CN103450682A - Carbon nanotube/polypyrrole composite sponge and preparation method thereof - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 74
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 150000003233 pyrroles Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 10
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229940117389 dichlorobenzene Drugs 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910021386 carbon form Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 8
- 238000007906 compression Methods 0.000 abstract description 8
- 238000004804 winding Methods 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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Abstract
The invention relates to carbon nanotube/polypyrrole composite sponge and a preparation method thereof, belonging to the field of the synthesis and application of carbon nanocomposites. The carbon nanotube/polypyrrole composite sponge is formed through stacking and winding composite tubes with microcosmic core-shell structures and has a porous structure, wherein each composite tube consists of a carbon nanotube and a uniform-thickness polypyrrole layer coated outside the carbon nanotube. The mass content of polypyrrole in the composite sponge is controllable; the composite sponge has good elasticity, good cyclic compression stability and excellent electrochemical properties; the carbon nanotube/polypyrrole composite sponge is prepared by the method which combines a chemical vapor deposition method, an adsorption composite method and an electrochemical polymerization method; the preparation method has ingenious conception and is simple and easy in operation.
Description
Technical field
The invention belongs to carbon nano-composite material and synthesize and Application Areas, relate to a kind of preparation method of carbon nano-composite material, particularly a kind of carbon nano-tube/poly pyrroles composite sponge and preparation method thereof.
Background technology
Carbon nanotube because it has unique structure and excellent performance, has caused widely and has paid close attention to since being found by Japanese Electronic Speculum expert S.Iijima from 1991.Along with carbon nanotube long filament, carbon nano-tube film, directional carbon nanotube array etc., the controlled preparation of the carbon nano-tube macroscopic body of different shape and structure is with synthetic, expanded greatly the Application Areas of carbon nanotube, and prepare the carbon nanometer macroscopic body with three-dimensional macro size, will contribute to realize the large-scale application of carbon nanotube.
The people such as osmanthus Xu Chun are by the method for chemical vapour deposition, synthesize a kind of carbon nanotube sponge that forms, has vesicular structure by carbon nanotube winding accumulation, at energy-absorbing damping, reinforced composite material, greasy dirt absorption and field of Environment Protection, represented abundant application potential.The people such as Li Peixu have studied the electrode material for super capacitor that the carbon nanotube sponge can be pressed as height aspect electrical condenser, but, because the energy storage mechanism of carbon nanotube is limit, the quality of carbon nanotube sponge is not higher than capacitance.Organic conductive polymkeric substance and carbon nanotube is compound, be the effective means that improves capacitive property.In numerous organic conductive polymkeric substance, polypyrrole is because it has cheap, environmental friendliness and the advantage such as synthetic easy, in the widespread use of ultracapacitor field.The people such as Jurewicz are compound by polypyrrole and multi-wall carbon nano-tube pipe powder, effectively improved the ratio electric capacity of matrix material; The people such as Schnoor realized polypyrrole and directional carbon nanotube array compound.And the matrix material of polypyrrole and carbon nanotube sponge not yet someone studies, how the microtexture of matrix material is optimized to regulation and control, further improve the chemical property of matrix material by composite means, widen the focus that its Application Areas is still research.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of carbon nano-tube/poly pyrroles composite sponge and preparation method thereof, by the method controlledly synthesis, go out to have vesicular structure, mechanical property is good, chemical property is excellent compound sponges material.
To achieve these goals, the technical solution used in the present invention is:
A kind of carbon nano-tube/poly pyrroles composite sponge, be entwined by the multiple-unit tube with microcosmic core shell structure is stacking, has vesicular structure, and described multiple-unit tube is by carbon nanotube and be coated on the outer uniform polypyrrole of a layer thickness of carbon nanotube and form.
Described vesicular structure is comprised of the mesopore of 2-50nm and the macropore of 50-100nm, and hole is produced by the stacking winding of described multiple-unit tube, and described stacking winding refers to that a large amount of multiple-unit tubes is unordered and is intertwined.
The thickness of described polypyrrole is preferably 5-80nm.
