CN109698342A - A kind of metal oxide-ordered carbon nanotube composite material and preparation method and application - Google Patents
A kind of metal oxide-ordered carbon nanotube composite material and preparation method and application Download PDFInfo
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- CN109698342A CN109698342A CN201811630221.1A CN201811630221A CN109698342A CN 109698342 A CN109698342 A CN 109698342A CN 201811630221 A CN201811630221 A CN 201811630221A CN 109698342 A CN109698342 A CN 109698342A
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Abstract
The present invention relates to a kind of metal oxide-ordered carbon nanotube composite material and preparation method and applications, the method are as follows: anodic oxidation aluminium formwork is immersed in carbon containing polymer solution, template is successively cleaned, dried and is heat-treated after separation of solid and liquid, obtains the ordered carbon nanotube containing template；Colloidal sol containing metal M element is added drop-wise in the ordered carbon nanotube containing template and carries out ripening, the template in products therefrom is removed using alkaline solution after ripening, then it is heat-treated at a certain temperature, obtains metal oxide-ordered carbon nanotube composite material.Method provided by the invention realizes the effective compound of metal oxide and ordered carbon nanotube, the carbon nanotube of ordered arrangement can be obtained, and metal oxide is evenly distributed on to the inner surface of ordered carbon nanotube, with better structural stability.In addition, the above method is easy to operate, applicability is wide, has a good application prospect in fields such as electrochemical energy storage, catalysis.
Description
Technical field
The present invention relates to field of lithium ion battery material preparation, and in particular to a kind of metal oxide-ordered carbon nanotube
Composite material and preparation method and application.
Background technique
Lithium ion battery has operating voltage height, energy density as a kind of novel, clean, chargeable power supply
The advantages such as height, light weight, self-discharge rate be low, have obtained answering extensively on the portable electronic devices such as mobile phone, laptop
With.By the optimization of many years, the performance of lithium ion battery electrode material is already close to the limit.
Carbon nanotube (CNTs) is had special hollow reticular structure and is formed with C-C Covalent bonding together, and C-C is covalent
Key majority uses sp2 hydridization, has superior mechanical property, while CNTs has that size is small, large specific surface area, good conductivity
Advantage.Also, compared to graphite, lithium ion can be not only embedded in pipe, can also be embedded in pipe gap, have more embedding lithiums
Position.Transition metal oxide has high theoretical lithium storage content, and specific capacity is much higher than graphite material, and cheap, right
Environmental nonpollution has higher safety.Carbon nanotube and metal oxide is compound, it can be in conjunction with the superiority of the two
Can, it is effectively improved the chemical property of lithium ion battery material.
CN108281622A discloses a kind of preparation side of porous composite negative pole material of transition metal oxide/carbon nanotube
Carbon nanotube is dispersed first in strong acid, is heated, obtains the CNTs of functionalization by method；By transition metal mixtures stirring and dissolving, then
CNTs after functionalization is added, is then precipitated in ultrasound, is obtained presoma after dry, is heat-treated after presoma is ground, instead
It should obtain the porous composite negative pole material of transition metal oxide/carbon nanotube.Carbon nanotube embeds transition in gained composite material
The hollow ball structure of metal oxide forms three-dimensional conductive network.CN103342384A discloses a kind of utilization self-supporting carbon
Nanotube films prepare carbon nanotube/metal oxide coaxial configuration method, by rationally controlling self-supporting carbon nanometer in raw material
Type, metal oxide type and the liquid organic precursor type of periosteum, and change carbon nano-tube film resolving system, adjust
Whole chemical vapor deposition combination process parameter has obtained metal oxide and has been evenly coated at carbon nano tube surface, and had coaxial
The composite material of structure.It is compound that CN101712452A discloses a kind of nano graphite flakes, carbon nanotube and transition metal oxide
Material and preparation method are obtained by growing carbon nanotube, while carrying transition metal oxide nano-particles on nano graphite flakes surface
To by nano graphite flakes, be grown in the carbon nanotube on nano graphite flakes surface and composite wood that transition metal oxide forms
Material, resulting materials have stereoscopic three-dimensional structure.CN103943838A discloses a kind of metal oxide nano-sheet and carbon nanotube
The preparation method of energy storage material, it is first carbon nano-tube modified with sulfonated polystyrene, then use the method for oil bath in the carbon of modified
Metal hydroxides presoma is grown on nanotube, obtains metal oxide nano-sheet and carbon nanotube energy storage material after calcining
Material.CN104616911A discloses a kind of preparation method of vertical carbon nanotube array/metal oxide composite, by metal
Organic compound presoma, cosolvent and carbon nano pipe array sample are packed into reactor, are passed through supercritical carbon dioxide after sealing,
And it is heated to predetermined temperature and carries out impregnation；Sample is subjected to low temperature pyrogenation in oxidizing atmosphere, Organometallic is closed
Object presoma is converted into metal oxide, to obtain the carbon nano pipe array three-dimensional knot that surface uniform load has metal oxide
Structure composite material.
The above method mainly carries out metal oxide and carbon nanotube by the modes such as depositing, be pyrolyzed compound, but obtains
Composite material in the general random growth of carbon nanotube, and metal oxide dispersion is on the surface of carbon nanotube, composite material
Structural stability is poor.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of metal oxide-ordered carbon nanotube composite material and
Preparation method and application can obtain the carbon nanotube of ordered arrangement, and metal oxide are evenly distributed on orderly carbon
The inner surface of nanotube, with better structural stability.
In order to achieve the above objectives, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of metal oxide-ordered carbon nanotube composite material, it is described
Method the following steps are included:
(1) anodic oxidation aluminium formwork is immersed in carbon containing polymer solution, template is successively carried out after separation of solid and liquid clear
It washes, dry and is heat-treated, obtain the ordered carbon nanotube containing template；
(2) by the colloidal sol containing metal M element be added drop-wise in the ordered carbon nanotube containing template that step (1) obtains into
Row ripening removes the template in products therefrom using alkaline solution after ripening, is then heat-treated, is obtained
Metal oxide-ordered carbon nanotube composite material.
According to the present invention, step (1) the anodic oxidation aluminium formwork both ends aperture.
According to the present invention, step (1) carbon polymer that contains is polypyrrole, polyacrylonitrile, polystyrene, polyvinyl pyrrole
Alkanone, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or polystyrene-polypropylene nitrile block copolymerization
At least one of object.
According to the present invention, the concentration of step (1) the carbon containing polymer solution is 0.01-0.5mg/L, such as be can be
0.01mg/L、0.05mg/L、0.1mg/L、0.15mg/L、0.2mg/L、0.25mg/L、0.3mg/L、0.35mg/L、0.4mg/L、
Specific point value between 0.45mg/L or 0.5mg/L and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the mass ratio of step (1) template and carbon containing polymer solution is 100:(1-10), such as can
To be 100:1,100:2,100:3,100:4,100:5,100:6,100:7,100:8,100:9 or 100:10 and above-mentioned number
Specific point value between value, as space is limited and for concise consideration, the present invention no longer exclusive list.
The template after dipping is cleaned using organic reagent in step (1) as a preferred technical solution, it is specific to grasp
As: using the template after at least one of n-hexane, normal octane, hexamethylene, ether or tetrahydrofuran cleaning dipping, then
Continue to clean using ethyl alcohol.
According to the present invention, step (1) drying is vacuum drying, and temperature is 60-120 DEG C, time 1-12h.
According to the present invention, the temperature of step (1) described heat treatment be 500-1000 DEG C, such as can be 500 DEG C, 550 DEG C,
600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or the tool between 1000 DEG C and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of step (1) described heat treatment be 1-5h, such as can be 1h, 1.5h, 2h, 2.5h,
Specific point value between 3h, 3.5h, 4h, 4.5h or 5h and above-mentioned numerical value, as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
According to the present invention, step (1) heat treatment carries out in protective atmosphere, and the protective atmosphere is argon gas
And/or nitrogen.
According to the present invention, step (2) the metal M is Al, Mn, Ti, Ni, Co, Zr, Zn, Fe, Mg, Nb, V, W, Ru, Ca
Or at least one of Cr.
Prepared by the conventional method that this field can be used in the colloidal sol containing metal M element described in step (2) of the present invention, answer
It is specifically chosen according to different metal M.Illustratively, when the metal M is titanium, the preparation method of the titanium colloidal sol
Are as follows: in protective atmosphere, titanium tetrachloride is added dropwise to mass ratio as the ethyl alcohol of 2:(0.5-2) and the mixed liquor of triethanolamine
In, 5-7h is kept the temperature at 80-100 DEG C, is diluted with water to and is completely dissolved, appropriate ammonium hydroxide is then added and forms clear solution.
As space is limited and for concise consideration, preparation side of the present invention no longer to the colloidal sol containing metal M element
Method is enumerated.
According to the present invention, the temperature of step (2) described ageing is 120-150 DEG C, such as can be 120 DEG C, 125 DEG C, 130
DEG C, 135 DEG C, 140 DEG C, 145 DEG C or the specific point value between 150 DEG C and above-mentioned numerical value, examining as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, the time of step (2) described ageing be 36-72h, such as can be 36h, 40h, 44h, 48h,
Specific point value between 52h, 56h, 60h, 64h, 68h or 72h and above-mentioned numerical value, as space is limited and for concise consideration,
The present invention no longer exclusive list.
According to the present invention, the product after ageing is cleaned by ultrasonic in step (2), then vacuum freeze drying.
According to the present invention, step (2) alkaline solution is sodium hydroxide solution and/or potassium hydroxide solution.
According to the present invention, the mass concentration of step (2) described alkaline solution be 5-20%, but such as 5%, 8%,
10%, the specific point value between 13%, 15%, 18% or 20% and above-mentioned numerical value is examined as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, temperature when removing template in step (2) using alkaline solution is 40-60 DEG C, such as be can be
Specific point value between 40 DEG C, 43 DEG C, 45 DEG C, 48 DEG C, 50 DEG C, 53 DEG C, 55 DEG C, 58 DEG C or 60 DEG C and above-mentioned numerical value, is limited to
Length and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the concrete operations of template are removed in step (2) are as follows: be immersed in the product obtained after ripening
In alkaline solution, material is rinsed to neutrality, vacuum drying using distilled water after template dissolution.
According to the present invention, the temperature of step (2) described heat treatment be 300-550 DEG C, such as can be 300 DEG C, 330 DEG C,
It is specific between 350 DEG C, 380 DEG C, 400 DEG C, 430 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 530 DEG C or 550 DEG C and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of step (2) described heat treatment be 1-6h, such as can be 1h, 2h, 3h, 4h, 5h or
Specific point value between 6h and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Second aspect, it is orderly that the present invention provides a kind of metal oxide-that method as described in relation to the first aspect is prepared
Carbon nano tube compound material, metal oxide is evenly distributed on the inner surface of ordered carbon nanotube in the composite material, described
The molar ratio of metal oxide and ordered carbon nanotube is (0.01-0.2): 1.
The third aspect, the present invention provide a kind of metal oxide as described in second aspect-ordered carbon nanotube composite wood
The application of material, the composite material can be applied to be modified anode material for lithium-ion batteries, greatly improve positive electrode
High rate performance and cyclical stability obtain high performance anode material for lithium-ion batteries.
Compared with prior art, the present invention at least has the advantages that
(1) method provided by the invention realizes the effective compound of metal oxide and ordered carbon nanotube, can obtain
The carbon nanotube of ordered arrangement, and metal oxide is evenly distributed on to the inner surface of ordered carbon nanotube, with more
Good structural stability.
(2) preparation method provided by the invention is easy to operate, and applicability is wide, can obtain high quality metal oxide and
The composite material that carbon nanotube is constituted, has huge application value in fields such as electrochemical energy storage, catalysis.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Following present invention typical case but non-limiting embodiment:
Embodiment 1
Titanium dioxide is evenly distributed on orderly in metal oxide manufactured in the present embodiment-ordered carbon nanotube composite material
The inner surface of carbon nanotube, wherein the molar ratio of titanium dioxide and ordered carbon nanotube is 0.1:1.
It is prepared in accordance with the following methods:
(1) by the anodic oxidation aluminium formwork of both ends aperture be immersed in concentration be 0.3mg/L polypyrrole solution in, template with
The mass ratio of carbon containing polymer solution is 100:3, filters after the completion of dipping, then successively cleans filter residue with normal octane and ethyl alcohol,
In 100 DEG C of vacuum drying 3h, the template after drying is placed in argon atmosphere, after being heat-treated 2h at 800 DEG C, is obtained containing mould
The ordered carbon nanotube of plate.
(2) under argon atmosphere environment, titanium tetrachloride is added drop-wise to the mixing of ethyl alcohol and triethanolamine that mass ratio is 2:1
In liquid, gained mixed liquor is kept the temperature into 6h at 90 DEG C, titanium tetrachloride is diluted with water to and is completely dissolved, then plus suitable ammonium hydroxide is straight
To formation transparency liquid；Transparency liquid is added dropwise in the ordered carbon nanotube containing template obtained in step (1), 150
DEG C ageing 36h, then will ageing product be cleaned by ultrasonic in distilled water, vacuum freeze drying obtains the titanium dioxide with template
The desciccate is dissolved in the sodium hydroxide that mass percentage is 10% by the ordered carbon nanotube of filling under conditions of 50 DEG C
It is sufficiently dry under vacuum condition with distilled water flushing material to neutral (pH=7) after template is completely dissolved in solution, 300
DEG C heat treatment 6h after obtain titanium dioxide-ordered carbon nanotube composite material.
The composite material prepared in the present embodiment is applied to the preparation process of lithium ion battery anode material lithium iron phosphate
In, electric discharge under the premise of other conditions are identical, compared with the composite material in no addition the present embodiment, when 0.1C
Specific capacity is promoted to 158mAh/g by 147mAh/g, and the conservation rate of 1C/0.1C is promoted to 95% by 87%.
Embodiment 2
Ceria is evenly distributed on orderly in metal oxide manufactured in the present embodiment-ordered carbon nanotube composite material
The inner surface of carbon nanotube, wherein the molar ratio of ceria and ordered carbon nanotube is 0.05:1.
It is prepared in accordance with the following methods:
(1) anodic oxidation aluminium formwork of both ends aperture is immersed in the polypyrrole solution that concentration is 0.02mg/L, template
Mass ratio with carbon containing polymer solution is 100:10, filters after the completion of dipping, is then successively cleaned with tetrahydrofuran and ethyl alcohol
Template after drying is placed in nitrogen atmosphere by filter residue in 120 DEG C of vacuum drying 1h, after being heat-treated 4h at 650 DEG C, is obtained
Ordered carbon nanotube containing template.
(2) appropriate cerous nitrate and citric acid are dissolved in a certain amount of ethanol solution, are prepared into vitreosol, it is molten
The molar concentration of cerium is controlled in 0.8mol/L in glue, which is added dropwise to the orderly carbon obtained in step (1) containing template
In nanotube, in 130 DEG C of ageing 48h, then ageing product is cleaned by ultrasonic in distilled water, vacuum freeze drying obtains band
The ordered carbon nanotube of the ceria filling of template, which, which is dissolved in mass percentage under conditions of 60 DEG C, is
In 8% sodium hydroxide solution, with distilled water flushing material to neutral (pH=7) after template is completely dissolved, under vacuum condition
It is sufficiently dry, ceria-ordered carbon nanotube composite material is obtained after 500 DEG C of heat treatment 2h.
The composite material prepared in the present embodiment is applied to the preparation process of lithium ion battery anode material lithium iron phosphate
In, electric discharge under the premise of other conditions are identical, compared with the composite material in no addition the present embodiment, when 0.1C
Specific capacity is promoted to 156mAh/g by 147mAh/g, and the conservation rate of 1C/0.1C is promoted to 91.5% by 87%.
Embodiment 3
Ruthenium-oxide is evenly distributed on orderly carbon in metal oxide manufactured in the present embodiment-ordered carbon nanotube composite material
The inner surface of nanotube, wherein the molar ratio of ruthenium-oxide and ordered carbon nanotube is 0.2:1.
It is prepared in accordance with the following methods:
(1) anodic oxidation aluminium formwork of both ends aperture is immersed in the polystyrene solution that concentration is 0.5mg/L, template
Mass ratio with carbon containing polymer solution is 100:1, filters after the completion of dipping, then successively cleans filter residue with ether and ethyl alcohol,
In 80 DEG C of vacuum drying 8h, the template after drying is placed in argon atmosphere, after being heat-treated 1.5h at 900 DEG C, is contained
The ordered carbon nanotube of template.
(2) ruthenium trichloride is dissolved in the aqueous solution of ethyl alcohol, so that the molar concentration of ruthenium is 0.5mol/L, uses hydroxide
Sodium adjusts the pH value of solution until generating vitreosol, and vitreosol is added dropwise to having containing template obtained in step (1)
In sequence carbon nanotube, in 120 DEG C of ageing 72h, then ageing product is cleaned by ultrasonic in distilled water, vacuum freeze drying obtains
To the ordered carbon nanotube of the ruthenium-oxide filling with template, which is dissolved in mass percentage under conditions of 60 DEG C
To use distilled water flushing material to neutral (pH=7), vacuum condition after template is completely dissolved in 15% sodium hydroxide solution
It is lower sufficiently dry, ruthenium-oxide-ordered carbon nanotube composite material is obtained after 400 DEG C of heat treatment 5h.
The composite material prepared in the present embodiment is applied to the preparation process of lithium ion battery anode material lithium iron phosphate
In, electric discharge under the premise of other conditions are identical, compared with the composite material in no addition the present embodiment, when 0.1C
Specific capacity promotes most 162mAh/g by 147mAh/g, and the conservation rate of 1C/0.1C is promoted to 96% by 87%.
Embodiment 4
Tungsten oxide is evenly distributed on orderly carbon in metal oxide manufactured in the present embodiment-ordered carbon nanotube composite material
The inner surface of nanotube, wherein the molar ratio of tungsten oxide and ordered carbon nanotube is 0.05:1.
It is prepared in accordance with the following methods:
(1) anodic oxidation aluminium formwork of both ends aperture is immersed in the polyacrylonitrile solution that concentration is 0.05mg/L, mould
The mass ratio of plate and carbon containing polymer solution is 100:8, filters after the completion of dipping, then successively cleans filter with normal octane and ethyl alcohol
Template after drying is placed in argon atmosphere by slag in 80 DEG C of vacuum drying 6h, after being heat-treated 3h at 750 DEG C, is contained
The ordered carbon nanotube of template.
(2) sodium tungstate is dissolved into deionized water, is configured to the solution of 0.35mol/L, hydrochloric acid is added dropwise thereto, constantly
Stirring, the pH value for adjusting solution is 2.0 or so, until becoming vitreosol, which is added dropwise in step (1) and is obtained
The ordered carbon nanotube containing template in, in 140 DEG C of ageing 40h, then will ageing product be cleaned by ultrasonic in distilled water, very
Vacuum freecing-dry obtains the ordered carbon nanotube of the tungsten oxide filling with template, and the desciccate is molten under conditions of 60 DEG C
In the sodium hydroxide solution that mass percentage is 10%, with distilled water flushing material to neutrality after template is completely dissolved
(pH=7), sufficiently dry under vacuum condition, tungsten oxide-ordered carbon nanotube composite material is obtained after 550 DEG C of heat treatment 1h.
The composite material prepared in the present embodiment is applied to the preparation process of lithium ion battery anode material lithium iron phosphate
In, electric discharge under the premise of other conditions are identical, compared with the composite material in no addition the present embodiment, when 0.1C
Specific capacity is promoted to 157mAh/g by 147mAh/g, and the conservation rate of 1C/0.1C is promoted to 94% by 87%.
Embodiment 5
Magnesium dioxide is evenly distributed on orderly in metal oxide manufactured in the present embodiment-ordered carbon nanotube composite material
The inner surface of carbon nanotube, wherein the molar ratio of magnesium dioxide and ordered carbon nanotube is 0.08:1.
It is prepared in accordance with the following methods:
(1) anodic oxidation aluminium formwork of both ends aperture is immersed in the polypyrrole solution that concentration is 0.15mg/L, template
Mass ratio with carbon containing polymer solution is 100:5, filters after the completion of dipping, then successively cleans filter with hexamethylene and ethyl alcohol
Template after drying is placed in argon atmosphere by slag in 100 DEG C of vacuum drying 4h, after being heat-treated 2h at 850 DEG C, is contained
There is the ordered carbon nanotube of template.
(2) magnesium nitrate and citric acid are dissolved into the aqueous solution of dehydrated alcohol, solution is constantly stirred in 80 DEG C of water-baths
It mixes, until generating vitreosol, which is added dropwise in the ordered carbon nanotube containing template obtained in step (1),
Then ageing product is cleaned by ultrasonic by 120 DEG C of ageing 48h in distilled water, vacuum freeze drying obtains the titanium dioxide with template
The desciccate is dissolved in the hydroxide that mass percentage is 20% by the ordered carbon nanotube of magnesium filling under conditions of 55 DEG C
It is sufficiently dry under vacuum condition with distilled water flushing material to neutral (pH=7) after template is completely dissolved in sodium solution,
Magnesium dioxide-ordered carbon nanotube composite material is obtained after 450 DEG C of heat treatment 4h.
The composite material prepared in the present embodiment is applied to the preparation process of lithium ion battery anode material lithium iron phosphate
In, electric discharge under the premise of other conditions are identical, compared with the composite material in no addition the present embodiment, when 0.1C
Specific capacity is promoted to 159mAh/g by 147mAh/g, and the conservation rate of 1C/0.1C is promoted to 93% by 87%.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of metal oxide-ordered carbon nanotube composite material preparation method, which is characterized in that the method includes with
Lower step:
(1) anodic oxidation aluminium formwork is immersed in carbon containing polymer solution, template is successively cleaned after separation of solid and liquid, is done
Dry and heat treatment, obtains the ordered carbon nanotube containing template；
(2) colloidal sol containing metal M element is added drop-wise in the ordered carbon nanotube containing template that step (1) obtains carry out it is old
Change is handled, and is removed the template in products therefrom using alkaline solution after ripening, is then heat-treated, obtains metal
Oxide-ordered carbon nanotube composite material.
2. the method as described in claim 1, which is characterized in that step (1) the anodic oxidation aluminium formwork both ends aperture.
3. method according to claim 1 or 2, which is characterized in that step (1) carbon polymer that contains is polypyrrole, poly- third
Alkene nitrile, polystyrene, polyvinylpyrrolidone, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or poly-
At least one of styrene-polyacrylonitrile block copolymer；
Preferably, the concentration of step (1) the carbon containing polymer solution is 0.01-0.5mg/L；
Preferably, the mass ratio of step (1) template and carbon containing polymer solution is 100:(1-10).
4. the method according to claim 1, which is characterized in that after utilization organic reagent is to dipping in step (1)
Template cleaned, concrete operations are as follows: at least one of using n-hexane, normal octane, hexamethylene, ether or tetrahydrofuran
Template after cleaning dipping, then continues to clean using ethyl alcohol.
5. method according to any of claims 1-4, which is characterized in that step (1) drying is vacuum drying, temperature
It is 60-120 DEG C, time 1-12h；
Preferably, the temperature of step (1) described heat treatment is 500-1000 DEG C；
Preferably, the time of step (1) described heat treatment is 1-5h；
Preferably, step (1) heat treatment carries out in protective atmosphere, and the protective atmosphere is argon gas and/or nitrogen.
6. the method according to claim 1 to 5, which is characterized in that step (2) the metal M be Al, Mn, Ti, Ni,
At least one of Co, Zr, Zn, Fe, Mg, Nb, V, Ru, W, Ca or Cr.
7. as the method according to claim 1 to 6, which is characterized in that the temperature of step (2) described ageing is 120-150
℃；
Preferably, the time of step (2) described ageing is 36-72h；
Preferably, the product after ageing is cleaned by ultrasonic in step (2), then vacuum freeze drying.
8. the method according to claim 1 to 7, which is characterized in that step (2) alkaline solution is sodium hydroxide
Solution and/or potassium hydroxide solution；
Preferably, the mass concentration of step (2) described alkaline solution is 5-20%；
Preferably, temperature when removing template in step (2) using alkaline solution is 40-60 DEG C；
Preferably, the concrete operations of template are removed in step (2) are as follows: the product obtained after ripening is immersed in alkaline solution
In, material is rinsed to neutrality, vacuum drying using distilled water after template dissolution.
Preferably, the temperature of step (2) described heat treatment is 300-550 DEG C；
Preferably, the time of step (2) described heat treatment is 1-6h.
9. the metal oxide that the method according to claim 1 is prepared-ordered carbon nanotube composite material,
It is characterized in that, metal oxide is evenly distributed on the inner surface of ordered carbon nanotube, the metal oxygen in the composite material
Compound and the molar ratio of ordered carbon nanotube are (0.01-0.2): 1.
10. the application of metal oxide as claimed in claim 9-ordered carbon nanotube composite material, which is characterized in that described
Composite material is applied to be modified anode material for lithium-ion batteries.
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