CN114122397A - Carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof - Google Patents

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

Info

Publication number
CN114122397A
CN114122397A CN202111187449.XA CN202111187449A CN114122397A CN 114122397 A CN114122397 A CN 114122397A CN 202111187449 A CN202111187449 A CN 202111187449A CN 114122397 A CN114122397 A CN 114122397A
Authority
CN
China
Prior art keywords
carbon
composite material
layer
mesoporous silica
coated mesoporous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111187449.XA
Other languages
Chinese (zh)
Other versions
CN114122397B (en
Inventor
易旭
廖寄乔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Jinsi Technology Co ltd
Original Assignee
Hunan Jinsi Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Jinsi Technology Co ltd filed Critical Hunan Jinsi Technology Co ltd
Priority to CN202111187449.XA priority Critical patent/CN114122397B/en
Publication of CN114122397A publication Critical patent/CN114122397A/en
Application granted granted Critical
Publication of CN114122397B publication Critical patent/CN114122397B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 dual-carbon-layer-coated mesoporous silica composite material and a preparation method and application thereof. The preparation method comprises the following steps of obtaining a nano silica material by silicate through a sol-gel method and a template method, carrying out adhesive adsorption on the nano silica material and a carbon nano tube under the action of a silane coupling agent and a dispersing agent, carrying out high-temperature calcination to form a carbon-coated mesoporous silica material connected with the carbon nano tube, and further coating carbon on the surface of the carbon-coated mesoporous silica material to obtain the SiO @ CNT/C composite material. The SiO @ CNT/C composite material can effectively inhibit the damage of an electrode caused by the volume expansion of the silicon monoxide, greatly improves the cycle performance of the electrode material in a lithium ion battery, simultaneously greatly improves the conductivity of the material due to the addition of the carbon nano tube, and reduces the generation of lithium dendrites, thereby effectively improving the first coulombic efficiency and the cycle performance of the lithium ion battery.

