CN114005985A - Molybdenum disulfide composite nitrogen-doped carbon material and preparation method and application thereof - Google Patents
Molybdenum disulfide composite nitrogen-doped carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly discloses a molybdenum disulfide composite nitrogen-doped carbon material, and a preparation method and application thereof. The invention relates to N-C @ MoS2The composite material integrates the high capacity of the layered molybdenum disulfide, multiple active sites doped with heteroatom nitrogen and high conductivity of soft carbon, has excellent electrochemical performance when used as a sodium ion battery cathode material, is prepared by a spray pyrolysis technology, has mild required conditions, is simple and easy to implement, has low cost,the doping is easy to realize, and the method has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a molybdenum disulfide composite nitrogen-doped carbon material, and a preparation method and application thereof.
Background
Among various advanced energy storage systems, sodium metal is low in price and abundant in natural resources, and Sodium Ion Batteries (SIBs) are considered as the best substitute for Lithium Ion Batteries (LIBs). Molybdenum disulfide (MoS)2) The vanadium layered compound with a graphene-like structure has a large specific surface area and a high theoretical specific capacity, and attracts wide attention as a negative electrode material of a sodium-ion battery, but the vanadium layered compound still has many defects, such as: low intrinsic conductivity, severe polarization, and low material utilization. In addition, the distance between the molybdenum disulfide layers is 0.62nm, and the specific radius of sodium ions is
Much larger, but due to a large amount of Na during charging and discharging+Diffusion-induced internal stresses still result in large volume expansion, limiting MoS2The application in SIBs.
Aiming at the characteristics, MoS is added2The electrochemical performance of the carbon nano-tube is improved by combining with various high-conductivity carbon matrixes.
Chinese patent CN106450181A discloses a preparation method of a molybdenum disulfide/nitrogen-doped carbon nanofiber pipe sleeve structure composite material. The synthesis process of the material is as follows: dissolving ammonium thiomolybdate and polymethyl methacrylate in a solvent, performing electrostatic spinning to obtain polymethyl methacrylate/ammonium thiomolybdate nanofibers, drying, performing plasma surface treatment, performing in-situ polymerization to obtain fibers coated with polypyrrole, washing, drying, performing high-temperature reduction in an argon/hydrogen mixed gas, and then performing high-temperature carbonization under an argon condition. However, the method has complex synthetic process and complex operation, and electrostatic spinning has high danger related to high voltage conditions; the residual waste materials in the reaction of each step are difficult to recycle and easy to recycleResource waste is caused; MoS in nanofiber tube-in-tube structures2The concentration of (A) is difficult to effectively and accurately regulate and control. Chinese patent CN109904408A discloses a MoS2A method for preparing a nano sheet embedded in a carbon substrate composite material. The material is prepared by placing an ammonium tetrathiomolybdate precursor in a specific reaction device at high temperature and high pressure to form MoS2a/C nanocomposite material. The carbon substrate can effectively prevent MoS2To alleviate MoS2Volume expansion during charge and discharge and improved conductivity. However, it has the following disadvantages: the synthesis process is complicated, the operation risk coefficient is high, and the high-temperature and high-pressure process is involved; the implementation conditions are relatively harsh. Chinese patent CN109346723A discloses MoS based on molybdenum foil load2A preparation method of a nano-sheet array structure. The material is prepared by MoO3And S powder is used as an evaporation source, and MoS is directly grown on the molybdenum foil by a chemical vapor deposition method2A nanosheet array structure. But the production process involves various chemical reactions of various materials, and has high requirements on equipment; in addition, the reaction source S powder participating in deposition is flammable, explosive, toxic and large in environmental pollution. Chinese patent CN107799757A discloses a MoS2A preparation method of a nitrogen-doped carbon sodium ion battery cathode material. The material takes melamine sponge as a template, and a layer of MoS grows under the hydrothermal condition2And obtaining a unique three-dimensional hollow structure through high-temperature carbonization. But the production process is relatively complex, the energy consumption is high, the danger is large, the processes of high-temperature high-pressure water heating, subsequent high-temperature flame roasting and the like are involved, the waste materials in the production process are difficult to recycle, and the resource waste is easily caused. Chinese patent CN112938941A discloses a preparation method of a nitrogen and sulfur co-doped graphene-molybdenum disulfide nano composite material, which comprises the steps of dissolving thiourea and a molybdenum source in ethanol, stirring in a constant-temperature water bath to obtain solution gel, drying and sintering at high temperature to obtain the nano composite material. However, the method needs longer time and large energy consumption, and is not suitable for mass production.
