithium bistrifluoromethylsulfonate imide, lithium nitrate, ethylene glycol dimethyl ether and 1, 3-dioxane, wherein the molar concentration of the lithium bistrifluoromethylsulfonate imide is 1mol L-1The mass fraction of lithium nitrate is 1%, and the volume ratio of ethylene glycol dimethyl ether to 1, 3-dioxane is 1: 1.
According to the invention, molybdenum and nitrogen are doped into the carbon nanoflower framework in a covalent bond form to serve as a sulfur framework material, a small amount of molybdenum and nitrogen are doped to increase the chemical adsorption of polysulfide ions, the high specific surface area is maintained, the carbon polarity is increased, the effective physical adsorption of the polysulfide ions is ensured, moreover, the flower-shaped structure is favorable for the rapid electron transfer and the rapid electrolyte ion diffusion, the utilization rate of sulfur is increased, and finally the comprehensive performance of the lithium-sulfur battery is synergistically improved.
The invention has the following beneficial effects:
1. in the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere, molybdenum and nitrogen exist in a carbon skeleton in a doped form, so that the polarity of carbon is changed, and physical adsorption is enhanced; meanwhile, the surface sites are still effectively exposed under the condition of not reducing the specific surface area and the pore volume of the material, so that the dissolution loss of lithium polysulfide is inhibited through the chemical adsorption effect, and the cycling stability and the capacity of the battery are improved. This is much better than the carbon nanoball that inhibits the loss of polysulfide ions by physical adsorption alone.
2. The molybdenum and nitrogen co-doped flower-shaped carbon nanospheres have the three-dimensional flower-shaped structure, so that the uniform dispersion of sulfur and discharge product lithium sulfide and the rapid permeation of electrolyte are facilitated, the overall conductivity of the electrode is improved, and the ion diffusion path is shortened.
3. The invention proves that the balance between chemical adsorption and physical adsorption in the electrochemical behavior of the lithium-sulfur battery is a key factor of sulfur main body design.
The data of the embodiment of the invention are described in detail.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a scanning electron microscope and high resolution image of three samples with different proportions, namely, 5%, 10% and 25% of Mo atoms in flower-type nanospheres and molybdenum-nitrogen co-doped flower-type carbon nanospheres (Mo-N-CNF); in fig. 1, (a) shows a Mo-N-CNF-5% SEM picture, (b) shows a Mo-N-CNF-10% SEM picture, (c) shows a Mo-N-CNF-25% SEM picture, and as can be seen from fig. 1, the molybdenum-nitrogen co-doped flower-type carbon nanoball is a three-dimensional flower-like structure composed of a plurality of graded porous carbon sheets, and each porous carbon sheet exhibits a curved wrinkle shape in morphology, increasing a specific surface area, and uniformly distributing molybdenum carbide thereon, and secondly, when the mass percentage of Mo atoms is respectively 5%, the "petal" morphology structure thereof is complete, which indicates that a small amount of molybdenum doping does not affect the morphology of the carbon nanoflower, and when the molybdenum content is further increased, partial collapse of the structure of the material can be observed as in the SEM picture of Mo-N-CNF-25%; comparing Mo-N-CNF-5% and Mo-N-CNF-10% scanning graphs, which show that the morphology of the molybdenum and nitrogen co-doped carbon nanoflower can partially collapse along with the gradual increase of the amount of ammonium molybdate tetrahydrate in material synthesis;
FIG. 2 is a transmission electron microscope image of Mo-N-CNF-10% of molybdenum and nitrogen co-doped flower-type carbon nanospheres;
FIG. 3 is an XRD (X-ray diffraction) diagram of a molybdenum and nitrogen co-doped flower-shaped carbon nanosphere; from the XRD pattern in figure 3, the characteristic diffraction peaks of the (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of the Mo-N-CNF-25% of the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere are shown to be 34.5 degrees, 38.0 degrees, 39.6 degrees, 52.3 degrees, 61.9 degrees, 69.8 degrees, 72.8 degrees, 75.0 degrees and 76.0 degrees, which just accords with the Mo of the hexagonal system2C peak position, which shows that excessive introduction of molybdenum leads to formation of obvious Mo on the surface of the material2C crystal phase, and Mo-N-CNF-10% and Mo-N-CNF-5% which are two samples with lower molybdenum content but can not detect Mo2The characteristic peak of C, the peak type of the material is similar to the pure carbon peak NFCF, probably because the molybdenum element content of the material is less, molybdenum and carbon are doped into the framework after forming a bond, and a crystal phase cannot be formed, so the material is shown in the form of a carbon peak, which is consistent with the result that the crystal lattice fringes of the molybdenum compound cannot be observed in a TEM image;
