CN119306226A - A kind of anti-fading carbon composite modified negative electrode material for power battery and preparation method thereof - Google Patents
A kind of anti-fading carbon composite modified negative electrode material for power battery and preparation method thereof Download PDFInfo
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Abstract
本发明提供一种动力电池用的抗衰减碳复合改性负极材料及其制备方法，属于新能源电池电极材料技术领域。其制备方法包括：将钛酸四乙酯和水加入到乙醇中，搅拌反应，收集白色沉淀产物A；将产物A与聚乙烯基膦酸加入到甲苯中，在氮气保护下加热进行反应，冷却至室温，收集固体产物B；将产物B加入到环己烷溶剂中形成悬浮液，搅拌条件下往悬浮液滴加正丁基锂溶液反应，收集固体产物C；将产物C与硅源加入到乙醇中，超声分散后搅拌反应，收集固体产物D；将产物D放入化学气相沉积反应炉中，选择乙炔气体为碳源，进行气相沉淀获得碳复合改性负极材料。上述方法获得的碳复合改性负极材料可以抑制硅体积膨胀，具有抗衰减性能。The present invention provides an anti-fading carbon composite modified negative electrode material for a power battery and a preparation method thereof, and belongs to the technical field of electrode materials for new energy batteries. The preparation method comprises: adding tetraethyl titanate and water to ethanol, stirring the reaction, and collecting a white precipitate product A; adding product A and polyvinylphosphonic acid to toluene, heating under nitrogen protection for reaction, cooling to room temperature, and collecting a solid product B; adding product B to a cyclohexane solvent to form a suspension, adding n-butyl lithium solution to the suspension under stirring conditions for reaction, and collecting a solid product C; adding product C and a silicon source to ethanol, stirring the reaction after ultrasonic dispersion, and collecting a solid product D; placing product D in a chemical vapor deposition reactor, selecting acetylene gas as a carbon source, and performing vapor phase precipitation to obtain a carbon composite modified negative electrode material. The carbon composite modified negative electrode material obtained by the above method can inhibit the volume expansion of silicon and has anti-fading performance.
Description
Technical Field
The invention relates to the technical field of new energy battery electrode materials, in particular to an anti-attenuation carbon composite modified anode material for a power battery and a preparation method thereof.
Background
Carbon-based negative electrode materials are widely used in secondary batteries due to their high electron conductivity, good cycle performance and abundant resources. Among them, the graphite negative electrode material is the most widely commercialized, but its theoretical capacity is only 372mAh/g and the rate capacity characteristic is poor, which limits its application in high energy density batteries, thereby deriving carbon composite modified negative electrode materials.
Currently, carbon composite modified anode materials mainly comprise silicon-carbon composite materials, silicon/graphite/carbon composite materials, carbon foam composite materials and MXene-based composite materials. The conventional silicon modification method of the silicon-carbon composite material is to form a carbon buffer layer on the surface of the silicon material, and the structure is that, on one hand, the capacity of the battery can be improved to make up the defect of the carbon material due to the high theoretical specific capacity of the silicon material, and on the other hand, the carbon buffer layer can inhibit the defect of volume expansion of the silicon material in the charge-discharge process. However, in practical use, it is found that the effect of improving the effect is not ideal by simply coating the surface of the silicon material with the carbon buffer layer, and the silicon carbon particles are not adhered to each other, so that a good conductive network cannot be formed, and the conductivity needs to be improved.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a preparation method of an anti-attenuation carbon composite modified anode material for a power battery, which takes a silicon source as a core, adopts a special adhesive system to coat a carbon layer on the surface of the silicon source, so that the adhesion degree of silicon-carbon particles is improved, and the adhesive system has conductivity and improves the conductivity.
The method comprises the following steps:
a preparation method of an anti-attenuation carbon composite modified anode material for a power battery comprises the following steps:
Step one, adding tetraethyl titanate and water into ethanol, stirring for reaction, collecting a white precipitate A after the reaction is finished, washing and drying in vacuum for later use;
Adding the product A obtained in the step one and polyvinyl phosphonic acid into toluene, uniformly stirring, heating to 100-120 ℃ under the protection of nitrogen for reaction, cooling to room temperature after the reaction is finished, collecting a solid product B, washing, and drying in vacuum for later use;
step three, adding the product B in the step two into a cyclohexane solvent to form a suspension, dropwise adding an n-butyllithium solution into the suspension under the argon protection and reaction temperature of-5~0 ℃ under the stirring condition, continuing the reaction after the dropwise adding is finished, heating to room temperature after the reaction is finished, collecting a solid product C, washing, and drying in vacuum for later use;
Step four, adding the product C obtained in the step three and a silicon source into ethanol, stirring for reaction after ultrasonic dispersion, collecting a solid product D after the reaction is finished, and drying in vacuum for later use;
and fifthly, placing the product D in the step four into a chemical vapor deposition reaction furnace, selecting acetylene gas as a carbon source, and performing vapor deposition to obtain the carbon composite modified anode material.
