CN104495790A - Method for preparing three-dimensional bowl-shaped porous carbon material based on carbon nanotube - Google Patents
Method for preparing three-dimensional bowl-shaped porous carbon material based on carbon nanotube Download PDFInfo
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Abstract
The invention discloses a method for preparing a three-dimensional bowl-shaped porous carbon material based on a carbon nanotube and relates to a preparation method of a porous carbon material and particularly relates to the method for preparing the three-dimensional bowl-shaped porous carbon material based on the carbon nanotube. The method disclosed by the invention aims to solve the problem that in the existing method, the preparation process is tedious, impurities can be introduced to the synthetic process inevitably, the price is high and posttreatment is complex. The method comprises the following steps: I, putting the carbon nanotube in a mixed acid of concentrated sulfuric acid and concentrated nitric acid, centrifugally washing after reflux reaction and then dialyzing, and drying; II, mixing polyvinylpyrrolidone, deionized water and the product in the step I and stirring and carrying out ultrasonic treatment; III, pouring the product in the step II into an injector I, pouring dimethicone into an injector II, and propelling matters in the injectors I and II into a PP receiver of a microfluidic device by virtue of an injection pump; IV, firstly curing and drying and pre-oxidizing after washing by normal hexane; and V, carbonizing to obtain the three-dimensional bowl-shaped porous carbon material.
Description
Technical field
The present invention relates to a kind of preparation method of porous carbon materials, particularly relate to a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube.
Background technology
Carbon nanotube from it since 1991 are found by Iijima, owing to having unique hollow structure, nano-scale, abnormal excellent physical chemical property, mechanical characteristics and the thermostability such as high aspect ratio and larger specific surface area, cause the extensive concern of scientific circles.It at numerous areas as solar cell, catalysis, environmental area and biotechnology industry etc. have a wide range of applications.Porous carbon materials, a kind of material with the pore texture of certain size and quantity, because it has larger specific surface area, high porosity and good electrical and thermal conductivity, be widely used in the field such as ultracapacitor, catalyzer and support of the catalyst, sorbent material, gas storage.
Three-dimensional porous carbon materials, particularly has the porous carbon materials of carbon nanotube or polymkeric substance participation preparation to be more and more subject to everybody attention.Lou etc. for presoma, have prepared the microporous carbon nanometer ball with high-ratio surface sum high specific capacitance with polypyrrole nanometer ball through processes such as carbonization-activations; Zhou etc. utilize Co nanoparticle will to open the CNTs growth in situ of port on activated carbon substrate as seed by electroless plating, thus obtain the three-dimensional layering mixed structure of nanotube and gac, can be used for high-performance super capacitor.By two-step approach, Zhu etc. prepare ordered mesopore carbon/carbon nano tube compound material three-dimensional conductive network.Obtain porous carbon compounded microbeads through carbonization, steam activation process again by solution polymerization after CNTs mixes with resol by Lu etc., porous compounded microbeads can be used for the research of the absorption of low-density lipoprotein in human serum after oversulfonate.
The common method preparing porous carbon materials has hard template method, soft template method, chemical activation method etc.
Porous carbon materials prepared by hard template method is the anti-phase replica of its template, inevitably can introduce some impurity, and preparation process is loaded down with trivial details in building-up process.
Soft template method prepares porous carbon materials, higher to the requirement of synthesis condition, and expensive price also limit its mass-producing application.
Traditional chemical activation method makes its subsequent treatment process become complicated owing to adding activator.
Summary of the invention
The present invention is the problem that preparation technology in existing method is loaded down with trivial details, building-up process inevitably can introduce impurity, expensive and aftertreatment is complicated in order to solve, and provides a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube.
A kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube of the present invention is carried out according to the following steps:
One, carbon nanotube is placed in the nitration mixture of the vitriol oil and concentrated nitric acid composition, back flow reaction 2h ~ 3h under temperature is 80 ~ 85 DEG C of conditions, carry out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 60 ~ 70 DEG C carries out drying, obtain the carbon nanotube powder handled well;
In the nitration mixture of the described vitriol oil and concentrated nitric acid composition, the volume ratio of the vitriol oil and concentrated nitric acid is (2 ~ 4): 1; The described vitriol oil is the vitriol oil of massfraction 95% ~ 99%, and described concentrated nitric acid is the concentrated nitric acid of massfraction 60% ~ 70%;
Two, the carbon nanotube powder handled well mixing polyvinylpyrrolidone, deionized water and step one obtained, low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains Composite Particles Disperse Phase solution;
The carbon nanotube powder handled well that described step one obtains and the mass ratio of polyvinylpyrrolidone are (0.2 ~ 5): 1;
The quality of described polyvinylpyrrolidone and the ratio of deionized water volume are 0.1g:(3 ~ 13) mL;
Three, Composite Particles Disperse Phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the Composite Particles Disperse Phase solution in No. 1 syringe and No. 2 syringes, obtain carbon nano-tube/poly V-Pyrol RC compounded microbeads;
No. 1 described syringe and No. 2 are connected with PTFE tube between syringe with syringe pump;
The volume ratio of the Composite Particles Disperse Phase solution in No. 1 described syringe and the dimethyl silicone oil in No. 2 syringes is 1:(10 ~ 20);
The propelling speed of No. 1 described syringe is 0.5:(110 ~ 130 with the ratio of the propelling speed of No. 2 syringes);
Four, it is that the loft drier of 60 ~ 70 DEG C solidifies 12h ~ 24h that carbon nano-tube/poly V-Pyrol RC compounded microbeads step 3 obtained is placed in temperature, then n-hexane is used 4 ~ 6 times, be placed in baking oven again and carry out oven dry preoxidation, obtain preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads;
Described oven dry preoxidation process is: be dry preoxidation 6h ~ 9h under the condition of 140 ~ 160 DEG C in temperature, is then dry preoxidation 1.5h ~ 2h under the condition of 270 ~ 290 DEG C in temperature;
Five, under nitrogen atmosphere, carbonizing treatment is carried out to the preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads that step 4 obtains, obtains three-dimensional bowl-shape porous carbon materials;
Described carbonizing treatment process is: be 700 ~ 800 DEG C with the temperature rise rate of 4 DEG C/min ~ 6 DEG C/min by room temperature to temperature, and is incubated 1.5h ~ 2.5h to be temperature be 700 ~ 800 DEG C in temperature;
The ratio that in the bowl-shape porous carbon materials of described three-dimensional, the quality of carbon nanotube and the residual C of polyvinylpyrrolidone measure is (1 ~ 20): 1.
In step 5 after high-temperature calcination (700-800 DEG C) process, polyvinylpyrrolidone carbonization, residual material mass is the residual C amount of polyvinylpyrrolidone, and carbon nanotube fusing point is higher than 700-800 DEG C, so carbon nanotube does not have carbonization while polyvinylpyrrolidone carbonization.
Beneficial effect of the present invention
Acid-treated carbon nanotube, polyvinylpyrrolidone (PVP) mixing are dissolved in deionized water and are mixed with the disperse phase solution with certain viscosity through supersound process by the present invention, by homemade micro fluidic device, using dimethyl silicone oil as moving phase, mixing solutions prepares carbon nanotube/PVP compounded microbeads as disperse phase, be cured again and preoxidation, then through calcination processing, the three-dimensional bowl-shape or bowl-shape porous carbon materials of class is finally obtained.Method of the present invention can not introduce impurity during the course, and preparation process is simple, safe and reliable, and environmentally friendly, and the prices of raw and semifnished materials used are cheap, and require not harsh to synthesis condition, the material of synthesis has good performance in electrochemistry.And method of the present invention then only needs simple aftertreatment, the porous carbon materials pattern obtained is peculiar, is a kind of fairly simple method preparing porous carbon materials easily, can be used for the field such as catalysis, ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the three-dimensional porous carbon material that test one obtains;
Fig. 2 is the SEM figure of the three-dimensional porous carbon material surface that test one obtains;
Fig. 3 is the three-dimensional porous carbon material XRD figure that test one obtains;
Fig. 4 is the cyclic voltammetry curve figure of the three-dimensional porous carbon material that test one obtains.