The present invention also provides the preparation method of described carbon nano-tube/poly pyrroles composite sponge, comprises the steps:
1) chemical Vapor deposition process: Reaktionsofen is set, in the indoor quartz substrate of putting into of its quartz reaction, is heated, pass into argon gas emptying reaction room air simultaneously; After quartz substrate reaches 820-940 ℃, under the mixed atmosphere of hydrogen/argon gas, in reaction chamber, pass into ferrocene/dichlorobenzene carbon source solution; After reaction under argon shield furnace cooling, collect the carbon nanotube sponge obtain being block in quartz substrate;
2) absorption composite algorithm: the carbon nanotube sponge block obtained is soaked into to pyrroles/acetone soln fully, after keeping certain hour, obtains the sponge block that absorption has the pyrroles, take out stand-by;
3) electrochemical polymerization method: electrochemical workstation is set, the absorption obtained is had to pyrroles's sponge block as working electrode, adopt platinum to electrode and silver/silver chloride reference electrode, be immersed in sodium perchlorate solution the certain hour of switching on, be adsorbed on the outer pyrroles of carbon nanotube wall electropolymerization occurs, form polypyrrole, obtain carbon nano-tube/poly pyrroles composite sponge.
In described step 1), for emptying reaction room air passes into argon flow amount, be 800mL/min; During reaction, hydrogen flowing quantity is 100-500mL/min, and argon flow amount is 2000mL/min, passes into simultaneously; The concentration of ferrocene/dichlorobenzene carbon source solution is 20-100mg/mL, and speed of feed is 0.1-0.3mL/min, and the reaction times is 4h; When cooling, argon flow amount is 100mL/min.
Described step 2) in, the concentration of pyrroles/acetone soln is 0.1-1mol/L, and soak time is 0.5-2h.
In described step 3), the concentration of sodium perchlorate solution is 0.1-0.5mol/L, and operating voltage is 0.5-0.9V, and be 5-30min conduction time.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention is owing to taking above technical scheme, and it has the following advantages:
1, composite sponge of the present invention has loop compression stability, and under 50% compressive strain, loop compression is not destroyed more than 1000 times, and in composite sponge, the mass content of polypyrrole is controlled.
2, the prepared carbon nano-tube/poly pyrroles of the present invention composite sponge, be the porous material that is three-dimensional block, and the matrix material than the Powdered and directional array in background technology, have more excellent mechanical property and structural stability, widened range of application.
3, the prepared carbon nano-tube/poly pyrroles of the present invention composite sponge, polypyrrole is coated on the outer wall of single-root carbon nano-tube uniformly, form core shell structure, the microtexture excellence, than simple carbon nanotube sponge, polypyrrole layer has effectively strengthened mechanical property, structural stability and the chemical property of composite sponge, simultaneously the even thickness of polypyrrole layer, controlled, guaranteed in matrix material the Effective Regulation of polypyrrole content.
4, the mode that the present invention adopts chemical Vapor deposition process, absorption composite algorithm and electrochemical polymerization method to combine prepares carbon nano-tube/poly pyrroles composite sponge, and the method is skillfully constructed, simple to operation, can on macroscopic view, prepare this material of three-dimensional block.
The accompanying drawing explanation
Fig. 1 (a) is its microcosmic core shell structure schematic perspective view of product prepared by the present invention.
Fig. 1 (b) is its microcosmic core shell structure schematic cross-section of product prepared by the present invention.
Fig. 2 (a) is that the stereoscan photograph of carbon nano-tube/poly pyrroles composite sponge (prepares characteristic parameter: pyrroles/acetone soln: 0.5mol/L; Sodium perchlorate solution: 0.3mol/L; The electrochemical polymerization time: 10 minutes).
Fig. 2 (b) is the transmission electron microscope photo (preparing same Fig. 2 of characteristic parameter (a)) of carbon nano-tube/poly pyrroles composite sponge.
Fig. 2 (c) is the cyclic voltammetry curve (preparing same Fig. 2 of characteristic parameter (a)) of carbon nano-tube/poly pyrroles composite sponge.
Fig. 3 (a) is that carbon nano-tube/poly pyrroles composite sponge and carbon nanotube sponge compression performance correlation curve (prepare characteristic parameter: pyrroles/acetone soln: 0.5mol/L; Sodium perchlorate solution: 0.2mol/L; The electrochemical polymerization time: 10 minutes).
Fig. 3 (b) is the circulation tube compression performance curve (preparing same Fig. 3 of characteristic parameter (a)) of carbon nano-tube/poly pyrroles composite sponge.
Fig. 4 is that the transmission electron microscope photo of carbon nano-tube/poly pyrroles composite sponge (prepares characteristic parameter: pyrroles/acetone soln: 0.1mol/L; Sodium perchlorate solution: 0.3mol/L; The electrochemical polymerization time: 10 minutes).
