Disclosure of Invention
In order to solve the problems of complex equipment, complex process, complex and time-consuming operation, low product utilization rate, low nitrogen doping content caused by the loss of a large amount of nitrogen doping precursors in the nitrogen doping process and the like in the preparation of nitrogen-doped carbon nanotube materials in the prior art, the invention provides a method for efficiently, quickly and massively synthesizing a high-nitrogen-content doped molybdenum disulfide/carbon nanotube composite material, the obtained material has high nitrogen content, the raw material utilization rate is obviously improved, the product does not need the processes of washing, separation, drying and the like, can be directly used for a lithium battery cathode material, and has good application performance.
In order to achieve the technical purpose, the invention provides a preparation method of a nitrogen-doped molybdenum disulfide/carbon nanotube composite material, which comprises the following steps:
(1) dispersing the acidified carbon nano tube in a formaldehyde aqueous solution to obtain a dispersion liquid A;
(2) dispersing melamine and ammonium tetrathiomolybdate into deionized water to obtain a dispersion liquid B;
(3) mixing the dispersion liquid A and the dispersion liquid B, heating to 50-80 ℃ for reaction for 10-60min, adjusting the pH of the reaction liquid to 7-9, heating in a sealed environment to 100-200 ℃ for hydrothermal reaction for 12-24 h, filtering, and drying to obtain black solid powder;
(4) and (4) placing the black solid powder obtained in the step (3) in a microwave reaction cavity, and heating for 10-60min at the microwave power of 300-1200W to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
In the above-mentioned production method, the concentration of the aqueous formaldehyde solution in the step (1) is not particularly limited, and in a preferred embodiment of the present invention, the concentration of formaldehyde is 37% to 40% by mass. Mixing the acidified carbon nano tube with formaldehyde solution according to the solid-to-liquid ratio of 1g (10-100) mL. Preferably, the mixture is uniformly mixed and dispersed in an ultrasonic mode, and the ultrasonic time is 5-30 min.
In the above preparation method, it should be understood by those skilled in the art that the acidified carbon nanotube is obtained by performing an acidification modification treatment on a carbon nanotube with a strong acid, and performing the acidification modification on the carbon nanotube is a technique well known to those skilled in the art, so long as the purpose of changing the kind and concentration of the functional group on the surface of the carbon nanotube to improve the water solubility thereof can be achieved, thereby satisfying the requirements of the present invention on the acidified carbon nanotube. For example, the carbon nanotubes are subjected to an acidification modification treatment with mixed acids (concentrated sulfuric acid and concentrated nitric acid, concentrated nitric acid and concentrated hydrochloric acid).
Among them, as a more specific embodiment, carbon nanotubes having the following properties are preferable in the selection of materials: diameter of 10-300nm, length of 2-30 μm, and specific surface area>100m2Per g, conductivity>100s/cm。
In the above production method, the dispersion liquid a and the dispersion liquid B are mixed in the step (3), and the dispersion liquid a is preferably poured into the dispersion liquid B. Mixing the acidified carbon nanotubes in the dispersion liquid A, the melamine in the dispersion liquid B and the ammonium tetrathiomolybdate in the dispersion liquid B in a ratio of 1:1-20:1-20 by weight. After mixing, the mixture is preferably mixed and dispersed uniformly in an ultrasonic mode, and the ultrasonic time is 5-30 min.
In the above preparation method, the pH of the reaction solution in the step (3) may be adjusted by using an organic base or an inorganic base, and as a more specific embodiment, the pH is selected from one or more of methylamine, ethylamine, ethylenediamine, propylamine, isopropylamine, triethanolamine, aniline, cyclohexylamine, o-aminophenol, 2-chlorophenol, potassium carbonate, sodium bicarbonate, potassium hydroxide, and sodium hydroxide.
In the preparation method, the hydrothermal reaction temperature in the step (3) is preferably 120-160 ℃, and the time is preferably 12-18 h.
In the preparation method, the power of the microwave reaction in the step (4) is preferably 600-1000W, and the time is preferably 10-30 min.
In the preparation method, the microwave reaction cavity is purged by nitrogen or inert gas before and during the microwave reaction, and preferably, argon is used for purging.
The technical purpose of the second aspect of the invention is to provide the nitrogen-doped molybdenum disulfide/carbon nanotube composite material prepared by the method. In the preparation process of the method, formaldehyde and melamine are mixed firstly to generate moderate crosslinking reaction to form a water-soluble nitrogen-doped precursor, and then hydrothermal reaction is carried out to carry out nitrogen doping on the carbon nano tube, so that the nitrogen-doped precursor and the carbon nano tube are easy to interact, conditions are created for uniformly fusing the composite material, and the nitrogen-doped process is more favorably realized; the subsequent microwave reaction has high heating speed and uniform heating, the nitrogen-doped precursor and the active component single-source precursor are heated and decomposed, and the carbon nano tube, the active component single-source precursor and the nitrogen-doped precursor are uniformly fused in the previous preparation process, so that the nitrogen doping of the carbon nano tube and the dispersion of the active component are more uniform, and the synthesis of the high-content nitrogen-doped molybdenum disulfide/carbon nano tube is more facilitated.
