CN114122397B - Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof - Google Patents

Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof Download PDF

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CN114122397B
CN114122397B CN202111187449.XA CN202111187449A CN114122397B CN 114122397 B CN114122397 B CN 114122397B CN 202111187449 A CN202111187449 A CN 202111187449A CN 114122397 B CN114122397 B CN 114122397B
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CN114122397A (en
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易旭
廖寄乔
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Hunan Jinsi Technology Co ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material, and a preparation method and application thereof. The silicate is subjected to a sol-gel method and a template method to obtain a nano silica material, the nano silica material is glued and adsorbed with the carbon nano tube under the action of a silane coupling agent and a dispersing agent, then the mesoporous silica material connected with the carbon nano tube is formed by high-temperature calcination, and then the surface of the mesoporous silica material is further coated with carbon, so that the SiO@CNT/C composite material is obtained. The SiO@CNT/C composite material can effectively inhibit the damage of an electrode caused by the volume expansion of silicon oxide, greatly improves the cycle performance of the electrode material in a lithium ion battery, and simultaneously greatly improves the conductivity of the material by adding the carbon nano tube, and reduces the generation of lithium dendrites, thereby effectively improving the first coulomb efficiency and the cycle performance of the lithium ion battery.

Description

Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof
Technical Field
The invention relates to a lithium ion battery cathode material, in particular to a carbon nano tube connected double-carbon layer coated mesoporous silica composite cathode material, and also relates to a preparation method of the carbon nano tube connected double-carbon layer coated mesoporous silica composite material and application of the carbon nano tube connected double-carbon layer coated mesoporous silica composite material as a lithium ion battery cathode material, belonging to the technical field of lithium batteries.
Background
With the rapid development of portable electronic devices, unmanned aerial vehicles, electric tools, and electric vehicles, rechargeable batteries having high energy density, high power density, high safety, and long life are attracting attention. Although lithium ion batteries based on conventional graphite negative electrode materials have found wide application, their relatively low theoretical energy density has limited their further development. Searching for alternative materials for graphite negative electrodes is a key to current secondary battery research.
Silicon is the lithium ion battery anode material with the highest specific capacity (4200 mAh) currently known, but the electrochemical performance is drastically deteriorated due to its huge volume effect (> 300%). Therefore, silicon oxide with smaller volume effect is a desirable choice. The silicon oxide (SiO) has small volume effect (150%) and high theoretical capacity (> 1500 mAh), and becomes a hot spot for researching lithium ion battery cathode materials in recent years.
Although the volume effect of the silicon oxide (SiO) is smaller than that of silicon, the electrical conductivity is poor, the cycle performance and the first coulombic efficiency are poor, because the structural expansion and shrinkage change of the silicon oxide (SiO) material damages the stability of the electrode structure in the charging and discharging processes, the material particles are broken and pulverized, the collapse and the peeling of the electrode material structure are caused, the electrode material loses electrical contact, the capacity of the negative electrode is finally attenuated rapidly, and the cycle performance of the lithium battery is deteriorated. In order to improve the cycle performance and the first coulombic efficiency, the study finds that the nano-chemical and the composite of the silicon oxide (SiO) are carried out, the surface of the silicon oxide (SiO) is coated with a carbon material as an expansion buffer layer, the electric conductivity of the silicon oxide (SiO) is increased, and the cycle performance and the first coulombic efficiency of the silicon oxide (SiO) can be greatly improved by carrying out the pre-lithiation treatment on the silicon oxide (SiO) material.
Chinese patent CN 104466142A discloses a silicon/silicon-oxygen-carbon/graphite composite negative electrode material for lithium ion battery, which is prepared by dispersing silicon material in liquid organic siloxane monomer, adding curing agent into ethanol-water acidic solution, mixing with graphite negative electrode material, calcining, granulating to obtain silicon/silicon-oxygen-carbon/graphite negative electrode material with different particle diameters. The method is characterized in that graphite is taken as a framework, the silicon material is effectively adsorbed on the surface of the graphite, the agglomeration of the silicon material is avoided, and the conductivity of the silicon material is increased. Chinese patent CN 112259737A discloses a method for preparing mesoporous spherical silicon oxide negative electrode material for lithium battery, which is to obtain spherical silicon dioxide (SiO) by Stober method under alkaline condition 2 ) Adding magnesium powder and carbon source, mixing, and calcining at high temperature to obtain bagThe mesoporous spherical Bao Tan silicon oxide (SiO) is obtained by acid washing, the conductivity of the material is greatly improved by the mesoporous spherical Bao Tan silicon oxide, and meanwhile, the surface is coated with carbon to form a buffer layer, so that the cycle performance and the first coulomb efficiency of the silicon oxide (SiO) cathode material are effectively improved. The two patent technologies start from different angles, and the defects of poor cycle performance and low initial coulombic efficiency of the lithium battery caused by the electric conductivity of the silicon-based anode material of the lithium battery and large volume expansion easily occurring in the use process are effectively overcome.