Further, in the first step, the mass ratio of the tetraethyl titanate to the water is 1:0.4-0.6, and the volume ratio of the ethanol to the tetraethyl titanate is 8-12:1.
Further, in the first step, the stirring speed is 300-500 rpm, the reaction time is 3-5 h, absolute ethyl alcohol is selected for washing, and the vacuum drying temperature is 60-80 ℃.
Further, in the second step, the mass ratio of the product A to the polyvinyl phosphonic acid to the toluene is 1:0.8-1.2:7.2-8.8.
Further, in the second step, the reaction time is 8-12 hours, toluene is selected for washing, and the vacuum drying temperature is 60-80 ℃.
Further, in the third step, the mass ratio of the product B to cyclohexane is 1:10-11, the mass fraction of n-butyllithium in the n-butyllithium solution is 15% -20%, cyclohexane is selected as the solvent, and the mass ratio of the n-butyllithium to the product B is 0.2-0.3:1.
Further, in the third step, the stirring speed is 200-300 rpm, the dropping speed of the n-butyl lithium solution is controlled to be 0.5-2 mL/min, the reaction time is 4-6 h, absolute ethyl alcohol is selected for washing, and the vacuum drying temperature is 40-60 ℃.
In the fourth step, mesoporous silicon dioxide powder is selected as a silicon source, the mass ratio of the product C to the silicon source is 1-3:1, the ultrasonic power is 200-300W for 30-60 min, so that the silicon source and the product C are fully dispersed in the solution to avoid agglomeration, the stirring speed is 300-500 rpm, the reaction time is 2-4 h, and the vacuum drying temperature is 60-80 ℃.
Further, in the fifth step, the vapor deposition reaction temperature is 600-800 ℃, the reaction pressure is 1-5 kpa, the lower pressure is favorable for the adsorption and diffusion of carbon source gas on the solid surface, and acetylene gas is introduced at the flow rate of 20-40 mL/min, and the reaction time is 2-4 hours.
The invention also provides an anti-attenuation carbon composite modified anode material for the power battery, which is prepared by adopting the preparation method.
Compared with the prior art, the invention has the beneficial characteristics that:
1. According to the invention, titanium dioxide with hydroxyl on the surface is obtained through reaction of tetraethyl titanate and water, hydroxyl on the titanium dioxide can be bonded with phosphonic acid groups of polyvinyl phosphonic acid, the titanium dioxide has conductivity, so that the modified polyvinyl phosphonic acid has conductivity, the polyvinyl phosphonic acid can improve the dispersibility of the titanium dioxide, prevent agglomeration of the titanium dioxide, enable an electronic conduction channel to be more smooth, supplement each other, then the modified polyvinyl phosphonic acid and n-butyllithium are mixed, lithium-containing modified polyvinyl phosphonic acid is obtained through reaction of the modified polyvinyl phosphonic acid and n-butyllithium, the special modified polyvinyl phosphonic acid is mixed with mesoporous silica solution, the polyvinyl phosphonic acid can be fully dispersed on gaps and surfaces of silica, and is well bonded with the silica, so that the surface and the inside of the mesoporous silica have conductivity, and through embedding lithium, the electrode is subjected to volume expansion in advance, so that the collapse of an electrode structure and the falling of an electrode material in the subsequent cycle charge and discharge process of a battery are avoided, and the cycle performance of the battery is remarkably improved.
