CN112331834B - Bulb-shaped O-MXn/C nano reactor and preparation method and application thereof - Google Patents

Bulb-shaped O-MXn/C nano reactor and preparation method and application thereof Download PDF

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CN112331834B
CN112331834B CN202011259401.0A CN202011259401A CN112331834B CN 112331834 B CN112331834 B CN 112331834B CN 202011259401 A CN202011259401 A CN 202011259401A CN 112331834 B CN112331834 B CN 112331834B
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巩飞龙
王翊骁
弓丽华
孟二超
张永辉
李峰
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Zhengzhou University of Light Industry
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Abstract

The invention belongs to the technical field of controllable preparation of transition metal chalcogenide materials, and relates to a bulb-shaped O-MXna/C nano reactor, a preparation method and application thereof. The method can controllably prepare the monodisperse bulb-shaped O-MX with adjustable X vacancy gradient and short-range uniform compounding of carbon and active materials by strictly controlling the formation of microemulsion, the ion exchange kinetic process and the heat treatment processnThe material prepared by the/C nano reactor has high-rate lithium storage performance and excellent cycle durability, and has great potential in the application field of lithium batteries.

Description

Bulb-shaped O-MXn/C nano reactor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of controllable preparation of transition metal chalcogenide materials, and relates to a bulb-shaped O-MXna/C nano reactor, a preparation method and application thereof.
Background
China has the advantages of abundant high-grade molybdenum/tungsten ore resources. The Luoyang Koelreuterio group company, Mo, is the first five Mo producers and the largest W producer worldwide. The three-channel molybdenum/tungsten ore which is fully owned and operated by the molybdenum industry of Luoyang is the molybdenum ore with the maximum proven world molybdenum reserves and the molybdenum ore with the second largest proven world tungsten reservesTungsten ore. Molybdenum/tungsten and related materials are key materials for high-tech device/product development, and related resources are valuable strategic assets in China. However, in many chemical material (including molybdenum/tungsten and related materials) manufacturing enterprises in our province, there are urgent problems of how to improve the technological content and the technical competitiveness of products, and break through the material concepts mainly based on resources and primary products. Most representative MoS2Materials are examples, which have unique physical and chemical properties, such as: the layers are combined by weak van der waals force, the band gap is adjustable from 1.2 to 1.9 eV, the theoretical specific capacity (670 mAh/g) is high, and the like, and the lithium ion battery cathode material is considered to be one of the lithium ion battery cathode materials with microstructure regulation and control and application prospects.
However, a single MoS is used2The lithium ion battery cathode material has limitations in performance, such as poor conductivity, excessive volume change during lithium removal/insertion, collapse of electrode material, and the like. In order to prepare a lithium ion battery cathode material with excellent performance, two or more materials are often adopted for compounding. MoS was first synthesized as described in the literature (Chemistry-A European Journal, 2018, 24, 11220)2Carbonizing the precursor to obtain MoS2C, microspheres; chinese patent (CN 111653750A) discloses a preparation method of a carbon nitride modified molybdenum disulfide lithium ion battery cathode material, which comprises the steps of firstly synthesizing carbon nitride, and then obtaining C through hydrothermal reaction3N4/MoS2Composite/material. Although the method strengthens MoS to a certain extent2The structure of the material is stable, but the compounding mode of the two materials belongs to ex-situ reaction, and the composite material obtained by the way has higher surface energy, carbon and MoS2Are not tightly complexed, i.e. carbon and MoS2The short-range recombination cannot be carried out, and lithium ions show difficult kinetic migration in the charging and discharging processes, so that the electrode materials prepared by the methods have limited improvement on the lithium storage performance. In addition, Chinese patent (CN 111755672A) discloses a preparation method and application of a molybdenum disulfide coated molybdenum dioxide negative electrode material, and the reversible capacity of the prepared material is 600 mAh/g after the prepared material is circulated for 120 circles under the current density of 0.2A/g; literature (Small 2019,15, 1805420) reportA molybdenum disulfide and carbon hybrid material is used as a lithium ion battery cathode, and the reversible capacity is 380 mAh/g after the material is circulated for 300 circles under the current density of 1A/g. In addition, the chinese invention patent (CN 2019110109709) discloses a preparation method of molybdenum sulfide/three-dimensional macroporous graphene; the Chinese invention patent (CN 2019106101634) adopts a method of combining electrostatic self-assembly and CVD to synthesize CNT/MoS2A composite material. Although the method realizes the improvement of the electrochemical lithium storage performance of the material, the method still has poor effect under the long-term circulation condition of high multiplying power (more than or equal to 5A/g), and simultaneously has the scientific problems of complex preparation process, difficult control of material microstructure, uneven compounding of carbon and active materials and the like.