The document (Elctrochim acta.285(2018)301-308) reports a nitrogen-doped carbon nanofiber @ MoS2A preparation method of the nano-sheet. The material is firstly synthesized into nitrogen-doped carbon nano-fiber by electrostatic spinning, and then the nitrogen-doped carbon nano-fiber is obtainedThe fibers are hydrothermally treated with molybdenum salt and thiourea, annealed and grown to obtain MoS2The nano sheet is compounded with carbon to enhance the conductivity, so that the nano sheet has good sodium storage performance. But the production process is complicated and involves multiple reactions such as electrostatic spinning, high-temperature hydrothermal reaction, annealing and the like. And the electrostatic spinning process device is complicated, needs higher electric field intensity and has high danger. The literature (RSC adv.5(2015)34777-2A graphene nanosheet three-dimensional porous composite material. The material takes sodium thiomolybdate as a sulfur source and a molybdenum source, hydrogen is introduced at the high temperature of 750 ℃ as a reducing agent, and ammonium thiomolybdate is reduced to generate MoS on the surface of carbon fiber2However, this method is highly dangerous because hydrogen is easily exploded.
The document (Can J Chem Eng.90(2012)330-2As carrier, polystyrene latex as template, (NH)4)2MoS4Spherical MoS is synthesized by ultrasonic spray pyrolysis of raw materials2/SiO2A composite material. The document (Appl Surf sci.523(2020)146470) first atomizes a solution containing molybdenum salt and makes it flow into a high-temperature diffusion flame, the flame uses propane gas as fuel, oxygen is continuously injected to maintain the height and temperature of the flame (3000 ℃), and the MoO is prepared by ultrasonic flame spray pyrolysis3Nanoparticles, then with thiourea in Ar/H2Reduction to MoS under conditions2Finally, coating with polydopamine, and synthesizing MoS through high-temperature carbonization2@ NC composite nanoparticle material.
To sum up, MoS is synthesized2The preparation methods of the base materials are various, but there are many disadvantages, such as: the traditional hydrothermal method has harsh reaction conditions, low yield and multiple uncontrollable factors, which causes poor repeatability; the sol-gel method has long required period and high requirement on raw materials; the electrostatic spinning method has complex production process and high production cost; the high-temperature calcination method has high danger and great pollution to the environment. Therefore, it is very important to find a preparation process with mild reaction conditions, high raw material utilization rate, low cost and environmental friendliness.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a molybdenum disulfide composite nitrogen dopantA heterocarbon material which is a nitrogen-doped carbon layer coated with MoS2The lamellar structure can improve the conductivity of the battery cathode material and effectively relieve the huge volume change of the electrode active material in the charge-discharge process, and the cathode material has excellent electrochemical performance.
In order to achieve the above object, the present invention provides a molybdenum disulfide composite nitrogen-doped carbon material, which is a lamellar structure, and comprises molybdenum disulfide and a carbon layer coated on the surface of the molybdenum disulfide, wherein carbon elements in the carbon layer are bonded with the molybdenum disulfide through van der waals force, the carbon layer is doped with nitrogen elements, and the nitrogen elements are bonded with the carbon elements in the carbon layer through chemical bonds; in the material, the mass fraction of molybdenum disulfide is 50-75%, and the mass fraction of carbon element is 20-40%.
The invention also aims to provide a preparation method of the molybdenum disulfide composite nitrogen-doped carbon material, which is used for preparing the N-C @ MoS with the lamellar structure by spray pyrolysis2Composite material aiming at solving the problem of the prior MoS preparation2The method for doping the carbon material with nitrogen has the problems of complex operation, harsh conditions and low utilization rate of raw materials.
