CN114005985B - 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 N-C@MoS of the invention 2 The composite material integrates the high capacity of layered molybdenum disulfide, multiple active sites doped with heteroatom nitrogen and high conductivity of soft carbon, is used as a negative electrode material of a sodium ion battery, has excellent electrochemical performance, is prepared by a spray pyrolysis technology, has mild required conditions, is simple and easy to operate, has low cost, is easy to dope, and 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
Sodium metal is a natural source of abundance in various advanced energy storage systems due to its low cost, and Sodium Ion Batteries (SIBs) are considered as the best alternatives to Lithium Ion Batteries (LIBs). Molybdenum disulfide (MoS) 2 ) The vanadium layered compound with the graphene-like structure has larger specific surface area and high theoretical specific capacity, and is widely focused as a negative electrode material of a sodium ion battery, but the vanadium layered compound still has a plurality of defects, such as: low intrinsic conductivity, serious polarization and low material utilization rate. In addition, the interlayer spacing of molybdenum disulfide is 0.62nm, the specific sodium ion radius
Much larger but due to the large amount of Na during charge and discharge + Internal stresses caused by diffusion still lead to a large volume expansion, limiting MoS 2 Practical application in SIBs.
Aiming at the characteristics, moS is 2 The electrochemical performance of the composite material is improved by combining the composite material with various high-conductivity carbonaceous matrixes.
Chinese patent CN106450181a discloses a method for preparing a molybdenum disulfide/nitrogen doped carbon nanofiber tube-in-tube structure composite material. The synthesis process of the material is as follows: dissolving ammonium thiomolybdate and polymethyl methacrylate in a solvent, carrying out electrostatic spinning to obtain polymethyl methacrylate/ammonium thiomolybdate nanofiber, drying, carrying out plasma surface treatment and in-situ polymerization to obtain a fiber with polypyrrole coated on the surface, washing, drying, carrying out high-temperature reduction under an argon/hydrogen mixed gas, and carrying out high-temperature carbonization under an argon condition. However, the method has complicated synthesis process, complex operation and high risk of the electrostatic spinning in relation to high-voltage conditions; the waste materials remained in the reaction of each step are difficult to recycle and use, and resource waste is easy to cause; moS in nanofiber tube-in-tube structures 2 The concentration of (2) is difficult to effectively and accurately regulate. Chinese patent CN109904408A discloses a MoS 2 A preparation method of a composite material with nano sheets embedded in a carbon substrate. The material is prepared by placing an ammonium tetrathiomolybdate precursor in a specific reaction device at high temperature and high pressure to form MoS 2 C nanocomposite. The carbon substrate can effectively prevent MoS 2 Is capable of relieving MoS 2 Volume expansion during charge and discharge and improved conductivity. But it has the following disadvantages: the synthesis process is complicated, the operation danger coefficient is high, and the high-temperature and high-pressure process is involved; the implementation conditions are severe. Chinese patent CN109346723a discloses a MoS based on molybdenum foil loading 2 The preparation method of the nano-sheet array structure. The material is MoO 3 And S powder is used as evaporation source, moS is directly grown on the molybdenum foil by chemical vapor deposition 2 A nanoplatelet array structure. However, the production process involves various chemical reactions of various materials, and has high requirements on equipment; in addition, the S powder which is a reaction source participating in deposition is inflammable, explosive, toxic and ring-aligningThe pollution to the environment is large. Chinese patent CN107799757a discloses a MoS 2 A preparation method of a nitrogen-doped carbon sodium ion battery anode material. The material takes melamine sponge as a template, and grows a layer of MoS under the hydrothermal condition 2 And (3) carbonizing at high temperature to obtain a unique three-dimensional hollow structure. However, the production process is relatively complex, high in energy consumption and high in danger, and relates to the processes of high-temperature high-pressure hydrothermal and subsequent high-temperature flame roasting, and waste materials in the production process are difficult to recycle and use, so that resource waste is easily caused. Chinese patent CN112938941a discloses a method for preparing nitrogen-sulfur co-doped graphene-molybdenum disulfide nanocomposite, which comprises dissolving thiourea and molybdenum source in ethanol, stirring in constant-temperature water bath to obtain solution gel, drying and sintering at high temperature to obtain nanocomposite. However, the method requires a long time, consumes large energy and is not suitable for mass production.