The technical purpose of the third aspect of the invention is to provide application of the nitrogen-doped molybdenum disulfide/carbon nanotube composite material, and the material can be used as a lithium ion battery cathode material and shows good cycle stability and rate capability.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, formaldehyde is used as a bridge in the preparation process of the nitrogen-doped molybdenum disulfide/carbon nanotube composite material, and the formaldehyde and melamine are subjected to moderate crosslinking to form the nitrogen-doped precursor, so that the problem of low nitrogen-doping efficiency caused by large loss of the nitrogen-doped precursor due to strong sublimation of the nitrogen-doped precursor in the heating process in the traditional solid nitrogen-doping reaction is avoided.
(2) In the preparation process, the formaldehyde and the melamine are subjected to a cross-linking reaction to form the water-soluble nitrogen-doped precursor, so that the nitrogen-doped precursor and the carbon nano tube are interacted and uniformly fused in the subsequent hydrothermal reaction, and the preparation of the high-nitrogen-content doped carbon nano tube material is realized.
(3) In the microwave reaction stage in the preparation process, the heating speed is high, the heating is uniform, on one hand, the loss caused by sublimation of the nitrogen-doped precursor due to slow temperature rise in the traditional reaction can be avoided, on the other hand, the nitrogen-doped precursor and the active component single-source precursor are heated and decomposed under the microwave condition, and as the carbon nano tube, the active component single-source precursor and the nitrogen-doped precursor are uniformly fused together in the previous preparation process, the nitrogen doping and the active component dispersion of the carbon nano tube are more uniform, and the synthesis of the high-nitrogen-content doped carbon nano tube is more facilitated.
(4) The microwave reaction in the preparation process adopts a solvent-free treatment mode, so that the post-treatment processes of washing, separating, drying and the like of the product are omitted, and the production process is simplified.
(5) The nitrogen-doped molybdenum disulfide/carbon nanotube composite material prepared by the method has good stability, is not easy to denature in air, is easy to store, has a large specific surface area, is used as a lithium ion battery cathode material, provides a good channel for lithium ion transmission, and shows a large specific capacity and a good cycling stability performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The acidified carbon nanotubes used in the following examples were prepared by the following method:
the carbon nanotubes used had the following properties: the carbon nanotube has a diameter of 10-300nm, a length of 2-30 μm, and a specific surface area>100m2Per g, conductivity>100s/cm。
Preparing acidified carbon nanotubes: filling 1g of carbon nanotube and 200mL of concentrated sulfuric acid into a three-neck flask, ultrasonically dispersing uniformly, slowly dropwise adding 60mL of concentrated nitric acid with the concentration of 70%, refluxing and stirring for 1h at 60 ℃, naturally cooling to room temperature, adding a large amount of deionized water for dilution, standing for layering, removing supernatant, dialyzing black precipitate at the bottom by using deionized water, replacing small molecules in the black precipitate, balancing the surface of the black precipitate, and obtaining the carbon nanotube aqueous dispersion which can be stably and uniformly dispersed for a long time. Freeze-drying the carbon nanotube aqueous dispersion to obtain acidified carbon nanotube powder, and placing the acidified carbon nanotube powder in a dryer for later use. The SEM image is shown in figure 1, the one-dimensional carbon nanotube structure can be clearly seen, the carbon nanotube wall after acidification treatment is smoother, the length of the tube is more than 3 mu m, and the tube diameter is 50nm-300 nm.
The nitrogen-doped molybdenum disulfide/carbon nanotube composite material of the invention is prepared in the embodiments 1-8:
example 1
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 3.0g of melamine and 5.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 60 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 2
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 5.0g of melamine and 8.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 60 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 3
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 10.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. And heating for 20min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 4
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 20 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 30min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 5
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 20 min. And then adding potassium hydroxide into the reaction liquid, adjusting the pH value of a reaction liquid system to 9.0, carrying out ultrasonic mixing uniformly, then pouring the reaction liquid into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min with the microwave power of 800W to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 6
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And then adding potassium hydroxide into the reaction liquid, adjusting the pH value of a reaction liquid system to 9.0, carrying out ultrasonic mixing uniformly, then pouring the reaction liquid into a high-pressure reaction kettle, and heating to 140 ℃ for reaction for 15 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min with the microwave power of 800W to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 7
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reaction for 15 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min with the microwave power of 800W to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
Example 8
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. And heating for 30min at the microwave power of 1000W to obtain the nitrogen-doped molybdenum disulfide/carbon nanotube composite material.