In order to achieve the purpose, the invention provides a preparation method of a molybdenum disulfide composite nitrogen-doped carbon material, which comprises the following steps:
s1, roasting the nitrogen-rich organic matter to obtain graphite-like carbon nitride (g-C)3N4)；
S2, g-C prepared in the step S13N4And ammonium tetrathiomolybdate is ultrasonically dispersed in deionized water, then a carbon-coated precursor and an initiator are sequentially added, and in-situ polymerization is carried out to obtain a composite material precursor;
s3, carrying out spray pyrolysis on the composite material precursor prepared in the step S2;
s4, carbonizing the spray pyrolysis product of the step S3 at high temperature under the protective atmosphere, and cooling to obtain N-C @ MoS2A composite material.
Preferably, in step S1, g-C is prepared3N4The specific process is as follows: nitrogen-rich organic matter is treated at 2-5 deg.c/minHeating up to 400-600 ℃ at a heating rate, and carrying out heat preservation and calcination for 2-4 h to obtain g-C3N4(ii) a The nitrogen-rich organic matter is at least one of guanidine hydrochloride, urea, melamine and thiourea.
Preferably, in step S2, the ammonium tetrathiomolybdate and the g-C3N4The mass ratio of (1) to (0.5-3).
Preferably, in step S2, the ultrasonic dispersion time is 2h to 4 h.
Preferably, in step S2, the carbon-coated precursor is at least one of pyrrole, aniline, dopamine and thiophene, and the initiator is ammonium persulfate.
More preferably, the molar ratio of the carbon-coated precursor to the initiator is 1 (1-3).
Preferably, in step S2, the reaction temperature of the in-situ polymerization is 0 ℃ to 5 ℃, and the reaction time is 12h to 14 h.
Preferably, in step S3, the carrier gas for spray pyrolysis is nitrogen, the flow rate of the carrier gas is 10L/min to 20L/min, and the pyrolysis temperature is 300 ℃ to 500 ℃.
Further preferably, the atomization power of the spray pyrolysis is 10W-20W, the outlet temperature is 30-40 ℃, and the collector current is 0.02A-0.04A.
Preferably, in step S4, the protective atmosphere is nitrogen, and the high-temperature carbonization process is performed by heating to 600-900 ℃ at a heating rate of 2-10 ℃/min, and maintaining the temperature for 2-4 h.
According to another aspect of the invention, the invention also provides an application of the molybdenum disulfide composite nitrogen-doped carbon material, which is applied to the preparation of the cathode material of the sodium ion energy storage device.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the molybdenum disulfide composite nitrogen-doped carbon material provided by the invention utilizes the advantages of large specific surface area and high theoretical specific capacity of molybdenum disulfide to prepare a special lamellar structure, and the outermost layer is a carbon coating layer, so that the conductivity of the material can be improved, and the volume effect in the charging and discharging process can be relieved; the introduction of heteroatom N on the carbon layer can provide a large number of active sites for the material.
(2) The invention relates to N-C @ MoS2The preparation method of the composite material is simple and the synthesis period is short. Preparation of MoS at present2The general method of the composite material is a hydrothermal method, but the hydrothermal method needs high-temperature and high-pressure steps, so that the dependence on production equipment is stronger; and the hydrothermal method has poor experimental repeatability and is not convenient to be amplified into batch experiments due to the lack of deep research on the control of influencing factors in the crystal nucleus forming process and the crystal growth process of the hydrothermal method. The invention utilizes a spray pyrolysis one-step method, has simple preparation steps and good repeatability, and the obtained product has high yield and uniformly dispersed components.
(3) The preparation method has the advantages of abundant available synthetic raw materials, no strict limitation, no pollution, simple used equipment, low energy consumption, low cost and easy realization of heteroatom doping, can prepare various novel micro-nano structures by adjusting the process, can effectively improve the electrochemical performance of the materials, and has great promotion effect on preparing and developing SIBs electrodes with high performance and long cycle life.