Description

Carbon nanotube-connected dual-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 nanotube-connected double-carbon-layer-coated mesoporous silicon oxide composite cathode material, and also relates to a preparation method of the carbon nanotube-connected double-carbon-layer-coated mesoporous silicon oxide composite material and application of the carbon nanotube-connected double-carbon-layer-coated mesoporous silicon oxide 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 with high energy density, high power density, high safety, and long life span have received much attention. Although lithium ion batteries based on conventional graphite negative electrode materials have achieved widespread use, their relatively low theoretical energy density has limited their further development. Finding alternative materials for graphite anodes is becoming the key to current secondary battery research.
Silicon is the lithium ion battery anode material with the highest known specific capacity (4200mAh), but the electrochemical performance is sharply deteriorated due to the huge volume effect (> 300%). Therefore, silicon oxide having a small volume effect is a more desirable choice. Among them, the volume effect (150%) of the silicon oxide (SiO) is small, and at the same time, the silicon oxide (SiO) has a high theoretical capacity (>1500mAh), and becomes a hot spot for the research of the negative electrode material of the lithium ion battery in recent years.
Although the volume effect of the silicon oxide (SiO) is smaller than that of silicon, the conductivity is poor, and the cycle performance and the first coulombic efficiency are poor, because the structural expansion and contraction change of the silicon oxide (SiO) material in the charging and discharging process destroys the stability of an electrode structure, leads to the breakage and pulverization of material particles, causes the collapse and the peeling of the electrode material structure, leads to the loss of the electric contact of the electrode material, and finally leads to the rapid attenuation of the capacity of a negative electrode, and leads to the deterioration of the cycle performance of a lithium battery. In order to improve the cycle performance and improve the first coulombic efficiency, researches show that the cycle performance and the first coulombic efficiency can be greatly improved by carrying out the prelithiation treatment on the silicon oxide (SiO) material by nano-converting and compounding the silicon oxide (SiO) and coating a carbon material on the surface of the silicon oxide (SiO) to serve as an expansion buffer layer so as to increase the conductive performance of the silicon oxide (SiO).
Chinese patent CN 104466142A discloses a silicon/silicon-oxygen-carbon/graphite composite negative electrode material for lithium ion batteries, which is prepared by dispersing silicon materials in liquid organic siloxane monomers, adding a curing agent into an ethanol-water acidic solution, mixing with a graphite negative electrode material, calcining, and granulating. The graphite is used as a framework, and the silicon material is effectively adsorbed on the surface of the graphite, so that the self-aggregation of the silicon material is avoided, and the conductivity of the silicon material is increased. Chinese patent CN 112259737A discloses a preparation method of a mesoporous spherical silicon oxide negative electrode material of a lithium battery, spherical silicon dioxide (SiO) is obtained by a Stober method under alkaline conditions2) The preparation method comprises the steps of adding magnesium powder and a carbon source, mixing, calcining at high temperature to obtain carbon-coated silicon oxide (SiO), and then pickling to obtain mesoporous spherical carbon-coated silicon oxide (SiO), wherein the mesoporous spherical carbon-coated silicon oxide greatly improves the conductivity of the material, and the surface of the mesoporous spherical carbon-coated silicon oxide forms a buffer layer, so that the cycle performance and the initial coulomb efficiency of the silicon oxide (SiO) cathode material are effectively improved. The two patent technologies are from different angles, and the defects of poor cycle performance and low first coulombic efficiency of the lithium battery caused by the conductivity of the silicon-based negative electrode material of the lithium battery and the high possibility of large volume expansion in the using process are effectively overcome.
Disclosure of Invention
The method aims at the defects that the lithium battery has poor cycle performance and low first coulombic efficiency due to poor conductivity of a silicon-based negative electrode material of the lithium battery and large volume expansion easily generated in the using process. The first objective of the present invention is to provide a carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material, which has a core-shell structure, the nano-silica particles with mesopores are cores, the dual-layer carbon coating is shells, the 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 dual-carbon-layer coated on the surface of the nano-silica particles can effectively improve the electrical conductivity of the nano-silica particles, and the two carbon layers coated on the surface of the nano-silica particles can effectively inhibit the damage of the nano-silica particles to the 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 nanotube-connected double-carbon-layer-coated mesoporous silica composite material, which has the advantages of simple operation, low cost, easy production control and contribution to large-scale production.
The third purpose of the invention is to provide an application of the carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material as a negative electrode material of a lithium ion battery, and the application of the carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material in the lithium ion battery can effectively improve the first coulombic efficiency and the cycle performance of the lithium ion battery.
In order to achieve the technical purpose, the invention provides a preparation method of a carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material, which comprises the following steps:
1) hydrolyzing silicate ester under the presence of a surfactant and under an acidic condition to obtain silica sol; adding a silane coupling agent and alkali liquor into silica sol for reaction to obtain silica gel, and performing centrifugal separation and drying on the silica gel to obtain a nano silica material;
2) ball-milling a nano silica material, a carbon nano tube, an organic carbon source and a dispersing agent in an aqueous medium to obtain slurry, spray-drying the slurry, and carrying out airflow crushing to obtain a precursor material, and calcining and washing the precursor material to obtain a carbon-coated silica material;