Embodiment
Embodiment one: a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube of present embodiment is carried out according to the following steps:
One, carbon nanotube is placed in the nitration mixture of the vitriol oil and concentrated nitric acid composition, back flow reaction 2h ~ 3h under temperature is 80 ~ 85 DEG C of conditions, carry out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 60 ~ 70 DEG C carries out drying, obtain the carbon nanotube powder handled well;
In the nitration mixture of the described vitriol oil and concentrated nitric acid composition, the volume ratio of the vitriol oil and concentrated nitric acid is (2 ~ 4): 1; The described vitriol oil is the vitriol oil of massfraction 95% ~ 99%, and described concentrated nitric acid is the concentrated nitric acid of massfraction 60% ~ 70%;
Two, the carbon nanotube powder handled well mixing polyvinylpyrrolidone, deionized water and step one obtained, low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains Composite Particles Disperse Phase solution;
The carbon nanotube powder handled well that described step one obtains and the mass ratio of polyvinylpyrrolidone are (0.2 ~ 5): 1;
The quality of described polyvinylpyrrolidone and the ratio of deionized water volume are 0.1g:(3 ~ 13) mL;
Three, Composite Particles Disperse Phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the Composite Particles Disperse Phase solution in No. 1 syringe and No. 2 syringes, obtain carbon nano-tube/poly V-Pyrol RC compounded microbeads;
No. 1 described syringe and No. 2 are connected with PTFE tube between syringe with syringe pump;
The volume ratio of the Composite Particles Disperse Phase solution in No. 1 described syringe and the dimethyl silicone oil in No. 2 syringes is 1:(10 ~ 20);
The propelling speed of No. 1 described syringe is 0.5:(110 ~ 130 with the ratio of the propelling speed of No. 2 syringes);
Four, it is that the loft drier of 60 ~ 70 DEG C solidifies 12h ~ 24h that carbon nano-tube/poly V-Pyrol RC compounded microbeads step 3 obtained is placed in temperature, then n-hexane is used 4 ~ 6 times, be placed in baking oven again and carry out oven dry preoxidation, obtain preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads;
Described oven dry preoxidation process is: be dry preoxidation 6h ~ 9h under the condition of 140 ~ 160 DEG C in temperature, is then dry preoxidation 1.5h ~ 2h under the condition of 270 ~ 290 DEG C in temperature;
Five, under nitrogen atmosphere, carbonizing treatment is carried out to the preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads that step 4 obtains, obtains three-dimensional bowl-shape porous carbon materials;
Described carbonizing treatment process is: be 700 ~ 800 DEG C with the temperature rise rate of 4 DEG C/min ~ 6 DEG C/min by room temperature to temperature, and is incubated 1.5h ~ 2.5h to be temperature be 700 ~ 800 DEG C in temperature;
The ratio that in the bowl-shape porous carbon materials of described three-dimensional, the quality of carbon nanotube and the residual C of polyvinylpyrrolidone measure is (1 ~ 20): 1.
In step 5 after high-temperature calcination (700-800 DEG C) process, polyvinylpyrrolidone carbonization, residual material mass is the residual C amount of polyvinylpyrrolidone, and carbon nanotube fusing point is higher than 700-800 DEG C, so carbon nanotube does not have carbonization while polyvinylpyrrolidone carbonization.