(4) N-C @ MoS prepared by the invention2The composite material is used as a negative electrode material of a sodium ion battery, is circulated for 100 circles under the current density of 200mA/g, can still maintain the specific capacity of about 542mAh/g, and has excellent electrochemical performance.
Drawings
FIG. 1 is a flow chart of the process for preparing a molybdenum disulfide composite nitrogen-doped carbon material according to the present invention;
FIG. 2 is a graph of N-C @ MoS prepared in example 1 of the present invention2SEM image of the cathode material of the sodium ion battery;
FIG. 3 is a graph of N-C @ MoS prepared in example 1 of the present invention2An X-ray diffraction pattern of the sodium-ion battery negative electrode material;
FIG. 4 is a graph of N-C @ MoS prepared in example 1 of the present invention2A charge-discharge curve chart of the negative electrode material of the sodium-ion battery;
FIG. 5 is a graph of N-C @ MoS prepared in example 1 of the present invention2Cycle performance diagram of the negative electrode material of the sodium ion battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The molybdenum disulfide composite nitrogen-doped carbon material provided by the invention is of a lamellar structure, and comprises molybdenum disulfide and a carbon layer coated on the surface of the molybdenum disulfide, wherein carbon elements in the carbon layer are combined with the molybdenum disulfide through van der Waals force, nitrogen elements are doped in the carbon layer, and the nitrogen elements are combined with the carbon elements in the carbon layer through chemical bonds; in the material, the mass fraction of molybdenum disulfide is 50-75%, and the mass fraction of carbon element is 20-40%.
The outermost layer of the molybdenum disulfide composite nitrogen-doped carbon material is a carbon layer, so that the conductivity of the material can be improved; the lithium-ion battery anode material is applied to the cathode material of a sodium-ion energy storage device, facilitates the extraction of sodium ions due to the special lamellar structure, and can effectively relieve MoS2The great volume change in the charging and discharging process improves the cycle stability of the cathode material; by introducing heteroatom nitrogen, more sodium storage active sites can be provided, so that the sodium storage active sites have higher specific capacity.
On the other hand, as shown in fig. 1, the preparation method of the molybdenum disulfide composite nitrogen-doped carbon material provided by the invention comprises the following steps:
s1, roasting the nitrogen-rich organic matter to obtain graphite-like carbon nitride (g-C)3N4)；
S2, g-C prepared in the step S13N4And ammonium tetrathiomolybdate is ultrasonically dispersed in deionized water, then a carbon-coated precursor and an initiator are sequentially added, and in-situ polymerization is carried out to obtain a composite material precursor;
s3, carrying out spray pyrolysis on the composite material precursor prepared in the step S2;
s4, carbonizing the spray pyrolysis product of the step S3 at high temperature under the protective atmosphere, and cooling to obtain N-C @ MoS2A composite material.
The invention utilizes tetrasulfideReduction synthesis of MoS by ammonium paramolybdate2And by reaction with g-C3N4The carbon-coated precursor is compounded in one step and then spray pyrolysis is carried out, so that MoS can be effectively inhibited2Provides more active sites for sodium storage (via g-C)3N4A large number of nitrogen atoms provided by decomposition); and the lamellar structure of the composite material can facilitate the desorption of sodium ions and relieve MoS2Volume change during charging and discharging. The preparation method has the advantages of easily obtained raw materials, mild reaction conditions, simple and convenient operation, greatly reduced cost and improved experimental safety.
In some embodiments, in step S1, g-C is prepared3N4The specific process is as follows: heating the nitrogen-rich organic matter to 400-600 ℃ at the heating rate of 2-5 ℃/min, and calcining for 2-4 h to obtain g-C3N4(ii) a Preferably, g-C is prepared3N4The heating rate is 3 ℃/min to 5 ℃/min, the calcining temperature is 500 ℃ to 550 ℃, and the heat preservation time is 2h to 3 h. Nitrogen-rich organics include, but are not limited to, guanidine hydrochloride, urea, melamine, or thiourea, preferably the nitrogen-rich organics are urea.