Disclosure of Invention
The method aims at the defects of poor cycle performance and low initial coulombic efficiency of the lithium battery caused by poor conductivity and large volume expansion in the use process of the silicon-based anode material of the lithium battery. The first object of the present invention is to provide a carbon nanotube-connected double carbon layer coated mesoporous silica composite material, which has a core-shell structure, wherein mesoporous nano silica particles are used as cores, a double carbon coating layer is used as shells, carbon nanotubes are mainly dispersed in the mesopores of the nano silica particles and connected between the nano silica particles and the nano silica particles, the carbon nanotubes dispersed in the mesopores of the nano silica particles and the double carbon layer coated on the surfaces of the nano silica particles can effectively improve the conductivity of the nano silica particles, and simultaneously, the two carbon layers coated on the surfaces of the nano silica particles can effectively inhibit the damage of the nano silica particles to an electrode material due to volume expansion in the use process.
The second purpose of the invention is to provide a preparation method of the carbon nano tube connected double carbon layer coated mesoporous silica composite material, which has simple operation, low cost and easy control of production, and is beneficial to mass production.
The third purpose of the invention is to provide the application of the carbon nano tube connected double-carbon layer coated mesoporous silica composite material as the negative electrode material of the lithium ion battery, and the application of the composite material in the lithium ion battery can effectively improve the first coulomb efficiency and the cycle performance of the lithium ion battery.
In order to achieve the technical aim, the invention provides a preparation method of a carbon nano tube connected double carbon layer coated mesoporous silica composite material, which comprises the following steps:
1) Hydrolyzing silicate in the presence of a surfactant under an acidic condition to obtain silica sol; adding a silane coupling agent and alkali liquor into silica sol to react to obtain silica gel, and centrifugally separating and drying the silica gel to obtain a nano silica material;
2) Ball milling a nano silicon oxide material, a carbon nano tube, an organic carbon source and a dispersing agent in an aqueous medium to obtain slurry, wherein the slurry is subjected to spray drying and jet milling to obtain a precursor material, and the precursor material is subjected to calcination and washing to obtain a carbon-coated silicon oxide material;
3) And (3) carrying out CVD gas phase deposition on the surface of the carbon-coated silica material to obtain the double-carbon-layer-coated mesoporous silica composite material.
According to the technical scheme, silicate is taken as a raw material and is subjected to hydrolysis under an acidic condition, so that the hydrolysis process is stably carried out, a surfactant is utilized in the hydrolysis process to form highly dispersed nano silica crystal nucleus particles, the crystal nucleus particles grow to form monodisperse nano silica particle gel under the action of an alkaline condition and a silane coupling agent, the nano silica particle gel, a carbon nano tube, an organic carbon source and the like are calcined under a high temperature condition, and the nano silica particle gel, the carbon nano tube and the organic carbon source and the like undergo complex chemical reactions such as pyrolysis carbonization, carbothermic reduction, template pore-forming (decomposition of the surfactant) and the like, so that the nano silica with the surface rich in mesopores is taken as a core, the nano silica particles and the nano silica particles are connected through the carbon nano tube, the mesopores of the nano silica contain the carbon nano tube, the surface of the nano silica is coated with a composite structure of a pyrolytic carbon layer, and the carbon nano tube is coated with a carbon layer by a CVD deposition method, so that the carbon nano tube connected double-carbon layer coated mesoporous silica composite material is formed. The double carbon layers outside the composite material can effectively form buffer, the pyrolytic carbon layer structure formed by the pyrolysis process of the inner layer is loose and contains a porous structure, the mechanical property is poor, the mechanical strength of the whole carbon layer can be effectively improved by further depositing the compact CVD carbon layer with the structure, meanwhile, the translational sliding between the carbon layer and the carbon layer can greatly reduce the pressure of the silica particles in the expansion process, the damage of the silica material to the electrode material caused by the expansion in the use process is effectively restrained, and the conductivity of the SiO@CNT/C composite material is greatly improved by the conductive network formed by the carbon nano tubes in the mesoporous silica and on the surface of the mesoporous silica, and the cycle performance and the first coulomb efficiency of the material are effectively improved.
As a preferred embodiment, the hydrolysis conditions are: the silicate is hydrolyzed in an alcohol-water mixed solution containing a surfactant and an acid catalyst, wherein the silicate accounts for 30-60% of the total hydrolysis system, the absolute ethyl alcohol accounts for 20-50% of the total hydrolysis system, the water accounts for 10-40% of the total hydrolysis system, the surfactant accounts for 0.5-2% of the total hydrolysis system, and the acid catalyst accounts for 0.1-2% of the total hydrolysis system. The silicon oxide crystal nucleus particles formed in the hydrolysis process can be dispersed under the action of the surfactant, meanwhile, the surfactant can be pyrolyzed in the high-temperature calcination process, and part of the surfactant volatilizes in a small molecular form to play a role in pore-forming. The mass percentage content of silicate is preferably 45% -55%. The mass percentage content of the absolute ethyl alcohol is preferably 30-40%. The mass percentage of water is preferably 20-30%. The mass percentage content of the acid catalyst is preferably 0.2-1%. The hydrolysis of silicate is preferably carried out under reaction conditions which are such that stable hydrolysis of silicate takes place.