Disclosure of Invention
In order to solve the technical problem, the invention provides a bulb-shaped O-MXna/C nano reactor, a preparation method and application thereof.
The technical scheme of the invention is realized as follows:
bulb-shaped O-MXnThe preparation method of the/C nano reactor comprises the following steps:
(1) respectively preparing an M salt water solution S1 solution and a cationic surfactant glycerol solution S2 solution;
(2) dropwise adding the S1 solution in the step (1) into the S2 solution to form water-in-oil microemulsion;
(3) adding an X compound into the microemulsion of the step (2), and preparing MX through hydrothermal reactionnA precursor;
(4) MX of step (3)nCarrying out heat treatment on the precursor to obtain the bulb-shaped O-MXna/C nano reactor.
The M salt in the step (1) is any one of sodium tungstate, ammonium tungstate, sodium molybdate or ammonium molybdate; the cationic surfactant is any one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, cetyl pyridine chloride, tetradecyl dimethyl pyridine ammonium bromide or tetradecyl dimethyl pyridine ammonium chloride.
The mass concentration of the S1 solution in the step (1) is 0.002-5 mmol/mL; the mass concentration of the S2 solution was 0.0025-0.4 mmol/mL.
The volume ratio of the S1 solution to the S2 solution in the step (2) is (0.5-100): 100.
the compound X in the step (3) is any one of thiourea, cysteine, selenourea, sodium selenate, biphenyl ditelluride or telluric acid; the mass ratio of the M salt to the X compound in the microemulsion is 1: (1-2), MXnThe value range of n in the precursor is 1.2-2.
The temperature of the hydrothermal reaction in the step (3) is 160-220 ℃, and the reaction time is 2-48 h.
The parameters of the heat treatment in the step (4) are as follows: the heating rate is 1-30 ℃/min, the calcination time is 0.5-8 h, the calcination temperature is 500-900 ℃, and the calcination atmosphere is inert gas.
Bulb-shaped O-MX prepared by the methodna/C nanoreactor, said bulb-like O-MXnM in the/C nano reactor is Mo or W, X is S, Se or Te, and the reactor has a monodisperse bulb-shaped morphology structure rich in X vacancies and uniform carbon recombination.
Bulb-shaped O-MXnThe application of the/C nano reactor in preparing a high-rate lithium storage material is characterized in that the lithium storage performance of the reactor is in a parabolic relation with X vacancy.
The invention has the following beneficial effects:
1. the invention takes a cationic surfactant as a soft template, and prepares the monodisperse bulb-shaped, X-vacancy-rich and uniform carbon-compounded O-MX in situ by combining a microemulsion method, ion exchange and heat treatment technologiesna/C nano reactor. The introduction of X vacancy and carbon can adjust the electronic structure of the material, effectively improve the intrinsic conductivity of the material and relieve the structural change and volume collapse of the material in the charge and discharge process.