Literature (Elctrochim acta.285 (2018) 301-308) reports a nitrogen doped carbon nanofiber @ MoS 2 A preparation method of a nano-sheet. The material synthesizes nitrogen doped carbon nano fiber through electrostatic spinning, and then the fiber, molybdenum salt and thiourea are hydrothermally annealed and grown to obtain MoS 2 The nano-sheet has good sodium storage performance due to the enhanced conductivity by being compounded with carbon. But the production process is complicated, and involves multi-step reactions such as electrostatic spinning and high-temperature hydrothermal reaction, annealing and the like. And the electrostatic spinning process has complex device, needs higher electric field intensity and has high danger. Document (RSC adv.5 (2015) 34777-34787) reports a defective MoS 2 A graphene nanoplatelet three-dimensional porous composite material. The material takes sodium thiomolybdate as a sulfur source and a molybdenum source, hydrogen is introduced at a high temperature of 750 ℃ as a reducing agent, ammonium thiomolybdate is reduced to generate MoS on the surface of carbon fiber 2 However, in this method, hydrogen is explosive and has a high risk.
Literature (Can J Chem Eng.90 (2012) 330-335) in SiO 2 As a carrier, polystyrene latex as a template, (NH) 4 ) 2 MoS 4 Spherical MoS is synthesized from raw materials by ultrasonic spray pyrolysis 2 /SiO 2 A composite material. The document (Appl Surf Sci.523 (2020) 146470) first atomizes a solution containing a molybdenum salt into a high-temperature diffusion flameThe flame takes propane gas as fuel, oxygen is continuously injected to maintain the height and temperature (3000 ℃) of the flame, and the MoO is prepared by ultrasonic flame spray pyrolysis 3 Nanoparticles, then with thiourea in Ar/H 2 Under the condition of reduction to MoS 2 Finally, poly-dopamine is coated and carbonized at high temperature to synthesize MoS 2 NC composite nanoparticle material.
On the whole, synthesize MoS 2 The preparation methods of the base materials are various, but there are many disadvantages, such as: the traditional hydrothermal method has the defects of harsh reaction conditions, low yield, more uncontrollable factors and poor repeatability; the sol-gel method has long period and high requirement on raw materials; the electrostatic spinning method has complicated production process and high production cost; the high-temperature calcination method has high risk and causes great pollution to the environment. Therefore, it is important to find a preparation process which is mild in reaction condition, high in raw material utilization rate, low in cost and environment-friendly.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a molybdenum disulfide composite nitrogen-doped carbon material which is formed by coating MoS with a nitrogen-doped carbon layer 2 The laminated structure of the anode material can be used as the anode material of the battery to improve the conductivity of the anode material, and can also effectively relieve the huge volume change of the electrode active material in the charge and discharge process.
In order to achieve the above purpose, the invention provides a molybdenum disulfide composite nitrogen-doped carbon material, which is of a lamellar structure, wherein the material comprises molybdenum disulfide and a carbon layer coated on the surface of the molybdenum disulfide, 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 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 further aims to provide a preparation method of the molybdenum disulfide composite nitrogen-doped carbon material, wherein the N-C@MoS with a lamellar structure is prepared by a spray pyrolysis method 2 Composite material for solving the existing MoS preparation 2 The method for doping the carbon material with nitrogen has the problems of complicated operation, harsh conditions and low utilization rate of raw materials.
In order to achieve the above 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 matters to obtain graphite-like carbon nitride (g-C) 3 N 4 )；
S2, g-C prepared in the step S1 3 N 4 Ultrasonically dispersing ammonium tetrathiomolybdate in deionized water, sequentially adding a carbon-coated precursor and an initiator, and carrying out in-situ polymerization to obtain a composite material precursor;
s3, carrying out spray pyrolysis on the composite material precursor prepared in the step S2;
s4, carbonizing the product of spray pyrolysis in the step S3 at high temperature in a protective atmosphere, and cooling to obtain N-C@MoS 2 A composite material.
Preferably, in step S1, g-C is prepared 3 N 4 The specific process of (2) is as follows: heating the nitrogen-rich organic matter to 400-600 ℃ at a heating rate of 2-5 ℃/min, and calcining for 2-4 h at a temperature maintaining time to obtain g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the 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-C 3 N 4 The mass ratio of (2) is 1 (0.5-3).