fig. 4 is a thermogravimetric diagram of a molybdenum and nitrogen co-doped flower-type carbon nanosphere. The molybdenum content of 3 samples with different proportions of Mo-N-CNF-5%, Mo-N-CNF-10% and Mo-N-CNF-25% can be seen in the figure;
FIG. 5 is an XPS graph of Mo-N-CNF-10% of molybdenum and nitrogen co-doped flower-type carbon nanospheres, which aims to illustrate the binding state and chemical composition thereof. As shown in the full spectrum, the visible peaks for carbon (C1s), nitrogen (N1s), oxygen (O1s), and molybdenum (Mo3d), respectively, are 284.6eV, 400.1eV, 532.0eV, 232.6eV, indicating that the molybdenum and nitrogen elements were successfully doped into the carbon nanoflower structure. From high resolution C1s spectra, except forIn addition to the C-C bond of 284.6eV, the C-N bond of 286.5eV, the C-O bond of 286.6eV, and the O-C ═ O bond of 277.7eV, a peak in binding energy of 284.1eV was observed, which was attributed to efficient binding by the C-Mo bond. The high resolution Mo3d pattern further confirms the presence of C-Mo bonds. As can be seen from the graph, two peaks with a binding energy of 228.6eV/231.3eV are designated as Mo2C-Mo bond of C. Two distinct doublets with binding energies of 230.4eV/234.2eV and 232.2eV/235.9eV were assigned to the higher order Mo species due to the fact that the small amount of molybdenum at the surface of the material was highly oxidized after exposure to air. Peaks at 229.4eV/231.9eV can be observed, indicating the presence of Mo in the nitride3+. This also allows the binding energy peak at 396.4eV to be attributed to the N — Mo bond by high resolution N1s XPS spectroscopy. In addition to this peak, other peaks with binding energies of 398.3eV, 400.8eV, 401.8eV and 403.9eV, respectively, indicate the presence of pyridine N, pyrrole N, graphite N and nitrogen oxide, which is a good indication that the N atom has also been doped into the carbon backbone through covalent bonds;
FIG. 6 is a TGA chart of a molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, wherein sulfur is only compounded in 72% of the sample results, so as to more accurately compare the influence of the structure on the performance;
FIG. 7 is an XRD (X-ray diffraction) diagram of a molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, and obvious crystalline sulfur peaks in Mo-N-CNF/S-5% and Mo-N-CNF/S-10% cannot be observed in the diagram, which proves that sulfur is highly dispersed on a multi-stage pore size and a carbon flower skeleton and cannot form a crystalline phase. In contrast, a distinct crystalline sulfur peak can be observed in the Mo-N-CNF/S-25% sample curve, indicating the presence of crystalline sulfur on the outer surface of the carbon matrix, since the specific surface area or pore volume of the material decreases with the introduction of more Mo into the carbon matrix, and thus the same amount of sulfur cannot be highly dispersed;
fig. 8 is a graph of rate performance of molybdenum and nitrogen co-doped flower-shaped carbon nanospheres/sulfur, and it can be seen from the graph that the battery capacity is higher under different rates, and the overall performance is better than that of a pure carbon-based material. Wherein, the Mo-N-CNF/S-10% sample has the best performance, and the specific discharge capacity can be 713mAh g under the high multiplying power of 5C-1. Due to maximum introduction of Mo atoms without reduction of carbon materialThe specific surface area and the pore diameter of the material matrix;
FIG. 9 is a graph of the cycle performance of the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres/sulfur, and the four composite materials are subjected to charge-discharge cycle for 400 circles under the current density of 1C. The first discharge specific capacities of four composite materials of N-CNF/S-72%, Mo-N-CNF/S-5%, Mo-N-CNF/S-10% and Mo-N-CNF/S-25% are respectively 570mAh g-1，812mAh g-1，949mAh g-1，766mAhg-1Wherein the Mo-N-CNF/S-10 percent can still maintain 713mAh g after 400 circles-1The average attenuation rate per circle is 0.062%;