In some embodiments, in step S2, ammonium tetrathiomolybdate and g-C3N4The mass ratio of (2) is 1 (0.5 to 3), preferably 1 (0.8 to 1.2), and more preferably 1: 1. If the ammonium tetrathiomolybdate content is too low, molybdenum disulfide formation is not favored, or the molybdenum disulfide content (active loading) in the composite is low. g-C3N4And the ultrasonic dispersion time of the ammonium tetrathiomolybdate is 2 to 4 hours.
In some embodiments, in step S2, the carbon-coated precursor includes, but is not limited to, pyrrole, aniline, dopamine or thiophene, and preferably, the precursor is pyrrole. The initiator is ammonium persulfate. The molar ratio of the carbon-coated precursor to the initiator is 1 (1-3). The reaction temperature of the carbon-coated precursor polymerization is 0-5 ℃, and the reaction time is 12-14 h. If the polymerization temperature is too high, side reactions in the polymerization process are increased, and more by-products are produced.
In some embodiments, in step S3, the carrier gas for spray pyrolysis is nitrogen, the carrier gas flow rate is 10L/min to 20L/min, the atomization power is 10W to 20W, the pyrolysis temperature is 300 ℃ to 500 ℃, the outlet temperature is 30 ℃ to 40 ℃, and the collector current is 0.02A to 0.04A.
In some embodiments, in step S4, the protective atmosphere used in the high-temperature carbonization process is nitrogen, and the temperature is raised to 600-900 ℃ at a temperature-raising rate of 2-10 ℃/min, and then the temperature is maintained for 2-4 h. Preferably, the heating rate is 5 ℃/min to 10 ℃/min, the reaction temperature is 700 ℃ to 800 ℃, and the heat preservation time is 2h to 3 h.
The above technical solution is described in detail below with reference to specific examples.
Example 1
This example provides an N-C @ MoS2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
g-C3N4the preparation of (1): weighing 10g of urea, placing the urea in a crucible, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining in a muffle furnace for 2h, and cooling to room temperature to obtain a crude product. The crude product is filtered, washed with water and dried to obtain g-C3N4。
(NH4)2MoS4@ CN @ PPY precursor preparation: weighing 260mg (NH)4)2MoS4Dissolved in 90mL of deionized water, and then added with 240mg g-C3N4Ultrasonic dispersion is carried out for 4h, 180 mu L monomer pyrrole is added, 1.8g initiator ammonium persulfate is added after 30min ultrasonic treatment, stirring reaction is carried out for 12h at the temperature of 5 ℃, and (NH) is obtained4)2MoS4@ CN @ PPY precursor.
N-C@MoS2Preparing a sodium ion battery negative electrode material: will be (NH)4)2MoS4Spray pyrolysis of the @ CN @ PPY precursor is carried out, the atomization power is 18W, the carrier gas is nitrogen, the flow rate is 15L/min, the pyrolysis temperature is 400 ℃, the outlet temperature is 38 ℃, and the collector current is 0.03A. Placing the obtained product in a tubular furnace for further high-temperature carbonization, heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h to obtain the final product N-C @ MoS2。
Morphology and Structure, compositional testing
As shown in FIG. 2, N-C @ MoS2Is a typical lamellar structure which can facilitate sodium ion deintercalation and can alleviate MoS2Volume change during charging and discharging; FIG. 3 is N-C @ MoS2Can be seen from the XRD profile of (a): N-C @ MoS2All diffraction peaks were associated with hexagonal phase MoS2(JCPDS 37-1492) matching, which shows that MoS is successfully synthesized2(ii) a In addition, the peak appearing at the position of 2 θ ═ 26 ° corresponds to (002) of amorphous carbon, which is formed due to the high temperature carbonization of polypyrrole, indicating that carbon successfully coats MoS2The carbon layer can improve the conductivity of the material, effectively relieve the volume change of the active material in the charge and discharge process, and improve the cycle stability of the cathode material. By thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS), the mass fraction of molybdenum disulfide in the composite was about 60%, and the carbon-nitrogen atomic ratio in the carbon layer was about 4: 1.