As a preferred embodiment, the silicate comprises ethyl orthosilicate, methyl orthosilicate, trimethyl orthosilicate, 3-aminopropyl triethoxysilane, (CH) 3 CH 2 ) 3 Si(CH 3 CH 2 ) 3 At least one of them. The silicon ester is ethyl orthosilicate and methyl orthosilicate, and the most preferable silicon ester is ethyl orthosilicate.
As a preferred embodiment, the acid catalyst comprises at least one of hydrochloric acid, sulfuric acid, formic acid, glacial acetic acid, polyacrylic acid, and a polybasic aryl carboxylic acid. These acids can be used as sol-gel catalysts, preferably hydrochloric acid in combination with glacial acetic acid, hydrochloric acid being used as the main catalyst (hydrochloric acid is usually dilute hydrochloric acid, for example, the concentration is 0.1 to 1 mol/L), and glacial acetic acid being used as buffer solution can effectively control the pH value to 1.5 to 2.0.
As a preferable embodiment, the surfactant is at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tridecyl polyoxyethylene ether and dodecyl dimethyl benzyl ammonium chloride. Preferred surfactants are cationic or nonionic surfactants. Most preferred is cetyltrimethylammonium bromide.
As a preferable scheme, the silane coupling agent is at least one of epoxy silane, vinyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and gamma-aminopropyl trimethoxysilane. A further preferred silane coupling agent is methyltriethoxysilane. The addition amount of the silane coupling agent is 20-50% of the mass of the silica sol.
As a preferable scheme, the addition amount of the alkali liquor is 2-5% of the mass of the silica sol; the alkali liquor is ammonia water. The preferred ammonia not only can be used as an alkaline reagent, but also can be used as a buffer reagent, thereby being beneficial to the generation of silica gel. The ammonia water is conventional industrial ammonia water.
As a preferable scheme, the temperature of the reaction is 20-60 ℃ and the time is 4-8 hours. The most preferable reaction temperature is 40-50 ℃, and the gel generation can be accelerated by increasing the temperature, but the reaction is too severe and easy to initiate the detonation and boiling due to the too high temperature.
As a preferable scheme, the mass ratio of the nano silicon oxide material to the carbon nano tube to the organic carbon source to the dispersing agent is 80-95:0.2-2:2-10:0.5-1.5.
As a preferred embodiment, the carbon nanotubes are multi-walled carbon nanotubes and/or single-walled carbon nanotubes. The carbon nanotubes are preferably single-walled carbon nanotubes; the single-wall carbon nano tube has smaller tube diameter and larger specific surface area, forms a connecting channel, can absorb and contact more nano silica materials, and has better conductivity. The diameter of the single-wall carbon nano tube is about 2nm, the nano tubes with the same mass fraction are added, the number of the single walls is more, the specific surface is larger, and the contacted nano silicon oxide material is more.
As a preferable scheme, the organic carbon source is at least one of sugar, organic acid and low-carbon alcohol; further preferably at least one of starch, sucrose, glucose, citric acid, succinic acid, and ethanol.
As a preferred embodiment, the dispersing agent is at least one of sodium hydroxycellulose, polyacrylic acid and sodium polyacrylate.
As a preferred embodiment, the conditions for the calcination are: under the protective atmosphere, the temperature is 500-1200 ℃ and the time is 1-12 h. The calcination temperature is preferably 700 to 1000 ℃. The calcination time is preferably 4 to 10 hours. Complex chemical reactions such as pyrolysis carbonization, carbothermic reduction, template pore-forming and the like occur in the calcination process.
As a preferred embodiment, the CVD deposition conditions are: under the protective atmosphere, the temperature is 500-1200 ℃ and the time is 1-12 h; at least one of natural gas, ethylene, ethane, acetylene and propane is used as a gas carbon source. A preferred gaseous carbon source is natural gas. The preferred temperature is 600 to 1000 ℃. The flow rate of the gaseous carbon source is 10ml to 100ml/min, more preferably 30ml to 60ml/min.
The washing process of the invention adopts dilute hydrochloric acid or dilute sulfuric acid and ionized water to repeatedly and alternately wash.
The invention also provides a carbon nano tube connected double carbon layer coated mesoporous silica composite material, which is obtained by the preparation method.
The carbon nanotube-connected double-layer carbon-coated mesoporous silica composite material has a core-shell structure, nano silica particles with mesopores are taken as cores, a double-layer carbon coating layer is taken as a shell, carbon nanotubes are connected between the nano silica particles, the carbon nanotubes are also dispersed in mesopores of the nano silica particles, the carbon nanotubes form a conductive network in the whole composite material, the conductivity is greatly improved, the double-carbon layer coated on the surface of the silica can also effectively improve the conductivity of the silica, and simultaneously, the two carbon layers coated on the surface of the silica can effectively inhibit the damage of the silica to an electrode material caused by volume expansion in the use process.
The invention also provides application of the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material, which is applied as a lithium ion battery anode material.
