CN110380028B - CNT/MoS 2 Lithium ion battery cathode material and preparation method thereof - Google Patents
CNT/MoS 2 Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a CNT/MoS 2 The negative electrode material of the lithium ion battery is prepared by the following method: 1) preparing a carbon oxide nanotube dispersion liquid; 2) preparation of OCNT/DC by electrostatic self-assembly + /MoO 4 2‑ (ii) a 3) CVD method for preparing CNT/SiO 2 /MoS 2 (ii) a 4) Etching SiO 2 Preparation of CNT/MoS 2 . The CNT/MoS provided by the invention 2 MoS in composite materials 2 The contact area with Li ions is larger, and MoS is improved 2 Electrochemical reactivity of (2), and further, CNT/MoS 2 MoS in composite material 2 The material is uniformly dispersed in the CNT network framework and is firmly combined, so that the material can obtain better cycling stability and rate capability when being applied to a lithium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to CNT/MoS 2 A lithium ion battery cathode material and a preparation method thereof.
Background
The electronic information industry has developed vigorously in recent years to highlight the advantages of LIBs (lithium ion batteries), such as small volume, long-term use, good environmental compatibility, and the like. However, the graphite negative electrode currently used in industry is limited by its specific capacity (372mAh/g), which hinders the application of LIB in hybrid electronic devices and electronic devices. Therefore, it is desirable to increase the specific capacity of the anode material.
In the past decades, with the introduction of nanomaterials, lithium ion battery anode materials with novel structures are being intensively explored. Among them, Transition Metal Disulfide (TMD) nanosheets have a two-dimensional (2D) structure and a large specific surface area compared to other bulk materials, which TMD materials have 2D characteristics, i.e., ultra-thin thickness and some unusual chemical, physical and electronic properties. When the TMD material is converted from a multilayer to a single layer, its energy band structure changes, from an indirect bandgap to a direct bandgap,and inter-valley spin coupling occurs. The peculiar photoelectric characteristics promote the application of the TMD material in the fields of information transmission, computers, lithium ion batteries, supercapacitors, health monitoring and the like, and endow the material with wide application prospects. The Mo-S bond in the molybdenum disulfide layer is a strong covalent bond, while the MoS2 layer is a weak bond coupled by Van der Waals forces, and thus it easily forms a single-layer structure, resulting in Li + The insertion/extraction is reversible. However, MoS 2 Electrodes suffer from large strain and low conductivity when cycled, resulting in rapid decay of electrode capacity and lower rate performance. There are two typical strategies to address these challenges: one is to synthesize MoS with nanometer thickness 2 A sheet to form a stable spatial structure, thereby relieving strain during cycling and obstacles to lithium ion diffusion; another approach is to grow MoS on carbon-based supports 2 To facilitate the migration of electrons and ions. CNTs (carbon nanotubes) have an extremely large specific surface area as a one-dimensional (1D) material. Theoretically, CNT and MoS will be combined 2 The materials are compounded, the respective advantages of the materials are embodied, and the high-performance lithium ion battery cathode material can be obtained. In the present study, CNT/MoS 2 The compound is mainly synthesized by a hydrothermal method, but the CNT/MoS synthesized by the hydrothermal method 2 The general crystallinity of the compound is lower, the number of lattice defects is more, the purity is not high, the effective insertion and removal of Li ions are hindered, and the electrochemical reversibility of the battery material is also influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing the CNT/MoS aiming at the defects in the prior art 2 The negative electrode material of the lithium ion battery takes CNT with a porous network structure as a framework and is two-dimensional MoS 2 The nano-sheets are uniformly and densely attached to the surface of the CNT, and the obtained negative electrode material has high specific capacity, good cycle stability and good rate capability.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provides a CNT/MoS 2 The lithium ion battery negative electrode material is prepared by the following method:
1) preparation of carbon nanotube Oxide (OCNT) dispersion: adding a multi-walled carbon nanotube, sulfuric acid and nitric acid into a three-neck flask, performing ultrasonic oxidation for 3-5 hours at the temperature of 40-50 ℃, filtering, washing and drying to obtain oxidized carbon nanotube powder, and adding the obtained oxidized carbon nanotube powder into deionized water to dissolve to obtain an OCNT dispersion liquid;
2) preparation of OCNT/DC by electrostatic self-assembly + /MoO 4 2- : adding DC5700 ((trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride) and ammonium molybdate tetrahydrate (H) into the OCNT dispersion liquid obtained in the step 1) 24 Mo 7 N 6 O 24 ·4H 2 O), stirring for 24h at room temperature for electrostatic self-assembly, dialyzing the obtained mixed solution for 72h, and drying after dialysis to obtain OCNT/DC + /MoO 4 2- A powder;
3) CVD method for preparing CNT/SiO 2 /MoS 2 : the OCNT/DC obtained in the step 2) + /MoO 4 2- Putting the powder and the sublimed sulfur powder into a tube furnace for annealing to obtain CNT/SiO 2 /MoS 2 A powder;
4) etching SiO 2 Preparation of CNT/MoS 2 : the CNT/SiO obtained in the step 3) 2 /MoS 2 Uniformly dispersing the powder in NaOH solution, stirring for 24h, washing the precipitate with deionized water and ethanol respectively, and vacuum drying to obtain CNT/MoS 2 And (3) powder.
According to the scheme, the length of the multi-wall carbon nanotube in the step 1) is 0.5-2 mu m, the tube diameter is less than 8nm, the purity is more than 95%, and the specific surface area is more than 500m 2 G, ash content < 1.5 wt.%. The surface of the carbon nano tube is damaged and oxidized by strong acid and then carries a certain amount of hydroxyl and carboxyl.
According to the scheme, the mass fraction of the sulfuric acid in the step 1) is 98%, the mass fraction of the nitric acid is 68%, and the mass volume ratio of the multi-walled carbon nanotube to the sulfuric acid to the nitric acid is 0.1-2 g: 120mL of: 40 mL.
According to the scheme, the concentration of the OCNT dispersion liquid in the step 1) is 1-10 mg/mL.
According to the scheme, the mass-to-volume ratio of the carbon oxide nanotubes to the silane coupling agent to the ammonium molybdate tetrahydrate in the OCNT dispersion liquid in the step 2) is 0.1-1 g: 2.5 mL: 2g of the total weight of the composition.
According to the scheme, the OCNT/DC in the step 3) + /MoO 4 2- The mass ratio of the powder to the sublimed sulfur powder is 1: 3 to 6.
According to the scheme, the annealing process conditions in the step 3) are as follows: heating to 800 ℃ at the room temperature and in the Ar atmosphere at the heating rate of 5 ℃/min, preserving the heat for 12h, and finally cooling along with the furnace. High temperature favors MoS 2 The crystal growth is realized, the longer reaction time is favorable for the complete grain growth, and the MoS with high crystallinity is synthesized based on the condition 2 。
According to the scheme, the concentration of the NaOH solution in the step 4) is 1mol/L, and the CNT/SiO 2 /MoS 2 The concentration of the powder dispersed in the NaOH solution is 1-10 g/L.
The invention also includes the CNT/MoS 2 The preparation method of the lithium ion battery cathode material comprises the following specific steps:
1) preparing a carbon oxide nanotube dispersion liquid: adding a multi-walled carbon nanotube, sulfuric acid and nitric acid into a three-neck flask, performing ultrasonic oxidation for 3-5 hours at the temperature of 40-50 ℃, filtering, washing and drying to obtain oxidized carbon nanotube powder, and adding the obtained oxidized carbon nanotube powder into deionized water to dissolve to obtain an OCNT dispersion liquid;
2) preparation of OCNT/DC by electrostatic self-assembly + /MoO 4 2- : adding DC5700 and ammonium molybdate tetrahydrate into the OCNT dispersion liquid obtained in the step 1), stirring at room temperature for 24 hours for electrostatic self-assembly, dialyzing the obtained mixed liquid for 72 hours, and drying after dialysis to obtain OCNT/DC + /MoO 4 2- Powder;
3) CVD method for preparing CNT/SiO 2 /MoS 2 : the OCNT/DC obtained in the step 2) + /MoO 4 2- Putting the powder and the sublimed sulfur powder into a tube furnace for annealing to obtain CNT/SiO 2 /MoS 2 Powder;
4) etching SiO 2 Preparation of CNT/MoS 2 : the CNT/SiO obtained in the step 3) 2 /MoS 2 Uniformly dispersing the powder in NaOH solution, stirring for 24h, washing precipitates with deionized water and ethanol respectively, and drying in vacuum to obtain the final productCNT/MoS 2 And (3) powder.