fig. 10 is a graph of cycle performance at 0.5C for molybdenum and nitrogen co-doped flower-type carbon nanoball/sulfur. In order to further investigate the stability of the synthetic material, the discharge specific capacity performance graph of a battery assembled by three molybdenum and nitrogen co-doped carbon nanoflowers after 1000 times of long cycles under 0.5C low rate shows that the cycle stability of the material Mo-N-CNF/S-10% is the best among the three materials, and the highest 1299mAh g of the first round is-1Also, after 1000 cycles, the highest retention capacity of 395mAh g is shown-1；
FIG. 11 is a graph showing the comparison of 72% and 85% of rate capability of molybdenum and nitrogen co-doped flower-type carbon nanospheres/sulfur, wherein under the condition that the rate is 0.2C, the specific discharge capacity of the composite material Mo-N-CNF/S85% -10% is 1030mAh g-1Compared with the Mo-N-CNF/S75-10 percent of the composite material, the content of the Mo-N-CNF/S is reduced; however, under the condition of high multiplying power of 5C, 85 percent of sulfur is loaded, and the specific discharge capacity of the material can still reach 653mAh g-1It can be seen that even when Mo-N-CNF/S-10% is loaded to a high sulfur content of 85%, it still exhibits unusual performance;
fig. 12 is a graph of cycle performance of molybdenum and nitrogen co-doped flower-type carbon nanospheres/sulfur at 72% compared to 85%. The specific capacity of Mo-N-CNF/S85-10% of initial discharge of the material is 795mAh g-1The specific discharge capacity after 400 cycles is 490mAh g-1The attenuation rate per turn was 0.0957%, and the coulombic efficiency was 92% or more.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
step one, preparation of silicon dioxide nanospheres:
weighing 2g of hexadecyl pyridine bromide and 1.2g of urea, mixing, stirring and dissolving in 60mL of water, dissolving 5g of tetraethyl orthosilicate in a mixed solution of 60mL of cyclohexane and 3mL of n-amyl alcohol, stirring for 60min at room temperature, transferring to a reaction kettle, reacting for 6h at 120 ℃, cooling, filtering, washing to obtain a white solid, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 6h to obtain the white silicon dioxide nanospheres.
Step two, preparation of the flower-shaped nanospheres:
weighing 2g of glucose and 2mL of glacial acetic acid, dissolving in 75mL of water, mixing 0.5g of the prepared silicon dioxide nanospheres in the solution, uniformly dispersing by ultrasonic, transferring to a 100 mL-specification polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction in a 180 ℃ oven for 12h, cooling, filtering, washing with water and ethanol sequentially, carrying out heat treatment on the powder collected after drying at 800 ℃ in Ar atmosphere for 2h, adding the obtained black powder into 20mL of 20% hydrofluoric acid solution, stirring to remove a silicon dioxide template, filtering and drying sequentially to obtain the nitrogen-doped carbon nanospheres with the barb-shaped structure.
Step three, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres:
ultrasonic treating of 100mg of flower-type carbon nanospheres and 100mg of CTAB (cetyl trimethyl ammonium bromide) in 30ml of deionized water for 2 hours, adding 50mg of ammonium molybdate tetrahydrate into the solution, continuing ultrasonic treating for 1 hour, transferring the solution into a 100ml reaction kettle, and carrying out hydrothermal reaction in an oven, wherein the reaction time is 10 hours, and the reaction temperature is 200 ℃. And then carrying out suction filtration on the solution, drying the solution at 100 ℃ for 10h, collecting the obtained solid powder, and annealing the solid powder in a tube furnace, wherein the ratio of argon to ammonia is 90:10, the carbonization temperature is 800 ℃, the carbonization time is 2h, and the heating rate is 5 ℃/min, so that the molybdenum and nitrogen co-doped flower-type carbon nanosphere Mo-N-CNF-25% with the Mo content of 25% is obtained.
Step four, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres/sulfur:
and (3) ball-milling and uniformly mixing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres and the elemental sulfur prepared in the third step according to the mass ratio of 3:7, putting the mixture into a volumetric flask with the specification of 25 x 40, reacting the mixture in an oven at 165 ℃ for 12 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the nitrogen-doped barbed carbon nanosphere/sulfur composite material Mo-N-CNF/S-25%.
