CN105140042A - Method for preparing bacterial cellulose/active carbon fiber/carbon nanotube film material and application - Google Patents
Method for preparing bacterial cellulose/active carbon fiber/carbon nanotube film material and application Download PDFInfo
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Abstract
A method for preparing a bacterial cellulose/active carbon fiber/carbon nanotube film material and application. The invention relates to a method for preparing a film material and application of the film material, and aims to solve the problem that an existing flexible electrode material is complicated in preparation technology and high in cost, and does not have good stability and mechanical property. The method includes: preparing standby bacterial cellulose, and preparing an active carbon fiber dispersion liquid; preparing a bacterial cellulose pulp; and preparing a composite material dispersion liquid, performing vacuum filtration on the bacterial cellulose pulp to form a film, and then adding the composite material dispersion liquid to continue to perform suction filtration and drying, thereby obtaining the bacterial cellulose/active carbon fiber/carbon nanotube film material. The material is applied to a supercapacitor. Large-scale production of the material can be realized, the preparation technology is simple, cost is low, and the stability and mechanical property of a conducting film material are good, and the supercapacitor made of the material has a very good capacitive character. The invention belongs to the technical field of nanometer materials.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of membrane material.
Background technology
Traditional energy sources approach exhaustion day by day, people are stimulated to go to find the alternative energy and effective energy storage device, and ultracapacitor has high power density and higher energy density, be applied to the field that hybrid electric vehicle, electric motor car, portable electric appts etc. are important, enjoy people to favor always.
Society is to quick growth that is flexible, flexible equipment energy storage demand, and people are badly in need of research and development inexpensive, soft, flexible ultracapacitor of future generation, and electrode material is most important part.But existing flexible electrode material complicated process of preparation, cost are high, do not possess good stability and mechanical property.Therefore, Bian with one simple, effectively, environmental protection, the preparation method that is applicable to large-scale production prepare high performance flexible electrode material and be even more important.
Summary of the invention
The object of the invention is to solve existing flexible electrode material complicated process of preparation, cost is high, does not possess good stability and the problem of mechanical property, a kind of preparation method and application thereof of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material is provided.
The preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material of the present invention, carries out as follows:
One, bacteria cellulose is cut into block and be immersed in deionized water for ultrasonic washing, then carry out freeze drying 15 ~ 30h with after liquid nitrogen frozen, obtain bacteria cellulose for subsequent use;
Two, bacteria cellulose for subsequent use is placed in tube furnace and carries out high temperature pyrolysis, obtain activated carbon fiber, then in activated carbon fiber, add surfactant, be redispersed in deionized water, obtain activated carbon fiber dispersion liquid;
Three, be immersed in deionized water for ultrasonic washing after bacteria cellulose being cut into block, be then placed in deionized water, stir and make it be uniformly dispersed, then transfer in refiner and stir, obtain bacteria cellulose slurry;
Four, in the carbon nano-tube of acidifying, add surfactant, then disperse in deionized water, to obtain carbon nano tube dispersion liquid; Carbon nano tube dispersion liquid is joined in activated carbon fiber dispersion liquid, stir and carbon nano-tube and activated carbon fiber are uniformly dispersed, obtain composite material dispersion liquid;
Five, by the bacteria cellulose slurry vacuum filtration film forming of step 3, then add composite material dispersion liquid and continue suction filtration film forming, then put into vacuum drying chamber and carry out drying, make bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material; Wherein in bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, the mass ratio of the activated carbon fiber of bacteria cellulose and step 2 is (15 ~ 1.5): 1; In bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, in bacteria cellulose and step 4, the mass ratio of the carbon nano-tube of acidifying is 1:(0.02 ~ 0.2).
The application of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material of the present invention refers to as application of electrode in ultracapacitor.