Fig. 5 is that the transmission electron microscope photo of carbon nano-tube/poly pyrroles composite sponge (prepares characteristic parameter: pyrroles/acetone soln: 1mol/L; Sodium perchlorate solution: 0.3mol/L; The electrochemical polymerization time: 30 minutes).
Embodiment
Carbon nano-tube/poly pyrroles composite sponge involved in the present invention has core shell structure on microcosmic, as shown in Figure 1 (a) and Fig 1 (b) shows, is coating uniformly one deck polypyrrole 2 on the outer wall of single-root carbon nano-tube 1, forms core shell structure, the microtexture excellence.
Describe embodiments of the present invention in detail below in conjunction with drawings and Examples.
Embodiment 1:
1) Reaktionsofen of chemical Vapor deposition process is set, in the indoor quartz substrate of putting into of its quartz reaction, is heated, pass into the argon gas emptying reaction room air of 800mL/min simultaneously; After quartz substrate reaches 860 ℃, the adjustment argon flow amount is 2000mL/min, passes into 300mL/min hydrogen, and to the ferrocene that passes into 60mg/mL in reaction chamber/dichlorobenzene carbon source solution, speed of feed is 0.13mL/min; After reaction 4h, furnace cooling under the argon shield of 100mL/min, collect the carbon nanotube sponge that obtains being block in quartz substrate.
2) cut 0.5 * 0.5 * 0.5cm
3carbon nanotube sponge block, pyrroles/acetone soln that it is immersed in to 0.5mol/L, after soaking 30 minutes, the pyrroles is adsorbed in the sponge block, takes out standby.
3) electrochemical workstation for electrochemical polymerization method is set, by step 2) absorption that obtains has pyrroles's sponge block as working electrode, adopt platinum to electrode and silver/silver chloride reference electrode, be immersed in the sodium perchlorate solution of 0.3mol/L, 0.8V operating voltage under, switch on 10 minutes, be adsorbed on the outer pyrroles of carbon nanotube wall electropolymerization occur, form polypyrrole, obtain carbon nano-tube/poly pyrroles composite sponge.
Weigh by before and after the polypyrrole load, record in the carbon nano-tube/poly pyrroles composite sponge sample prepared, the content of polypyrrole is 52.4wt%.Fig. 2 (a) and Fig. 2 (b) are respectively scanning electron microscope and the transmission electron microscope photo of carbon nano-tube/poly pyrroles composite sponge.Can find out that from Fig. 2 (a) and Fig. 2 (b) carbon nano-tube/poly pyrroles composite sponge is to be coated the stacking vesicular structure be entwined of carbon nanotube of polypyrrole by outer wall, on microcosmic, the uniform polypyrrole 2 of carbon nanotube 1 outer cladding a layer thickness, form the microcosmic core shell structure, the thickness of polypyrrole layer is in the 18nm left and right.Fig. 2 (c) is that this carbon nano-tube/poly pyrroles composite sponge is as electrode material for super capacitor, the cyclic voltammetry curve recorded under the sweep velocity of 200mV/s, with simple carbon nanotube sponge, compare, be increased to 255.4F/g than capacitance by 10.1F/g, the chemical property of carbon nano-tube/poly pyrroles composite sponge significantly promotes.
Embodiment 2:
The difference of the present embodiment and embodiment 1 is: adopt the sodium perchlorate solution that concentration is 0.2mol/L in step 3).The composite sponge product for preparing gained, the content of polypyrrole is 50.3wt%.Fig. 3 (a) is the contrast of carbon nano-tube/poly pyrroles composite sponge and carbon nanotube sponge compression curve, can find out, under identical compressive strain, the stress value of composite sponge obviously increases, and mechanical property strengthens.Fig. 3 (b) is carbon nano-tube/poly pyrroles composite sponge compression cycle curve, and compressive strain is 50%, from cyclic curve, can find out, composite sponge has good elasticity and structural stability under the condition of Repeated Compression.
Embodiment 3:
The difference of the present embodiment and embodiment 1 is: the pyrroles/acetone soln that adopts 0.1mol/L step 2).The composite sponge product for preparing gained, the content of polypyrrole is 18.2wt%.The transmission electron microscope photo that Fig. 4 is this composite sponge, can measure from this figure, and in this composite sponge, the thickness of polypyrrole layer, at 5-8nm, is significantly less than embodiment 1.