3) and depositing a carbon layer on the surface of the carbon-coated silicon oxide material through CVD gas phase to obtain the double-carbon-layer-coated mesoporous silicon oxide composite material.
The technical scheme of the invention is that silicate ester is firstly hydrolyzed under acidic condition as raw material to ensure that the hydrolysis process is carried out stably, in the hydrolysis process, surfactant is utilized to form highly dispersed nano silica crystal nucleus particles, the crystal nucleus particles grow under alkaline condition and the presence of silane coupling agent to form monodisperse nano silica particle gel, the nano silica particle gel, carbon nano tubes, organic carbon source and the like are calcined under high temperature condition, and through complex chemical reactions such as pyrolysis carbonization, carbothermic reduction, template pore-forming (decomposition of surfactant) and the like, nano silica with rich mesopores on the surface is finally formed as a core, the nano silica particles and the nano silica particles are connected through the carbon nano tubes, the mesopores of the nano silica contain the carbon nano tubes, and the surface of the nano silica is coated with a composite structure of a pyrolytic carbon layer, and coating a carbon layer by a CVD (chemical vapor deposition) method to form the carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material. The double carbon layers outside the composite material can effectively form buffering, the pyrolysis carbon layer formed in the pyrolysis process in the inner layer is loose in structure 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 a compact CVD carbon layer with a structure, meanwhile, the pressure of the silicon oxide particles in the expansion process can be greatly reduced by the translational sliding between the carbon layer and the carbon layer, the damage to the electrode material caused by expansion of the silicon oxide material in the use process is effectively inhibited, the conductivity of the SiO @ CNT/C composite material is greatly increased due to the fact that the conductive network is formed by the carbon nano tubes in the silicon oxide mesopores and on the surface of the silicon oxide mesopores, and the cycle performance and the first coulombic efficiency of the material are effectively improved.
As a preferred embodiment, the hydrolysis conditions are: silicate ester is hydrolyzed in alcohol-water mixed solution containing a surfactant and an acid catalyst, and in the whole hydrolysis system, the silicate ester accounts for 30-60% by mass, absolute ethyl alcohol accounts for 20-50% by mass, water accounts for 10-40% by mass, the surfactant accounts for 0.5-2% by mass, and the acid catalyst accounts for 0.1-2% by mass. The silica crystal nucleus particles formed in the hydrolysis process can be dispersed under the action of the surfactant, and meanwhile, the surfactant can be pyrolyzed in the high-temperature calcination process, and part of the surfactant is volatilized in a micromolecule form, so that the pore-forming effect is realized. The content of silicate ester is preferably 45-55% by mass. The mass percentage content of the absolute ethyl alcohol is preferably 30-40%. The mass percentage content of the water is preferably 20-30%. The mass percentage content of the acid catalyst is preferably 0.2-1%. The preferred reaction conditions are such that hydrolysis of the silicate proceeds stably.
As a preferred scheme, the silicate comprises ethyl orthosilicate, methyl orthosilicate, trimethyl orthosilicate, 3-aminopropyltriethoxysilane, (CH)3CH2)3Si(CH3CH2)3At least one of them. The silicon ester is tetraethoxysilane and methyl orthosilicate, and the most preferable silicate is tetraethoxysilane.
As a preferred embodiment, the acid catalyst comprises at least one of hydrochloric acid, sulfuric acid, formic acid, glacial acetic acid, polyacrylic acid, and polyaryl carboxylic acid. The acids can be used as a catalyst of sol-gel, preferably a combination of hydrochloric acid and glacial acetic acid, the hydrochloric acid is used as a main catalyst (dilute hydrochloric acid is generally used as hydrochloric acid, and the concentration is 0.1-1 mol/L, for example), and the glacial acetic acid is used as a buffer solution and can effectively control the pH value to be 1.5-2.0.
In a preferred 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 surfactants or nonionic surfactants. Most preferably cetyltrimethylammonium bromide.
In a preferred embodiment, the silane coupling agent is at least one of epoxy silane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and gamma-aminopropyltrimethoxysilane. A further preferred silane coupling agent is methyltriethoxysilane. The adding amount of the silane coupling agent is 20-50% of the mass of the silica sol.
As a preferred scheme, the addition amount of the alkali liquor is 2-5% of the mass of the silica sol; the alkali liquor is ammonia water. Preferred aqueous ammonia can be used as both an alkaline reagent and a buffering reagent to facilitate the formation of silica gel. The ammonia water is conventional industrial ammonia water.
As a preferable scheme, the reaction temperature is 20-60 ℃ and the reaction time is 4-8 hours. The most preferable reaction temperature is 40-50 ℃, the gel generation can be accelerated by increasing the temperature, but the bumping is easily caused by too violent reaction at too high temperature.
Preferably, the mass ratio of the nano silica material to the carbon nano tubes, the organic carbon source and the dispersing agent is 80-95: 0.2-2: 2-10: 0.5-1.5.
As a preferable scheme, the carbon nanotube is a multi-wall carbon nanotube and/or a single-wall carbon nanotube. The carbon nanotubes are preferably single-walled carbon nanotubes; the pipe diameter of the single-walled carbon nanotube is selected to be smaller, the specific surface area is larger, a connecting channel is formed, more nano silica materials can be adsorbed and contacted, and the conductivity is better. The pipe diameter of the single-walled carbon nanotube is about 2nm, the number of single walls can be more by adding the nanotubes with the same mass fraction, the specific surface is larger, and the contact amount of the nano silica material is more.
As a preferable scheme, the organic carbon source is at least one of saccharides, organic acids and lower alcohols; more preferably at least one of starch, sucrose, glucose, citric acid, succinic acid, and ethanol.
As a preferable embodiment, the dispersant is at least one of sodium hydroxy cellulose, polyacrylic acid and sodium polyacrylate.
As a preferred embodiment, the calcination conditions are: under the protective atmosphere, the temperature is 500-1200 ℃, and the time is 1-12 h. The calcination temperature is preferably 700-1000 ℃. The calcination time is preferably 4 to 10 hours. In the calcining process, complex chemical reactions such as pyrolysis carbonization, carbon thermal reduction, template pore-forming and the like occur.