An SEM image of the nitrogen-doped molybdenum disulfide/carbon nanotube composite material obtained in example 8 is shown in fig. 2, and it can be clearly seen that a molybdenum disulfide nanosheet uniformly grows on the surface of a one-dimensional carbon nanotube, and shows a compact one-dimensional structure, which is beneficial to good conductivity of the nitrogen-doped carbon nanotube and MoS2The active components are combined to exert more excellent electrochemical performance.
Comparative example 1
In the step (1), formaldehyde solution is not used, and deionized water is used for replacing:
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of deionized water, and placed in an ultrasonic instrument to be uniformly dispersed, and the dispersion A was recorded.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating the mixture for 30min at the microwave power of 1000W to obtain a comparative composite material.
Comparative example 2
In the step (2), ammonium tetrathiomolybdate is not added:
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating the mixture for 30min at the microwave power of 1000W to obtain a comparative composite material.
Comparative example 3
And (3) adjusting the pH value of the reaction solution without adding alkali liquor, and directly carrying out hydrothermal reaction after uniformly mixing the dispersion solution A and the dispersion solution B:
(1) 1.0g of acidified carbon nanotubes was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine and 12.0g of ammonium tetrathiomolybdate were weighed into 40mL of deionized water, and the mixture was placed in an ultrasonic apparatus and uniformly dispersed by ultrasonic, and the dispersion B was recorded.
(3) And mixing the dispersion liquid A and the dispersion liquid B, uniformly mixing by ultrasonic waves, pouring the reaction liquid into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating the mixture for 30min at the microwave power of 1000W to obtain a comparative composite material.
The materials of examples 1-8 and comparative examples 1-3 are used as the negative electrode material of the lithium ion battery. The synthesized nitrogen-doped molybdenum disulfide/carbon nanotube composite material is used as an active component, a 2016 type battery shell, a metal lithium sheet (phi 16 mm multiplied by 1mm) and 1.0M LiPF are selected6The mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) is used as electrolyte, and Celgard2300 microporous polypropylene coal membrane is used as battery diaphragm. The materials are assembled into a button cell in a glove box filled with Ar gas, and the test is carried out after the working electrode is fully soaked by the electrolyte. The method comprises the following five steps:
(1) size mixing
The material used has a large specific surface and is easy to adsorb moisture in the air, so the material for preparing the electrode is firstly dried fully in a vacuum drying oven at 120 ℃ to remove the surface moisture. Then adding an active substance, a conductive additive (acetylene black) and a binder (PVDF) into the dispersant according to the mass percentage of 80:10:10N-methylpyrrolidone (NMP) mixed grinding, resulting in uniform mixing of the materials, making a viscous slurry.
(2) Coating film
The resulting viscous paste was uniformly coated on a copper foil (thickness of about 100 μm). The specific operation is as follows: 1) the copper foil of moderate size is cut and laid flat on a table top. 2) Removing stains on the surface of the copper foil. 3) The slurry was dispersed on a copper foil and uniformly spread on the copper foil using a die. 4) The copper foil coated with the slurry was dried in a vacuum drying oven at 120 ℃ for 12 hours.
(3) Roller compaction
After the completion of drying, the copper foil coated with the slurry was rolled with a small-sized rolling machine to prevent the electrode material from falling off from the surface of the copper foil.
(4) Tabletting
And cutting the rolled film into a plurality of circular electrode slices with the diameter of 12mm by using a manual slicer. In order to prevent the coating film from falling off during charge and discharge cycles, it was pressed into a sheet by an oil press. And taking out and weighing after drying, and waiting for battery loading.
(5) Assembled battery
The process of assembling the button cells was carried out in a glove box filled with Ar gas. The battery is assembled according to the sequence of negative battery shell/electrolyte/working electrode plate/electrolyte/diaphragm/lithium plate/positive battery shell. And standing for 24 hours, and carrying out electrochemical test after the electrolyte is fully soaked.
And carrying out charge and discharge tests on the assembled button type simulation battery. The material of example 8 was used at a voltage in the range of 0.01 to 3.0V and at a current of 100mA g-1The results of the cycle stability test at the current density of (a) are shown in fig. 3. The nitrogen content in the electrode materials of examples 1-8 and comparative examples 1-3, as well as the corresponding first charge-discharge capacity and the discharge capacity after 100 charge-discharge tests are shown in table 1. Wherein the content of nitrogen element is determined by element analysis.
According to test data, the content of nitrogen doped in the composite material is improved, and the nitrogen content can reach 5.0 percent at most; secondly, the specific capacity of the button cell for the first discharge is increased, and the first discharge capacity in the embodiment 8 can reach 1101.9 mAh g-1Compared with the comparative example 1, the reversible capacity retention rate is increased by about 14%, compared with the comparative example 2, the reversible capacity retention rate is increased by about 207%, compared with the comparative example 3, the reversible capacity retention rate is still high after 100 cycles, the reversible capacity retention rate exceeds 80.0%, and the reversible capacity retention rate is up to 89.0%, which shows that the material prepared by the invention has high reversible capacity and good cycle performance.
TABLE 1