Preferably, in step S2, the time of the ultrasonic dispersion is 2 to 4 hours.
Preferably, in step S2, the carbon-coated precursor is at least one of pyrrole, aniline, dopamine and thiophene, and the initiator is ammonium persulfate.
Further preferably, the molar ratio of the carbon-coated precursor and the initiator is 1 (1-3).
Preferably, in the step S2, the reaction temperature of the in-situ polymerization is 0-5 ℃ and the reaction time is 12-14 h.
Preferably, in the 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 ℃.
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 the step S4, the protective atmosphere is nitrogen, the high-temperature carbonization process is to heat up to 600-900 ℃ at a heating rate of 2-10 ℃/min, and the heat is preserved for 2-4 h.
According to another aspect of the invention, the invention also provides application of the molybdenum disulfide composite nitrogen-doped carbon material in preparation of a negative electrode material of a sodium ion energy storage device.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
(1) The molybdenum disulfide composite nitrogen-doped carbon material is prepared into a special lamellar structure by utilizing the advantages of large specific surface area and high theoretical specific capacity of molybdenum disulfide, and the carbon coating layer is arranged on the outermost layer, so that the conductivity of the material can be improved, and the volume effect in the charge-discharge process can be relieved; the introduction of heteroatom N on the carbon layer can provide a number of active sites for the material.
(2) The N-C@MoS of the invention 2 The preparation method of the composite material is simple and the synthesis period is short. At present prepare MoS 2 The 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 strong; and in many aspects of control of crystal nucleus formation process and crystal growth process, there is no in-depth research, so that experiment repeatability is poor and batch experiment is inconvenient to scale up. The invention utilizes a spray pyrolysis one-step method, has simple preparation steps and good repeatability, and the obtained product has high yield and uniform component dispersion.
(3) The preparation method of the invention has the advantages of abundant synthetic raw materials, no strict limitation, green and pollution-free, simple using 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 pushing effect on preparing and developing SIBs electrodes with high performance and long cycle life.
(4) N-C@MoS prepared by the method 2 The composite material is used as a negative electrode material of a sodium ion battery, circulates for 100 circles under the current density of 200mA/g, and the specific capacity can still be maintained to be about 542mAh/g, so that the composite material has excellent electrochemical performance.
Drawings
FIG. 1 is a process flow diagram of the preparation of 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 invention 2 SEM images of the negative electrode material of the sodium ion battery;
FIG. 3 is a N-C@MoS prepared in example 1 of the present invention 2 An X-ray diffraction pattern of a negative electrode material of the sodium ion battery;
FIG. 4 is a graph of N-C@MoS prepared in example 1 of the invention 2 A charge-discharge curve diagram of the negative electrode material of the sodium ion battery;
FIG. 5 is a N-C@MoS prepared in example 1 of the present invention 2 Cycling performance diagram of the negative electrode material of sodium ion battery.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of 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 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 negative electrode material is applied to a negative electrode material of a sodium ion energy storage device, is convenient for sodium ion deintercalation due to a special lamellar structure, and can effectively relieve MoS 2 The huge volume change in the charge and discharge process improves the circulation stability of the anode material; by introducing heteroatom nitrogen, more active sites for sodium storage can be provided, which results in 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 matters to obtain graphite-like carbon nitride (g-C) 3 N 4 )；
S2, g-C prepared in the step S1 3 N 4 Ultrasonically dispersing ammonium tetrathiomolybdate in deionized water, sequentially adding a carbon-coated precursor and an initiator, and carrying out in-situ polymerization to obtain a composite material precursor;
s3, carrying out spray pyrolysis on the composite material precursor prepared in the step S2;
s4, carbonizing the product of spray pyrolysis in the step S3 at high temperature in a protective atmosphere, and cooling to obtain N-C@MoS 2 A composite material.
The invention utilizes the ammonium tetrathiomolybdate to reduce and synthesize MoS 2 And by combining with g-C 3 N 4 The carbon-coated precursor is subjected to one-step compounding and then spray pyrolysis, so that MoS can be effectively inhibited 2 Providing more active sites for sodium storage (by g-C 3 N 4 A large number of nitrogen atoms provided by the decomposition); the laminated structure of the composite material can facilitate the sodium ion deintercalation and relieve MoS 2 Volume change during charge and discharge. The preparation method has the advantages that the raw materials are easy to obtain, the reaction condition is mild, the operation is simple and convenient, the cost can be greatly reduced, and the experimental safety is improved.
