CN106315550B - A kind of preparation method of carbon nanotube cavernous body - Google Patents
A kind of preparation method of carbon nanotube cavernous body Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention discloses a kind of preparation methods of carbon nanotube sponge material, the spongy carbon material of the carbon nanotube is formed by one or more carbon nanotube groups, with ultralow density, good self-supporting energy, excellent cycle compressibility, super-hydrophobicity, good absorption property, it can be widely used as power electrode material, sorbing material, sensor, heat-barrier material etc., preparation method provided by the invention is simple for process, it is easy to operate, it is produced on a large scale, specific capacitance in aqueous electrolyte may be up to 129 F/g, and there is good cyclical stability, it is suitable for large-scale promotion application.
Description
Technical field
The present invention relates to the compound preparation sides for being formed by spongy carbon nano-tube macroscopic body of one or more carbon nanotubes
Method belongs to carbon nanomaterial synthesis and application field.
Background technology
Carbon nanotube can regard as it is a kind of crimped by graphene made of tubular structure, because it is with high intensity, Ultralight
Amount, perfect electrology characteristic have become the research hotspot of international material research field.Carbon nanotube powder is unfavorable for carbon nanotube
Direct utilization, and the application field of carbon nanotube can be made to obtain greatly with the carbon nano-tube macroscopic body of self supporting structure
It expands.It is carbon nano-tube film, carbon nanotube sponge, carbon nano pipe array, carbon nano-tube fibre etc. to study at present more.Its
The carbon nanotube sponge of middle three-dimensional structure since it is with big specific surface area, high porosity, low-density, high conductivity etc.,
The fields such as energy storage, catalyst carrier, super-hydrophobic layer, water process, greasy dirt absorption, aerospace, artificial-muscle, electrochemistry micro-system
Suffer from wide application and development space.Three dimensional carbon nanotubes macroscopic body structure can be divided into each diversity and isotropy two
Kind.K. Hata（K. Hata, D. N. Futaba, K. Mizuno, T. Namai, M. Yumura, S. Iijima,
Science, 2004, 306, 1362.）Et al. report the carbon nano pipe array that vertical-growth is prepared by vapour deposition process,
D. N. Futaba（D. N. Futaba, K. Hata, T. Yamada, T. Hiraoka, Y. Hayamizu, Y.
Kakudate, O. Tanaike, H. Hatori, M. Yumura, S. Iijima, Nat. Mater. 2006, 5,
987.）Et al. be prepared for carbon nano pipe array film.Jiang Kaili（Chinese invention patent, publication number：CN101607704A）It utilizes
Chemical vapour deposition technique is prepared for carbon nano-tube bundle.The carbon nanotube sponge of isotropy is by the crisscross winding accumulation of carbon nanotube
Made of unordered poroid three dimensional carbon nanotubes gel, have many advantages, such as that light-weight, porosity is high, flexibility is good.Permitted spring etc. in osmanthus（In
State's patent of invention, publication number：CN101607704A）Using dichloro-benzenes as carbon source, it is prepared for by the method for chemical vapor deposition more
Wall carbon nano tube sponge.The method of carbon nanotube sponge made above is mainly chemical vapour deposition technique, and preparation process is complicated,
Condition is harsh, prepared carbon nanotube sponge finite volume, the problems such as growth cycle is long.K. H. Kim (K. H.
Kim, Y. Oh, M. F. Islam, Adv. Funct. Mater. 2013,23,377.) et al. pass through critical point drying
Method prepares single wall carbon nanotube gel.Critical-point drying method is although single-walled carbon nanotube gel can be prepared, and there is also steps
Rapid complexity, composition are single, the big problem of carbon nanotube loss amount, it is difficult to prepare with scale.Therefore simple, direct preparation is developed
The technology of carbon nanotube sponge macroscopic body, has a very important significance the extensive use of carbon nanotube.