2. The body bulb-shaped O-MX prepared by the inventionnThe electrochemical lithium storage test is carried out on the/C nano reactor, and the result shows that: at a current density of 5A/g, O-MXnThe electrode of the/C nano reactor is circulated for 700 timesAnd the specific capacity of 361 mAh/g is still maintained, and excellent rate capability and durability are shown.
3. The invention provides a universal method for preparing a high-rate lithium storage material by introducing abundant vacancies and uniform carbon recombination in a sulfide carrier, and the material obtained by the method has better high-rate performance and cycling stability.
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 described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows MoS in example 12Field Emission Scanning Electron Microscope (FESEM) photographs of the precursors.
FIG. 2 is the O-MoS in example 11.5Field Emission Scanning Electron Microscope (FESEM) photographs of/C nanoreactors.
FIG. 3 shows O-MoS in example 11.5Elemental surface analysis diagram of/C nano-reactor.
FIG. 4 shows O-MoS in example 11.5XRD pattern of/C nano-reactor.
FIG. 5 shows O-MoS in example 11.5Multiplying power performance diagram of the/C nano reactor electrode.
FIG. 6 shows O-MoS in example 11.5Cycle performance diagram of/C nanoreactor electrodes at a current density of 5A/g.
FIG. 7 shows Electron Paramagnetic Resonance (EPR) spectra of the nanoreactors of examples 4, 5, 6 and 7.
FIG. 8 is a graph showing results of an element analysis Table (EDS) and X-ray photoelectron spectroscopy (XPS) of the nano-reactor in examples 4, 5, 6, and 7.
FIG. 9 is a graph comparing reversible capacities of the nanoreactor electrodes of examples 4, 5,1, and 7 after cycling for 200 cycles at a current density of 5A/g.
FIG. 10 shows O-WS in example 81.2a/C nanoreactor Field Emission Scanning Electron Microscope (FESEM) photograph.
FIG. 11 shows O-MoSe in example 101.8a/C nanoreactor Field Emission Scanning Electron Microscope (FESEM) photograph.
FIG. 12 shows O-MoTe in example 121.5a/C nanoreactor Field Emission Scanning Electron Microscope (FESEM) photograph.
FIG. 13 shows O-WSe in example 131.2a/C nanoreactor Field Emission Scanning Electron Microscope (FESEM) photograph.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 0.1 mmol of sodium molybdate in 1 mL of aqueous solution to form S1 solution; dissolving 0.5mmol of dodecyl trimethyl ammonium bromide in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 0.1 mmol of corresponding cysteine into the microemulsion; finally carrying out hydrothermal reaction for 2h at 220 ℃ to prepare MoS2The FESEM photograph of the precursor is shown in FIG. 1, and the morphology of the precursor is in the shape of a hollow open bulb.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 20 ℃/min, the calcination time is 6 h, the calcination temperature is 700 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoS1.5The FESEM photo of the/C nano-reactor is shown in figure 2: O-MoS obtained by heat treatment1.5The shape and structure of the/C nano reactor are not changed and still are monodisperse and bulb-shaped, but the carbon polymer in the precursor is carbonized in situ to obtain carbon and activityAn electrode material of short-range recombination of materials; the element plane analysis diagram is shown in FIG. 3, and the O-MoS is known from FIG. 31.5Four elements of Mo, S, C and O exist in the/C nano reactor and are uniformly distributed; the XRD pattern is shown in figure 4, and the material can be proved to be a composite of molybdenum disulfide and carbon by the XRD pattern of figure 4.
Example 2
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 5mmol of sodium molybdate in 50 mL of aqueous solution to form S1 solution; dissolving 20mmol of dodecyl trimethyl ammonium chloride in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 10 mmol of corresponding cysteine into the microemulsion; finally, carrying out hydrothermal reaction for 48 h at 160 ℃ to prepare MoS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 20 ℃/min, the calcination time is 6 h, the calcination temperature is 700 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoS1.5a/C nano reactor.