The carbon nanotube-connected double-layer carbon-coated mesoporous silica composite material is applied to a lithium ion battery: the SiO@CNT/C composite material comprises the following components in percentage by mass: siO@CNT/C composite material (80-95%):conductive agent SP (2-10%):binder SBR (2-5.5%):thickener CMC (1-4.5%) is mixed in proportion, deionized water is added and stirred uniformly to prepare slurry with the viscosity of 2500-3500 CPS, and then the slurry and lithium sheets are assembled into the button cell in a glove box.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the SiO@CNT/C composite material provided by the invention can not only effectively inhibit the expansion of the silica particles in the charging process, but also greatly increase the conductivity of the material, reduce the generation of lithium crystal branches, and prolong the service life and the first coulomb efficiency of the battery material.
The preparation method of the SiO@CNT/C composite material provided by the invention is simple to operate, low in cost and beneficial to mass production.
The SiO@CNT/C composite material provided by the invention can be applied to a lithium ion battery cathode material, so that the first coulomb efficiency and the cycle performance of the lithium ion battery can be effectively improved.
Drawings
FIGS. 1 and 2 are scanning electron micrographs of the SiO@CNT/C composite material prepared in example 1.
FIG. 3 is a charge and discharge curve of a button cell made of the SiO@CNT/C composite material prepared in example 1.
FIG. 4 is a charge and discharge curve of a button cell made of the SiO@CNT/C composite material prepared in example 2.
FIG. 5 is a charge and discharge curve of a button cell made of the SiO@CNT/C composite material prepared in example 3.
FIG. 6 is a charge and discharge curve of a button cell made of the SiO@CNT/C composite material prepared in example 4.
Fig. 7 is a charge-discharge curve of a button cell made of the sio@c composite material prepared in comparative example 1.
Fig. 8 is a charge-discharge curve of a button cell made of the sio@c composite material prepared in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Unless otherwise indicated, all starting materials and reagents in the examples below were as usual as commercially available.
Example 1
The embodiment provides a preparation method of a mesoporous SiO@CNT/C composite anode material, which comprises the following steps:
1) Mixing 60ml deionized water and 80ml absolute ethyl alcohol uniformly, mixing 0.88g cetyl trimethyl ammonium bromide uniformly, adding 0.8ml dilute hydrochloric acid (0.1 mol/L) and 0.2ml glacial acetic acid, stirring uniformly, adding 100ml ethyl orthosilicate, continuing stirring for 5min, stopping stirring, and standing for 60min until the liquid becomes transparent from turbidity. A mixed solution a was obtained.
2) The vessel containing the above mixed solution A was placed in a water bath at 45℃and 100ml of methyltriethoxysilane was added thereto, and 4ml of aqueous ammonia was further stirred for 6 hours. And then centrifugally separating and drying to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silicon oxide material, 25g of single-walled carbon nanotube aqueous slurry with 0.4% content, 4.65g of starch and 0.25g of sodium hydroxycellulose (CMC) are weighed according to the mass ratio of 90:0.2:9.3:0.5, CMC is firstly dissolved in water to prepare a clear aqueous solution with 0.5%, then the single-walled carbon nanotube aqueous slurry, the monodisperse nano silicon oxide material and the starch are sequentially added, ball milling is carried out for 1 hour, and stirring is uniform. Then spray drying, wherein the inlet temperature of the spray dryer is 180 ℃, the outlet temperature is 90 ℃, and the flow rate of hot air is 0.5m 3 A/min; jet milling, the classifying frequency of the jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5kg/min.
4) And (3) placing the crushed materials into a tube furnace which is filled with nitrogen for protection, calcining for 4 hours at 900 ℃, naturally cooling to room temperature, taking out, and repeatedly washing with dilute hydrochloric acid and water to obtain the carbon nano tube connected primary carbon-coated mesoporous silica material.
5) And (3) loading the carbon nanotube-connected primary carbon-coated silicon oxide material into a CVD furnace, introducing natural gas with the flow of 45ml/min, calcining for 4 hours at 900 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving with a 200-mesh screen to obtain the carbon nanotube-connected double-layer carbon-coated mesoporous SiO@CNT/C composite anode material.
Example 2
1) Mixing 60ml deionized water and 80ml absolute ethyl alcohol uniformly, mixing 0.90g dodecyl trimethyl ammonium bromide uniformly, adding 0.8ml dilute hydrochloric acid (0.1 mol/L) and 0.2ml glacial acetic acid, stirring uniformly, adding 100ml tetraethoxysilane, continuing stirring for 5min, stopping stirring, and standing for 60min until the liquid becomes transparent from turbidity. A mixed solution a was obtained.
2) The vessel containing the above mixed solution A was placed in a water bath at 45℃and 100ml of methyltriethoxysilane was added thereto, and 4ml of aqueous ammonia was further stirred for 6 hours. And then centrifugally separating and drying to obtain the monodisperse nano silica material.
3) 42.5g of mono-disperse nano silica material, 25g of single-wall carbon nano tube aqueous slurry with the content of 0.4%, 5g of starch and 0.25g of sodium hydroxycellulose (CMC) are respectively weighed according to the mass ratio of 85:0.2:10:0.5, CMC is firstly dissolved in water to prepare a clear aqueous solution with the content of 0.5%, and then the single-wall carbon nano tube aqueous slurry, the mono-disperse nano silica material and the starch are sequentially added, ball milling is carried out for 1 hour and stirring is uniform. Then spray drying, wherein the inlet temperature of the spray dryer is 180 ℃, the outlet temperature is 90 ℃, and the flow rate of hot air is 0.5m 3 A/min; jet milling, the classifying frequency of the jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5kg/min.