2. According to the invention, the mesoporous silica surface is coated with the specially modified polyvinyl phosphonic acid, the carbon source generated by vapor phase precipitation has good binding force with the coating layer, the existence of titanium dioxide on the polyvinyl phosphonic acid can promote the adsorption, dissociation and diffusion processes of carbon source gas, titanium atoms can be embedded into the lattice structure of the carbon material, the electronic structure and conductivity of the carbon material are changed, and meanwhile, the doping can enhance the mechanical properties of the carbon material, such as the strength and toughness of the carbon nanotube.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
To facilitate the practice of the invention, the reagents used in the examples and comparative examples will now be described:
Tetraethyl titanate, marchantia white;
ethanol, absolute ethanol, shanghai Colon chemical industry;
polyvinyl phosphonic acid, shanghai microphone forest biochemical technology;
toluene, shanghai XiangHeyi chemical technology;
Cyclohexane, hengshuo chemical Co., ltd;
n-butyllithium, shaoxing Hualun chemical industry;
the silicon source is mesoporous silicon dioxide, the granularity is less than or equal to 20um, the aperture is more than or equal to 200nm, and the Hangzhou Jikang new material;
Acetylene, guangzhou Guangdong Jia gas;
Carboxymethyl cellulose, shandong Chengxin chemical industry.
Example 1
An anti-attenuation carbon composite modified anode material for a power battery, which comprises the following steps:
Step one, adding tetraethyl titanate and water into ethanol according to the mass ratio of 1:0.4, stirring and reacting at room temperature at the stirring speed of 300rpm for 3 hours, collecting a white precipitate A after the reaction, washing with absolute ethanol, and vacuum drying at 60 ℃ for 12 hours for later use;
Adding the product A obtained in the step one and polyvinyl phosphonic acid into toluene, uniformly stirring, heating to 100 ℃ under the protection of nitrogen for reaction for 8 hours, cooling to room temperature after the reaction is finished, collecting a solid product B, washing with toluene, and vacuum drying at 60 ℃ for 12 hours for later use;
Step three, adding the product B obtained in the step two into a cyclohexane solvent, wherein the mass ratio of the product B to the cyclohexane is 1:10, forming a suspension, dropping n-butyllithium solution into the suspension under the protection of argon, reducing the temperature to-5 ℃, controlling the dropping speed of the n-butyllithium solution to be 0.5mL/min under the stirring condition of the temperature, continuously reacting for 4 hours after the dropping is finished, heating to room temperature after the reaction is finished, collecting a solid product C, washing the solid product C by absolute ethyl alcohol, and vacuum drying the solid product C for 12 hours at 40 ℃ for later use, wherein the mass ratio of n-butyllithium in the n-butyllithium solution is 15%, cyclohexane is selected as the solvent, and the mass ratio of n-butyllithium to the product B is 0.2:1;
Adding the product C from the step three and a silicon source into ethanol, wherein the mass ratio of the silicon source to the product C to the ethanol is 1:1:20, stirring for reaction after ultrasonic dispersion, carrying out ultrasonic treatment for 30min, wherein the ultrasonic power is 200W, the stirring speed is 300rpm, the reaction time is 2h, collecting a solid product D after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12h for later use;
and fifthly, putting the product D obtained in the step four into a chemical vapor deposition reaction furnace, introducing argon (Ar) as a protective gas before reaction, controlling the flow to be 50mL/min for 5min so as to remove air in the reaction furnace, selecting acetylene gas as a carbon source, introducing the acetylene gas into the chemical vapor deposition reaction furnace at the flow of 20mL/min, heating to 600 ℃, reacting at the reaction pressure of 1kpa, performing vapor deposition for 2h, stopping introducing the acetylene gas after the reaction is finished, naturally cooling the reaction furnace to room temperature under the protection of the Ar so as to prevent the generated carbon coating layer from being damaged due to the reaction with oxygen in the air, and taking out the product, thus obtaining the product.