In some embodiments, in step S1, g-C is prepared 3 N 4 The specific process of (2) is as follows: heating the nitrogen-rich organic matter to 400-600 ℃ at a heating rate of 2-5 ℃/min, and calcining for 2-4 h at a temperature maintaining time to obtain g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, g-C is prepared 3 N 4 The temperature rising rate is 3 ℃/min-5 ℃/min, the calcining temperature is 500 ℃ to 550 ℃, and the heat preservation time is 2 h-3 h. Nitrogen-rich organics include, but are not limited toGuanidine hydrochloride, urea, melamine or thiourea, preferably the nitrogen-rich organic is urea.
In some embodiments, in step S2, ammonium tetrathiomolybdate and g-C 3 N 4 The mass ratio of (2) is 1 (0.5-3), preferably 1 (0.8-1.2), and more preferably 1:1. If the content of the ammonium tetrathiomolybdate is too low, the formation of molybdenum disulfide is not facilitated, or the content (active load) of the molybdenum disulfide in the composite material is low. g-C 3 N 4 And the time for ultrasonic dispersion of the ammonium tetrathiomolybdate is 2-4 hours.
In some embodiments, in step S2, the carbon-coated precursor includes, but is not limited to, pyrrole, aniline, dopamine or thiophene, preferably the precursor is pyrrole. The initiator is ammonium persulfate. The molar ratio of the carbon coating precursor to the initiator is 1 (1-3). The reaction temperature of the polymerization of the carbon-coated precursor 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-20L/min, the atomization power is 10W-20W, the pyrolysis temperature is 300-500 ℃, the outlet temperature is 30-40 ℃, and the collector current is 0.02A-0.04A.
In some embodiments, in step S4, the protective atmosphere used in the high-temperature carbonization process is nitrogen, and the temperature is maintained for 2-4 hours after the temperature is raised to 600-900 ℃ at a heating rate of 2-10 ℃/min. Preferably, the heating rate is 5-10 ℃/min, the reaction temperature is 700-800 ℃, and the heat preservation time is 2-3 h.
The following describes the above technical scheme in detail with reference to specific embodiments.
Example 1
The embodiment provides an N-C@MoS 2 The preparation method of the sodium ion battery anode material comprises the following steps:
g-C 3 N 4 is prepared from the following steps: 10g of urea is weighed and placed in a crucible, the temperature is raised to 550 ℃ at a heating rate of 5 ℃/min, the urea is calcined in a muffle furnace for 2 hours, and the crude product is obtained after cooling to room temperature. Will beThe crude product is filtered, washed and dried to obtain g-C 3 N 4 。
(NH 4 ) 2 MoS 4 Preparation of a @ CN@PPY precursor: weigh 260mg (NH) 4 ) 2 MoS 4 Dissolved in 90mL deionized water, and 240mg g-C was added 3 N 4 Ultrasonic dispersing for 4h, adding 180 mu L of monomer pyrrole, adding 1.8g of initiator ammonium persulfate after ultrasonic treatment for 30min, and stirring at 5 ℃ for reacting for 12h to obtain (NH) 4 ) 2 MoS 4 @CN@PPY precursor.
N-C@MoS 2 Preparing a sodium ion battery anode material: will (NH) 4 ) 2 MoS 4 Spray pyrolysis of the precursor @ CN@PPY, wherein 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. The obtained product is placed in a tube furnace for further high-temperature carbonization, the temperature is raised to 700 ℃ at the heating rate of 5 ℃/min, and the heat is preserved for 2 hours, thus obtaining the final product N-C@MoS 2 。
Morphology and structure, composition testing
As shown in FIG. 2, N-C@MoS 2 Is a typical lamellar structure which can facilitate the deintercalation of sodium ions and can alleviate MoS 2 Volume change during charge and discharge; FIG. 3 is an N-C@MoS 2 As can be seen from the XRD pattern of (c): N-C@MoS 2 All diffraction peaks are associated with hexagonal phase MoS 2 (JCPDS 37-1492) match, which shows that MoS is successfully synthesized 2 The method comprises the steps of carrying out a first treatment on the surface of the Furthermore, the peak appearing at the position of 2θ=26° corresponds to (002) of amorphous carbon due to the formation of polypyrrole by high-temperature carbonization, indicating that carbon was successfully coated with MoS 2 The 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 cycling stability of the anode material. The mass fraction of molybdenum disulfide in the composite material is about 60% by thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS), and the carbon-nitrogen atomic ratio in the carbon layer is about 4:1.