The invention firstly oxidizes the multi-wall carbon nano-tube to obtain oxidized carbon nano-tube powder with hydroxyl and carboxyl on the surface, and then carries out electrostatic self-assembly in the presence of DC5700 and ammonium molybdate tetrahydrate to obtain OCNT/DC + /MoO 4 2- Powder, the electrostatic self-assembly technique utilizes two groups of DC 5700: on one hand, the methoxy group of DC5700 is hydrolyzed to form a hydroxyl group in aqueous solution, and can react with the hydroxyl group and the carboxyl group on the OCNT to form a hydrogen bond; on the other hand, DC5700 itself has electron-deficient N + ions, and can form ionic bonds with negatively charged molybdate ions, so as to realize electrostatic self-assembly in an aqueous solution, the electrostatic self-assembly technology enables the OCNT, DC5700 and molybdate ions to be combined on a molecular layer, and the molybdate ions can be uniformly dispersed in a CNT network framework and firmly combined due to the action force of hydrogen bonds and ionic bonds. Then preparing CNT/SiO by CVD method 2 /MoS 2 Powder, MoS synthesized by CVD method 2 The thickness of the nano-sheet is only 3 layers, the nano-sheet is uniformly dispersed in the CNT skeleton matrix, and SiO is etched finally 2 Preparation of CNT/MoS 2 A lithium ion battery cathode material.
The invention has the beneficial effects that: 1. the CNT/MoS provided by the invention 2 MoS in composite material 2 The material is synthesized by a CVD method, compared with MoS synthesized by a hydrothermal method 2 Better crystallinity and higher purity, and the synthesized MoS 2 The precursor OCNT/DC with even dispersion of each phase is synthesized by a self-assembly method + /MoO 4 2- Powder of CNT/MoS obtained by CVD reaction 2 MoS in composite materials 2 The contact area with Li ions is larger, and MoS is improved 2 Electrochemical reactivity of (2). In addition, CNT/MoS 2 MoS in composite material 2 The material is uniformly dispersed in a CNT network framework and firmly combined, so that the material can obtain better circulation stability and rate capability when being applied to a lithium ion battery cathode material after post-treatment, and even when the current density is 4000mA/g, the electrode still keeps the structural stability and shows the high specific volume of 885m mAh/gAmount of the compound (A).
2. The invention adopts a self-assembly method to facilitate the synthesis of a precursor OCNT/DC with uniformly dispersed phases + /MoO 4 2- The method is simple and feasible, can be carried out at room temperature, and adopts a CVD method to prepare CNT/MoS at the later stage 2 The composite material has the advantages of simple required process system, high reaction speed, simplicity, convenience and high efficiency, can realize continuous large-area synthesis, and has industrial application prospect.