Activated carbon fiber has good chemical stability, conductivity and fake capacitance energy storage characteristic, is considered to the extremely potential electrode material for super capacitor of one.Bacteria cellulose, its film has hyperfine network structure, and the bacteria cellulose after cracking can make carbon nano-fiber, gained activated carbon fiber function admirable.
Bacteria cellulose is obtained by the fermentation of microbe, its function admirable, aboundresources, environmental friendliness, film has hyperfine network structure, high-crystallinity, high-purity, high mechanical properties, the focus of domestic and international Material Field research is become as a kind of emerging environmental friendliness shaped material, bacteria cellulose contains a large amount of hydroxyls, have good hydrophily, easily Hydrogenbond occurs with other water miscible macromolecules, thus bacteria cellulose has natural advantage as composite material.
Carbon nano-tube is extensively concerned due to the structure of its uniqueness, chemical property, hot property and electrical property.Its application has related to the many-sides such as nano electron device, catalyst carrier, hydrogen storage material and composite material.When itself and other material with carbon element Application of composite has broad prospects in ultracapacitor aspect.
The present invention utilizes a kind of low cost, environmentally friendly and can the preparation method of scale, by vacuum filtration, prepares membrane material and is assembled into capacitor with this.Structure shows membrane material good mechanical performance, has good capacitive properties and excellent recycling.Therefore, the application of this membrane material in ultracapacitor has wide commercial promise.
Beneficial effect of the present invention: (1) utilizes the characteristic such as the hyperfine network configuration of bacteria cellulose and excellent mechanical property, as base load nano active material, can be prepared into ultracapacitor self-supporting self-supporting flexible electrode; (2) the direct Pintsch process of the hyperfine network configuration of bacteria cellulose is utilized to prepare activated carbon fiber; (3) be produced on a large scale, preparation technology be simple, energy-conservation, reaction condition is gentle, toxicity is little, cheaper starting materials is easy to get that cost is low, membrane material stability and mechanical property good; (4) be directly used as electrode of super capacitor and there is good capacitive character.
Accompanying drawing explanation
Fig. 1 is the photo of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material prepared by embodiment 1;
Cyclic voltammetry curve under the different scanning speed of the work electrode prepared with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that Fig. 2 obtains for embodiment 1 in 6M potassium hydroxide electrolyte; Wherein a is 10mV/s, b be 20mV/s, c is 50mV/s;
The constant current charge-discharge curve of work electrode in 6M potassium hydroxide electrolyte prepared with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that Fig. 3 obtains for embodiment 1; Wherein a is 1mA/cm
2, b is 2mA/cm
2, c is 5mA/cm
2, d is 10mA/cm
2, e is 15mA/cm
2;
The AC impedance spectrogram of the work electrode with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material prepared of Fig. 4 for obtaining in embodiment 1;
Cyclic voltammetry curve under the different scanning speed of the work electrode prepared with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that Fig. 5 obtains for embodiment 2 in 6M potassium hydroxide electrolyte; Wherein a is 10mV/s, b be 30mV/s, c is 50mV/s;
The constant current charge-discharge curve of work electrode in 6M potassium hydroxide electrolyte prepared with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that Fig. 6 obtains for embodiment 2; Wherein a is 1mA/cm
2, b is 2mA/cm
2, c is 5mA/cm
2, d is 10mA/cm
2, e is 15mA/cm
2;
The AC impedance spectrogram of the work electrode with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material prepared of Fig. 7 for obtaining in embodiment 2;
The work electrode prepared with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that Fig. 8 obtains for embodiment 1 ~ 2 in 6M potassium hydroxide electrolyte according to the ratio capacitance curve of constant current charge-discharge curve calculation gained, wherein a is BC-ACF-CNT-1, b is BC-ACF-CNT-2.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material of present embodiment, carry out as follows:
One, bacteria cellulose is cut into block and be immersed in deionized water for ultrasonic washing, then carry out freeze drying 15 ~ 30h with after liquid nitrogen frozen, obtain bacteria cellulose for subsequent use;