As a preferred scheme, 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. The preferred gaseous carbon source is natural gas. The preferable temperature is 600-1000 ℃. The flow rate of the gaseous carbon source is 10ml to 100ml/min, and more preferably 30ml to 60 ml/min.
The washing process of the invention adopts dilute hydrochloric acid or dilute sulfuric acid and ionized water for repeated and alternate washing.
The invention also provides a carbon nanotube connected dual-carbon-layer-coated mesoporous silica composite material, which is prepared by the preparation method.
The double-layer carbon-coated mesoporous silica composite material connected by the carbon nano tubes has a core-shell structure, nano silica particles with mesopores are used as cores, the double-layer carbon coating is used as shells, the carbon nano tubes are connected among the nano silica particles, the carbon nano tubes are dispersed in the mesopores of the nano silica particles, the carbon nano tubes form a conductive network in the whole composite material, the conductive performance is greatly improved, the double carbon layers coated on the surface of the silica can also effectively improve the conductive performance of the silica, and meanwhile, the two carbon layers coated on the surface of the silica can effectively inhibit the damage of the electrode material caused by volume expansion of the silica in the using process.
The invention also provides an application of the carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material as a lithium ion battery cathode material.
The carbon nanotube-connected double-layer carbon-coated mesoporous silica composite material is applied to lithium ion batteries: the SiO @ CNT/C composite material comprises the following components in percentage by mass: mixing the SiO @ CNT/C composite material (80-95%), the conductive agent SP (2-10%), the binder SBR (2-5.5%), the thickening agent CMC (1-4.5%), adding deionized water, uniformly stirring to prepare slurry with the viscosity of 2500-3500 CPS, and then assembling the slurry and a lithium sheet in a glove box to form the button cell.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the SiO @ CNT/C composite material provided by the invention not only can effectively inhibit the expansion of the silicon monoxide particles in the charging process, but also can greatly increase the conductivity of the material, simultaneously reduce the generation of lithium crystal branches, and increase the service life and the first coulombic 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 large-scale production.
The SiO @ CNT/C composite material provided by the invention is applied as a lithium ion battery cathode material, so that the first coulombic efficiency and the cycle performance of a lithium ion battery can be effectively improved.
Drawings
FIGS. 1 and 2 are scanning electron micrographs of the SiO @ CNT/C composite prepared in example 1.
FIG. 3 is a charge and discharge curve of a button cell made of the SiO @ CNT/C composite prepared in example 1.
FIG. 4 is a charge and discharge curve of a button cell made of the SiO @ CNT/C composite prepared in example 2.
FIG. 5 shows the charge and discharge curves of button cells made of the SiO @ CNT/C composite prepared in example 3.
FIG. 6 shows the charge and discharge curves of button cells made of the SiO @ CNT/C composite prepared in example 4.
Fig. 7 is a charge and discharge curve of a button cell made of the SiO @ C composite material prepared in comparative example 1.
Fig. 8 is a charge and 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 the embodiments of the present invention are not limited thereto.
All the raw materials and reagents in the following examples are commercially available conventional raw materials and reagents unless otherwise specified.
Example 1
The embodiment provides a preparation method of a mesoporous SiO @ CNT/C composite anode material, which comprises the following steps:
1) 60ml of deionized water and 80ml of absolute ethyl alcohol are taken and uniformly mixed, 0.88g of hexadecyl trimethyl ammonium bromide is uniformly mixed, 0.8ml of dilute hydrochloric acid (0.1mol/L) and 0.2ml of glacial acetic acid are added and uniformly stirred, then 100ml of tetraethoxysilane is added and continuously stirred for 5min, the stirring is stopped, and the mixture is kept stand for 60min until the liquid becomes transparent from turbidity. To obtain a mixed solution A.
2) The vessel containing the mixed solution A was placed in a water bath at 45 ℃ and 100ml of methyltriethoxysilane and 4ml of ammonia were added thereto and stirred for 6 hours. Then centrifugal separation and drying are carried out to obtain the monodisperse nano silica material.
3) Respectively weighing 45g of monodisperse nano silica material, 25g of single-walled carbon nanotube aqueous slurry with the content of 0.4%, 4.65g of starch and 0.25g of sodium hydroxy cellulose (CMC) according to the mass ratio of 90:0.2:9.3:0.5, dissolving the CMC in water to prepare 0.5% clear aqueous solution, then sequentially adding the single-walled carbon nanotube aqueous slurry, the monodisperse nano silica material and the starch, ball-milling for 1 hour and uniformly stirring. Then spray drying with inlet temperature of 180 deg.C, outlet temperature of 90 deg.C, and hot air flow rate of 0.5m3Min; and (3) carrying out jet milling, wherein the classification frequency of a jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5 kg/min.
4) And putting the crushed material into a tube furnace which is filled with nitrogen for protection and is calcined for 4h at 900 ℃, naturally cooling to room temperature, taking out the material and repeatedly washing the material by using dilute hydrochloric acid and water to obtain the primary carbon-coated mesoporous silica material connected with the carbon nano tubes.
5) And (2) filling the primary carbon-coated silicon monoxide material connected with the carbon nano tubes into a CVD (chemical vapor deposition) furnace, introducing natural gas at the flow rate of 45ml/min, calcining for 4h at 900 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving by using a 200-mesh sieve to obtain the double-layer carbon-coated mesoporous SiO @ CNT/C composite negative electrode material connected with the carbon nano tubes.
Example 2
1) 60ml of deionized water and 80ml of absolute ethyl alcohol are taken and uniformly mixed, 0.90g of dodecyl trimethyl ammonium bromide is uniformly mixed, 0.8ml of dilute hydrochloric acid (0.1mol/L) and 0.2ml of glacial acetic acid are added and uniformly stirred, then 100ml of tetraethoxysilane is added and continuously stirred for 5min, the stirring is stopped, and the mixture is kept stand for 60min until the liquid becomes transparent from turbidity. To obtain a mixed solution A.
2) The vessel containing the mixed solution A was placed in a water bath at 45 ℃ and 100ml of methyltriethoxysilane and 4ml of ammonia were added thereto and stirred for 6 hours. Then centrifugal separation and drying are carried out to obtain the monodisperse nano silica material.