4) And (3) placing the crushed materials into a tube furnace which is filled with nitrogen for protection, calcining for 10 hours at 850 ℃, naturally cooling to room temperature, taking out, and repeatedly washing with dilute hydrochloric acid and water to obtain the carbon nano tube connected primary carbon-coated mesoporous silica material.
5) And (3) loading the carbon nanotube-connected primary carbon-coated silicon oxide material into a CVD furnace, introducing natural gas with the flow of 50ml/min, calcining for 10 hours at 900 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving with a 200-mesh screen to obtain the carbon nanotube-connected double-layer carbon-coated mesoporous SiO@CNT/C composite anode material.
Example 3
1) Mixing 60ml deionized water and 80ml absolute ethyl alcohol uniformly, mixing 0.88g cetyl trimethyl ammonium bromide uniformly, adding 0.8ml diluted hydrochloric acid (0.1 mol/L) and 0.2ml glacial acetic acid, stirring uniformly, adding 90ml trimethyl orthosilicate, continuing stirring for 5min, stopping stirring, and standing for 60min until the liquid becomes transparent from turbidity. A mixed solution a was obtained.
2) The vessel containing the above mixed solution A was placed in a water bath at 45℃and 100ml of methyltriethoxysilane was added thereto, and 4ml of aqueous ammonia was further stirred for 6 hours. And then centrifugally separating and drying to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silicon oxide material, 25g of single-walled carbon nanotube aqueous slurry with 0.4% content, 4.65g of starch and 0.25g of sodium hydroxycellulose (CMC) are weighed according to the mass ratio of 90:0.2:9.3:0.5, CMC is firstly dissolved in water to prepare a clear aqueous solution with 0.5%, then the single-walled carbon nanotube aqueous slurry, the monodisperse nano silicon oxide material and the starch are sequentially added, ball milling is carried out for 1 hour, and stirring is uniform. Then spray drying, wherein the inlet temperature of the spray dryer is 180 ℃, the outlet temperature is 90 ℃, and the flow rate of hot air is 0.5m 3 A/min; jet milling, the classifying frequency of the jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5kg/min.
4) And (3) placing the crushed materials into a tube furnace which is filled with nitrogen for protection, calcining for 4 hours at 700 ℃, naturally cooling to room temperature, taking out, and repeatedly washing with dilute hydrochloric acid and water to obtain the carbon nano tube connected primary carbon-coated mesoporous silica material.
5) And (3) loading the carbon nanotube-connected primary carbon-coated silicon oxide material into a CVD furnace, introducing natural gas with the flow of 45ml/min, calcining for 4 hours at 600 ℃ under nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving with a 200-mesh screen to obtain the carbon nanotube-connected double-layer carbon-coated mesoporous SiO@CNT/C composite anode material.
Example 4
1) Mixing 60ml deionized water and 80ml absolute ethyl alcohol uniformly, mixing 0.88g cetyl trimethyl ammonium bromide uniformly, adding 0.8ml dilute hydrochloric acid (0.1 mol/L) and 0.2ml glacial acetic acid, stirring uniformly, adding 100ml ethyl orthosilicate, continuing stirring for 5min, stopping stirring, and standing for 60min until the liquid becomes transparent from turbidity. A mixed solution a was obtained.
2) The vessel containing the above mixed solution A was placed in a water bath at 45℃and 100ml of methyltriethoxysilane was added thereto, and 4ml of aqueous ammonia was further stirred for 6 hours. And then centrifugally separating and drying to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silicon oxide material, 25g of single-walled carbon nanotube aqueous slurry with 0.4% content, 4.65g of starch and 0.25g of sodium polyacrylate are weighed according to the mass ratio of 90:0.2:9.3:0.5, firstly, sodium polyacrylate is dissolved in water to prepare a clear aqueous solution with 0.5%, then, the single-walled carbon nanotube aqueous slurry, the monodisperse nano silicon oxide material and the starch are sequentially added, ball milling is carried out for 1 hour, and stirring is carried out uniformly. Then spray drying, wherein the inlet temperature of the spray dryer is 180 ℃, the outlet temperature is 90 ℃, and the flow rate of hot air is 0.5m 3 A/min; jet milling, the classifying frequency of the jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5kg/min.
4) And (3) placing the crushed materials into a tube furnace which is filled with nitrogen for protection, calcining for 10 hours at 600 ℃, naturally cooling to room temperature, taking out, and repeatedly washing with dilute hydrochloric acid and water to obtain the carbon nano tube connected primary carbon-coated mesoporous silica material.
5) And (3) loading the carbon nanotube-connected primary carbon-coated silicon oxide material into a CVD furnace, introducing natural gas with the flow of 45ml/min, calcining at 600 ℃ for 10 hours under nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving with a 200-mesh screen to obtain the carbon nanotube-connected double-layer carbon-coated mesoporous SiO@CNT/C composite anode material.
Comparative example 1
The difference from example 1 is that no carbon nanotubes were added and the rest of the process was the same.