Example 2:
step one, preparation of silicon dioxide nanospheres:
weighing 2g of hexadecyl pyridine bromide and 1.2g of urea, mixing, stirring and dissolving in 60mL of water, dissolving 5g of tetraethyl orthosilicate in a mixed solution of 60mL of cyclohexane and 3mL of n-amyl alcohol, stirring for 60min at room temperature, transferring to a reaction kettle, reacting for 6h at 120 ℃, cooling, filtering, washing to obtain a white solid, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 6h to obtain the white silicon dioxide nanospheres.
Step two, preparation of the flower-shaped nanospheres:
weighing 2g of glucose and 2mL of glacial acetic acid, dissolving in 75mL of water, mixing 0.5g of the prepared silicon dioxide nanospheres in the solution, uniformly dispersing by ultrasonic, transferring to a 100 mL-specification polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction in a 180 ℃ oven for 12h, cooling, filtering, washing with water and ethanol sequentially, carrying out heat treatment on the powder collected after drying at 800 ℃ in Ar atmosphere for 2h, adding the obtained black powder into 20mL of 20% hydrofluoric acid solution, stirring to remove a silicon dioxide template, filtering and drying sequentially to obtain the nitrogen-doped carbon nanospheres with the barb-shaped structure.
Step three, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres:
ultrasonic treating of 100mg of flower-type carbon nanospheres and 100mg of CTAB (cetyl trimethyl ammonium bromide) in 30ml of deionized water for 2 hours, adding 25mg of ammonium molybdate tetrahydrate into the solution, continuing ultrasonic treating for 1 hour, transferring the solution into a 100ml reaction kettle, and carrying out hydrothermal reaction in an oven, wherein the reaction time is 10 hours, and the reaction temperature is 200 ℃. And then carrying out suction filtration on the solution, drying the solution at 100 ℃ for 10h, collecting the obtained solid powder, and annealing the solid powder in a tube furnace, wherein the ratio of argon to ammonia is 90:10, the carbonization temperature is 800 ℃, the carbonization time is 2h, and the heating rate is 5 ℃/min, so that the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere Mo-N-CNF-10% with the Mo content of 10% is obtained.
Step four, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres/sulfur:
and (3) ball-milling and uniformly mixing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres and elemental sulfur prepared in the third step according to the mass ratio of 3:7, putting the mixture into a volumetric flask with the specification of 25 x 40, reacting in an oven at 165 ℃ for 12 hours, and cooling to room temperature after the reaction is finished to obtain the nitrogen-doped barbed carbon nanosphere/sulfur composite material Mo-N-CNF/S-10%.
Example 3:
step one, preparation of silicon dioxide nanospheres:
weighing 2g of hexadecyl pyridine bromide and 1.2g of urea, mixing, stirring and dissolving in 60mL of water, dissolving 5g of tetraethyl orthosilicate in a mixed solution of 60mL of cyclohexane and 3mL of n-amyl alcohol, stirring for 60min at room temperature, transferring to a reaction kettle, reacting for 6h at 120 ℃, cooling, filtering, washing to obtain a white solid, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 6h to obtain the white silicon dioxide nanospheres.
Step two, preparation of the flower-shaped nanospheres:
weighing 2g of glucose and 2mL of glacial acetic acid, dissolving in 75mL of water, mixing 0.5g of the prepared silicon dioxide nanospheres in the solution, uniformly dispersing by ultrasonic, transferring to a 100 mL-specification polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction in a 180 ℃ oven for 12h, cooling, filtering, washing with water and ethanol sequentially, carrying out heat treatment on the powder collected after drying at 800 ℃ in Ar atmosphere for 2h, adding the obtained black powder into 20mL of 20% hydrofluoric acid solution, stirring to remove a silicon dioxide template, filtering and drying sequentially to obtain the nitrogen-doped carbon nanospheres with the barb-shaped structure.