3) 42.5g of monodisperse nano-silica material and 0.4 percent of single-walled carbon nanotube aqueous slurry 2 are respectively weighed according to the mass ratio of 85:0.2:10:0.55g of starch, 5g of sodium hydroxy cellulose (CMC) and 0.25g of CMC, wherein the CMC is dissolved in water to prepare 0.5 percent of clear aqueous solution, and then the aqueous slurry of the single-walled carbon nanotube, the monodisperse nano silica material and the starch are sequentially added, ball-milled for 1 hour and evenly stirred. Then spray drying with inlet temperature of 180 deg.C, outlet temperature of 90 deg.C, and hot air flow rate of 0.5m3Min; and (3) carrying out jet milling, wherein the classification frequency of a jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5 kg/min.
4) And putting the crushed material into a tube furnace which is filled with nitrogen for protection and is calcined for 10h at 850 ℃, naturally cooling to room temperature, taking out the material and repeatedly washing the material by using dilute hydrochloric acid and water to obtain the primary carbon-coated mesoporous silica material connected with the carbon nano tubes.
5) And (2) filling the primary carbon-coated silicon monoxide material connected with the carbon nano tubes into a CVD (chemical vapor deposition) furnace, introducing natural gas at the flow rate of 50ml/min, calcining at 900 ℃ for 10h in a nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving by using a 200-mesh sieve to obtain the double-layer carbon-coated mesoporous SiO @ CNT/C composite negative electrode material connected with the carbon nano tubes.
Example 3
1) 60ml of deionized water and 80ml of absolute ethyl alcohol are taken and uniformly mixed, 0.88g of hexadecyl trimethyl ammonium bromide is uniformly mixed, 0.8ml of dilute hydrochloric acid (0.1mol/L) and 0.2ml of glacial acetic acid are added and uniformly stirred, then 90ml of trimethyl orthosilicate is added and continuously stirred for 5min, the stirring is stopped, and the mixture is kept still for 60min until the liquid is changed from turbid to transparent. To obtain a mixed solution A.
2) The vessel containing the mixed solution A was placed in a water bath at 45 ℃ and 100ml of methyltriethoxysilane and 4ml of ammonia were added thereto and stirred for 6 hours. Then centrifugal separation and drying are carried out to obtain the monodisperse nano silica material.
3) Respectively weighing 45g of monodisperse nano silica material, 25g of single-walled carbon nanotube aqueous slurry with the content of 0.4%, 4.65g of starch and 0.25g of sodium hydroxy cellulose (CMC) according to the mass ratio of 90:0.2:9.3:0.5, dissolving the CMC in water to prepare 0.5% clear aqueous solution, then sequentially adding the single-walled carbon nanotube aqueous slurry, the monodisperse nano silica material and the starch, ball-milling for 1 hour and uniformly stirring. Then spray-dryingDrying at inlet temperature of 180 deg.C, outlet temperature of 90 deg.C, and hot air flow rate of 0.5m3Min; and (3) carrying out jet milling, wherein the classification frequency of a jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5 kg/min.
4) And putting the crushed material into a tube furnace with nitrogen protection, calcining for 4h at 700 ℃, 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 connected with the carbon nano tubes.
5) And (2) filling the primary carbon-coated silicon monoxide material connected with the carbon nano tubes into a CVD (chemical vapor deposition) furnace, introducing natural gas at the flow rate of 45ml/min, calcining for 4h at the temperature of 600 ℃ in the nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving by using a 200-mesh sieve to obtain the double-layer carbon-coated mesoporous SiO @ CNT/C composite negative electrode material connected with the carbon nano tubes.
Example 4
1) 60ml of deionized water and 80ml of absolute ethyl alcohol are taken and uniformly mixed, 0.88g of hexadecyl trimethyl ammonium bromide is uniformly mixed, 0.8ml of dilute hydrochloric acid (0.1mol/L) and 0.2ml of glacial acetic acid are added and uniformly stirred, then 100ml of tetraethoxysilane is added and continuously stirred for 5min, the stirring is stopped, and the mixture is kept stand for 60min until the liquid becomes transparent from turbidity. To obtain a mixed solution A.
2) The vessel containing the mixed solution A was placed in a water bath at 45 ℃ and 100ml of methyltriethoxysilane and 4ml of ammonia were added thereto and stirred for 6 hours. Then centrifugal separation and drying are carried out to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silica material, 25g of single-walled carbon nanotube aqueous slurry with the content of 0.4%, 4.65g of starch and 0.25g of sodium polyacrylate are respectively weighed according to the mass ratio of 90:0.2:9.3:0.5, the sodium polyacrylate is firstly dissolved in water to prepare 0.5% clear aqueous solution, then the single-walled carbon nanotube aqueous slurry, the monodisperse nano silica material and the starch are sequentially added, and the mixture is ball-milled for 1 hour and stirred uniformly. Then spray drying with inlet temperature of 180 deg.C, outlet temperature of 90 deg.C, and hot air flow rate of 0.5m3Min; and (3) carrying out jet milling, wherein the classification frequency of a jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5 kg/min.
4) And putting the crushed material into a tube furnace filled with nitrogen protection, calcining for 10h at 600 ℃, 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 connected with the carbon nano tubes.
5) And (2) filling the primary carbon-coated silicon monoxide material connected with the carbon nano tubes into a CVD (chemical vapor deposition) furnace, introducing natural gas at the flow rate of 45ml/min, calcining at 600 ℃ for 10h in a nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving by using a 200-mesh sieve to obtain the double-layer carbon-coated mesoporous SiO @ CNT/C composite negative electrode material connected with the carbon nano tubes.
Comparative example 1
The difference from example 1 is that carbon nanotubes are not added, and the process is the same in the other ways.
1) 60ml of deionized water and 80ml of absolute ethyl alcohol are taken and uniformly mixed, 0.88g of hexadecyl trimethyl ammonium bromide is uniformly mixed, 0.8ml of dilute hydrochloric acid (0.1mol/L) and 0.2ml of glacial acetic acid are added and uniformly stirred, then 100ml of tetraethoxysilane is added and continuously stirred for 5min, the stirring is stopped, and the mixture is kept stand for 60min until the liquid becomes transparent from turbidity. To obtain a mixed solution A.