Example 3
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium molybdate in 30 mL of aqueous solution to form S1 solution; dissolving 10 mmol of hexadecyl pyridine bromide in 100 mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 5mmol of thiourea into the microemulsion; finally carrying out hydrothermal reaction for 24 h at 200 ℃ to prepare MoS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 20 ℃/min, the calcination time is 6 h, the calcination temperature is 700 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoS1.5a/C nano reactor.
Example 4
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium molybdate in 30 mL of aqueous solution to form S1 solution; dissolving 10 mmol of hexadecyl pyridine bromide in 100 mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 5mmol of thiourea into the microemulsion; finally carrying out hydrothermal reaction for 24 h at 200 ℃ to prepare MoS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, placing sulfur powder at the upstream of a heating tube, wherein the heating rate is 5 ℃/min, the calcination time is 8 h, the calcination temperature is 900 ℃, the calcination atmosphere is argon, and the product is the body-shaped bulb-shaped O-MoS2The EPR spectrum of the/C nano-reactor is shown in figure 7. As is apparent from FIG. 7, since sulfur powder was added during the heat treatment, the heat treatment resulted in O-MoS free from S vacancies2a/C nano reactor. The EDS and XPS results are shown in FIG. 8, and it can be seen from FIG. 8 that the material containing no S vacancies is obtained in this example.
Example 5
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium molybdate in 30 mL of aqueous solution to form S1 solution; dissolving 10 mmol of hexadecyl pyridine bromide in 100 mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 5mmol of thiourea into the microemulsion; finally carrying out hydrothermal reaction for 24 h at 200 ℃ to prepare MoS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 10 ℃/min, the calcination time is 6 h, the calcination temperature is 800 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoS1.8The EPR spectrum of the/C nano-reactor is shown in figure 7, and the EDS and XPS results are shown in figure 8.
Example 6
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium molybdate in 30 mL of aqueous solution to form S1 solution; 10 mmol of hexadecyl bromideDissolving pyridine in 100 mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 5mmol of thiourea into the microemulsion; finally carrying out hydrothermal reaction for 24 h at 200 ℃ to prepare MoS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 20 ℃/min, the calcination time is 6 h, the calcination temperature is 700 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoS1.5The EPR spectrum of the/C nano-reactor is shown in figure 7, and the EDS and XPS results are shown in figure 8.
Example 7
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium molybdate in 30 mL of aqueous solution to form S1 solution; dissolving 10 mmol of hexadecyl pyridine bromide in 100 mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 5mmol of thiourea into the microemulsion; finally carrying out hydrothermal reaction for 24 h at 200 ℃ to prepare MoS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 30 ℃/min, the calcination time is 6 h, the calcination temperature is 500 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoS1.2The EPR spectrum of the/C nano reactor is shown in figure 7, the EDS and XPS result graph is shown in figure 8, the place with the g factor of 2.003 in the EPR spectrum is a standard site of the S vacancy, and as can be seen from figure 7, the doping amount of O can be controlled by changing the heat treatment parameters so as to realize the controllable adjustment of the S vacancy. The faster the temperature rise rate and the lower the heat treatment temperature, the more the amount of O doping and the richer the corresponding S vacancies. The above conclusion can also be obtained from the EDS and XPS results of fig. 8. FIG. 9 is a graph comparing the capacity of the nanoreactor electrodes of examples 4, 5,1, and 7 after cycling at 5A/g for 200 cycles. It can be seen that: O-MoS1.5the/C electrode has the most suitable S vacancy concentration and shows the highest reversible capacity (412 mAh g)-1）。
Example 8
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 5mmol of sodium tungstate in 50 mL of aqueous solution to form S1 solution; dissolving 20mmol of dodecyl trimethyl ammonium chloride in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 10 mmol of corresponding cysteine into the microemulsion; finally, carrying out hydrothermal reaction for 48 h at 160 ℃ to prepare WS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 30 ℃/min, the calcination time is 6 h, the calcination temperature is 500 ℃, the calcination atmosphere is argon, and the product is the body-shaped bulb-shaped O-WS1.2The FESEM photograph of the/C nano-reactor is shown in FIG. 10.