Drawings
FIG. 1 shows CNT/MoS prepared in example 1 of the present invention 2 Composite, Bulk MoS prepared in comparative example 1 2 And CNT/Bulk MoS prepared in comparative example 2 2 An X-ray electron diffraction (XRD) pattern of the complex;
FIG. 2 shows CNT/MoS prepared in example 1 2 Composite, Bulk MoS prepared in comparative example 1 2 And CNT/Bulk MoS prepared in comparative example 2 2 A Raman spectrum (Raman) map of the complex;
FIG. 3 shows CNT/MoS prepared in example 1 2 Composite, Bulk MoS prepared in comparative example 1 2 And CNT/Bulk MoS prepared in comparative example 2 2 A cycle performance curve and coulombic efficiency plot for the composite at 1000mA/g for 250 cycles;
FIG. 4 shows CNT/MoS prepared in example 1 2 Composite, Bulk MoS prepared in comparative example 1 2 And CNT/Bulk MoS prepared in comparative example 2 2 A rate performance graph of the composite;
FIG. 5 shows CNT/MoS prepared in example 1 2 Scanning Electron Microscope (SEM) images of the composite material.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
Preparation of CNT/MoS 2 The composite material comprises the following steps:
1) preparation of carbon oxide nanotube (OCNT) dispersion: weighing 1g of multi-wall carbon nano-tube (the length is 0.5-2 mu m, the tube diameter is less than 8nm, the purity is 95 percent, and the specific surface area is more than 500 m) 2 And/g, the ash content is less than 1.5wt percent), 120mL of sulfuric acid (with the mass fraction of 98 percent) and 40mL of nitric acid (with the mass fraction of 68 percent) are weighed and added into a three-neck flask together, ultrasonic oxidation is carried out for 5 hours at the temperature of 50 ℃, then suction filtration and washing are carried out until small molecules are completely removed and the pH value is close to 7, and then drying is carried out, so that carbon oxide nanotube powder is obtained. 0.25g of carbon oxide nanotube powder was added to 100mL of deionized water and sufficiently dispersed to obtain an OCNT dispersion.
2) Preparation of OCNT/DC by electrostatic self-assembly + /MoO 4 2- : 2.5mL of DC5700, 2g of ammonium molybdate tetrahydrate (H) was added to the above OCNT dispersion 24 Mo 7 N 6 O 24 ·4H 2 O), stirring with magnet at room temperature for 24h for electrostatic self-assembly, dialyzing the obtained mixed solution for 72h (Mw: 8000- + /MoO 4 2- Powder;
3) CVD method for preparing CNT/SiO 2 /MoS 2 : 2g of OCNT/DC prepared as described above + /MoO 4 2- Putting the powder and 10g of sublimed sulfur powder into a tube furnace, heating to 800 ℃ at the room temperature at the heating rate of 5 ℃/min in Ar atmosphere, carrying out heat preservation annealing at 800 ℃ for 12h, and finally cooling along with the furnace to obtain CNT/SiO 2 /MoS 2 A powder;
4) etching SiO 2 Preparation of CNT/MoS 2 : 0.2g of CNT/SiO prepared as described above was added 2 /MoS 2 Uniformly dispersing the powder in 50mL NaOH solution (1mol/L), stirring for 24h, washing precipitates with deionized water and ethanol respectively, and drying in vacuum to obtain CNT/MoS 2 A composite powder.
CNT/MoS prepared in this example was subjected to a Bruker D8DISCOVER target-rotating X-ray diffractometer 2 The components and the crystal structure of the composite material are tested, and the CNT/MoS prepared by the embodiment is subjected to a LabRAM HR Evolution Raman (Raman) spectrometer with the excitation wavelength of 633nm 2 The material composition and phase thickness of the composite material were tested. From the XRD spectrum of FIG. 1, CNT/MoS 2 The CNTs in the composite showed a weak diffraction peak at 25.8 ° for the (002) crystal plane of the carbon; MoS 2 Showing the electrical connections at 14.2, 32.6, 39.4, 44,diffraction peaks at 49.6 °, 58.4 °, 60.1 °, 69 °, corresponding to the (002), (100) + (101), (103), (006), (105), (110), (008), (200) + (201) crystal planes of molybdenum disulfide, respectively, indicate that the porous skeletal structure of the CNT acts as a