Step three, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres:
ultrasonic treating of 100mg of flower-type carbon nanospheres and 100mg of CTAB (cetyl trimethyl ammonium bromide) in 30ml of deionized water for 2 hours, adding 12mg of ammonium molybdate tetrahydrate into the solution, continuing ultrasonic treating for 1 hour, transferring the solution into a 100ml reaction kettle, and carrying out hydrothermal reaction in an oven, wherein the reaction time is 10 hours, and the reaction temperature is 200 ℃. And then carrying out suction filtration on the solution, drying the solution at 100 ℃ for 10h, collecting the obtained solid powder, and annealing the solid powder in a tube furnace, wherein the ratio of argon to ammonia is 90:10, the carbonization temperature is 800 ℃, the carbonization time is 2h, and the heating rate is 5 ℃/min, so that the molybdenum and nitrogen co-doped flower-type carbon nanosphere Mo-N-CNF-5% with the Mo content of 5% is obtained.
Step four, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres/sulfur:
uniformly ball-milling and mixing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres and the elemental sulfur prepared in the third step according to the mass ratio of 3:7, putting the mixture into a volumetric flask with the specification of 25 multiplied by 40, reacting the mixture in an oven at 165 ℃ for 12 hours, and cooling the mixture to room temperature after the reaction is finished to obtain the nitrogen-doped barbed carbon nanosphere/sulfur composite material Mo-N-CNF/S-5%
Example 4:
step one, preparation of silicon dioxide nanospheres:
weighing 2g of hexadecyl pyridine bromide and 1.2g of urea, mixing, stirring and dissolving in 60mL of water, dissolving 5g of tetraethyl orthosilicate in a mixed solution of 60mL of cyclohexane and 3mL of n-amyl alcohol, stirring for 60min at room temperature, transferring to a reaction kettle, reacting for 6h at 120 ℃, cooling, filtering, washing to obtain a white solid, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 6h to obtain the white silicon dioxide nanospheres.
Step two, preparation of the flower-shaped nanospheres:
weighing 2g of glucose and 2mL of glacial acetic acid, dissolving in 75mL of water, mixing 0.5g of the prepared silicon dioxide nanospheres in the solution, uniformly dispersing by ultrasonic, transferring to a 100 mL-specification polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction in a 180 ℃ oven for 12h, cooling, filtering, washing with water and ethanol sequentially, carrying out heat treatment on the powder collected after drying at 800 ℃ in Ar atmosphere for 2h, adding the obtained black powder into 20mL of 20% hydrofluoric acid solution, stirring to remove a silicon dioxide template, filtering and drying sequentially to obtain the nitrogen-doped carbon nanospheres with the barb-shaped structure.
Step three, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres:
ultrasonic treating of 100mg of flower-type carbon nanospheres and 100mg of CTAB (cetyl trimethyl ammonium bromide) in 30ml of deionized water for 2 hours, adding 25mg of ammonium molybdate tetrahydrate into the solution, continuing ultrasonic treating for 1 hour, transferring the solution into a 100ml reaction kettle, and carrying out hydrothermal reaction in an oven, wherein the reaction time is 10 hours, and the reaction temperature is 200 ℃. And then carrying out suction filtration on the solution, drying the solution at 100 ℃ for 10h, collecting the obtained solid powder, and annealing the solid powder in a tube furnace, wherein the ratio of argon to ammonia is 90:10, the carbonization temperature is 800 ℃, the carbonization time is 2h, and the heating rate is 5 ℃/min, so that the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere Mo-N-CNF-10% with the Mo content of 10% is obtained.
Step four, preparing the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres/sulfur:
mixing and ball-milling the molybdenum and nitrogen co-doped flower-shaped carbon nanospheres prepared in the third step according to the proportion of 85 percent of sulfur filled, filling the mixture into a volumetric flask with the specification of 25 multiplied by 40, reacting in an oven at 165 ℃ for 12 hours, and cooling to room temperature after the reaction is finished to obtain the nitrogen-doped barbed carbon nanosphere/sulfur composite material Mo-N-CNF/S85-10 percent.
And (3) knotting: the variables for examples 1, 2, 3 were different in molybdenum content and a comparison of the properties was made at 72% loading. Examples 2, 5 are both 10% molybdenum with the variation that example 5 is 85% sulfur loaded compared to example 2.