Acid-treated carbon nanotube, polyvinylpyrrolidone (PVP) mixing are dissolved in deionized water and are mixed with the disperse phase solution with certain viscosity through supersound process by present embodiment, by homemade micro fluidic device, using dimethyl silicone oil as moving phase, mixing solutions prepares carbon nanotube/PVP compounded microbeads as disperse phase, be cured again and preoxidation, then through calcination processing, the three-dimensional bowl-shape or bowl-shape porous carbon materials of class is finally obtained.The method of present embodiment can not introduce impurity during the course, and preparation process is simple, safe and reliable, and environmentally friendly, and the prices of raw and semifnished materials used are cheap, and require not harsh to synthesis condition, the material of synthesis has good performance in electrochemistry.And the method for present embodiment then only needs simple aftertreatment, the porous carbon materials pattern obtained is peculiar, is a kind of fairly simple method preparing porous carbon materials easily, can be used for the field such as catalysis, ultracapacitor.
Embodiment two: present embodiment and embodiment one unlike: in the nitration mixture that the vitriol oil described in step one and concentrated nitric acid form, the volume ratio of the vitriol oil and concentrated nitric acid is 3:1.Other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the vitriol oil described in step one is the vitriol oil of massfraction 98%.Other steps and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the concentrated nitric acid described in step one is the concentrated nitric acid of massfraction 65%.Other steps and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the carbon nanotube powder handled well that the step one described in step 2 obtains and the mass ratio of polyvinylpyrrolidone are 2:1.Other steps and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the quality of the polyvinylpyrrolidone described in step 2 and the ratio of deionized water volume are 0.1g:10mL.Other steps and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the propelling speed of described in step 3 No. 1 syringe is 0.5:120 with the ratio of the propelling speed of No. 2 syringes.Other steps and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the carbon nano-tube/poly V-Pyrol RC compounded microbeads in step 4, step 3 obtained be placed in temperature be 65 DEG C loft drier solidify 24h.Other steps and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the oven dry preoxidation process described in step 4 is: being dry preoxidation 8h under the condition of 150 DEG C in temperature, is then dry preoxidation 2h under the condition of 280 DEG C in temperature.Other steps and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the carbonizing treatment process described in step 5 is: be 750 DEG C with the temperature rise rate of 5 DEG C/min by room temperature to temperature, and is incubated 2h to be temperature be 750 DEG C in temperature.Other steps and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten unlike: the ratio that in the bowl-shape porous carbon materials of the three-dimensional described in step 5, the quality of carbon nanotube and the residual C of polyvinylpyrrolidone measure is 10:1.Other steps and parameter identical with one of embodiment one to ten.
Beneficial effect of the present invention is verified with following test
Test one: a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube of this test is carried out according to the following steps:
One, carbon nanotube is placed in the nitration mixture of the vitriol oil and concentrated nitric acid composition, back flow reaction 3h under temperature is 80 DEG C of conditions, carries out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 70 DEG C carries out drying, obtains the carbon nanotube powder handled well;
In the nitration mixture of the described vitriol oil and concentrated nitric acid composition, the volume ratio of the vitriol oil and concentrated nitric acid is 3:1; The described vitriol oil is the vitriol oil of massfraction 98%, and described concentrated nitric acid is the concentrated nitric acid of massfraction 65%;
Two, the carbon nanotube powder handled well mixing polyvinylpyrrolidone, deionized water and step one obtained, low whipping speed is 300r/min and ultrasonic frequency is process 10h under the condition of 40KHz, obtains Composite Particles Disperse Phase solution;
The carbon nanotube powder handled well that described step one obtains and the mass ratio of polyvinylpyrrolidone are 2:1;
The quality of described polyvinylpyrrolidone and the ratio of deionized water volume are 0.1g:10mL;
Three, Composite Particles Disperse Phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the Composite Particles Disperse Phase solution in No. 1 syringe and No. 2 syringes, obtain carbon nano-tube/poly V-Pyrol RC compounded microbeads;
No. 1 described syringe and No. 2 are connected with PTFE tube between syringe with syringe pump;
The volume ratio of the Composite Particles Disperse Phase solution in No. 1 described syringe and the dimethyl silicone oil in No. 2 syringes is 1:20;
The propelling speed of No. 1 described syringe is 0.5:120 with the ratio of the propelling speed of No. 2 syringes;
Four, it is that the loft drier of 65 DEG C solidifies 24h that carbon nano-tube/poly V-Pyrol RC compounded microbeads step 3 obtained is placed in temperature, then n-hexane is used 5 times, be placed in baking oven again and carry out oven dry preoxidation, obtain preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads;
Described oven dry preoxidation process is: be dry preoxidation 8h under the condition of 150 DEG C in temperature, is then dry preoxidation 2h under the condition of 280 DEG C in temperature;
Five, under nitrogen atmosphere, carbonizing treatment is carried out to the preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads that step 4 obtains, obtains three-dimensional bowl-shape porous carbon materials;
Described carbonizing treatment process is: be 750 DEG C with the temperature rise rate of 5 DEG C/min by room temperature to temperature, and is incubated 2h to be temperature be 750 DEG C in temperature;
The ratio that in the bowl-shape porous carbon materials of described three-dimensional, the quality of carbon nanotube and the residual C of polyvinylpyrrolidone measure is 10:1.