nucleation template, resulting in well-crystallized MoS 2 . As seen by the Raman spectrum of fig. 2, the peaks at 1572 and 1345 are the CNT peaks, corresponding to the D and G peaks, respectively, of graphite; and fingerprint pattern E of molybdenum disulfide 1 2g And A 1g Are respectively positioned at 388.7cm -1 And 407cm -1 Description of CNT/MoS 2 Medium MoS 2 About 3 layers. CNT/MoS with LAND (CT2001A) battery system 2 Testing of the cycling stability and rate capability of the composite, CNT/MoS 2 The compound is an active substance of a lithium ion battery cathode material, the counter electrode is a lithium sheet, and the active substance: acetylene black: PVDF (w/w) ═ 8: 1: 1. as shown in FIG. 3, which is a cycle performance curve and coulombic efficiency chart of the composite material at 250 cycles under 1000mA/g, the CNT/MoS can be known by measuring the cycle stability 2 The initial capacity of the electrode is 1600mAh/g, which is close to the theoretical specific capacity of molybdenum disulfide of 1672mAh/g, the initial specific capacity under the current density of 1000mA/g is 1135mAh/g, and even after the electrode is circulated for 250 circles, the specific capacity is still 1066 mAh/g; as shown in FIG. 4, which is a graph of the rate capability of the composite material, it can be seen from the rate capability that CNT/MoS is measured even at a high current density of 4000mA/g 2 The electrode still exhibited a high specific capacity of 885 mAh/g. CNT/MoS prepared in this example was subjected to Zeiss Ultra Plus Field Emission Scanning Electron Microscopy (FESEM) 2 The morphology of the composite material is characterized, a scanning electron microscope image is shown in FIG. 5, and as can be seen from the image, the composite material is a porous network structure, wherein CNT is a bent tubular structure with the diameter of about 20-40nm, and an interconnected network structure, MoS, is formed 2 Nano-sheets are uniformly attached on CNT, CNT and MoS 2 The nanosheets are tightly bound.
Comparative example 1
Bulk MoS 2 (molybdenum disulfide bulk) purchased from Shanghai Allantin Biotechnology Ltd with a purity of 99.5%.
Comparison of this by Bruker D8DISCOVER target-transfer X-ray diffractometerExample Bulk MoS 2 The compositions and crystal structures of (1) were tested, and the Bulk MoS of this comparative example was analyzed by LabRAM HR Evolution Raman (Raman) spectrometer with an excitation wavelength of 633nm 2 The composition of the material, phase thickness were tested. Bulk MoS is shown by the XRD spectrum of FIG. 1 2 The crystallinity of (a) is high, showing all sharp diffraction peaks of molybdenum disulfide. Bulk MoS, as seen by Raman spectra in FIG. 2 2 Fingerprint peak E of 1 2g And A 1g Are respectively positioned at 385cm -1 And 411cm -1 Description of Bulk MoS 2 The number of layers (a) is many, exceeding 5. Bulk MoS using LAND (CT2001A) battery system 2 Test of cycling stability and rate capability of 2 The active material is the negative electrode material of the lithium ion battery, the counter electrode is a lithium sheet, and the active material: acetylene black: PVDF (w/w) ═ 8: 1: 1. shown in FIG. 3 as Bulk MoS 2 The cycle stability is measured by a cycle performance curve and a coulombic efficiency chart of 250 cycles under 1000mA/g, namely Bulk MoS 2 The initial capacity of the electrode is 950mAh/g, the initial specific capacity is 477mAh/g under the current density of 1000mA/g, and the specific capacity is only 82 mAh/g after the electrode is circulated for 250 circles; shown in FIG. 4 as Bulk MoS 2 The multiplying power performance graph shows that the Bulk MoS is measured under the condition of high current density of 4000mA/g 2 The electrode only exhibits a specific capacity of 12 mAh/g.
Comparative example 2
Preparation of CNT/Bulk MoS 2 The method comprises the following steps:
1) preparation of carbon nanotube Oxide (OCNT) dispersion: an OCNT dispersion was prepared in the same manner as in example 1.