2) The vessel containing the mixed solution A was placed in a water bath at 45 ℃ and 100ml of methyltriethoxysilane and 4ml of ammonia were added thereto and stirred for 6 hours. Then centrifugal separation and drying are carried out to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silica material, 4.75g of starch and 0.25g of sodium hydroxy cellulose (CMC) are respectively weighed according to the mass ratio of 90:9.5:0.5, the CMC is firstly dissolved in water to prepare 0.5 percent of clear aqueous solution, then the monodisperse nano silica material and the starch are sequentially added into the solution, and the mixture is ball-milled for 1 hour and stirred uniformly. Then spray drying with inlet temperature of 180 deg.C, outlet temperature of 90 deg.C, and hot air flow rate of 0.5m3Min; and (3) carrying out jet milling, wherein the classification frequency of a jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5 kg/min.
4) And putting the crushed material into a tube furnace which is filled with nitrogen for protection and is calcined for 4 hours at 900 ℃, naturally cooling to room temperature, taking out the material, and repeatedly washing the material by using dilute hydrochloric acid and water to obtain the primary carbon-coated mesoporous silica material.
5) And (2) loading the primary carbon-coated silicon monoxide material into a CVD (chemical vapor deposition) furnace, introducing natural gas at the flow rate of 45ml/min, calcining at 900 ℃ for 4h in a nitrogen atmosphere, naturally cooling to room temperature, taking out, and sieving by using a 200-mesh sieve to obtain the double-layer carbon-coated mesoporous SiO @ CNT/C composite negative electrode material.
Comparative example 2
The difference from the embodiment 1 is that no carbon nano tube is added, the carbon coating has only one layer, and the rest ways and the process are the same.
1) 60ml of deionized water and 80ml of absolute ethyl alcohol are taken and uniformly mixed, 0.88g of hexadecyl trimethyl ammonium bromide is uniformly mixed, 0.8ml of dilute hydrochloric acid (0.1mol/L) and 0.2ml of glacial acetic acid are added and uniformly stirred, then 100ml of tetraethoxysilane is added and continuously stirred for 5min, the stirring is stopped, and the mixture is kept stand for 60min until the liquid becomes transparent from turbidity. To obtain a mixed solution A.
2) The vessel containing the mixed solution A was placed in a water bath at 45 ℃ and 100ml of methyltriethoxysilane and 4ml of ammonia were added thereto and stirred for 6 hours. Then centrifugal separation and drying are carried out to obtain the monodisperse nano silica material.
3) 45g of monodisperse nano silica material, 4.75g of starch and 0.25g of sodium hydroxy cellulose (CMC) are respectively weighed according to the mass ratio of 90:9.5:0.5, the CMC is firstly dissolved in water to prepare 0.5 percent of clear aqueous solution, then the monodisperse nano silica material and the starch are sequentially added into the solution, and the mixture is ball-milled for 1 hour and stirred uniformly. Then spray drying with inlet temperature of 180 deg.C, outlet temperature of 90 deg.C, and hot air flow rate of 0.5m3Min; and (3) carrying out jet milling, wherein the classification frequency of a jet mill is 25HZ, the pressure is 3.6MPa, and the feeding speed is 0.5 kg/min.
4) And putting the crushed material into a tube furnace with nitrogen protection, calcining for 4h 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 prepared into button cells, and electrochemical performance was measured: the materials obtained in the above embodiments are respectively mixed according to the proportion of SiO @ CNT/C (85%): conductive agent SP (10%): binder SBR (3.5%): thickening agent CMC (1.5%), film coating, slicing and assembling into 2025 button type lithium ion battery in a glove box. The electrolyte is 1mol/L LiPF6/(EC + DMC), and the diaphragm is Celgard2400 membrane.
The assembled battery was subjected to a constant current charge-discharge experiment using a chanhe battery program-controlled tester of wuhan blue-electron company LANHE.
FIG. 1 and FIG. 2 are SEM representation diagrams of SiO @ CNT/C material. FIGS. 3 to 6 are respectively charge and discharge curves of the button cell made of the SiO @ CNT/C composite material prepared in examples 1 to 4 at 25 ℃ and at 0.1C rate; fig. 7 and 8 are charge and discharge curves of button cells made of comparative examples 1 and 2 at a rate of 0.1C at 25 ℃.
The first discharge specific capacity of the button cell made of the SiO @ CNT/C composite material in the embodiment 1 can reach 1665.7mAh/g, the reversible specific capacity is also up to 1488.6mAh/g, and the first coulombic efficiency is 89.36%.
The first discharge specific capacity of the button cell made of the SiO @ CNT/C composite material in the embodiment 2 can reach 1586.8mAh/g, the reversible specific capacity is also up to 1423.3mAh/g, and the first coulombic efficiency is 89.69%.
The first discharge specific capacity of the button cell made of the SiO @ CNT/C composite material of the embodiment 3 is 1494.3mAh/g, the reversible specific capacity is 1231mAh/g, and the first coulombic efficiency is 82.38%.
The first discharge specific capacity of the button cell made of the SiO @ CNT/C composite material of embodiment 4 is 1589.6mAh/g, the reversible specific capacity is 1306.6mAh/g, and the first coulombic efficiency is 82.19%.
In examples 3 and 4, the first reversible specific capacity and the first efficiency were lower than those of examples 1 and 2, which is probably due to the incomplete reduction of the silica material to the silica material at 600 ℃ in the temperature of carbon coating and carbon reduction, and the presence of a portion of inactive silica phase leading to a reduction in its capacity and first coulombic efficiency.
The primary discharge specific capacity of the button cell made of the SiO/C composite material of the comparative example 1 is 1597mAh/g, the reversible specific capacity is 1318.4mAh/g, and the primary coulombic efficiency is 82.56%.
The primary discharge specific capacity of the button cell made of the SiO/C composite material of the comparative example 2 is 1575.3mAh/g, the reversible specific capacity is 1240.1mAh/g, and the primary coulombic efficiency is 78.72%.
As can be seen from comparative examples 1 and 2, the reversible specific capacity and the first coulombic efficiency of the material are lower than those of the material in examples 1 and 2 when the CNT is not added, which shows that the CNT plays a role of a conductive network in the material and greatly improves the conductive performance 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 of 200 cycles of the first 4 examples and the 2 comparative examples of the SiO @ CNT/C material button cell under the condition of 25 ℃ and the current density of 0.1C, and as can be seen from Table 1, the capacity of the cell made of the SiO @ CNT/C composite material in examples 1-2 has very small capacity attenuation. Examples 3 to 4 have poor conductivity and large capacity fade compared to examples 1 and 2 because of the presence of the siloxane hetero phase and comparative examples 1 to 2 have no CNT added. 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
Figure BDA0003299843000000121
Figure BDA0003299843000000131