1) Mixing 60ml deionized water and 80ml absolute ethyl alcohol uniformly, mixing 0.88g cetyl trimethyl ammonium bromide uniformly, adding 0.8ml dilute hydrochloric acid (0.1 mol/L) and 0.2ml glacial acetic acid, stirring uniformly, adding 100ml ethyl orthosilicate, continuing stirring for 5min, stopping stirring, and standing for 60min until the liquid becomes transparent from turbidity. A mixed solution a was obtained.
2) The vessel containing the above mixed solution A was placed in a water bath at 45℃and 100ml of methyltriethoxysilane was added thereto, and 4ml of aqueous ammonia was further stirred for 6 hours. And then centrifugally separating and drying to obtain the monodisperse nano silica material.
3) According to the mass ratio of 90:9.5:0.5, 45g of monodisperse nano silica material, 4.75g of starch and 0.25g of sodium hydroxycellulose (CMC) are respectively weighed, CMC is firstly dissolved in water to prepare a clear water solution with the concentration of 0.5 percent, then the monodisperse nano silica material and the starch are sequentially added into the solution, ball milling is carried out for 1 hour, and stirring is uniform. Then spray drying, wherein the inlet temperature of the spray dryer is 180 ℃, the outlet temperature is 90 ℃, and the flow rate of hot air is 0.5m 3 A/min; jet milling, the classifying frequency of the jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5kg/min.
4) And (3) placing the crushed materials into a tube furnace which is filled with nitrogen for protection, calcining for 4 hours at 900 ℃, naturally cooling to room temperature, taking out, and repeatedly washing with dilute hydrochloric acid and water to obtain the primary carbon-coated mesoporous silica material.
5) And (3) loading the primary carbon-coated silica material into a CVD furnace, introducing natural gas with the flow of 45ml/min, calcining for 4 hours at 900 ℃ under nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving with a 200-mesh screen to obtain the double-layer carbon-coated mesoporous SiO@CNT/C composite anode material.
Comparative example 2
The difference from example 1 is that no carbon nanotubes are added, only one layer of carbon coating is provided, and the rest of the process is the same.
1) Mixing 60ml deionized water and 80ml absolute ethyl alcohol uniformly, mixing 0.88g cetyl trimethyl ammonium bromide uniformly, adding 0.8ml dilute hydrochloric acid (0.1 mol/L) and 0.2ml glacial acetic acid, stirring uniformly, adding 100ml ethyl orthosilicate, continuing stirring for 5min, stopping stirring, and standing for 60min until the liquid becomes transparent from turbidity. A mixed solution a was obtained.
2) The vessel containing the above mixed solution A was placed in a water bath at 45℃and 100ml of methyltriethoxysilane was added thereto, and 4ml of aqueous ammonia was further stirred for 6 hours. And then centrifugally separating and drying to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silica material, 4.75g of starch and 0.25g of sodium hydroxycellulose (CMC) are respectively weighed according to the mass ratio of 90:9.5:0.5, CMC is firstly dissolved in water to prepare a clear water solution with the concentration of 0.5 percent, then the monodisperse nano silica material and the starch are sequentially added into the solution, ball milling is carried out for 1 hour, and stirring is uniform. Then spray drying, wherein the inlet temperature of the spray dryer is 180 ℃, the outlet temperature is 90 ℃, and the flow rate of hot air is 0.5m 3 A/min; jet milling, the classifying frequency of the jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5kg/min.
4) And (3) placing the crushed materials into a tube furnace which is filled with nitrogen for protection, calcining for 4 hours at 900 ℃, naturally cooling to room temperature, taking out, repeatedly washing with dilute hydrochloric acid and water, and spray-drying to obtain the primary carbon-coated mesoporous silica material.
Example 5
The materials obtained in examples 1 to 4 and comparative examples 1 to 2 were respectively prepared into button cells, and electrochemical performance tests were performed: the materials obtained in the above examples were mixed according to the ratio of SiO@CNT/C (85%):conductive agent SP (10%):binder SBR (3.5%):thickener CMC (1.5%), respectively, coated, sliced, and assembled into 2025 button lithium ion battery in glove box. The electrolyte is LiPF 6/(EC+DMC) with the concentration of 1mol/L, and the diaphragm is Celgard2400 membrane.
And adopting a LANHE battery program control tester of the Wuhan blue electric company to carry out constant current charge and discharge experiments on the assembled battery.
FIGS. 1 and 2 are SEM characterization graphs of SiO@CNT/C materials. FIGS. 3 to 6 are charge and discharge graphs of button cells made of the SiO@CNT/C composite materials prepared in examples 1 to 4 at 25℃and 0.1C magnification, respectively; fig. 7 and 8 are charge and discharge curves of comparative examples 1 and 2 at a rate of 0.1C at 25 ℃.
The SiO@CNT/C composite material of the embodiment 1 is prepared into a button cell, the first discharge specific capacity can reach 1665.7mAh/g, the reversible specific capacity can reach 1488.6mAh/g, and the first coulomb efficiency is 89.36%.