Invention content
The purpose of the present invention is to provide a kind of carbon nanotube sponge inexpensive, that shaped volumes are controllable, simple and convenient is macro
One or more of body and preparation method thereof is seen, while realizing multi wall, single-walled carbon nanotube, double-walled, few-wall carbon nanotube and is mixed
Merging forms sponge macroscopic body structure, effectively improves the electric conductivity of carbon nanotube cavernous body, recycles compressibility, electrochemical stability
And production cost is reduced, the invention is realized in this way：
A kind of preparation method of carbon nanotube cavernous body, is as follows：
a）Carbon nanotube is immersed in H2SO4（Mass fraction 95.0-98.0%）And HNO3 （Mass fraction 65.0-68.0%）
By volume 3：In 1 mixed liquor being mixed to form, 2 h of return stirring at 70 DEG C is filtered, with distilled water flushing filter residue to eluate
For neutrality, filter residue is dissolved in distilled water, is configured to the acidification carbon nano-tube solution of a concentration of 0.5-5 mg/ml；
b）By sponge successively with ethyl alcohol, acetone, distillation water washing after, be transferred to acidification carbon nano-tube solution in infiltrate 2-
Then 100 min are infiltrated in acidification carbon nano-tube solution in 30-60 DEG C of drying after taking-up, so repeat 1-5 times, obtain again
Obtain sponge compound；
c）Sponge compound after drying is placed in tube furnace, inert gas is passed through, 20- is heat-treated in 450-600 DEG C
40 min obtain the carbon nanotube sponge.
Preferably, in the preparation method of carbon nanotube cavernous body of the present invention, the sponge is polyurethane sponge.
Preferably, in the preparation method of carbon nanotube cavernous body of the present invention, the inert gas is argon gas or nitrogen
Gas, gas flow are 0.02-1 L/min.
Preferably, in the preparation method of carbon nanotube cavernous body of the present invention, the carbon nanotube is single
At least one of pipe, multi-walled carbon nanotube.
Carbon nanotube sponge prepared by the present invention is that flexible, blocky volume is controllable, cellular carbon of Ultra light-weight is received
Mitron macroscopic body is by the macroscopic body material of carbon nanotube disordered networks shape porous structure in microcosmic point, and the present invention can be direct
Synthesis in arbitrary shape carbon nanotube block structure, can according to require batch prepare.The carbon nanotube foam have it is light-weight,
Large specific surface area, cycle good compression property, good conductivity, thermal conductivity be low, shape memory function, in aqueous electrolyte
Specific capacitance may be up to 129 F/g, and there is good cyclical stability, can be used as ultracapacitor and secondary cell from propping up
Support electrode material, electrode diffusion layer of fuel cell and catalyst support, mechanics, electric sensor material, organic, greasy dirt absorption
Material, heat-barrier material, noise absorbing material etc. have high application value.
Compared with prior art, beneficial effects of the present invention are embodied in：
1. different from existing chemical vapour deposition technique, desivac, critical-point drying method, preparation method of the present invention is without complexity
Air source, carbon nanotube loss amount it is small, processing procedure is simple, and the time is short, and preparation temperature is low, be suitble to large-scale production.
2. the present invention can quickly be prepared the carbon sponge self supporting structure of arbitrary dimension arbitrary shape by size, this is traditional
Learn what vapour deposition process cannot achieve.
3. the present invention can prepare the carbon nanotube of single composition, it is reachable that ultralight carbon nanotube sponge minimum weight can be prepared
0.5 mg/cm3, can also be the mixture of a variety of carbon nanotubes, such as single wall, few-wall carbon nanotube or variety classes carbon nanometer
Pipe mixture, the spongy carbon nano-structured preparation method being made of multi-walled carbon nanotube can only be prepared by breaking through conventional gas-phase.
Description of the drawings
Fig. 1 is the cavernous body schematic diagram that embodiment 1 obtains.
Fig. 2 is the scale diagrams of the multi-walled carbon nanotube cavernous body prepared by embodiment 1.
Fig. 3 is the flexibility test result schematic diagram of single-walled carbon nanotube cavernous body prepared by embodiment.
Fig. 4 is SEM figure of the single-walled carbon nanotube cavernous body of embodiment preparation under different enlargement ratios.
Fig. 5 is the single-walled carbon nanotube obtained using embodiment and multi-walled carbon nanotube mixture cavernous body as electrode, 6
M KOH、1 M H2SO4Specific capacitance in solution and current density relational graph.
Specific implementation mode
Material source involved by embodiment：
Polyurethane sponge is purchased from Nantong great Gong sponges Co., Ltd (faint yellow polyurethane sponge)；
Multi-walled carbon nanotube：It buys in Shenzhen nanometer port limited liability company (L-MWNT-1020)；
Single-walled nanotube:It buys in Shenzhen nanometer port limited liability company（SWNT-2）；
If not remaining reagent and material illustrate, bought by commercial sources.