Claims (10)

1. A preparation method of a carbon nanotube-connected dual-carbon-layer-coated mesoporous silica composite material is characterized by comprising the following steps: the method comprises the following steps:
1) hydrolyzing silicate ester under the presence of a surfactant and under an acidic condition to obtain silica sol; adding a silane coupling agent and alkali liquor into silica sol for reaction to obtain silica gel, and performing centrifugal separation and drying on the silica gel to obtain a nano silica material;
2) ball-milling a nano silica material, a carbon nano tube, an organic carbon source and a dispersing agent in an aqueous medium to obtain slurry, spray-drying the slurry, and carrying out airflow crushing to obtain a precursor material, and calcining and washing the precursor material to obtain a carbon-coated silica material;
3) and depositing a carbon layer on the surface of the carbon-coated silicon oxide material through CVD gas phase to obtain the double-carbon-layer-coated mesoporous silicon oxide composite material.
2. The method for preparing a carbon nanotube-linked dual-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps: the hydrolysis conditions are as follows: silicate ester is hydrolyzed in alcohol-water mixed solution containing a surfactant and an acid catalyst, and in the whole hydrolysis system, the silicate ester accounts for 30-60% by mass, absolute ethyl alcohol accounts for 20-50% by mass, 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.
3. The method for preparing the carbon nanotube-linked dual-carbon-layer-coated mesoporous silica composite material according to claim 2, wherein the method comprises the following steps:
the silicate ester comprises ethyl orthosilicate, methyl orthosilicate, trimethyl sulfonate orthosilicate, 3-aminopropyl triethoxysilane, (CH)3CH2)3Si(CH3CH2)3At least one of (1);
the acid catalyst comprises at least one of hydrochloric acid, sulfuric acid, formic acid, glacial acetic acid, polyacrylic acid and polybasic aryl carboxylic acid;
the surfactant is at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tridecyl polyoxyethylene ether and dodecyl dimethyl benzyl ammonium chloride.
4. The method for preparing a carbon nanotube-linked dual-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps:
the adding amount of the silane coupling agent is 20-50% of the mass of the silica sol;
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 a carbon nanotube-linked dual-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 a carbon nanotube-linked dual-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps:
the mass ratio of the nano silica material to the carbon nano tube, the organic carbon source and the dispersing agent is 80-95: 0.2-2: 2-10: 0.5-1.5;
the carbon nano tube is a multi-wall carbon nano tube and/or a single-wall carbon nano tube;
the organic carbon source is at least one of saccharides, organic acids and low-carbon alcohols;
the dispersant is at least one of sodium hydroxy cellulose, polyacrylic acid and sodium polyacrylate.
7. The method for preparing the carbon nanotube-linked dual-carbon-layer-coated mesoporous silica composite material according to claim 6, wherein the method comprises the following steps: the calcining conditions are as follows: under the protective atmosphere, the temperature is 500-1200 ℃, and the time is 1-12 h.
8. The method for preparing a carbon nanotube-linked dual-carbon-layer-coated mesoporous silica composite material according to claim 1, wherein the method comprises the following steps: the CVD deposition conditions are as follows: 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; the flow rate of the gas carbon source is 10 ml/min to 100 ml/min.
9. A carbon nanotube connected double-carbon-layer-coated mesoporous silica composite material is characterized in that: the preparation method of any one of claims 1 to 8.
10. The use of the carbon nanotube-linked dual-carbon-coated mesoporous silica composite material according to claim 9, wherein: the material is applied as a negative electrode material of a lithium ion battery.
CN202111187449.XA 2021-10-12 2021-10-12 Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof Active CN114122397B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111187449.XA CN114122397B (en) 2021-10-12 2021-10-12 Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111187449.XA CN114122397B (en) 2021-10-12 2021-10-12 Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114122397A true CN114122397A (en) 2022-03-01
CN114122397B CN114122397B (en) 2023-11-10