In order to verify the electrochemical performance of the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material prepared in examples 1-5 of the invention, the composite material is prepared into a positive pole piece, and then the positive pole piece and a metal lithium negative pole piece are assembled into a button cell. The method comprises the following specific steps: and uniformly mixing the prepared molybdenum and nitrogen co-doped flower-type carbon nanosphere/sulfur composite material, conductive carbon and 5% PVDF in a mass ratio of 8:1:1 while adding a proper amount of NMP, uniformly stirring for 24 hours to form slurry with a certain viscosity, uniformly coating the slurry on a smooth aluminum foil by using a 150-micrometer automatic coating instrument, and drying in a vacuum drying oven at 60 ℃ for 10 hours. Then, a 12mm slicer is used for manufacturing a circular pole piece, a CR2025 button battery shell is used for assembling the battery, and the whole assembling process is carried out in a glove box. The glove box is required to be filled with high-purity argon shielding gas, and the water content and the oxygen content are both less than 0.1 ppm. To makeThe obtained pole piece is a positive pole, a commercial PP film is a diaphragm, a metal lithium piece is a negative pole, a gasket elastic sheet is added and placed into a battery shell according to a specific sequence, and 1mol L of the gasket elastic sheet is added in a proper amount-1Lithium bistrifluoromethanesulfonimide (LiTFSI) was dissolved in 1, 3-dioxolane DOL ethylene glycol dimethyl ether DME solution at a volume ratio of 1:1 and contained 1.0% LiNO3The assembled battery is tightly sealed by a battery packaging machine and is kept stand for 12 hours to be tested.
Electrochemical application: placing the button cell on a cell cabinet to test the rate capability, and respectively setting seven programs of 0.2C, 0.5C, 1C, 2C, 3C, 5C and 0.2C, wherein each program runs five circles to detect the rate capability of the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere lithium-sulfur cell; and meanwhile, the cycle performance of the molybdenum and nitrogen co-doped flower-shaped carbon nanosphere lithium-sulfur battery is tested by cycling 500 cycles under the 1C program.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material is characterized in that: the flower-shaped carbon nanosphere is formed by doping molybdenum and nitrogen into a flower-shaped carbon nanosphere framework in a covalent bond mode, the flower-shaped carbon nanosphere framework is formed by unfolding and arranging a plurality of petal-shaped porous carbon sheets with one end as a common base point and the other end in a petal shape, and the covalent bond comprises a C-Mo bond and a C-N bond.
2. The molybdenum-nitrogen co-doped flower-type carbon nanosphere/sulfur composite of claim 1, wherein: the diameter of the molybdenum-nitrogen co-doped flower-type carbon nanosphere is 200-250nm, the thickness of the petal-type porous carbon sheet is 8-20nm, the gap between the petal-type carbon walls is 10-30nm, and the overall specific surface area of the material is 400-600m2g-1The pore volume is 1.1-1.8cm3g-1Left and right.
3. The molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material as claimed in claim 1, wherein: the mass fraction of the molybdenum atoms in the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres is 4-10%, and the mass fraction of the nitrogen in the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres is 4-8%.
4. The molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material as claimed in claim 1, wherein: nitrogen in the composite material is derived from the use of precursor chitosan and the introduction of ammonia gas in the annealing process, and molybdenum is derived from the introduction of molybdate in the hydrothermal process.
5. The molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material as claimed in claim 1, wherein: the non-crystalline sulfur enters the pore structure of the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres through the capillary action after being melted by sulfur, and is uniformly dispersed on the petal-shaped porous carbon sheets, wherein the mass fraction of the non-crystalline sulfur accounts for 65-75 wt%.
6. A preparation method of a molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material is characterized by comprising the following steps of:
(1) preparing hard template silicon dioxide nanospheres;
(2) ultrasonically dissolving and dispersing the silicon dioxide nanosphere mixed chitosan prepared in the step (1) in deionized water to form a uniform mixed solution, transferring the mixed solution to a reaction kettle for carbonization, performing suction filtration, washing and drying once to obtain coffee powder, annealing in an argon atmosphere, and etching a silicon dioxide nanosphere hard template by using an etching solution to obtain a flower-type carbon nanosphere;
(3) ultrasonically dispersing the flower-shaped carbon nanospheres and hexadecyl trimethyl ammonium bromide in water, then adding molybdate into the solution for further ultrasonic dispersion, pouring the solution with uniform ultrasonic dispersion into a reaction kettle for hydrothermal reaction, performing suction filtration, drying and collecting powder; carrying out high-temperature annealing treatment on the obtained powder in the mixed gas atmosphere of argon and ammonia gas to obtain molybdenum-nitrogen co-doped flower-shaped carbon nanospheres;
(4) and assembling a sulfur simple substance in the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres by a melt infiltration method to obtain the corresponding molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material.