Example 2
An anti-attenuation carbon composite modified anode material for a power battery, which comprises the following steps:
step one, adding tetraethyl titanate and water into ethanol according to the mass ratio of 1:0.6, stirring and reacting at room temperature at the stirring speed of 500rpm for 5 hours, collecting a white precipitate A after the reaction, washing with absolute ethanol, and vacuum drying at 80 ℃ for 14 hours for later use;
adding the product A obtained in the step one and polyvinyl phosphonic acid into toluene, uniformly stirring, heating to 120 ℃ under the protection of nitrogen for reaction for 12 hours, cooling to room temperature after the reaction is finished, collecting a solid product B, washing with toluene, and drying in vacuum at 80 ℃ for 14 hours for later use;
step three, adding the product B obtained in the step two into a cyclohexane solvent, wherein the mass ratio of the product B to the cyclohexane is 1:11, forming a suspension, dropwise adding an n-butyllithium solution into the suspension under the protection of argon, and stirring at the temperature of 300rpm, wherein the dropwise adding speed of the n-butyllithium solution can be controlled at 2mL/min, continuing the reaction after the dropwise adding is finished, reacting for 6 hours, heating to room temperature after the reaction is finished, collecting a solid product C, washing with absolute ethyl alcohol, and vacuum drying at 60 ℃ for 14 hours for later use, wherein the mass fraction of n-butyllithium in the n-butyllithium solution is 20%, the solvent is cyclohexane, and the mass ratio of n-butyllithium to the product B is 0.3:1;
Adding the product C from the step three and a silicon source into ethanol, wherein the mass ratio of the silicon source to the product C to the ethanol is 1:3:30, stirring for reaction after ultrasonic dispersion, carrying out ultrasonic treatment for 60min, wherein the ultrasonic power is 300W, the stirring speed is 500rpm, the reaction time is 4h, collecting a solid product D after the reaction is finished, and carrying out vacuum drying at 80 ℃ for 14h for later use;
and fifthly, putting the product D obtained in the step four into a chemical vapor deposition reaction furnace, introducing argon (Ar) as a protective gas before reaction, controlling the flow to be 50mL/min for 5min so as to remove air in the reaction furnace, selecting acetylene gas as a carbon source, introducing the acetylene gas into the chemical vapor deposition reaction furnace at the flow of 40mL/min, heating to 800 ℃, reacting at the reaction pressure of 5kpa, performing vapor deposition for 4h, stopping introducing the acetylene gas after the reaction is finished, naturally cooling the reaction furnace to room temperature under the protection of the Ar so as to prevent the generated carbon coating layer from being damaged due to the reaction with oxygen in the air, and taking out the product, thus obtaining the product.
Example 3
An anti-attenuation carbon composite modified anode material for a power battery, which comprises the following steps:
Step one, adding tetraethyl titanate and water into ethanol according to the mass ratio of 1:0.6, stirring and reacting at room temperature at the stirring speed of 500rpm for 3 hours, collecting a white precipitate A after the reaction, washing with absolute ethanol, and vacuum drying at 80 ℃ for 12 hours for later use;
Adding the product A obtained in the step one and polyvinyl phosphonic acid into toluene, uniformly stirring the mixture, heating the mixture to 110 ℃ under the protection of nitrogen for reaction for 10 hours, cooling the mixture to room temperature after the reaction is finished, collecting a solid product B, washing the solid product B with toluene, and drying the solid product B in vacuum at 70 ℃ for 13 hours for later use;
Step three, adding the product B obtained in the step two into a cyclohexane solvent, wherein the mass ratio of the product B to the cyclohexane is 1:10, forming a suspension, dropping n-butyllithium solution into the suspension under the protection of argon, reducing the temperature to-2 ℃, controlling the dropping speed of the n-butyllithium solution to be 1.2mL/min under the stirring condition of the temperature, continuously reacting for 5 hours after the dropping is finished, heating to room temperature after the reaction is finished, collecting a solid product C, washing with absolute ethyl alcohol, and drying in vacuum for 14 hours at 50 ℃ for later use, wherein the mass ratio of n-butyllithium in the n-butyllithium solution is 15%, cyclohexane is selected as the solvent, and the mass ratio of n-butyllithium to the product B is 0.2:1;
Adding the product C from the step three and a silicon source into ethanol, wherein the mass ratio of the silicon source to the product C to the ethanol is 1:2:25, stirring for reaction after ultrasonic dispersion, carrying out ultrasonic treatment for 50min, wherein the ultrasonic power is 260W, the stirring speed is 400rpm, the reaction time is 3h, collecting a solid product D after the reaction is finished, and carrying out vacuum drying at 70 ℃ for 13h for later use;
And fifthly, putting the product D obtained in the step four into a chemical vapor deposition reaction furnace, introducing argon (Ar) as a protective gas before reaction, controlling the flow to be 50mL/min for 5min so as to remove air in the reaction furnace, selecting acetylene gas as a carbon source, introducing the acetylene gas into the chemical vapor deposition reaction furnace at the flow of 30mL/min, heating to 700 ℃, reacting at the reaction pressure of 3kpa, performing vapor deposition for 3h, stopping introducing the acetylene gas after the reaction is finished, naturally cooling the reaction furnace to room temperature under the protection of the Ar so as to prevent the generated carbon coating layer from being damaged due to the reaction with oxygen in the air, and taking out the product, thus obtaining the product.