Example 9
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium tungstate in 30 mL of aqueous solution to form S1 solution; dissolving 10 mmol of dodecyl dimethyl benzyl ammonium chloride in 100 mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 5mmol of thiourea into the microemulsion; finally carrying out hydrothermal reaction at 200 ℃ for 24 h to prepare WS2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 10 ℃/min, the calcination time is 6 h, the calcination temperature is 800 ℃, the calcination atmosphere is argon, and the product is the body-shaped bulb-shaped O-WS1.8a/C nano reactor.
Example 10
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 5mmol ammonium molybdate in 50 mL aqueous solution to form S1 solution; dissolving 20mmol of dodecyl trimethyl ammonium chloride in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 10 mmol of corresponding selenourea into the microemulsion; finally carrying out hydrothermal reaction at 160℃ for 48h, preparing MoSe2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 10 ℃/min, the calcination time is 6 h, the calcination temperature is 800 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoSe bulb1.8The FESEM photograph of the/C nanoreactor is shown in FIG. 11.
Example 11
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of sodium molybdate in 30 mL of aqueous solution to form S1 solution; dissolving 15 mmol of dodecyl trimethyl ammonium chloride in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 7mmol of corresponding selenourea into the microemulsion; finally, carrying out hydrothermal reaction for 48 h at 180 ℃ to prepare MoSe2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 10 ℃/min, the calcination time is 6 h, the calcination temperature is 800 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoSe bulb1.8a/C nano reactor.
Example 12
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of sodium molybdate in 30 mL of aqueous solution to form S1 solution; dissolving 15 mmol of dodecyl trimethyl ammonium chloride in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 7mmol of corresponding telluric acid into the microemulsion; finally carrying out hydrothermal reaction for 48 h at 180 ℃ to prepare MoTe2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 20 ℃/min, the calcination time is 6 h, the calcination temperature is 700 ℃, the calcination atmosphere is argon, and the product is the bubbly O-MoTe1.5The FESEM photograph of the/C nanoreactor is shown in FIG. 12.
Example 13
A lamp of the present embodimentVesicular O-MXnThe preparation method of the/C nano reactor comprises the following steps:
dissolving 0.1 mmol of sodium tungstate in 1 mL of aqueous solution to form S1 solution; dissolving 0.5mmol of dodecyl trimethyl ammonium bromide in 50-200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 0.1 mmol of corresponding selenourea into the microemulsion; finally, carrying out hydrothermal reaction for 2h at 220 ℃ to prepare WSe2The FESEM photograph of the precursor is shown in FIG. 1.
Putting the precursor into a tube furnace for heat treatment, wherein the heating rate is 30 ℃/min, the calcining time is 6 h, the calcining temperature is 500 ℃, the calcining atmosphere is argon, and the product is the body-shaped bulb-shaped O-WSe1.2The FESEM photograph of the/C nanoreactor is shown in FIG. 13.
Example 14
A bulb-shaped O-MX of this examplenThe preparation method of the/C nano reactor comprises the following steps:
dissolving 3 mmol of ammonium tungstate in 30 mL of aqueous solution to form S1 solution; dissolving 15 mmol of dodecyl trimethyl ammonium chloride in 200mL of glycerol to form an S2 solution; dropwise adding the S1 solution into the S2 solution to form water-in-oil microemulsion; adding 7mmol of corresponding biphenyl ditelluride into the microemulsion; finally, carrying out hydrothermal reaction for 48 h at 180 ℃ to prepare the WTE2And (3) precursor.
Placing the precursor in a tube furnace for heat treatment, wherein the heating rate is 30 ℃/min, the calcination time is 6 h, the calcination temperature is 500 ℃, the calcination atmosphere is argon, and the product is the bubbly O-WTE1.2a/C nano reactor.