The SiO@CNT/C composite material of the embodiment 2 can reach a first discharge specific capacity of 1586.8mAh/g, a reversible specific capacity of 1423.3mAh/g and a first coulomb efficiency of 89.69%.
The SiO@CNT/C composite material of example 3 is prepared into a button cell with a first discharge specific capacity of 1494.3mAh/g, a reversible specific capacity of 1231mAh/g and a first coulomb efficiency of 82.38%.
The SiO@CNT/C composite material of example 4 is prepared into a button cell with a first discharge specific capacity of 1589.6mAh/g and a reversible specific capacity of 1306.6mAh/g, and has a first coulomb efficiency of 82.19%.
In examples 3 and 4, the first reversible specific capacity and first efficiency were lower than in examples 1 and 2, probably due to incomplete reduction of the silica material to the silica material at 600 c, with a portion of the inactive silica phase leading to a decrease in its capacity and first coulombic efficiency.
The SiO/C composite material of comparative example 1 is prepared into a button cell with the first discharge specific capacity of 1597mAh/g, the reversible specific capacity of 1318.4mAh/g and the first coulomb efficiency of 82.56%.
The SiO/C composite material of comparative example 2 is prepared into a button cell with the first discharge specific capacity of 1575.3mAh/g and the reversible specific capacity of 1240.1mAh/g, and the first coulomb efficiency of 78.72%.
As can be seen from comparative examples 1 and 2, the reversible specific capacity or the first coulombic efficiency is lower than that of examples 1 and 2 without CNT, which suggests that CNT acts as a conductive network in the material, greatly improving the conductive properties of the material. The first coulombic efficiency of the SiO@CNT/C composite material in the lithium ion battery is increased.
Table 1 shows the capacity retention data for the first 4 examples and 2 comparative examples at 200 cycles at 25℃and 0.1C current density for SiO@CNT/C material button cells, and as can be seen from Table 1, the capacity fading for the cells made of the SiO@CNT/C composite materials of examples 1-2 is very small. Examples 3 to 4 were poor in conductivity and large in capacity fading due to the presence of the siloxane hetero-phase, as compared with examples 1 and 2, since comparative examples 1 to 2 were not added with CNT. Namely, the SiO@CNT/C material lithium battery cathode material provided by the invention can be applied to a battery, so that the cycling stability of the battery can be improved, and the service life of the battery can be prolonged.
TABLE 1

Claims (10)

1. A preparation method of a carbon nano tube connected double carbon layer coated mesoporous silica composite material is characterized by comprising the following steps: the method comprises the following steps:
1) Hydrolyzing silicate in the presence of a surfactant under an acidic condition to obtain silica sol; adding a silane coupling agent and alkali liquor into silica sol to react to obtain silica gel, and centrifugally separating and drying the silica gel to obtain a nano silica material; the surfactant is at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tridecyl polyoxyethylene ether and dodecyl dimethyl benzyl ammonium chloride; the addition amount of the silane coupling agent is 20% -50% of the mass of the silica sol; the silane coupling agent is at least one of epoxy silane, vinyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and gamma-aminopropyl trimethoxysilane;
2) Ball milling a nano silicon oxide material, a carbon nano tube, an organic carbon source and a dispersing agent in an aqueous medium to obtain slurry, wherein the slurry is subjected to spray drying and jet milling to obtain a precursor material, and the precursor material is subjected to calcination and washing to obtain a carbon-coated silicon oxide material;
3) And (3) carrying out CVD gas phase deposition on the surface of the carbon-coated silica material to obtain the double-carbon-layer-coated mesoporous silica composite material.
2. The method for preparing the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps: the hydrolysis conditions are as follows: the silicate is hydrolyzed in an alcohol-water mixed solution containing a surfactant and an acid catalyst, wherein the silicate accounts for 30-60% by mass, the absolute ethyl alcohol accounts for 20-50% by mass, the water accounts for 10-40% by mass, the surfactant accounts for 0.4-2% by mass, and the acid catalyst accounts for 0.1-2% by mass in the whole hydrolysis system.
3. The method for preparing the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material according to claim 2, wherein the method comprises the following steps:
the silicate comprises at least one of tetraethoxysilane, methyl orthosilicate, trimethyl orthosilicate sulfonate and 3-aminopropyl triethoxysilane;
the acid catalyst comprises at least one of hydrochloric acid, sulfuric acid, formic acid, glacial acetic acid, polyacrylic acid and polybasic aryl carboxylic acid.
4. The method for preparing the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps:
the addition amount of the alkali liquor is 2% -5% of the mass of the silica sol; the alkali liquor is ammonia water.
5. The method for preparing the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps: the reaction temperature is 20-60 ℃ and the reaction time is 4-8 hours.
6. The method for preparing the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps: the mass ratio of the nano silicon oxide material to the carbon nano tube to the organic carbon source to the dispersing agent is 80-95:0.2-2:2-10:0.5-1.5;
the carbon nanotubes are multi-wall carbon nanotubes and/or single-wall carbon nanotubes;
the organic carbon source is at least one of saccharides, organic acid and low-carbon alcohol;
the dispersing agent is at least one of sodium hydroxycellulose, polyacrylic acid and sodium polyacrylate.