Comparative example 1
The preparation method of the carbon composite anode material of the asphalt coated silicon source comprises the following steps:
Dispersing mesoporous silica and carboxymethyl cellulose in an aqueous solution of ethanol, wherein the mass ratio of the mesoporous silica to the carboxymethyl cellulose is 5:3, regulating the solid content of slurry to be 35%, obtaining mixed slurry with the viscosity of 1600cP, carrying out spray granulation on a spray dryer with the inlet temperature of 220 ℃ and the outlet temperature of 130 ℃ at a feeding speed of 60mL/min, transferring a sample after spray granulation to an atmosphere furnace, heating to 850 ℃ at a heating speed of 5 ℃ at a nitrogen flow of 5L/min, carrying out pyrolysis treatment for 3 hours, and naturally cooling to room temperature, and then sieving with a 200-mesh sieve to obtain silicon-carbon small particles.
And secondly, uniformly mixing the silicon-carbon small particles with the low-temperature asphalt, transferring the mixture into a fusion coating machine, performing high-temperature sintering treatment at a mass ratio of 10:3 on the silicon-carbon small particles to the low-temperature asphalt, stirring and heating to 450 ℃ at a heating rate of 2 ℃ per minute under a nitrogen flow of 5L/min and a stirring speed of 100rpm, placing the mixture in an atmosphere furnace after the material is cooled to room temperature, performing mechanical crushing and sieving with a 200-mesh sieve at a heating rate of 5 ℃ per minute under a nitrogen flow of 5L/min for 4 hours at a heating rate of 1050 ℃, and performing high-temperature sintering treatment, cooling to room temperature to obtain the product.
Comparative example 2
A preparation method of the carbon composite modified anode material comprises the following steps:
Firstly, adding polyvinyl phosphonic acid into a cyclohexane solvent, wherein the mass ratio of the polyvinyl phosphonic acid to the cyclohexane is 1:10, forming a suspension, dropwise adding n-butyl lithium solution into the suspension under the condition of stirring at the temperature of minus 5 ℃ under the protection of argon, wherein the stirring speed is 200rpm, the dropping speed of the n-butyl lithium solution can be controlled at 0.5mL/min, continuing to react after the dropwise adding is finished, reacting for 4 hours, heating to room temperature after the reaction is finished, collecting a solid product E, washing with absolute ethyl alcohol, and vacuum drying at 40 ℃ for 12 hours for later use, wherein the mass fraction of n-butyl lithium in the n-butyl lithium solution is 15%, the mass ratio of the n-butyl lithium to the polyvinyl phosphonic acid is 0.2:1;
Adding the product E and a silicon source in the step I into ethanol, wherein the mass ratio of the silicon source to the product E to the ethanol is 1:1:20, stirring for reaction after ultrasonic dispersion, carrying out ultrasonic treatment for 30min, wherein the ultrasonic power is 200W, the stirring speed is 300rpm, the reaction time is 2h, collecting a solid product F after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12h for later use;
And thirdly, putting the product F obtained in the second step into a chemical vapor deposition reaction furnace, introducing argon (Ar) as a protective gas before reaction, controlling the flow at 50mL/min for 5min so as to remove air in the reaction furnace, selecting acetylene gas as a carbon source, introducing the acetylene gas into the chemical vapor deposition reaction furnace at the flow of 20mL/min, heating to 600 ℃, reacting at the reaction pressure of 1kpa, performing vapor deposition for 2h, stopping introducing the acetylene gas after the reaction is finished, naturally cooling the reaction furnace to room temperature under the protection of the Ar so as to prevent the generated carbon coating layer from being damaged due to the reaction with oxygen in the air, and taking out the product, thus obtaining the product.
And (3) battery testing:
The negative electrode materials obtained in the above examples and comparative examples were used in a battery for experiments. The battery assembling process comprises the steps of mixing a negative electrode material, a conductive agent (SP), CMC and SBR according to the mass ratio of 95:1.5:1.5:2, and coating the mixture on a copper foil to obtain a negative electrode plate. And uniformly mixing positive active substances of lithium cobaltate, a conductive agent (SP) and PVDF according to the mass ratio of 96.5:2:1.5, and coating the mixture on an aluminum foil to obtain the positive electrode plate. The electrolyte is 1mol/L LiPF6+EC+EMC, and the membrane is a polyethylene/propylene composite microporous membrane. They are assembled into a battery.