7. The method comprises the following steps:
(1) synthesis of hard template silicon dioxide nanospheres
Adding 2g of cetyl pyridine bromide and 1.2g of urea into 60ml of deionized water, ultrasonically dissolving to form a homogeneous mixed solution of the cetyl pyridine bromide and the urea, preparing a mixed solution of 60 cyclohexane, 5ml of n-amyl alcohol and 5g of tetraethyl orthosilicate, mixing the two solutions into a three-neck flask with a proper volume, mechanically stirring for 1h at room temperature, wherein the stirring speed is between 500 and 2500rmp, then transferring the mixed solution into a reaction kettle, reacting for 6h at 120 ℃, then sequentially filtering, washing and drying to obtain a light yellow or white solid, and calcining for 6h at 550 ℃ in a muffle furnace to obtain silicon dioxide nanospheres;
(2) preparation of flower-shaped nanospheres
Taking 0.5g of the silicon dioxide nanospheres prepared in the step (1), mixing 1g of chitosan, ultrasonically dissolving and dispersing in 75ml of deionized water to form a uniform mixed solution, transferring the mixed solution to a reaction kettle, reacting in a 180 ℃ oven for 12 hours, carrying out suction filtration, washing and drying once to obtain coffee powder, annealing in an argon atmosphere of a 800 ℃ tube furnace for 2 hours, and etching away a silicon dioxide nanosphere hard template by using an etching solution to obtain a flower-shaped carbon nanosphere;
(3) preparation of molybdenum-nitrogen co-doped flower-type carbon nanospheres
Weighing 100mg of the flower-type carbon nanosphere obtained in the step (2) and 100mg of cetyl trimethyl ammonium bromide serving as a surfactant in 30ml of water, ultrasonically dispersing, then adding 12-50 mg of molybdate into the solution for further ultrasonic dispersion, pouring the solution with uniform ultrasonic dispersion into a reaction kettle, carrying out hydrothermal reaction in a drying oven at 200 ℃ for 10 hours, carrying out suction filtration, drying and collecting powder; annealing the powder at the high temperature of 800 ℃ for 2h in the mixed gas atmosphere of argon and ammonia gas to obtain a target product molybdenum-nitrogen co-doped flower-shaped carbon nanosphere;
(4) preparation of molybdenum and nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material
And (3) ball-milling and uniformly mixing the molybdenum-nitrogen co-doped flower-shaped carbon nanospheres prepared in the step (3) and elemental sulfur according to the mass ratio of 3:7, putting the mixture into a volumetric flask, reacting in an oven at 165 ℃ for 12 hours, and cooling to room temperature after the reaction is finished to obtain the nitrogen-doped barbed carbon nanosphere/sulfur composite material.
8. The method for preparing the molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material as claimed in claim 6, wherein the volume ratio of argon gas to ammonia gas in the annealing atmosphere in the step (3) is 9:1-7: 3.
9. A method for applying the molybdenum-nitrogen co-doped flower-type carbon nanosphere/sulfur composite material in the positive electrode of a lithium-sulfur battery based on the molybdenum-nitrogen co-doped flower-type carbon nanosphere/sulfur composite material in any one of claims 1 to 5, wherein the method comprises the following steps: uniformly mixing the molybdenum-nitrogen co-doped flower-shaped carbon nanosphere/sulfur composite material, conductive carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector in vacuum at the temperature of 60 ℃, and then rolling and slicing the aluminum foil current collector to obtain the lithium-sulfur battery anode.
10. A lithium-sulfur battery comprises a negative electrode, electrolyte, a diaphragm and a shell, and is characterized in that: the lithium-sulfur battery positive electrode prepared by the method of claim 8, wherein the negative electrode is a lithium sheet, and the electrolyte is a mixed solution of lithium bistrifluoromethylsulfonate imide, lithium nitrate, ethylene glycol dimethyl ether and 1, 3-dioxane, wherein the molar concentration of the lithium bistrifluoromethylsulfonate imide is 1mol L-1The mass fraction of lithium nitrate is 1%, and the volume ratio of ethylene glycol dimethyl ether to 1, 3-dioxane is 1: 1.
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