Electrochemical performance test
For N-C @ MoS, as shown in FIG. 4 (Charge and discharge curves)2The sodium ion battery negative electrode material is subjected to electrochemical test, and the charge and discharge curves of the 5 th circle and the 10 th circle are almost overlapped, which shows that the electrode has high reversibility. As shown in FIG. 5 (Loop Performance graph), for N-C @ MoS2The cathode material of the sodium-ion battery is subjected to electrochemical test, and N-C @ MoS is carried out at a current density of 200mA/g2The discharge specific capacity of the electrode is maintained stably, and 542mAh/g can be maintained after the electrode is cycled for 100 circles.
Example 2
This example provides an N-C @ MoS2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
g-C3N4the preparation of (1): weighing 10g of guanidine hydrochloride, placing the guanidine hydrochloride into a crucible, heating to 500 ℃ at the heating rate of 3 ℃/min, calcining in a muffle furnace for 3h, and cooling to room temperature to obtain a crude product. The crude product is filtered, washed with water and dried to obtain g-C3N4。
(NH4)2MoS4@ CN @ PANI precursor preparation: 80mg (NH) are weighed4)2MoS4Dissolved in 90mL of deionized water and thenAdding 240mg g-C3N4Ultrasonic dispersion is carried out for 3h, monomer aniline 180 mu L is added, 1.8g of initiator ammonium persulfate is added after 30min of ultrasonic treatment, stirring reaction is carried out for 12h under the condition of 2 ℃, and (NH) is obtained4)2MoS4@ CN @ PANI precursor.
N-C@MoS2Preparing a sodium ion battery negative electrode material: will be (NH)4)2MoS4Spray pyrolysis of the @ CN @ PANI precursor is carried out, the atomization power is 20W, the carrier gas is nitrogen, the flow rate is 15L/min, the pyrolysis temperature is 350 ℃, the outlet temperature is 35 ℃, and the collector current is 0.03A. Placing the obtained product in a tubular furnace for further high-temperature carbonization, heating to 900 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h to obtain the final product N-C @ MoS2。
By detection, the N-C @ MoS prepared in the example2The cathode material of the sodium-ion battery has excellent electrochemical performance, and can circulate for 100 circles under the current density of 200mA/g, wherein N-C @ MoS is2The specific discharge capacity of the negative electrode material of the sodium ion battery can be maintained at 524 mAh/g.
Example 3
This example provides an N-C @ MoS2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
g-C3N4the preparation of (1): examples g to C3N4Preparation procedure of (1) with g-C in example 13N4The preparation steps are the same.
(NH4)2MoS4@ CN @ PPY precursor preparation: weighing 480mg (NH)4)2MoS4Dissolved in 90mL of deionized water, and then added with 240mg g-C3N4Ultrasonic dispersion is carried out for 4h, 360 mu L monomer pyrrole is added, 3.6g initiator ammonium persulfate is added after 30min ultrasonic treatment, stirring reaction is carried out for 12h at the temperature of 0 ℃, and (NH) is obtained4)2MoS4@ CN @ PPY precursor.
N-C@MoS2Preparing a sodium ion battery negative electrode material: will be (NH)4)2MoS4Spray pyrolysis of @ CN @ PPY precursor with atomizing power of 20W, nitrogen as carrier gas, flow rate of 20L/min and pyrolysis temperature350 deg.C, exit temperature 35 deg.C, collector current 0.04A. Placing the obtained product in a tubular furnace for further high-temperature carbonization, heating to 800 ℃ at the heating rate of 8 ℃/min, and preserving heat for 3h to obtain the final product N-C @ MoS2。
By detection, the N-C @ MoS prepared in the example2The cathode material of the sodium-ion battery has excellent electrochemical performance, and can circulate for 100 circles under the current density of 200mA/g, wherein N-C @ MoS is2The specific discharge capacity of the negative electrode material of the sodium ion battery can be maintained at 525 mAh/g.
Example 4
This example provides an N-C @ MoS2The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
g-C3N4the preparation of (1): examples g to C3N4Preparation procedure of (1) with g-C in example 13N4The preparation steps are the same.