Electrochemical performance test
As shown in FIG. 4 (charge-discharge curve), for N-C@MoS 2 Negative sodium ion batteryThe electrode material is subjected to electrochemical test, and charge and discharge curves of the 5 th turn and the 10 th turn of the cycle almost coincide, so that the electrode has high reversibility. As shown in FIG. 5 (cycle performance chart), for N-C@MoS 2 Electrochemical test is carried out on the negative electrode material of the sodium ion battery, and N-C@MoS is carried out under the current density of 200mA/g 2 The specific discharge capacity of the electrode is kept stable, and 542mAh/g can be maintained after the electrode is cycled for 100 circles.
Example 2
The embodiment provides an N-C@MoS 2 The preparation method of the sodium ion battery anode material comprises the following steps:
g-C 3 N 4 is prepared from the following steps: 10g of guanidine hydrochloride is weighed and placed in a crucible, the temperature is raised to 500 ℃ at a heating rate of 3 ℃/min, the mixture is calcined in a muffle furnace for 3 hours, and the mixture is cooled to room temperature to obtain a crude product. Filtering, washing and drying the crude product to obtain g-C 3 N 4 。
(NH 4 ) 2 MoS 4 Preparation of @ CN@PANI precursor: 80mg (NH) 4 ) 2 MoS 4 Dissolved in 90mL deionized water, and 240mg g-C was added 3 N 4 Ultrasonic dispersing for 3h, adding 180 mu L of monomer aniline, adding 1.8g of initiator ammonium persulfate after ultrasonic treatment for 30min, and stirring at 2 ℃ for reacting for 12h to obtain (NH) 4 ) 2 MoS 4 @CN@PANI precursor.
N-C@MoS 2 Preparing a sodium ion battery anode material: will (NH) 4 ) 2 MoS 4 Spray pyrolysis of the precursor @ CN@PANI, wherein 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. The obtained product is placed in a tube furnace for further high-temperature carbonization, the temperature is raised to 900 ℃ at the heating rate of 10 ℃/min, and the heat is preserved for 2 hours, thus obtaining the final product N-C@MoS 2 。
Through detection, N-C@MoS prepared in the embodiment 2 The negative electrode material of the sodium ion battery has excellent electrochemical performance, and circulates for 100 circles under the current density of 200mA/g, and the N-C@MoS 2 The specific discharge capacity of the negative electrode material of the sodium ion battery can be maintained at 524mAh/g.
Example 3
The embodiment provides an N-C@MoS 2 The preparation method of the sodium ion battery anode material comprises the following steps:
g-C 3 N 4 is prepared from the following steps: example g-C 3 N 4 The procedure for the preparation of (C) is as in example 1 g-C 3 N 4 The preparation steps are the same.
(NH 4 ) 2 MoS 4 Preparation of a @ CN@PPY precursor: 480mg (NH) 4 ) 2 MoS 4 Dissolved in 90mL deionized water, and 240mg g-C was added 3 N 4 Ultrasonic dispersing for 4h, adding 360 mu L of monomer pyrrole, adding 3.6g of initiator ammonium persulfate after ultrasonic treatment for 30min, and stirring at 0 ℃ for reacting for 12h to obtain (NH) 4 ) 2 MoS 4 @CN@PPY precursor.
N-C@MoS 2 Preparing a sodium ion battery anode material: will (NH) 4 ) 2 MoS 4 Spray pyrolysis of the precursor @ CN@PPY, wherein the atomization power is 20W, the carrier gas is nitrogen, the flow rate is 20L/min, the pyrolysis temperature is 350 ℃, the outlet temperature is 35 ℃, and the collector current is 0.04A. The obtained product is placed in a tube furnace for further high-temperature carbonization, the temperature is raised to 800 ℃ at the heating rate of 8 ℃/min, and the heat is preserved for 3 hours, thus obtaining the final product N-C@MoS 2 。
Through detection, N-C@MoS prepared in the embodiment 2 The negative electrode material of the sodium ion battery has excellent electrochemical performance, and circulates for 100 circles under the current density of 200mA/g, and the N-C@MoS 2 The specific discharge capacity of the negative electrode material of the sodium ion battery can be maintained to be 525mAh/g.