It is acidified carbon nano-tube solution preparation method：
Multi-walled carbon nanotube/single-walled nanotube/double-walled carbon nano-tube/few-wall carbon nanotube is added to H2SO4（Quality point
Number 95.0-98.0%）And HNO3 （Mass fraction 65.0-68.0%）With volume ratio 3:In 1 mixed liquor being mixed with, 70 DEG C
Lower 2 h of return stirring is filtered, and takes filter residue that filter residue is then dissolved in distilled water until eluate is neutrality with distilled water flushing
In, obtain acidification multi-walled carbon nanotube/single-walled nanotube/double-walled carbon nano-tube/few-wall carbon nanotube solution of various concentration.
Embodiment 1
（1）It is acidified multi-walled carbon nanotube solution preparation step：Multi-walled carbon nanotube is added to H2SO4（95.0-98.0%）
And HNO3 （65.0-68.0%）Volume ratio is 3:In 1 mixed liquor, 2 h of return stirring at 70 DEG C filters, takes filter residue to distill
Water rinses, until eluate is neutrality, then filter residue is dissolved in distilled water, obtains the acidification multi wall of a concentration of 5 mg/ml
Carbon nano-tube solution；
（2）By polyurethane sponge（Polyvinyl sponge can also be used in concrete operations）It is cut into 4.5 × 3.5 × 2 cm's
Cuboid（It, can be according to requiring sponge being cut into required size and shape in specific implementation process）, pass through successively respectively
Ethyl alcohol, acetone, distillation water washing and after drying, then it is immersed into step（1）In the acidification multi-walled carbon nanotube solution of acquisition（Solution
It is totally submerged sponge）, after impregnating 2 min, take out sponge and be positioned under 30 DEG C of baking oven dry 24 h, be then immersed into again
In above-mentioned multi-walled carbon nanotube solution, submergence-drying steps are so repeated 2 times（I.e. total immersion is moistened-is dried 3 times）, obtain sponge
Compound (the dry sponge body of absorption multi-walled carbon nanotube)；
（3）By step（2）Sponge compound after 3rd drying is put into tube furnace, is fully passed through nitrogen, gas flow
It is set as 1 L/min and is warming up to 450 DEG C（Heating rate is 2 DEG C/min）, 40 min are heat-treated, that is, form flexible bubble
Foam shape carbon nanotube sponge, density are 2 mg/cm3。
For the carbon nanotube sponge photo that the present embodiment obtains as shown in Figure 1, in Fig. 1, a is step（2）In successively through ethyl alcohol,
Sponge after acetone, distillation water washing；B is step（2）The sponge compound of acquisition；C is step（3）The carbon nanotube of acquisition
Sponge.
Fig. 2 is the dimensional drawing of prepared carbon nanotube sponge, in Fig. 2, a, b, c be carbon nanotube sponge length and width,
Height, d is the rectangle view of carbon nanotube sponge, from Figure 2 it can be seen that the specific size of the sponge is 4.5 × 3.8 × 1.8 cm.It should
Carbon nanotube sponge electrochemical capacitance performance in 6 M KOH is as shown in table 1, and the test of the specific capacitance is all made of chronoptentiometry, puts
Electric current is 0.5-20 A/g.
Embodiment 2
Polyurethane sponge is cut into the cuboid of 4.5 × 3.5 × 2 cm, respectively through ethyl alcohol, acetone, distillation water washing, and
After drying, it is immersed in a concentration of 5 mg/ml acidifications single-walled nanotube solution, after impregnating 2 min, 30 DEG C is positioned over after taking-up
Dry 24 h, so repeat immersion-drying 2 times under baking oven, obtain the dry sponge body of absorption carbon nanotube；
The dry sponge body of above-mentioned absorption carbon nanotube is put into tube furnace, through being fully passed through nitrogen, gas flow is
0.1 L/min is warming up to 500 DEG C（2℃/min ）, flexible foam-like carbon nanometer can be formed after thermally treated 40 min
Pipe cavernous body, density are 2 mg/cm3。
Fig. 3 is carbon nanotube sponge flexibility test result (the specific test method foundation document prepared by the present embodiment
L.F. Shen, J. Wang, G.Y. Xu, H.S. Li, H. Dou, X.G. Zhang. Advanced Energy
Materials, 2015,5 (3), 1400977. disclosed methods).In Fig. 3, a, b, c are the process for compressing carbon nanotube sponge,
D, e is respectively the process that compressed carbon nanotube sponge release restores, and e is the carbon nanotube sea that original state is restored to after being released
Silk floss, as seen from Figure 3, prepared carbon nanotube sponge have good elasticity.
