CN108155356A - A kind of carbon package titania aerogel lithium ion battery negative material and preparation method thereof - Google Patents
A kind of carbon package titania aerogel lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN108155356A CN108155356A CN201711250018.7A CN201711250018A CN108155356A CN 108155356 A CN108155356 A CN 108155356A CN 201711250018 A CN201711250018 A CN 201711250018A CN 108155356 A CN108155356 A CN 108155356A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 present invention relates to a kind of preparation methods of carbon package titania aerogel lithium ion battery negative material, belong to nano material preparation and electrochemical material field.Titanium source, aqueous hydrochloric acid solution and absolute ethyl alcohol are mixed to get the first reaction solution according to certain molar ratio；First reaction solution is mixed with a certain amount of hydrous ethanol solution, still aging acquisition xerogel；Organic carbon matrix precursor and organic solvent are mixed to get the second reaction solution according to certain molar ratio；By obtained xerogel and the second reaction solution Hybrid Heating, organic composite titania aerogel is dried to obtain by CO 2 supercritical after reaction；Aeroge is placed in high-temperature heat treatment under inert gas conditions, obtains carbon package titania aerogel.Carbon prepared by the present invention wraps up titania aerogel material and still keeps 133mAh/g height ratio capacities after 3000 cycles under 10C high current densities, can be used as a kind of high performance lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of carbon to wrap up titania aerogel lithium ion battery negative material and preparation method thereof, especially
It is related to nano material preparation and electrochemical material, belongs to lithium ion battery preparing technical field.
Background technology
Lithium ion battery is main a kind of electrochemical storage device in modern society, in portable communications, wearable device
Part, electric vehicle etc. are widely used；In addition, also have on Space Science and Technology, robot and various smart machines huge
Prospect.Lithium ion battery has many advantages, such as energy density height, memory-less effect, pollutes small, energy conservation and environmental protection.But lithium at present
Ion battery technology has some potential safety problems there are the shortcomings of operating temperature section is narrow, and thermal stability is poor.Meanwhile now
Lithium ion battery quick charge-discharge technology be not mature enough, constitute obstacle to the large-scale functionization of lithium ion battery.Therefore,
High security and stability are developed, and the battery material with fast charging and discharging ability has become lithium ion battery technology research
Emphasis.
Nanometer titanic oxide material as a kind of electrode material of the lithium ion battery of stabilization can realize lithium ion can
Inverse intercalation/deintercalation, while the higher (~1.75V vs.Li of its reaction potential+/ Li), it is not easy to form solid electrolyte interface (SEI)
Film effectively improves stability and the safety of electrode.But due to the poorly conductive of titanic oxide material, very big shadow
The charge/discharge capacity and high rate performance of battery are rung.
Carbon doping/package is the main means for the chemical property for being effectively improved nanometer titanic oxide material.Document at present
There is the shortcomings of preparation process is complicated, cost of material is high for the carbon package titanium dioxide nano material technology of preparing of report.In addition,
The carbon package titanic oxide material prepared in report by template can not realize effective control of structure and ingredient, exist
The problems such as particle size is big, carbon content is high is unfavorable for the raising of material cell performance.
Invention content
The technology of the present invention solves the problems, such as：Overcome the deficiencies in the prior art proposes a kind of carbon package titanium dioxide airsetting
Glue lithium ion battery negative material and preparation method thereof, this method is complicated for carbon package titanic oxide material synthetic method, nothing
Method realizes accurate the problems such as controlling of structure and ingredient, in order to further improve the battery performance of carbon package titanic oxide material,
It realizes the application on lithium ion battery, and simplifies material and preparation process, this method is received to further improve carbon package
The electrode performance of rice titanic oxide material, while simplify material preparation process, cost of material is reduced, the present invention proposes a kind of carbon packet
Wrap up in the preparation method of titania aerogel lithium ion battery negative material, by sol-gel method and organic carbon matrix precursor from
The method of assembling, obtains the mesohole nano-titanium dioxide material with carbon package, and material has good chemical property and fills
Discharge-rate performance, can be as the electrode material of high performance lithium ion battery.
The present invention technical solution be：
A kind of carbon wraps up titania aerogel lithium ion battery negative material, which wraps up titanium dioxide for carbon
Aeroge, not less than 10nm, carbon content is not more than 10% in the aperture of the aeroge.
A kind of the step of preparation method of carbon package titania aerogel lithium ion battery negative material, this method, wraps
It includes：
(1) titanium source compound, hydrochloric acid and absolute ethyl alcohol are mixed, under room temperature, after stirring evenly, obtains first
Reaction solution；
(2) the first reaction solution that step (1) obtains with the ethanol solution of water is mixed, poured into culture dish, it is quiet
Ageing is put, obtains titania gel；
(3) organic carbon matrix precursor and organic solvent are mixed, under room temperature, after stirring evenly, it is anti-obtains second
Answer solution；
(4) titania gel that step (2) obtains is immersed in the second reaction solution that step (3) obtains, then
It is put into retort and is stood under heating condition, obtain the titania gel of organic molecule package, the organic molecule packet that will be obtained
The titania gel wrapped up in carries out supercritical drying processing, obtains light yellow clear aeroge, and the light yellow clear that will be obtained
Aeroge takes out from retort；
(5) aeroge that step (4) obtains is put into alumina crucible, hot place is carried out under the conditions of inert gas shielding
Reason obtains the titania aerogel lithium ion battery negative material of carbon package.
In the step (1), titanium source compound is butyl titanate, isopropyl titanate, tetraethyl titanate, titanium tetrachloride
One or more of mixture；The titanium source compound accounts for the 1%~10% of the first reaction solution volume；It is described
Hydrochloric acid and ethyl alcohol volume ratio be 0.01~0.05:100；
In the step (2), the mass ratio of water and ethyl alcohol is 5~20 in the ethanol solution of water：100；
Still aging temperature is 20-50 DEG C, and the still aging time is 12-24 hours；
The volume ratio of the ethanol solution of first reaction solution and water is 1：0.5-1.5；
In the step (3), organic carbon matrix precursor is：Bisphenol A diglycidyl ether, hexahydro phthalic acid glycidol
One or more kinds of mixing of ester, phthalic acid ethylene oxidic ester, the bicyclic diene of titanium dioxide, polyol shrinkaging glycerin ether
Object；Organic solvent is：Tetrahydrofuran, 1,3- dioxolanes, glycol dimethyl ether, 1,4- dioxanes one or more
Mixture；
Organic carbon matrix precursor accounts for the 1%~10% of the second reaction solution volume；
In the step (4), titanium source compound in organic carbon matrix precursor and the first reaction solution in the second reaction solution
Mass ratio be 5~40:100；The temperature of standing is 50-100 DEG C, and time of repose is 12-36 hours；
In the step (5), the condition being heat-treated is：600- is heated to the heating rate of 5-10 DEG C/min
900 DEG C, 0.5-6 hours are kept the temperature, is cooled to room temperature, carbon package titania aerogel negative material is obtained after grinding.
Advantageous effect
(1) carbon package titania aerogel lithium cell cathode material preparation method proposed by the present invention passes through collosol and gel
Chemical process reduces the size of nano particle, improves the electro-chemical activity of material；By forming meso-hole structure, improve
The specific surface area of material increases the contact area between electrode and electrolyte；It is wrapped up, improved by the carbon on nano particle surface layer
The electric conductivity and electrode performance of titanium dioxide cathode material.Above-mentioned improvement effectively increases the storage of lithium ion battery negative material
Lithium specific capacity, cycle performance and high rate performance.In addition, the sol-gel method that the present invention uses does not need to add in the originals such as template
Reason, preparation process and simple for process are advantageously implemented industrialized production.Lithium ion battery negative material grain size prepared by this method
It is small, carbon content is low, battery performance is good, simple for process and at low cost.
(2) the invention discloses a kind of carbon package titania aerogel lithium ion battery negative material preparation method,
Belong to nano material preparation and electrochemical material field.The preparation method of the present invention includes the following steps：(1) by titanium source, hydrochloric acid
With absolute ethyl alcohol the first reaction solution is mixed to get according to certain molar ratio；(2) by first reaction solution and centainly
The hydrous ethanol solution mixing of amount, still aging acquisition xerogel；(3) by organic carbon matrix precursor and organic solvent according to certain
Molar ratio is mixed to get the second reaction solution；(4) xerogel that the step (2) obtains with the second reaction solution is mixed and added
Heat is dried to obtain organic composite titania aerogel by CO 2 supercritical after reaction；(5) aeroge is placed in
High-temperature heat treatment under inert gas conditions obtains carbon package titania aerogel.Carbon package titanium dioxide prepared by the present invention
Aerogel material still keeps 133mAh/g height ratio capacities under 10C high current densities after 3000 cycles, can be used as a kind of high property
The lithium ion battery negative material of energy.
(3) in carbon package titania aerogel negative material is prepared, to solve the technical issues of existing, the present invention is logical
The method for crossing organic carbon matrix precursor and titania gel self assembly, formed on titania gel surface one layer it is uniform and stable
Organic coating, organic coating generates carbon wrapping layer by in-situ carburization in follow-up heat treatment process.This method can be effective
Carbon package titania aerogel nanostructured and grain size are controlled, and can be by adjusting organic carbon matrix precursor ingredient and proportioning
Adjust the element component content of final product.In addition, this method colloidal sol prepare in without using template, only by adjustment the
The proportioning of titanium source compound, hydrochloric acid and absolute ethyl alcohol in one reaction solution, water content and reaction condition etc. in hydrous ethanol solution
Element, and prepare the mesoporous material with larger specific surface area and large aperture using the method for supercritical drying.
Description of the drawings
Fig. 1 is the X-ray powder diffraction collection that carbon wraps up titania aerogel material, shows titanium dioxide into rutile titania
Ore deposit crystal structure；
Fig. 2 is the scanning electron microscope (SEM) photograph that carbon wraps up titania aerogel material, it can be seen that carbon wraps up nano titania
Even particle distribution, without apparent agglomeration；
Fig. 3 is the transmission electron microscope picture that carbon wraps up titania aerogel material, it can be seen that carbon wraps up titanium dioxide sodium rice
Mean particle size is 5nm or so.
Fig. 4 is the x-ray photoelectron spectroscopy figure that carbon wraps up titania aerogel material；
Fig. 5 is the x-ray photoelectron spectroscopy figure that carbon wraps up carbon in titania aerogel material, can be with by C1s power spectrums
Prove the presence of carbon wrapping layer；
Fig. 6 is the Raman spectrogram that carbon wraps up titania aerogel material, by being located at 1345cm in spectrogram-1With
1590cm-1Characteristic peak to prove the presence of carbon wrapping layer.
Fig. 7 is nitrogen adsorption-desorption curve that carbon wraps up titania aerogel material；
Fig. 8 is the pore size distribution curve figure that carbon wraps up titania aerogel material, and surface sample has meso-hole structure, high
Specific surface area (~236m2/ g) and big mesoporous pore size distribution (~11nm)；
Fig. 9 is that carbon wraps up charging and discharging curve of the titania aerogel material as negative electrode of lithium ion battery, in 0.1C electricity
Reversible specific capacity is up to 215mAh/g under current density；
Figure 10 is that carbon wraps up charge-discharge magnification performance map of the titania aerogel material as negative electrode of lithium ion battery, can
With find out material under 1C, 5C, 10C, 20C current density specific capacity up to 195,177,159 and 127mAh/g.Show that material has
There is good high rate performance；
Figure 11 is that carbon wraps up fast charging and discharging cycle performance of the titania aerogel material as negative electrode of lithium ion battery
Figure, it can be seen that specific capacity maintains 133mAh/g, coulombic efficiency to material after 3000 cycles under 10C high magnification current densities
Close to 100%.Show that material has good high rate cyclic stability.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
4.4 grams of butyl titanates and 0.2 milliliter of hydrochloric acid are added in 20 milliliters of ethyl alcohol, it is anti-that first is obtained after stirring evenly
Answer solution.1.5 ml deionized waters are added in 20 milliliters of ethyl alcohol, hydrous ethanol solution is obtained after stirring evenly.By described in
Upper hydrous ethanol solution is slowly added into the first reaction solution, is stirred at ambient temperature, and colloidal sol then is poured into culture dish
In, and be aged 24 hours under the conditions of 30 DEG C, obtain water white transparency titania gel.1 gram of bisphenol A diglycidyl ether is added
Enter into 10 milliliters of tetrahydrofurans, the second reaction solution is obtained after stirring evenly.The upper titania gel and second is anti-
Solution mixing is answered to be put into retort, and 24 hours are stood under 70 DEG C of heating conditions, obtains light yellow clear xerogel.It will be dry
Gel cooling is dried by CO 2 supercritical, obtains light yellow clear aeroge.Finally aeroge is taken out, in argon gas gas
It is heat-treated 4 hours under the conditions of 800 DEG C in atmosphere, the rate of heat addition is 10 DEG C/min.Finally obtain carbon package titania aerogel material
Material.
Fig. 1 is the X-ray powder diffraction collection that carbon wraps up titania aerogel material, shows titanium dioxide into rutile titania
Ore deposit crystal structure；
Fig. 2 is the scanning electron microscope (SEM) photograph that carbon wraps up titania aerogel material, it can be seen that carbon wraps up nano titania
Even particle distribution, without apparent agglomeration；Fig. 3 is the transmission electron microscope picture that carbon wraps up titania aerogel material, can be seen
Go out carbon package sodium titanium rice grain average grain diameter for 5nm or so.
Fig. 4 is the x-ray photoelectron spectroscopy figure that carbon wraps up titania aerogel material；Fig. 5 wraps up titanium dioxide airsetting for carbon
The x-ray photoelectron spectroscopy figure of carbon in glue material, the presence of carbon wrapping layer can be proved by C1s power spectrums；Fig. 6 wraps up two for carbon
The Raman spectrogram of titania aerogel material, by being located at 1345cm in spectrogram-1And 1590cm-1Characteristic peak to prove carbon
The presence of wrapping layer.
Fig. 7 is nitrogen adsorption-desorption curve that carbon wraps up titania aerogel material；Fig. 8 wraps up titanium dioxide for carbon
The pore size distribution curve figure of aerogel material, surface sample have meso-hole structure, high-specific surface area (~236m2/ g) and it is big mesoporous
Pore-size distribution (~11nm).
Fig. 9 is that carbon wraps up charging and discharging curve of the titania aerogel material as negative electrode of lithium ion battery, in 0.1C electricity
Reversible specific capacity is up to 215mAh/g under current density；Figure 10 wraps up titania aerogel material for carbon and is born as lithium ion battery
The charge-discharge magnification performance map of pole, it can be seen that material under 1C, 5C, 10C, 20C current density specific capacity up to 195,177,
159 and 127mAh/g.Show that material has good high rate performance；Figure 11 wraps up titania aerogel material as lithium for carbon
The fast charging and discharging cycle performance figure of ion battery cathode, it can be seen that material follows for 3000 times under 10C high magnification current densities
Specific capacity maintains 133mAh/g after ring, and coulombic efficiency is close to 100%.Show that material is stablized with good high rate cyclic
Property.
Embodiment 2
4.0 grams of butyl titanates and 0.1 milliliter of hydrochloric acid are added in 20 milliliters of ethyl alcohol, it is anti-that first is obtained after stirring evenly
Answer solution.2 ml deionized waters are added in 20 milliliters of ethyl alcohol, hydrous ethanol solution is obtained after stirring evenly.On described
Hydrous ethanol solution is slowly added into the first reaction solution, is stirred at ambient temperature, then pours into colloidal sol in culture dish,
And be aged 24 hours under the conditions of 25 DEG C, obtain water white transparency titania gel.1 gram of bisphenol A diglycidyl ether is added in
Into 15 milliliters of tetrahydrofurans, the second reaction solution is obtained after stirring evenly.The upper titania gel is reacted with second
Solution mixing is put into retort, and stand 12 hours under 80 DEG C of heating conditions, obtains light yellow clear xerogel.It will be dry solidifying
Glue cooling is dried by CO 2 supercritical, obtains light yellow clear aeroge.Finally aeroge is taken out, in argon gas atmosphere
In be heat-treated 2 hours under the conditions of 700 DEG C, the rate of heat addition is 10 DEG C/min.Finally obtain carbon package titania aerogel material.
Embodiment 3
5.5 grams of butyl titanates and 0.2 milliliter of hydrochloric acid are added in 20 milliliters of ethyl alcohol, it is anti-that first is obtained after stirring evenly
Answer solution.3.8 ml deionized waters are added in 30 milliliters of ethyl alcohol, hydrous ethanol solution is obtained after stirring evenly.By described in
Upper hydrous ethanol solution is slowly added into the first reaction solution, is stirred at ambient temperature, and colloidal sol then is poured into culture dish
In, and be aged 20 hours under the conditions of 25 DEG C, obtain water white transparency titania gel.2 grams of bisphenol A diglycidyl ethers are added
Enter into 15 milliliters of tetrahydrofurans, the second reaction solution is obtained after stirring evenly.The upper titania gel and second is anti-
Solution mixing is answered to be put into retort, and 20 hours are stood under 70 DEG C of heating conditions, obtains light yellow clear xerogel.It will be dry
Gel cooling is dried by CO 2 supercritical, obtains light yellow clear aeroge.Finally aeroge is taken out, in argon gas gas
It is heat-treated 4 hours under the conditions of 650 DEG C in atmosphere, the rate of heat addition is 10 DEG C/min.Finally obtain carbon package titania aerogel material
Material.
Embodiment 4
5.6 grams of butyl titanates and 0.1 milliliter of hydrochloric acid are added in 25 milliliters of ethyl alcohol, it is anti-that first is obtained after stirring evenly
Answer solution.2.5 ml deionized waters are added in 25 milliliters of ethyl alcohol, hydrous ethanol solution is obtained after stirring evenly.By described in
Upper hydrous ethanol solution is slowly added into the first reaction solution, is stirred at ambient temperature, and colloidal sol then is poured into culture dish
In, and be aged 24 hours under the conditions of 25 DEG C, obtain water white transparency titania gel.By 0.8 gram of bisphenol A diglycidyl ether
It is added in 10 milliliters of tetrahydrofurans, the second reaction solution is obtained after stirring evenly.By the upper titania gel and second
Reaction solution mixing is put into retort, and stand 24 hours under 60 DEG C of heating conditions, obtains light yellow clear xerogel.It will
Xerogel cooling is dried by CO 2 supercritical, obtains light yellow clear aeroge.Finally aeroge is taken out, in argon gas
It is heat-treated 1 hour under the conditions of 850 DEG C in atmosphere, the rate of heat addition is 10 DEG C/min.Finally obtain carbon package titania aerogel
Material.
Embodiment 5
4.1 grams of butyl titanates and 0.1 milliliter of hydrochloric acid are added in 20 milliliters of ethyl alcohol, it is anti-that first is obtained after stirring evenly
Answer solution.0.85 ml deionized water is added in 20 milliliters of ethyl alcohol, hydrous ethanol solution is obtained after stirring evenly.By described in
Upper hydrous ethanol solution is slowly added into the first reaction solution, is stirred at ambient temperature, and colloidal sol then is poured into culture dish
In, and be aged 18 hours under the conditions of 35 DEG C, obtain water white transparency titania gel.By 0.5 gram of bisphenol A diglycidyl ether
It is added in 10 milliliters of tetrahydrofurans, the second reaction solution is obtained after stirring evenly.By the upper titania gel and second
Reaction solution mixing is put into retort, and stand 24 hours under 70 DEG C of heating conditions, obtains light yellow clear xerogel.It will
Xerogel cooling is dried by CO 2 supercritical, obtains light yellow clear aeroge.Finally aeroge is taken out, in argon gas
It is heat-treated 2 hours under the conditions of 700 DEG C in atmosphere, the rate of heat addition is 10 DEG C/min.Finally obtain carbon package titania aerogel
Material.
Claims (10)
1. a kind of carbon wraps up titania aerogel lithium ion battery negative material, it is characterised in that：The negative material is carbon packet
Titania aerogel is wrapped up in, not less than 10nm, carbon content is not more than 10% in the aperture of the aeroge.
2. a kind of preparation method of carbon package titania aerogel lithium ion battery negative material, it is characterised in that this method
Step includes：
(1) titanium source compound, hydrochloric acid and absolute ethyl alcohol are mixed, under room temperature, after stirring evenly, obtains the first reaction
Solution；
(2) the first reaction solution that step (1) obtains with the ethanol solution of water is mixed, is then aged, obtains titanium dioxide
Titanium gel；
(3) organic carbon matrix precursor and organic solvent are mixed, under room temperature, after stirring evenly, it is molten obtains the second reaction
Liquid；
(4) titania gel that step (2) obtains is immersed in the second reaction solution that step (3) obtains, then heated
Under the conditions of stood, obtain organic molecule package titania gel, by obtained organic molecule wrap up titanium dioxide
Gel carries out supercritical drying processing, obtains aeroge；
(5) aeroge that step (4) obtains is heat-treated, the titania aerogel lithium ion battery for obtaining carbon package is born
Pole material.
3. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (1), titanium source compound is butyl titanate, isopropyl titanate, tetraethyl titanate, four
The mixture of one or more of titanium chloride.
4. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (1), the titanium source compound accounts for the 1%~10% of the first reaction solution volume；
The hydrochloric acid and the volume ratio of ethyl alcohol are 0.01~0.05:100.
5. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (2), the mass ratio of water and ethyl alcohol is 5~20 in the ethanol solution of water：100, first
The volume ratio of the ethanol solution of reaction solution and water is 1：0.5-1.5.
6. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (2), still aging temperature is 20-50 DEG C, and the still aging time is small for 12-24
When.
7. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (3), organic carbon matrix precursor is：Bisphenol A diglycidyl ether, the contracting of hexahydro phthalic acid
Water glyceride, phthalic acid ethylene oxidic ester, the bicyclic diene of titanium dioxide, polyol shrinkaging glycerin ether it is one or more kinds of
Mixture；Organic solvent is：Tetrahydrofuran, 1,3- dioxolanes, glycol dimethyl ether, 1,4- dioxanes one or two
Above mixture.
8. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (3), organic carbon matrix precursor account for the second reaction solution volume 1%~
10%.
9. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (4), titanium source in organic carbon matrix precursor and the first reaction solution in the second reaction solution
The mass ratio of compound is 5~40:100；The temperature of standing is 50-100 DEG C, and time of repose is 12-36 hours.
10. a kind of preparation side of carbon package titania aerogel lithium ion battery negative material according to claim 2
Method, it is characterised in that：In the step (5), the condition being heat-treated is：Inert gas shielding, with 5-10 DEG C/min's
Heating rate is heated to 600-900 DEG C, keeps the temperature 0.5-6 hours, is cooled to room temperature, grinds.
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| CN110880589A (en) * | 2019-11-25 | 2020-03-13 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102671587A (en) * | 2012-05-31 | 2012-09-19 | 上海应用技术学院 | Titanium dioxide/carbon hybrid aerogel material and preparation method thereof |
| CN103035917A (en) * | 2013-01-09 | 2013-04-10 | 北京科技大学 | Preparation method of silicon dioxide/ carbon composite negative electrode material for lithium ion battery |
| CN105591080A (en) * | 2016-01-18 | 2016-05-18 | 北京科技大学 | Preparation method of lithium ion battery cathode material SiOX-TiO2/C |
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| CN102671587A (en) * | 2012-05-31 | 2012-09-19 | 上海应用技术学院 | Titanium dioxide/carbon hybrid aerogel material and preparation method thereof |
| CN103035917A (en) * | 2013-01-09 | 2013-04-10 | 北京科技大学 | Preparation method of silicon dioxide/ carbon composite negative electrode material for lithium ion battery |
| CN105591080A (en) * | 2016-01-18 | 2016-05-18 | 北京科技大学 | Preparation method of lithium ion battery cathode material SiOX-TiO2/C |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110880589A (en) * | 2019-11-25 | 2020-03-13 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN110880589B (en) * | 2019-11-25 | 2021-04-06 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
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