2) Preparation of OCNT/DC/Bulk MoS 2 : 2.5mL of DC5700, 0.5g of Bulk MoS were added to the above OCNT dispersion 2 Stirring with magnet at room temperature for 24h, dialyzing the obtained mixture for 72h (Mw 8000- 2 Powder;
3) preparation of CNT/SiO by carbonization 2 /Bulk MoS 2 : 2g of OCNT/DC/Bulk MoS 2 The powder is placed in a tube oven and subsequently, in an Ar atmosphere, at room temperature in 5 ℃Heating to 800 deg.C at min heating rate, annealing at 800 deg.C for 12h, and cooling with furnace to obtain CNT/SiO 2 /Bulk MoS 2 ；
4) Etching SiO 2 Preparation of CNT/Bulk MoS 2 : 0.2g of CNT/SiO prepared as described above was added 2 /Bulk MoS 2 Uniformly dispersing the powder in 50mL NaOH solution (1mol/L), stirring for 24h, washing precipitates with deionized water and ethanol respectively, and drying in vacuum to obtain CNT/Bulk MoS 2 And (c) a complex.
CNT/Bulk MoS prepared for this comparative example using a Bruker D8DISCOVER target-rotating X-ray diffractometer 2 The components and the crystal structure of the composite are tested, and the CNT/Bulk MoS prepared in the comparative example is subjected to a LabRAM HR Evolution Raman (Raman) spectrometer with the excitation wavelength of 633nm 2 The composition of the material and the phase thickness of the composite were tested. From the XRD spectrum of FIG. 1, CNT/Bulk MoS 2 CNTs in composites versus Bulk MoS 2 The crystallinity of (2) is so much inferior that the diffraction peak thereof is not substantially seen. As can be seen from the Raman spectrum of FIG. 2, CNT/Bulk MoS 2 Fingerprint peak E of 1 2g And A 1g Are respectively positioned at 385cm -1 And 411cm -1 The number of layers is large, and exceeds 5. CNT/Bulk MoS with LAND (CT2001A) battery system 2 Testing of the cycling stability and rate capability of the composites, CNT/Bulk MoS 2 The compound is an active substance of a lithium ion battery cathode material, the counter electrode is a lithium sheet, and the active substance: acetylene black: PVDF (w/w) ═ 8: 1: 1. Shown in FIG. 3 as CNT/Bulk MoS 2 The circulation performance curve and the coulombic efficiency graph of the compound are 250 cycles under 1000mA/g, and the CNT/Bulk MoS can be obtained by measuring the circulation stability 2 The initial capacity of the electrode is 1071 mAh/g, the initial specific capacity under the current density of 1000mA/g is 930mAh/g, and after 250 cycles, the specific capacity is only 288 mAh/g; shown in FIG. 4 as CNT/Bulk MoS 2 The multiplying power performance of the composite is shown in a figure, and the measured multiplying power performance shows that under the high current density of 4000mA/g, CNT/Bulk MoS 2 The electrode exhibited a specific capacity of only 478 mAh/g.
Claims (9)
1. CNT/MoS 2 The lithium ion battery cathode material is characterized by being prepared by the following method:
1) preparing a carbon oxide nanotube dispersion liquid: adding a multi-walled carbon nanotube, sulfuric acid and nitric acid into a three-neck flask, performing ultrasonic oxidation for 3-5 hours at the temperature of 40-50 ℃, filtering, washing and drying to obtain oxidized carbon nanotube powder, and adding the obtained oxidized carbon nanotube powder into deionized water to dissolve to obtain an OCNT dispersion liquid;
2) preparation of OCNT/DC by electrostatic self-assembly + /MoO 4 2- : adding (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride and ammonium molybdate tetrahydrate into the OCNT dispersion liquid obtained in the step 1), stirring for 24 hours at room temperature for electrostatic self-assembly, dialyzing the obtained mixed liquid for 72 hours, and drying after dialysis to obtain OCNT/DC + /MoO 4 2- Powder;
3) CVD method for preparing CNT/SiO 2 /MoS 2 : the OCNT/DC obtained in the step 2) + / MoO 4 2- Putting the powder and the sublimed sulfur powder into a tube furnace for annealing to obtain CNT/SiO 2 /MoS 2 Powder;
4) etching SiO 2 Preparation of CNT/MoS 2 : the CNT/SiO obtained in the step 3) 2 /MoS 2 Uniformly dispersing the powder in NaOH solution, stirring for 24h, washing precipitates with deionized water and ethanol respectively, and drying in vacuum to obtain CNT/MoS 2 And (3) powder.