The SEM scanning electron microscope (SEM) photographs for the carbon nanotube cavernous body that the present embodiment obtains are as shown in figure 4, a, b, c are respectively in Fig. 4
Amplification 50 times, b500 times and 20,000 times under the conditions of scanning electron microscope (SEM) photograph, from fig. 4, it can be seen that the cavernous body show it is good porous
Shape open-celled structure, cavernous body inside are blocked without duct, and hole diameter is about at 200-500 μm.In addition, from high power scanning electron microscope
Figure c can be seen that sponge supporter is made of carbon pipe, and between crosslinked carbon pipe, also form many pore passage structures, hole
Road diameter is less than 200 nm, and the porous structure of the cavernous body is conducive to the diffusion of electrolyte solution.
The carbon nanotube sponge that the present embodiment obtains electrochemical capacitance performance in 6 M KOH is as shown in table 1, the survey of the specific capacitance
Examination is all made of chronoptentiometry, and discharge current is 0.5-20 A/g.
Embodiment 3
Polyurethane sponge is cut into required size（4.5×3.5×2 cm）, washed respectively through ethyl alcohol, acetone, distillation
It washs, and after drying, then is immersed in the acidification for being acidified single-walled carbon nanotube solution and a concentration of 1 mg/ml by a concentration of 1 mg/ml
Multi-walled carbon nanotube solution mixes（By volume 1：1 mixing）In obtained mixing carbon pipe (1mg/ml) solution, by 100 min
Immersion after, dry 8 h are positioned under 60 DEG C of baking oven after taking-up, so repeat immersion-drying 1 time, is obtained and is adsorbed carbon and receive
The dry sponge body of mitron；
The dry sponge body of above-mentioned absorption carbon nanotube is put into tube furnace, through being fully passed through argon gas, gas flow is
0.5 L/min is warming up to 600 DEG C（2℃/min）, can be formed after thermally treated 20 min flexible single-walled carbon nanotube with
Multi-walled carbon nanotube cavernous body, density are 0.8 mg/cm3。
The carbon nanotube cavernous body that the present embodiment obtains is electrode in 1M H2SO4Pass through time-measuring electric potential in 6M KOH solutions
Obtained specific capacitance and current density relationship such as Fig. 5,（Test method is shown in document：W.L. Bai, H. Tong, Z.Z. Gao,
S.H. Yue, S.C. Xing, S.Y. Dong, L.F. Shen, J.P. He, X.Z. Zhang, Y.Y. Liang,
J. Mater. Chem. A, 2015, 3,21891）, as seen from Figure 5, in acid H2SO4 In electrolyte, prepared by the present embodiment
Carbon nanotube cavernous body shows and sees better capacitance characteristic, the bigger in alkaline KOH of the specific capacitance ratio in acidity uses
Time-measuring electric potential is in 1M H2SO4Obtained specific capacitance value such as chart 1, discharge current 0.5-20A/g in acidic electrolysis bath.
Embodiment 4
Polyurethane sponge is cut into the cuboid of 4.5 × 3.5 × 2 cm, respectively through ethyl alcohol, acetone, distillation water washing, and
It after drying, then is immersed in be acidified in single-walled carbon nanotube solution through a concentration of 2 mg/ml and impregnates 2 min, 30 are positioned over after taking-up
DEG C baking oven under dry 24 h, so repeat immersion-drying 1 time, obtain the dry sponge body for adsorbing carbon nanotube；
The dry sponge body of above-mentioned absorption carbon nanotube is put into tube furnace, through being fully passed through nitrogen, gas flow is
0.1 L/min is warming up to 600 DEG C（Heating rate is 2 DEG C/min）, flexible foam can be formed after thermally treated 20 min
Shape carbon nanotube cavernous body, density are 1.0 mg/cm3.The specific capacitance such as table at 6 M KOH obtained using chronoptentiometry
Shown in 1, discharge current is 0.5-20 A/g.