(1) the bowl-shape porous carbon materials of three-dimensional adopting model to be S-4800 field emission surface sweeping Electronic Speculum to obtain test one and surface thereof are scanned, obtain SEM figure as depicted in figs. 1 and 2, as can be seen from Fig. 1 and Fig. 2, the bowl-shape porous carbon materials of three-dimensional that test one obtains has special bowl-shape pattern and vesicular structure, such porous carbon materials has great specific surface area, can be used for the field such as catalysis, solar cell.
(2) model is adopted to be that the X-ray diffractometer of D8ADVANCE is analyzed the bowl-shape porous carbon materials of three-dimensional that test one obtains, obtaining XRD figure as shown in Figure 3, is carbon nanotube greying characteristic peak by showing the diffraction peak occurred near 26 ° in Fig. 3.
(3) adopt LK98B II electrochemical analysis system to test the bowl-shape porous carbon materials of three-dimensional that test one obtains, obtain cyclic voltammetry curve figure as shown in Figure 4, from Fig. 4 figure, demonstrate resulting materials there is good electrical property.
Claims (10)
1. prepare a method for three-dimensional bowl-shape porous carbon materials based on carbon nanotube, it is characterized in that a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube is carried out according to the following steps:
One, carbon nanotube is placed in the nitration mixture of the vitriol oil and concentrated nitric acid composition, back flow reaction 2h ~ 3h under temperature is 80 ~ 85 DEG C of conditions, carry out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 60 ~ 70 DEG C carries out drying, obtain the carbon nanotube powder handled well;
In the nitration mixture of the described vitriol oil and concentrated nitric acid composition, the volume ratio of the vitriol oil and concentrated nitric acid is (2 ~ 4): 1; The described vitriol oil is the vitriol oil of massfraction 95% ~ 99%, and described concentrated nitric acid is the concentrated nitric acid of massfraction 60% ~ 70%;
Two, the carbon nanotube powder handled well mixing polyvinylpyrrolidone, deionized water and step one obtained, low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains Composite Particles Disperse Phase solution;
The carbon nanotube powder handled well that described step one obtains and the mass ratio of polyvinylpyrrolidone are (0.2 ~ 5): 1;
The quality of described polyvinylpyrrolidone and the ratio of deionized water volume are 0.1g:(3 ~ 13) mL;
Three, Composite Particles Disperse Phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the Composite Particles Disperse Phase solution in No. 1 syringe and No. 2 syringes, obtain carbon nano-tube/poly V-Pyrol RC compounded microbeads;
No. 1 described syringe and No. 2 are connected with PTFE tube between syringe with syringe pump;
The volume ratio of the Composite Particles Disperse Phase solution in No. 1 described syringe and the dimethyl silicone oil in No. 2 syringes is 1:(10 ~ 20);
The propelling speed of No. 1 described syringe is 0.5:(110 ~ 130 with the ratio of the propelling speed of No. 2 syringes);
Four, it is that the loft drier of 60 ~ 70 DEG C solidifies 12h ~ 24h that carbon nano-tube/poly V-Pyrol RC compounded microbeads step 3 obtained is placed in temperature, then n-hexane is used 4 ~ 6 times, be placed in baking oven again and carry out oven dry preoxidation, obtain preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads;
Described oven dry preoxidation process is: be dry preoxidation 6h ~ 9h under the condition of 140 ~ 160 DEG C in temperature, is then dry preoxidation 1.5h ~ 2h under the condition of 270 ~ 290 DEG C in temperature;