The first discharge capacity of 0.1C, the first charge-discharge efficiency, the capacity retention after 50 weeks of cycling at a rate of 0.5C, the capacity retention after 50 weeks of cycling at a rate of 1C were tested, and the test results thereof are shown in the following table:
| 0.1C first discharge capacity (mAh/g) | First charge and discharge efficiency (%) | Capacity retention after 50 weeks of cycling at 0.5C magnification (%) | Capacity retention after 50 weeks of cycling at 1C magnification (%) | |
| Example 1 | 884.1 | 90.3 | 79.4 | 68.9 |
| Example 2 | 869.3 | 90.5 | 81.3 | 70.6 |
| Example 3 | 881.6 | 91.6 | 78.7 | 70.1 |
| Comparative example 1 | 733.9 | 71.4 | 62.3 | 53.9 |
| Comparative example 2 | 664.8 | 65.3 | 61.7 | 55.4 |
As can be seen from the above test results, all of examples 1 to 3 of the present invention have a high first charge-discharge capacity, a high first efficiency and an excellent long-cycle capacity retention. The values for both comparative example 1 and comparative example 2 are much lower than for examples 1-3. The attenuation-resistant carbon composite modified anode material has the characteristics of high conductivity, high capacity, high-rate charge and discharge performance and long cycle.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (10)
1. The preparation method of the anti-attenuation carbon composite modified anode material for the power battery is characterized by comprising the following steps of:
Step one, adding tetraethyl titanate and water into ethanol, stirring for reaction, collecting a white precipitate A after the reaction is finished, washing and drying in vacuum for later use;
Adding the product A obtained in the step one and polyvinyl phosphonic acid into toluene, uniformly stirring, heating to 100-120 ℃ under the protection of nitrogen for reaction, cooling to room temperature after the reaction is finished, collecting a solid product B, washing, and drying in vacuum for later use;
Step three, adding the product B in the step two into a cyclohexane solvent to form a suspension, dropwise adding an n-butyllithium solution into the suspension under the argon protection and reaction temperature of-5~0 ℃ under the stirring condition, continuing the reaction after the dropwise adding is finished, heating to room temperature after the reaction is finished, collecting a solid product C, washing, and drying in vacuum for later use;
Step four, adding the product C obtained in the step three and a silicon source into ethanol, stirring for reaction after ultrasonic dispersion, collecting a solid product D after the reaction is finished, and drying in vacuum for later use;
and fifthly, placing the product D in the step four into a chemical vapor deposition reaction furnace, selecting acetylene gas as a carbon source, and performing vapor deposition to obtain the carbon composite modified anode material.
2. The preparation method of claim 1, wherein in the first step, the mass ratio of the tetraethyl titanate to the water is 1:0.4-0.6, and the volume ratio of the ethanol to the tetraethyl titanate is 8-12:1.
3. The method according to claim 1, wherein the stirring speed in the first step is 300 to 500rpm; the reaction time is 3-5 h, absolute ethyl alcohol is selected for washing, and the vacuum drying temperature is 60-80 ℃.
4. The preparation method of claim 1, wherein the mass ratio of the product A to the polyvinyl phosphonic acid to the toluene in the second step is 1:0.8-1.2:7.2-8.8.
5. The preparation method of the catalyst according to claim 1, wherein the reaction time in the second step is 8-12 hours, toluene is selected for washing, and the vacuum drying temperature is 60-80 ℃.
6. The preparation method of the lithium ion battery pack, according to claim 1, is characterized in that in the third step, the mass ratio of the product B to cyclohexane is 1:10-11, the mass fraction of n-butyllithium in the n-butyllithium solution is 15% -20%, cyclohexane is selected as a solvent, and the mass ratio of the n-butyllithium to the product B is 0.2-0.3:1.
7. The preparation method of the lithium-n-butyl compound as claimed in claim 1, wherein in the third step, the stirring speed is 200-300 rpm, the dropping speed of the n-butyllithium solution is controlled to be 0.5-2 mL/min, the reaction time is 4-6 h, the washing is performed by using absolute ethyl alcohol, and the vacuum drying temperature is 40-60 ℃.
8. The preparation method of the silicon source according to claim 1, wherein mesoporous silicon dioxide powder is selected as the silicon source in the fourth step, the mass ratio of the product C to the silicon source is 1-3:1, the ultrasonic power is 200-300W for 30-60 min, the stirring speed is 300-500 rpm, the reaction time is 2-4 h, and the vacuum drying temperature is 60-80 ℃.
9. The preparation method according to claim 1, wherein in the fifth step, the vapor deposition reaction temperature is 600-800 ℃, the reaction pressure is 1-5 kpa, acetylene gas is introduced at a flow rate of 20-40 ml/min, and the reaction time is 2-4 hours.
10. An anti-attenuation carbon composite modified anode material for a power battery, which is characterized by being prepared by the preparation method according to any one of claims 1-9.
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