7. The method for preparing the carbon nanotube-linked double-carbon-layer-coated mesoporous silica composite material according to claim 6, wherein the method comprises the following steps: the conditions of the calcination are as follows: under the protective atmosphere, the temperature is 500-1200 ℃ and the time is 1-12 h.
8. The method for preparing the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps: the CVD deposition conditions were: under the protective atmosphere, the temperature is 500-1200 ℃ and the time is 1-12 h; taking at least one of natural gas, ethylene, ethane, acetylene and propane as a gas carbon source; the flow rate of the gas carbon source is 10 ml-100 ml/min.
9. A carbon nanotube connected double carbon layer coated mesoporous silica composite material is characterized in that: the method according to any one of claims 1 to 8.
10. The use of a carbon nanotube-bonded double carbon layer coated mesoporous silica composite as defined in claim 9, wherein: the material is applied as a negative electrode material of a lithium ion battery.
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CN114899398B (en) * 2022-04-20 2024-01-26 同济大学 Preparation and application of boron-nitrogen co-doped carbon nanotube coated silicon oxide composite material
CN115286871B (en) * 2022-09-15 2023-06-06 扬州工业职业技术学院 Halogen-free flame-retardant conductive polypropylene material
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101633505A (en) * 2009-08-25 2010-01-27 郑文芝 SiO2 nanoscale porous material with aerogel property prepared by microwave reaction and preparation method thereof
WO2013029212A1 (en) * 2011-09-03 2013-03-07 深圳市贝特瑞新能源材料股份有限公司 Lithium-ion battery negative electrode material, preparation method therefor, and lithium-ion battery
CN103280560A (en) * 2013-05-20 2013-09-04 北京科技大学 Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery
CN103346302A (en) * 2013-07-01 2013-10-09 华南师范大学 Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof
CN105609743A (en) * 2016-03-06 2016-05-25 河北工业大学 Preparation method for SiO<x>-C-CNT composite material of lithium-ion battery negative electrode
CN106865558A (en) * 2017-03-22 2017-06-20 伊科纳诺（北京）科技发展有限公司 Normal pressure prepares the method and obtained aerosil of aerosil
CN107994217A (en) * 2017-11-23 2018-05-04 广东工业大学 The preparation method and lithium ion battery of silicon based composite material are covered in a kind of double-contracting
CN110697724A (en) * 2019-11-22 2020-01-17 上海应用技术大学 Silicon dioxide aerogel and preparation method thereof
CN110767877A (en) * 2019-09-20 2020-02-07 乳源东阳光磁性材料有限公司 Lithium ion battery silicon monoxide negative electrode material and preparation method and application thereof
CN111276677A (en) * 2020-01-13 2020-06-12 湖州金灿新能源科技有限公司 Carbon nano material/amorphous carbon/silicon monoxide composite material and preparation method thereof
CN111564611A (en) * 2020-04-07 2020-08-21 河南电池研究院有限公司 Silicon-oxygen-carbon composite material, preparation method and lithium battery material
CN112678807A (en) * 2020-12-28 2021-04-20 成都硅宝科技股份有限公司 Modified silicon monoxide/carbon nano tube composite negative electrode material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102157731B (en) * 2011-03-18 2015-03-04 上海交通大学 Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101633505A (en) * 2009-08-25 2010-01-27 郑文芝 SiO2 nanoscale porous material with aerogel property prepared by microwave reaction and preparation method thereof
WO2013029212A1 (en) * 2011-09-03 2013-03-07 深圳市贝特瑞新能源材料股份有限公司 Lithium-ion battery negative electrode material, preparation method therefor, and lithium-ion battery
CN103280560A (en) * 2013-05-20 2013-09-04 北京科技大学 Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery
CN103346302A (en) * 2013-07-01 2013-10-09 华南师范大学 Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof
CN105609743A (en) * 2016-03-06 2016-05-25 河北工业大学 Preparation method for SiO<x>-C-CNT composite material of lithium-ion battery negative electrode
CN106865558A (en) * 2017-03-22 2017-06-20 伊科纳诺（北京）科技发展有限公司 Normal pressure prepares the method and obtained aerosil of aerosil
CN107994217A (en) * 2017-11-23 2018-05-04 广东工业大学 The preparation method and lithium ion battery of silicon based composite material are covered in a kind of double-contracting
CN110767877A (en) * 2019-09-20 2020-02-07 乳源东阳光磁性材料有限公司 Lithium ion battery silicon monoxide negative electrode material and preparation method and application thereof
CN110697724A (en) * 2019-11-22 2020-01-17 上海应用技术大学 Silicon dioxide aerogel and preparation method thereof
CN111276677A (en) * 2020-01-13 2020-06-12 湖州金灿新能源科技有限公司 Carbon nano material/amorphous carbon/silicon monoxide composite material and preparation method thereof
CN111564611A (en) * 2020-04-07 2020-08-21 河南电池研究院有限公司 Silicon-oxygen-carbon composite material, preparation method and lithium battery material
CN112678807A (en) * 2020-12-28 2021-04-20 成都硅宝科技股份有限公司 Modified silicon monoxide/carbon nano tube composite negative electrode material and preparation method thereof

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