Embodiment 4:
The difference of the present embodiment and embodiment 1 is: the pyrroles/acetone soln that adopts 1mol/L step 2); In step 3), be 30 minutes conduction time.The composite sponge product for preparing gained, the content of polypyrrole is 88.3wt%.The transmission electron microscope photo that Fig. 5 is this composite sponge, can measure from this figure, the about 60nm of the thickness of polypyrrole layer in this composite sponge, and this thickness significantly is greater than embodiment 1.
The various embodiments described above are only for illustrating the present invention, and wherein the parameter of each step, implementation condition etc. all can change to some extent, and every equivalents of carrying out on the basis of technical solution of the present invention and improvement, all should not get rid of outside protection scope of the present invention.
Claims (7)
1. a carbon nano-tube/poly pyrroles composite sponge, is characterized in that, by the multiple-unit tube with microcosmic core shell structure is stacking, is entwined, and has vesicular structure, and described multiple-unit tube is by carbon nanotube and be coated on the outer uniform polypyrrole of a layer thickness of carbon nanotube and form.
2. carbon nano-tube/poly pyrroles composite sponge according to claim 1, is characterized in that, described vesicular structure is comprised of the mesopore of 2-50nm and the macropore of 50-100nm.
3. carbon nano-tube/poly pyrroles composite sponge according to claim 1, is characterized in that, the thickness of described polypyrrole is 5-80nm.
4. the preparation method of carbon nano-tube/poly pyrroles composite sponge according to claim 1, is characterized in that, comprises the steps:
1) chemical Vapor deposition process: Reaktionsofen is set, in the indoor quartz substrate of putting into of its quartz reaction, is heated, pass into argon gas emptying reaction room air simultaneously; After quartz substrate reaches 820-940 ℃, under the mixed atmosphere of hydrogen/argon gas, in reaction chamber, pass into ferrocene/dichlorobenzene carbon source solution; After reaction under argon shield furnace cooling, collect the carbon nanotube sponge obtain being block in quartz substrate;
2) absorption composite algorithm: the carbon nanotube sponge block obtained is soaked into to pyrroles/acetone soln fully, after keeping certain hour, obtains the sponge block that absorption has the pyrroles, take out stand-by;
3) electrochemical polymerization method: electrochemical workstation is set, the absorption obtained is had to pyrroles's sponge block as working electrode, adopt platinum to electrode and silver/silver chloride reference electrode, be immersed in sodium perchlorate solution the certain hour of switching on, be adsorbed on the outer pyrroles of carbon nanotube wall electropolymerization occurs, form polypyrrole, obtain carbon nano-tube/poly pyrroles composite sponge.
5. carbon nano-tube/poly pyrroles composite sponge preparation method according to claim 4, is characterized in that, in described step 1), for emptying reaction room air passes into argon flow amount, is 800mL/min; During reaction, hydrogen flowing quantity is 100-500mL/min, and argon flow amount is 2000mL/min, passes into simultaneously; The concentration of ferrocene/dichlorobenzene carbon source solution is 20-100mg/mL, and speed of feed is 0.1-0.3mL/min, and the reaction times is 4h; When cooling, argon flow amount is 100mL/min.
6. carbon nano-tube/poly pyrroles composite sponge preparation method according to claim 4, is characterized in that described step 2) in, the concentration of pyrroles/acetone soln is 0.1-1mol/L, soak time is 0.5-2h.
7. carbon nano-tube/poly pyrroles composite sponge preparation method according to claim 4, is characterized in that, in described step 3), the concentration of sodium perchlorate solution is 0.1-0.5mol/L, and operating voltage is 0.5-0.9V, and be 5-30min conduction time.
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| CN103980668A (en) * | 2014-05-30 | 2014-08-13 | 哈尔滨工业大学 | Preparation method of carbon nano-tube/amorphous carbon/epoxy resin composite material |
| CN103979528A (en) * | 2014-05-30 | 2014-08-13 | 哈尔滨工业大学 | One-step method for preparing hyperelastic carbon nanotube/amorphous carbon composite all-carbon sponge |
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| CN106432721A (en) * | 2016-09-30 | 2017-02-22 | 同济大学 | Method for preparing carbon nano-tubes/polypyrrole nano-particles with performance of metamaterials |
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| CN103979528A (en) * | 2014-05-30 | 2014-08-13 | 哈尔滨工业大学 | One-step method for preparing hyperelastic carbon nanotube/amorphous carbon composite all-carbon sponge |
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