Five, under nitrogen atmosphere, carbonizing treatment is carried out to the preoxidation carbon nano-tube/poly V-Pyrol RC compounded microbeads that step 4 obtains, obtains three-dimensional bowl-shape porous carbon materials;
Described carbonizing treatment process is: be 700 ~ 800 DEG C with the temperature rise rate of 4 DEG C/min ~ 6 DEG C/min by room temperature to temperature, and is incubated 1.5h ~ 2.5h to be temperature be 700 ~ 800 DEG C in temperature;
The ratio that in the bowl-shape porous carbon materials of described three-dimensional, the quality of carbon nanotube and the residual C of polyvinylpyrrolidone measure is (1 ~ 20): 1.
2. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, is characterized in that the volume ratio of the vitriol oil and concentrated nitric acid in the nitration mixture of the vitriol oil described in step one and concentrated nitric acid composition is 3:1.
3. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, it is characterized in that the vitriol oil described in step one is the vitriol oil of massfraction 98%, the concentrated nitric acid described in step one is the concentrated nitric acid of massfraction 65%.
4. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, is characterized in that the mass ratio of the carbon nanotube powder handled well that the step one described in step 2 obtains and polyvinylpyrrolidone is 2:1.
5. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, is characterized in that the quality of the polyvinylpyrrolidone described in step 2 and the ratio of deionized water volume are 0.1g:10mL.
6. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, is characterized in that the propelling speed of described in step 3 No. 1 syringe is 0.5:120 with the ratio of the propelling speed of No. 2 syringes.
7. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, it is characterized in that the carbon nano-tube/poly V-Pyrol RC compounded microbeads in step 4, step 3 obtained be placed in temperature be 65 DEG C loft drier solidify 24h.
8. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, it is characterized in that the oven dry preoxidation process described in step 4 is: be dry preoxidation 8h under the condition of 150 DEG C in temperature, is then dry preoxidation 2h under the condition of 280 DEG C in temperature.
9. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, it is characterized in that the carbonizing treatment process described in step 5 is: be 750 DEG C with the temperature rise rate of 5 DEG C/min by room temperature to temperature, and be incubated 2h to be temperature be 750 DEG C in temperature.
10. a kind of method preparing three-dimensional bowl-shape porous carbon materials based on carbon nanotube according to claim 1, is characterized in that the ratio that in the bowl-shape porous carbon materials of three-dimensional described in step 5, the quality of carbon nanotube and the residual C of polyvinylpyrrolidone measure is 10:1.
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| CN105551831A (en) * | 2016-01-11 | 2016-05-04 | 上海交通大学 | Preparation method and application of bowl-like nitrogen-doped carbon hollow particle |
| CN108377638A (en) * | 2018-03-06 | 2018-08-07 | 南京航空航天大学 | A kind of Co/C composite electromagnetics wave absorbing agent and preparation method thereof |
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| CN101066756A (en) * | 2007-06-11 | 2007-11-07 | 湖南大学 | Process of preparing carbon naotube foam |
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| CN108377638A (en) * | 2018-03-06 | 2018-08-07 | 南京航空航天大学 | A kind of Co/C composite electromagnetics wave absorbing agent and preparation method thereof |
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