2. The CNT/MoS of claim 1 2 The lithium ion battery cathode material is characterized in that the length of the multi-wall carbon nanotube in the step 1) is 0.5-2 mu m, the tube diameter is less than 8nm, the purity is more than 95%, and the specific surface area is more than 500m 2 G, ash content < 1.5 wt.%.
3. The CNT/MoS of claim 1 2 The lithium ion battery negative electrode material is characterized in that in the step 1), the mass fraction of sulfuric acid is 98%, the mass fraction of nitric acid is 68%, and the mass volume ratio of the multi-walled carbon nanotube to the sulfuric acid to the nitric acid is 0.1-2 g: 120mL of: 40mL。
4. The CNT/MoS of claim 1 2 The lithium ion battery cathode material is characterized in that the concentration of the OCNT dispersion liquid in the step 1) is 1-10 mg/mL.
5. The CNT/MoS of claim 1 2 The lithium ion battery negative electrode material is characterized in that the mass-to-volume ratio of the carbon oxide nanotubes to the (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride to the ammonium molybdate tetrahydrate in the OCNT dispersion liquid in the step 2) is 0.1-1 g: 2.5 mL: 2g of the total weight of the composition.
6. The CNT/MoS of claim 1 2 The lithium ion battery cathode material is characterized in that the OCNT/DC in the step 3) + / MoO 4 2- The mass ratio of the powder to the sublimed sulfur powder is 1: 3 to 6.
7. The CNT/MoS of claim 1 2 The lithium ion battery cathode material is characterized in that the annealing process conditions in the step 3) are as follows: heating to 800 ℃ at the room temperature and in the Ar atmosphere at the heating rate of 5 ℃/min, preserving the heat for 12h, and finally cooling along with the furnace.
8. The CNT/MoS of claim 1 2 The lithium ion battery cathode material is characterized in that the concentration of the NaOH solution in the step 4) is 1mol/L, and the CNT/SiO is 2 /MoS 2 The concentration of the powder dispersed in the NaOH solution is 1-10 g/L.
9. The CNT/MoS of any one of claims 1 to 8 2 The preparation method of the lithium ion battery cathode material is characterized by comprising the following specific steps of:
1) preparing a carbon oxide nanotube dispersion liquid: adding a multi-walled carbon nanotube, sulfuric acid and nitric acid into a three-neck flask, performing ultrasonic oxidation for 3-5 hours at the temperature of 40-50 ℃, filtering, washing and drying to obtain oxidized carbon nanotube powder, and adding the obtained oxidized carbon nanotube powder into deionized water to dissolve to obtain an OCNT dispersion liquid;
2) preparation of OCNT/DC by electrostatic self-assembly + /MoO 4 2- : adding (trimethoxysilylpropyl) octadecyl dimethyl ammonium chloride and ammonium molybdate tetrahydrate into the OCNT dispersion liquid obtained in the step 1), stirring for 24 hours at room temperature for electrostatic self-assembly, dialyzing the obtained mixed liquid for 72 hours, and drying after dialysis to obtain OCNT/DC + /MoO 4 2- A powder;
3) CVD method for preparing CNT/SiO 2 /MoS 2 : the OCNT/DC obtained in the step 2) + / MoO 4 2- Putting the powder and the sublimed sulfur powder into a tube furnace for annealing to obtain CNT/SiO 2 /MoS 2 Powder;
4) etching SiO 2 Preparation of CNT/MoS 2 : the CNT/SiO obtained in the step 3) 2 /MoS 2 Uniformly dispersing the powder in NaOH solution, stirring for 24h, washing the precipitate with deionized water and ethanol respectively, and vacuum drying to obtain CNT/MoS 2 And (3) powder.
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