Examples of the effects of the invention
According to the conventional manufacturing method of button batteries, the O-MoS prepared in the example 1 is used1.5the/C nano reactor electrode is used as a button cell cathode for testing, the rate performance graph is shown in figure 5, and the cycle performance graph under the current density of 5A/g is shown in figure 6.
From FIG. 5, it can be seen that O-MoS1.5the/C nano reactor electrode has excellent rate performance, namely the reversible capacity is 361 mAh under the current density of 5A/g(ii)/g; under the current density of 10A/g, the reversible capacity is 211 mAh/g; the reversible capacity was 98 mAh/g at a current density of 20A/g.
As can be seen from FIG. 6, at a current density of 5A/g, O-MoS1.5The specific capacity of 361 mAh/g is still kept after 700 times of circulation of the/C nano reactor electrode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. Bulb-shaped O-MXnThe preparation method of the/C nano reactor is characterized by comprising the following steps:
(1) respectively preparing an M salt water solution S1 solution and a cationic surfactant glycerol solution S2 solution;
(2) dropwise adding the S1 solution in the step (1) into the S2 solution to form water-in-oil microemulsion;
(3) adding an X compound into the microemulsion of the step (2), and preparing MX through hydrothermal reactionnA precursor;
(4) MX of step (3)nCarrying out heat treatment on the precursor to obtain the bulb-shaped O-MXna/C nano reactor.
2. The bulbous O-MX of claim 1nThe preparation method of the/C nano reactor is characterized by comprising the following steps: the M salt in the step (1) is any one of sodium tungstate, ammonium tungstate, sodium molybdate or ammonium molybdate; the cationic surfactant is any one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, cetyl pyridine chloride, tetradecyl dimethyl pyridine ammonium bromide or tetradecyl dimethyl pyridine ammonium chloride.
3. The bulbous O-MX of claim 2nC nanometer transThe preparation method of the reactor is characterized by comprising the following steps: the mass concentration of the S1 solution in the step (1) is 0.002-5 mmol/mL; the mass concentration of the S2 solution was 0.0025-0.4 mmol/mL.
4. The bulbous O-MX of claim 1nThe preparation method of the/C nano reactor is characterized by comprising the following steps: the volume ratio of the S1 solution to the S2 solution in the step (2) is (0.5-100): 100.
5. the bulbous O-MX of claim 4nThe preparation method of the/C nano reactor is characterized by comprising the following steps: the compound X in the step (3) is any one of thiourea, cysteine, selenourea, sodium selenate, biphenyl ditelluride or telluric acid; the mass ratio of the M salt to the X compound in the microemulsion is 1: (1-2), MXnThe value range of n in the precursor is 1.2-2.
6. The bulbous O-MX of claim 5nThe preparation method of the/C nano reactor is characterized by comprising the following steps: the temperature of the hydrothermal reaction in the step (3) is 160-220 ℃, and the reaction time is 2-48 h.
7. The bulbous O-MX of claim 1nThe preparation method of the/C nano reactor is characterized in that the parameters of the heat treatment in the step (4) are as follows: the heating rate is 1-30 ℃/min, the calcination time is 0.5-8 h, the calcination temperature is 500-900 ℃, and the calcination atmosphere is inert gas.
8. Encapsulated O-MX prepared by the method of any one of claims 1 to 7nthe/C nano reactor is characterized in that: the bulb shape of O-MXnM in the/C nano reactor is Mo or W, X is S, Se or Te, and the reactor has a monodisperse bulb-shaped morphology structure rich in X vacancies and uniform carbon recombination.
9. The bulbous O-MX of claim 8nPreparation of high power/C nano reactorThe application of the lithium material is characterized in that: the lithium storage performance of the reactor is parabolic in relation to the X vacancies.
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