(NH4)2MoS4@ CN @ PPY precursor preparation: this example (NH)4)2MoS4Preparation procedure of @ CN @ PPY and example 1 (NH)4)2MoS4The preparation procedure was the same for @ CN @ PPY.
N-C@MoS2Preparing a sodium ion battery negative electrode material: will be (NH)4)2MoS4Spray pyrolysis of the @ CN @ PPY precursor is carried out, the atomization power is 20W, the carrier gas is nitrogen, the flow rate is 20L/min, the pyrolysis temperature is 500 ℃, the outlet temperature is 40 ℃, and the collector current is 0.03A. Placing the obtained product in a tube furnace for further high-temperature carbonization, heating to 700 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h to obtain the final product N-C @ MoS2。
By detection, the N-C @ MoS prepared in the example2The cathode material of the sodium-ion battery has excellent electrochemical performance, and can circulate for 100 circles under the current density of 200mA/g, wherein N-C @ MoS is2The specific discharge capacity of the negative electrode material of the sodium ion battery can maintain 540 mAh/g.
As can be seen from the above examples, the N-C @ MoS prepared by the present invention2The cathode material of the sodium ion battery has excellent electrochemical performance, high specific capacity and stable circulationThe qualitative is good.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The molybdenum disulfide composite nitrogen-doped carbon material is characterized in that: the material is of a lamellar structure and comprises molybdenum disulfide and a carbon layer coated on the surface of the molybdenum disulfide, wherein carbon elements in the carbon layer are combined with the molybdenum disulfide through van der Waals force, nitrogen elements are doped in the carbon layer, and the nitrogen elements are combined with the carbon elements in the carbon layer through chemical bonds; in the material, the mass fraction of molybdenum disulfide is 50-75%, and the mass fraction of carbon element is 20-40%.
2. A method for preparing the molybdenum disulfide composite nitrogen-doped carbon material as claimed in claim 1, characterized by comprising the following steps:
s1, roasting the nitrogen-rich organic matter to obtain g-C3N4；
S2, g-C prepared in the step S13N4And ammonium tetrathiomolybdate is ultrasonically dispersed in deionized water, then a carbon-coated precursor and an initiator are sequentially added, and in-situ polymerization is carried out to obtain a composite material precursor;
s3, carrying out spray pyrolysis on the composite material precursor prepared in the step S2;
s4, carbonizing the spray pyrolysis product of the step S3 at high temperature under the protective atmosphere, and cooling to obtain N-C @ MoS2A composite material.
3. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 2, characterized in that: in step S1, g-C is prepared3N4The specific process is as follows: heating the nitrogen-rich organic matter to 400-600 ℃ at the heating rate of 2-5 ℃/min, and calcining for 2-4 h to obtain g-C3N4(ii) a The nitrogen-rich organic matter is at least one of guanidine hydrochloride, urea, melamine and thiourea.
4. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 2, characterized in that: in step S2, the ammonium tetrathiomolybdate and the g-C3N4The mass ratio of (1) to (0.5-3).
5. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 2, characterized in that: in step S2, the carbon-coated precursor is at least one of pyrrole, aniline, dopamine, and thiophene, and the initiator is ammonium persulfate.
6. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 5, wherein: the molar ratio of the carbon-coated precursor to the initiator is 1 (1-3).
7. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 2, characterized in that: in step S2, the reaction temperature of the in-situ polymerization is 0-5 ℃, and the reaction time is 12-14 h.
8. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 2, characterized in that: in step S3, the carrier gas for spray pyrolysis is nitrogen, the flow rate of the carrier gas is 10L/min-20L/min, and the pyrolysis temperature is 300 ℃ to 500 ℃.
9. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 2, characterized in that: in step S4, the protective atmosphere is nitrogen, and the high-temperature carbonization process is to heat up to 600-900 ℃ at a heating rate of 2-10 ℃/min and keep the temperature for 2-4 h.
10. The application of the molybdenum disulfide composite nitrogen-doped carbon material as claimed in claim 1, wherein: the method is applied to the preparation of the cathode material of the sodium ion energy storage device.
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