Family

ID=80441859

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111187449.XA Active CN114122397B (en) 2021-10-12 2021-10-12 Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114122397B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114899398A (en) * 2022-04-20 2022-08-12 同济大学 Preparation and application of boron-nitrogen co-doped carbon nanotube coated silicon oxide composite material
CN115286871A (en) * 2022-09-15 2022-11-04 扬州工业职业技术学院 Halogen-free flame-retardant conductive polypropylene material
CN115775885A (en) * 2022-11-14 2023-03-10 佛山市格瑞芬新能源有限公司 Silica anode material and preparation method and application thereof
CN115986094A (en) * 2023-03-01 2023-04-18 江苏正力新能电池技术有限公司 Pre-lithiated silicon oxide negative electrode material with core-shell structure and preparation method and application thereof

Citations (13)

* 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
US20140147751A1 (en) * 2011-03-18 2014-05-29 Jun Yang Silicon-carbon Composite Anode Material for Lithium Ion Batteries and A Preparation Method 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

Patent Citations (13)

* 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
US20140147751A1 (en) * 2011-03-18 2014-05-29 Jun Yang Silicon-carbon Composite Anode Material for Lithium Ion Batteries and A 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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114899398A (en) * 2022-04-20 2022-08-12 同济大学 Preparation and application of boron-nitrogen co-doped carbon nanotube coated silicon oxide composite material
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
CN115286871A (en) * 2022-09-15 2022-11-04 扬州工业职业技术学院 Halogen-free flame-retardant conductive polypropylene 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
CN115775885A (en) * 2022-11-14 2023-03-10 佛山市格瑞芬新能源有限公司 Silica anode material and preparation method and application thereof
CN115775885B (en) * 2022-11-14 2024-02-06 佛山市格瑞芬新能源有限公司 Silicon-oxygen anode material and preparation method and application thereof
CN115986094A (en) * 2023-03-01 2023-04-18 江苏正力新能电池技术有限公司 Pre-lithiated silicon oxide negative electrode material with core-shell structure and preparation method and application thereof

Also Published As

Publication number Publication date
CN114122397B (en) 2023-11-10

Similar Documents

Publication Publication Date Title
CN114122397B (en) Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof
CN104577045B (en) A kind of lithium ion battery silicon-carbon composite and preparation method thereof
CN104617276B (en) Lithium rechargeable battery porous silicon/carbon compound cathode materials and preparation method thereof
EP3454399A1 (en) Method for preparing boron-doped porous carbon sphere
CN104009210B (en) A kind of porous silicon/carbon composite material, Preparation method and use
CN112186188B (en) Silicon-based negative electrode material and preparation method and application thereof
CN112886015B (en) Three-dimensional carbon-silicon composite material
CN106058228A (en) Core-shell structure silicon-carbon composite material as well as preparation method and application thereof
CN102437318A (en) Preparation method for silicon-carbon composite material, prepared silicon-carbon composite material, lithium ion battery anode containing silicon-carbon composite material and battery
CN112259737B (en) Preparation method of mesoporous spherical silicon oxide negative electrode material of lithium battery
WO2021120155A1 (en) Nano-tin-silicon composite negative electrode material, and preparation method therefor and use thereof
CN103346302A (en) Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof
CN108666543B (en) Sponge-like C-SiC composite material and preparation method thereof
CN112635727A (en) Silica particles with core-shell structure, preparation method thereof, negative electrode material and battery
CN104617270A (en) Preparation method of spherical hollow lithium titanate/graphene composite material as lithium battery negative material
CN110137465A (en) A kind of carbon@Fe2O3@carbosphere composite material and its application
CN113178552A (en) High-tap-density porous silicon-carbon composite material, preparation method thereof and application of negative electrode of lithium ion battery
CN110854373B (en) Composite negative electrode material and preparation method thereof
CN114314564B (en) Carbon nanotube conductive network coated SiO@C composite material and preparation method and application thereof
CN113422011A (en) Carbon nanotube-in-tube @ manganese dioxide nanosheet composite material and preparation and application thereof
CN114628684B (en) High-energy-density quick-charging graphite composite material and preparation method thereof
CN114044508B (en) Hard carbon microsphere and preparation method and application thereof
CN109817952B (en) Lithium ion battery cathode and preparation method thereof
CN110921647A (en) Hard carbon microsphere with adjustable morphology and pore structure, preparation method and application thereof
CN107317012B (en) High-performance Si/C composite material for negative electrode material of lithium ion secondary battery and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant