CN104167295B - Carbon nano tube surface loaded nano cobaltosic oxide composite material and preparation method thereof - Google Patents
Carbon nano tube surface loaded nano cobaltosic oxide composite material and preparation method thereof Download PDFInfo
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- CN104167295B CN104167295B CN201410134471.1A CN201410134471A CN104167295B CN 104167295 B CN104167295 B CN 104167295B CN 201410134471 A CN201410134471 A CN 201410134471A CN 104167295 B CN104167295 B CN 104167295B
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Abstract
The embodiment of the invention discloses a carbon nano tube surface loaded nano cobaltosic oxide composite material and a preparation method thereof. The preparation method comprises the following steps: deionized water and DMF are weighed according to a ratio of 1:1 to 1:9 to obtain a mixed solvent; purified carbon nano tube and the mixed solvent are weighed according to the compounding concentration of 0.1-1g/L, and ultrasonic processing is performed for 10-60min; cobalt(II) acetate tetrahydrate of which the concentration is 10-60g/L relative to carbon nano tube dispersion liquid is weighed, and cobalt(II) acetate tetrahydrate is dispersed in the carbon nano tube dispersion liquid and stirred evenly; the obtained mixed solution is put in a hydrothermal tank with a tetrafluoroethylene liner and then cooled along with a furnace; after the solution is cooled to room temperature, black deposits are cleaned by a centrifuge; and baking is performed until a sample is dried. Co3O4 particles of the carbon nano tube surface loaded nano cobaltosic oxide composite material prepared by the method are cubic and uniform in size, have a side length smaller than 7nm, and are uniformly distributed on the surface of the carbon nano tube.
Description
Technical field
The invention belongs to field of nanocomposite materials, it is related to a kind of CNT area load nano-cobaltic-cobaltous oxide
(Co3O4) composite and preparation method thereof, this composite can be used for being catalyzed, ultracapacitor or lithium ion cell electrode.
Background technology
Cobalto-cobaltic oxide Co3O4It is a kind of important inorganic material, in electrochemistry, catalyst, magnetic fluid, biomedicine etc.
There is huge application prospect in field.By preparing nano Co3O4Co can be significantly improved3O4Activity, thus improving Co3O4In each neck
The performance in domain.But nano Co3O4It is also easy to produce reunion, be generally required for nano material is coated on specific carrier material, thus
Reach the purposes such as the activity improving nano material and its stability.CNT (CNT) stable chemical nature, has excellent electricity
, calorifics, mechanics, optics, magnetic performance, have high-specific surface area as monodimension nanometer material, limit specific surface area up to
2630m2/ g is so as to become ideal support materials.Preparation is combined with CNT and can not only effectively disperse Co3O4,
And be more beneficial for improving the ability of conduct electronics, improve the electric conductivity of material, be catalyzed, surpassing such that it is able to improve it
The application performance in the level field such as capacitor or lithium ion battery.
The Co of existing preparation on CNT3O4Nano-particle has that distribution density is low, nanoparticle size is excessive,
Distribution of sizes is uneven, skewness or there is agglomeration on the carbon nanotubes, thus affect CNT/
Co3O4The performance of composite.The impact to performance for the shapes and sizes of oxide is very big, at present, prepares on the carbon nanotubes
Co3O4And other oxide is mainly based on spherical, and cube Co3O4Have than spherical bigger ratio table under identical volume
Area is it would be possible to obtain more excellent performance.The present invention is prepared for mutually disperseing on CNT surface, uniform in size, point
The nano cubic Co that cloth is uniform, granule is tiny3O4.
Content of the invention
For solving the above problems, it is an object of the invention to provide a kind of CNT area load nano-cobaltic-cobaltous oxide
Composite and preparation method thereof, the CNT area load nano-cobaltic-cobaltous oxide composite prepared by the method
Co3O4Granule is cube, uniform in size, and the length of side is less than 7nm, has certain space, about 1-10nm each other, uniformly
It is distributed in CNT surface.
For achieving the above object, the technical scheme is that：
A kind of preparation method of CNT area load nano-cobaltic-cobaltous oxide composite, comprises the following steps：
Weigh deionized water and the dimethylformamide DMF that ratio is 1: 1-1: 9, obtain mixing molten after mixing and stirring
Agent；
Weigh CNT and mixed solvent after purified process by the matched proportion density of 0.1-1g/L, CNT is put
Enter and in mixed solvent, carry out ultrasonic 10-60 minute, obtain CNT dispersion liquid；
Weigh four hydration cobaltous acetate, cobalt is II valency, wherein four hydration cobaltous acetate are with respect to the concentration of CNT dispersion liquid
For 10-60g/L, four hydration cobaltous acetate are dissolved in CNT dispersion liquid, stir；
Solution after will be mixed above puts into the hydro-thermal tank with tetrafluoroethene liner, wherein the filling volumetric ratio of hydro-thermal tank
Example is 1/5-1/2, is warmed up to 100-150 DEG C with 1 DEG C/min -10 DEG C/min of programming rate, and temperature retention time is 1.5h-10h,
Furnace cooling afterwards；
After being cooled to room temperature, solution is poured out, with centrifuge, black deposit is cleaned, cleanout fluid adopts ethanol molten
Liquid, the number of times of cleaning is at 3-5 time；
The black deposit having cleaned is baked to sample drying at 40-80 DEG C, obtains CNT area load and receive
Rice cobaltosic oxide composite material.
Preferably, the concrete purification step of the CNT after purified process is：By 0.5g chemical vapor deposition
The CNT that CVD is prepared is added in 100ml concentrated nitric acid, first ultrasonic disperse 30min, post-heating backflow 4h, removes carbon
Catalyst granules in nanotube simultaneously connects corresponding functional group, mixture cooled and filtered in carbon nano tube surface, spend from
Sub- water cleans repeatedly until filtrate is in neutrality, 6h is dried at 100 DEG C in atmosphere.
And, a kind of CNT area load nano-cobaltic-cobaltous oxide composite, described CNT area load
Nano-cobaltic-cobaltous oxide composite is prepared by method as described above, and Cobalto-cobaltic oxide material becomes nano cubic structure
Uniformly it is attached to the surface of CNT.
Preferably, described nano cubic structure be smaller in size than 7nm, Co3O4Gap between nano cubic granule is 1-
10nm.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) Co of carbon nano tube surface3O4Nano-particle is evenly distributed, this Co3O4Grain crystalline is good, is isometric particle,
Uniform in size, the length of side is less than 7nm, there is uniform pore, about 1-10nm each other, is evenly distributed on the table of CNT
Face；
(2) CNT has larger specific surface area, good electric conductivity and thermal conduction characteristic, CNT and Co3O4?
Grain is in close contact, and is conducive to the quick transmission of electronics.
(3) CNT and cobaltosic oxide nano Interaction between particles, it is to avoid the accumulation again of carbon pipe and oxide
The reunion of nano-particle.
(4) this method preparation process is simple and controlled and repeatable good, is suitable for volume production.
Brief description
Fig. 1 is the preparation method of CNT area load nano-cobaltic-cobaltous oxide composite of the embodiment of the present invention
Flow chart of steps；
Fig. 2 is the one scan Electronic Speculum of the CNT area load nano-cobaltic-cobaltous oxide composite of the embodiment of the present invention
Figure；
Fig. 3 is the another scanning electricity of the CNT area load nano-cobaltic-cobaltous oxide composite of the embodiment of the present invention
Mirror figure；
Fig. 4 is the transmission electron microscope of the CNT area load nano-cobaltic-cobaltous oxide composite through the embodiment of the present invention
Figure；
Fig. 5 is the XRD figure of the CNT area load nano-cobaltic-cobaltous oxide composite through the embodiment of the present invention.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiies
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, thin to the present invention below
In section description, detailed describe some specific detail sections.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
Referring to Fig. 1, it show a kind of CNT area load nano-cobaltic-cobaltous oxide composite wood of the embodiment of the present invention
The flow chart of steps of the preparation method of material, it comprises the following steps：
S10, weighs the deionized water that ratio is 1: 1-1: 9 and dimethylformamide DMF, is mixed after mixing and stirring
Bonding solvent；
S20, weighs CNT and mixed solvent after purified process by the matched proportion density of 0.1-1g/L, nano-sized carbon
Pipe is put into and is carried out ultrasonic 10-60 minute in mixed solvent, obtains CNT dispersion liquid；
Wherein, in concrete application example, the concrete purification step of CNT can be, by 0.5g chemical vapor deposition
The CNT that CVD is prepared is added in 100ml concentrated nitric acid, first ultrasonic disperse 30min, post-heating backflow 4h, removes carbon
Catalyst granules in nanotube simultaneously connects corresponding functional group, mixture cooled and filtered in carbon nano tube surface, spend from
Sub- water cleans repeatedly until filtrate is in neutrality, 6h is dried at 100 DEG C in atmosphere.
S30, weighs four hydration cobaltous acetate, and cobalt is II valency, and wherein four hydration cobaltous acetate are with respect to CNT dispersion liquid
Concentration is 10-60g/L, four hydration cobaltous acetate is dissolved in CNT dispersion liquid, stirs；
In following concrete application example, cobalt is hydrated cobaltous acetate for four hydration cobaltous acetate referred to as four of II valency
(II).
S40, will be mixed above after solution put into the hydro-thermal tank with tetrafluoroethene liner, the wherein filling of hydro-thermal tank is held
Long-pending ratio is 1/5-1/2, and that is, reaction solution volume accounts for the 20%-50% of hydro-thermal tank cumulative volume, with 1 DEG C/min -10 DEG C/min
Programming rate be warmed up to 100-150 DEG C, temperature retention time be 1.5h-10h, rear furnace cooling；
S50, after being cooled to room temperature, pours out solution, is cleaned black deposit with centrifuge, cleanout fluid adopts ethanol
Solution, the number of times of cleaning is at 3-5 time；
S60, the black deposit having cleaned is baked to sample drying at 40-80 DEG C, obtains CNT surface and bears
Carry nano-cobaltic-cobaltous oxide composite.
By procedure declaration made above, the present invention prepares carbon nano tube surface load using above method and receives
Rice cobaltosic oxide composite material, preparation process is simple and controlled and repeatable good, is suitable for volume production.
Therefore, corresponding with method, further embodiment of this invention provides the CNT prepared by said method
Area load nano-cobaltic-cobaltous oxide composite, is respectively embodiment of the present invention preparation referring to Fig. 2 to Fig. 5, Fig. 2 and Fig. 3
Carbon nano tube surface loads the scanning electron microscope (SEM) photograph of nano-cobaltic-cobaltous oxide composite, and Fig. 4 is transmission electron microscope picture, and Fig. 5 is XRD
Figure.From Fig. 2 to Fig. 4, Cobalto-cobaltic oxide material becomes nano cubic even structure to be attached to the surface of CNT, and nanometer is stood
Square structure be smaller in size than 7nm, Co3O4Gap between nano cubic granule is 1-10nm.Referring to Fig. 5, energy in X-ray diffraction
It is clearly visible (002) diffraction maximum of CNT.
CNT area load nano-cobaltic-cobaltous oxide composite below will be described by multiple specific embodiments
Preparation process.Hydro-thermal tank used in specific embodiment is market and buys, and its typical volume is 20ml, 50ml, 100ml
And 250ml.In specific embodiment, the cumulative volume of mixed solution can cover reaction solution volume by ratio adjustment and account for hydro-thermal
The 20%-50% of tank cumulative volume.
Embodiment 1
Weigh DMF8ml, deionized water 2ml, stir, obtain mixed solvent.Weigh the CNT after purification process
4mg, puts into mixed solvent CNT and carries out ultrasonic 60 minutes, obtain CNT dispersion liquid.Weigh four hydration cobaltous acetate
(II) 400mg, four hydrations cobaltous acetate (II) is dissolved in and obtains CNT dispersion liquid, be stirred to and be completely dissolved.By above solution
Put into the hydro-thermal tank that there is the volume of tetrafluoroethene liner for 20ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 50%, symbol
The filling volume fraction of the hot tank of Heshui requires, and is warmed up to 120 DEG C with 1 DEG C/minute of programming rate, temperature retention time 1.5h, after with stove
Cooling.With centrifuge, microparticle is carried out, cleaning adopts alcoholic solution, and the number of times of cleaning is at 5 times.It is baked at 40 DEG C
Sample drying, that is, obtain CNT area load nano-cobaltic-cobaltous oxide composite.
Embodiment 2
Weigh DMF10ml, deionized water 10ml, stir, obtain solvent.Weigh the CNT after purification process
2mg, puts into solvent CNT and carries out ultrasonic 10 minutes, obtain CNT dispersion liquid.Weigh four hydration cobaltous acetate (II)
200mg, four hydrations cobaltous acetate (II) is dissolved in mixed solvent, is stirred to and is completely dissolved.Above solution is put into tetrafluoro second
The volume of alkene liner is the hydro-thermal tank of 50ml, and the cumulative volume that reaction solution accounts for hydro-thermal tank is about 40%, meets the filling of hydro-thermal tank
Volume fraction requires, and is warmed up to 150 DEG C with 5 DEG C/minute of programming rate, temperature retention time 5h, rear furnace cooling.Will be micro- with centrifuge
Granule is carried out, and cleaning adopts alcoholic solution, and the number of times of cleaning is at 3 times.It is baked to sample drying at 80 DEG C, that is, received
Rice carbon pipe surface load nano-cobaltic-cobaltous oxide composite.
Embodiment 3
Weigh DMF27ml, deionized water 3ml, stir, obtain solvent.Weigh the CNT after purification process
30mg, puts into solvent CNT and carries out ultrasonic 40 minutes, obtain CNT dispersion liquid.Weigh four hydration cobaltous acetate (II)
1800mg, four hydrations cobaltous acetate (II) is dissolved in mixed solvent, is stirred to and is completely dissolved.Above solution is put into tetrafluoro second
The volume of alkene liner is the hydro-thermal tank of 100ml, and the cumulative volume that reaction solution accounts for hydro-thermal tank is about 30%, meets the filling of hydro-thermal tank
Volume fraction requires, and is warmed up to 130 DEG C with 10 DEG C/minute of programming rate, temperature retention time 10h, rear furnace cooling.Will with centrifuge
Microparticle is carried out, and cleaning adopts alcoholic solution, and the number of times of cleaning is at 5 times.It is baked to sample drying at 60 DEG C, that is, obtain
CNT area load nano-cobaltic-cobaltous oxide composite.
Embodiment 4
Weigh DMF40ml, deionized water 10ml, stir, obtain solvent.Weigh the CNT after purification process
30mg, puts into solvent CNT and carries out ultrasonic 30 minutes, obtain CNT dispersion liquid.Weigh four hydration cobaltous acetate (II)
1000mg, four hydrations cobaltous acetate (II) is dissolved in mixed solvent, is stirred to and is completely dissolved.Above solution is put into volume is
The hydro-thermal tank of 250ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 20%, and the filling volume fraction meeting hydro-thermal tank requires,
It is warmed up to 140 DEG C with 5 DEG C/minute of programming rate, temperature retention time 4h, rear furnace cooling.With centrifuge, microparticle is carried out,
Cleaning adopts alcoholic solution, and the number of times of cleaning is at 4 times.It is baked to sample drying at 40 DEG C, that is, obtain CNT surface and bear
Carry nano-cobaltic-cobaltous oxide composite.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (4)
1. a kind of preparation method of CNT area load nano-cobaltic-cobaltous oxide composite it is characterised in that include with
Lower step：
S10, weighs deionized water and the dimethylformamide DMF that ratio is 1: 1-1: 9, obtains mixing molten after mixing and stirring
Agent；
S20, weighs CNT and mixed solvent after purified process by the matched proportion density of 0.1-1g/L, CNT is put
Enter and in mixed solvent, carry out ultrasonic 10-60 minute, obtain CNT dispersion liquid；
S30, weighs four hydration cobaltous acetate, and cobalt is II valency, and wherein four hydration cobaltous acetate are with respect to the concentration of CNT dispersion liquid
For 10-60g/L, four hydration cobaltous acetate are dissolved in CNT dispersion liquid, stir；
S40, will be mixed above after solution put into the hydro-thermal tank with tetrafluoroethene liner, wherein the filling volumetric ratio of hydro-thermal tank
Example is 1/5-1/2, is warmed up to 100-150 DEG C with 1 DEG C/min -10 DEG C/min of programming rate, and temperature retention time is 1.5h-10h,
Furnace cooling afterwards；
S50, after being cooled to room temperature, pours out solution, is cleaned black deposit with centrifuge, and cleanout fluid adopts ethanol molten
Liquid, the number of times of cleaning is at 3-5 time；
S60, the black deposit having cleaned is baked to sample drying at 40-80 DEG C, obtains CNT area load and receives
Rice cobaltosic oxide composite material.
2. the preparation method of CNT area load nano-cobaltic-cobaltous oxide composite according to claim 1, its
It is characterised by, the concrete purification step of the CNT after purified process in S20 is：By 0.5g chemical vapor deposition
The CNT that CVD is prepared is added in 100ml concentrated nitric acid, first ultrasonic disperse 30min, post-heating backflow 4h, removes carbon
Catalyst granules in nanotube simultaneously connects corresponding functional group, mixture cooled and filtered in carbon nano tube surface, spend from
Sub- water cleans repeatedly until filtrate is in neutrality, 6h is dried at 100 DEG C in atmosphere.
3. a kind of CNT area load nano-cobaltic-cobaltous oxide composite is it is characterised in that described CNT surface
Load nano-cobaltic-cobaltous oxide composite is prepared by the arbitrary described method of such as claim 1-2, Cobalto-cobaltic oxide
Co3O4Material becomes nano cubic even structure to be attached to the surface of CNT.
4. CNT area load nano-cobaltic-cobaltous oxide composite according to claim 3 is it is characterised in that institute
State the 7nm that is smaller in size than, Co of nano cubic structure3O4Gap between nano cubic granule is 1-10nm.
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| CN105390700B (en) * | 2015-11-16 | 2019-11-29 | 哈尔滨工业大学 | A method of by adding metal oxide/carbon composite modification lithium-ion battery anode |
| CN108269976A (en) * | 2017-12-19 | 2018-07-10 | 中南大学 | Cobalt-based lithium ion battery negative material preparation method |
| CN110993969A (en) * | 2019-12-03 | 2020-04-10 | 哈尔滨工程大学 | Coquassia flower pistil hollow carbonization tube composite Co3O4H of (A) to (B)2O2Electro-reduction catalyst |
| CN111740083B (en) * | 2020-06-12 | 2021-07-30 | 萧县鑫辉源电池有限公司 | Carbon-coated porous Co3O4Microsphere lithium ion battery cathode material and preparation method thereof |
| CN112611792B (en) * | 2020-12-01 | 2022-09-27 | 常州大学 | Multi-walled carbon nanotube/cobaltosic oxide for preparing electrochemical sensor for detecting caffeic acid |
| CN113224329A (en) * | 2021-04-30 | 2021-08-06 | 南京工业大学 | Co3O4/MXene composite catalyst and preparation method and application thereof |
| CN113634255A (en) * | 2021-08-24 | 2021-11-12 | 武汉理工大学 | Loaded Co3O4Preparation method of granular nano carbon composite catalytic material |
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