Embodiment 5
Polyurethane sponge is cut into the cuboid of 4.5 × 3.5 × 2 cm, respectively through ethyl alcohol, acetone, distillation water washing, and
It after drying, is immersed in the acidification single-walled carbon nanotube solution of a concentration of 0.5 mg/ml, after impregnating 2 min, taking-up is positioned over 30
DEG C baking oven under dry 24 h, obtain the dry sponge body of absorption carbon nanotube；
The dry sponge body of above-mentioned absorption carbon nanotube is put into tube furnace, nitrogen is fully passed through, gas flow is
0.02 L/min is warming up to 500 DEG C（Heating rate is 2 DEG C/min）, flexible bubble can be formed after thermally treated 40 min
Foam shape carbon nanotube cavernous body, density are 0.5 mg/cm3.Using chronoptentiometry in 1M H2SO4In obtained specific capacitance such as
Shown in table 1, discharge current is 0.5-20 A/g.
Using chronoptentiometry detect above-described embodiment or carbon nanotube cavernous body electrochemical capacitance performance,（Test method
See document：W.L. Bai, H. Tong, Z.Z. Gao, S.H. Yue, S.C. Xing, S.Y. Dong, L.F.
Shen, J.P. He, X.Z. Zhang, Y.Y. Liang, J. Mater. Chem. A, 2015, 3,21891）, as a result
As shown in table 1, charging and discharging currents are identical.
The electrochemical capacitance performance of the different carbon nanotubes of table 1 and its mixture
By calculating specific capacitance using chronoptentiometry to embodiment 1-5 samples, multi wall carbon is used as can be seen from Table 1
Cavernous body such as embodiment 1 prepared by nanotube, shows relatively high capacitance under alkaline condition.Pass through embodiment 2,4
Comparison with 5 is found, the carbon nanotube sponge of different densities is obtained using prepared by different experimental conditions, in same nature
In electrolyte, obtained specific capacitance is almost the same, and influence of the experiment condition in embodiment to capacitance is smaller, when using acid electricity
Solve liquid 1M H2SO4 When condition test, as a result shows in acid condition than specific capacitance bigger under alkaline condition, illustrate acid item
Capacitive property is more preferable under part.In addition it is compared and is found by embodiment 1,2 and 3, different carbon nanotubes is mixed into preparation
Carbon nanotube cavernous body still has good capacitive property, these are the result shows that the carbon nanotube sponge prepared using this method
With good capacitive property, it is suitable as electrode material.
Main experimental parameter in 2 specific embodiment of table
It is described above to be only used as presently preferred embodiments of the present invention and application, the limitation of the present invention is should not be construed as, it is all
The invention for being modification, replacement and the change in the other forms made of technological thought based on the present invention and realizing belongs to this hair
Bright protection domain.Can several change can be cooked the present invention under the premise of not departing from the present invention for those skilled in the art
Into and modification, these improvement and modification are also considered as protection scope of the present invention.
Claims (4)
1. a kind of preparation method of carbon nanotube cavernous body, which is characterized in that be as follows：
a）Carbon nanotube is immersed in H2SO4And HNO3By volume 3：In 1 mixed liquor being mixed to form, return stirring 2 at 70 DEG C
H is filtered, and is neutrality with distilled water flushing filter residue to eluate, then filter residue is dissolved in distilled water, is configured to a concentration of
The acidification carbon nano-tube solution of 0.5-5 mg/ml；
b）By sponge successively with ethyl alcohol, acetone, distillation water washing after, be transferred to acidification carbon nano-tube solution in infiltrate 2-100
Then min is infiltrated in acidification carbon nano-tube solution, so repeats 1-5 times, obtain sea in 30-60 DEG C of drying after taking-up again
Continuous compound；
c）Sponge compound after drying is placed in tube furnace, inert gas is passed through, 20-40 is heat-treated in 450-600 DEG C
Min obtains the carbon nanotube sponge.
2. the preparation method of carbon nanotube cavernous body according to claim 1, which is characterized in that the sponge is polyurethane sea
It is continuous.
3. the preparation method of carbon nanotube cavernous body according to claim 2, which is characterized in that the inert gas is argon gas
Or nitrogen, gas flow are 0.02-1 L/min.
4. according to the preparation method of one of the claim 1-3 carbon nanotube cavernous bodies, which is characterized in that the carbon nanotube
For at least one of single-walled carbon nanotube, multi-walled carbon nanotube.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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