Example 4
The embodiment provides an N-C@MoS 2 The preparation method of the sodium ion battery anode material comprises the following steps:
g-C 3 N 4 is prepared from the following steps: example g-C 3 N 4 The procedure for the preparation of (C) is as in example 1 g-C 3 N 4 The preparation steps are the same.
(NH 4 ) 2 MoS 4 Preparation of a @ CN@PPY precursor: this example (NH) 4 ) 2 MoS 4 The procedure for the preparation of @ CN@PPY was as described in example 1 (NH) 4 ) 2 MoS 4 The preparation procedure for the @ CN@PPY was the same.
N-C@MoS 2 Preparing a sodium ion battery anode material: will (NH) 4 ) 2 MoS 4 Spray pyrolysis of the precursor @ CN@PPY, wherein 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. The obtained product is placed in a tube furnace for further high-temperature carbonization, the temperature is raised to 700 ℃ at the heating rate of 10 ℃/min, and the heat is preserved for 2 hours, thus obtaining the final product N-C@MoS 2 。
Through detection, N-C@MoS prepared in the embodiment 2 The negative electrode material of the sodium ion battery has excellent electrochemical performance, and circulates for 100 circles under the current density of 200mA/g, and the N-C@MoS 2 The specific discharge capacity of the negative electrode material of the sodium ion battery can be maintained to be 540mAh/g.
From the above examples, it can be seen that the N-C@MoS prepared according to the present invention 2 The negative electrode material of the sodium ion battery has excellent electrochemical performance, high specific capacity and good cycling stability.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A preparation method of a molybdenum disulfide composite nitrogen-doped carbon material is characterized by comprising the following steps: 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%;
the preparation method of the molybdenum disulfide composite nitrogen-doped carbon material comprises the following steps:
s1, roasting the nitrogen-rich organic matters to obtain g-C 3 N 4 ；
S2, g-C prepared in the step S1 3 N 4 And performing ultrasonic dispersion on the ammonium tetrathiomolybdate in deionized water, sequentially adding a carbon-coated precursor and an initiator, and performing in-situ polymerization to obtain a composite material precursor, wherein the carbon-coated precursor is at least one of pyrrole, aniline, dopamine and thiophene, and the initiator is ammonium persulfate;
s3, carrying out spray pyrolysis on the composite material precursor prepared in the step S2, wherein the pyrolysis temperature is 300-500 ℃, carrier gas for spray pyrolysis is nitrogen, and the flow rate of the carrier gas is 10-20L/min;
s4, carbonizing the product of spray pyrolysis in the step S3 at high temperature in a protective atmosphere, and cooling to obtain N-C@MoS 2 The high-temperature carbonization temperature of the composite material is 600-900 ℃.
2. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 1, wherein the method comprises the following steps: in step S1, g-C is prepared 3 N 4 The specific process of (2) is as follows: heating the nitrogen-rich organic matter to 400-600 ℃ at a heating rate of 2-5 ℃/min, and calcining for 2-4 h at a temperature maintaining time to obtain g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the The nitrogen-rich organic matter is at least one of guanidine hydrochloride, urea and melamine.
3. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 1, wherein the method comprises the following steps: in step S2, the ammonium tetrathiomolybdate and the g-C 3 N 4 The mass ratio of (2) is 1 (0.5-3).
4. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 1, wherein the method comprises the following steps: the molar ratio of the carbon coating precursor to the initiator is 1 (1-3).
5. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 1, wherein the method comprises the following steps: in the step S2, the reaction temperature of the in-situ polymerization is 0-5 ℃ and the reaction time is 12-14 h.
6. The method for preparing the molybdenum disulfide composite nitrogen-doped carbon material according to claim 1, wherein the method comprises the following steps: in the step S4, the protective atmosphere is nitrogen, the heating rate in the high-temperature carbonization process is 2-10 ℃/min, and the temperature is kept for 2-4 h.
7. The application of the molybdenum disulfide composite nitrogen-doped carbon material prepared by the preparation method of the molybdenum disulfide composite nitrogen-doped carbon material according to claim 1 is characterized in that: the method is applied to the preparation of the negative electrode material of the sodium ion energy storage device.
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