Two, bacteria cellulose for subsequent use is placed in tube furnace and carries out high temperature pyrolysis, obtain activated carbon fiber, then in activated carbon fiber, add surfactant, be redispersed in deionized water, obtain activated carbon fiber dispersion liquid;
Three, be immersed in deionized water for ultrasonic washing after bacteria cellulose being cut into block, be then placed in deionized water, stir and make it be uniformly dispersed, then transfer in refiner and stir, obtain bacteria cellulose slurry;
Four, in the carbon nano-tube of acidifying, add surfactant, then disperse in deionized water, to obtain carbon nano tube dispersion liquid; Carbon nano tube dispersion liquid is joined in activated carbon fiber dispersion liquid, stir and carbon nano-tube and activated carbon fiber are uniformly dispersed, obtain composite material dispersion liquid;
Five, by the bacteria cellulose slurry vacuum filtration film forming of step 3, then add composite material dispersion liquid and continue suction filtration film forming, then put into vacuum drying chamber and carry out drying, make bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material; Wherein in bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, the mass ratio of the activated carbon fiber of bacteria cellulose and step 2 is (15 ~ 1.5): 1; In bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, in bacteria cellulose and step 4, the mass ratio of the carbon nano-tube of acidifying is 1:(0.02 ~ 0.2).
Activated carbon fiber has good chemical stability, conductivity and fake capacitance energy storage characteristic, is considered to the extremely potential electrode material for super capacitor of one.Bacteria cellulose, its film has hyperfine network structure, and the bacteria cellulose after cracking can make carbon nano-fiber, gained activated carbon fiber function admirable.
Bacteria cellulose is obtained by the fermentation of microbe, its function admirable, aboundresources, environmental friendliness, film has hyperfine network structure, high-crystallinity, high-purity, high mechanical properties, the focus of domestic and international Material Field research is become as a kind of emerging environmental friendliness shaped material, bacteria cellulose contains a large amount of hydroxyls, have good hydrophily, easily Hydrogenbond occurs with other water miscible macromolecules, thus bacteria cellulose has natural advantage as composite material.
Carbon nano-tube is extensively concerned due to the structure of its uniqueness, chemical property, hot property and electrical property.Its application has related to the many-sides such as nano electron device, catalyst carrier, hydrogen storage material and composite material.When itself and other material with carbon element Application of composite has broad prospects in ultracapacitor aspect.
Present embodiment utilizes a kind of low cost, environmentally friendly and can the preparation method of scale, by vacuum filtration, prepares membrane material and is assembled into capacitor with this.Structure shows membrane material good mechanical performance, has good capacitive properties and excellent recycling.Therefore, the application of this membrane material in ultracapacitor has wide commercial promise.
The beneficial effect of present embodiment: (1) utilizes the characteristic such as the hyperfine network configuration of bacteria cellulose and excellent mechanical property, as base load nano active material, can be prepared into ultracapacitor self-supporting self-supporting flexible electrode; (2) the direct Pintsch process of the hyperfine network configuration of bacteria cellulose is utilized to prepare activated carbon fiber; (3) be produced on a large scale, preparation technology be simple, energy-conservation, reaction condition is gentle, toxicity is little, cheaper starting materials is easy to get that cost is low, membrane material stability and mechanical property good; (4) be directly used as electrode of super capacitor and there is good capacitive character.
In present embodiment, freeze drying is carried out in freeze drier, and bacteria cellulose is commercially available prod.
Embodiment two: present embodiment and embodiment one unlike: described bacteria cellulose is bacteria cellulose leftover pieces.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the condition of the supersound washing described in step one is ultrasonic time 10h, and each hour changes deionized water.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the method for the high temperature degradation described in step 2 is: bacteria cellulose for subsequent use is placed in porcelain boat, then puts into tube furnace; Argon gas or nitrogen 3 ~ 8h is passed in tube furnace, and using argon gas or nitrogen as protection gas; Again by tube furnace with the ramp to 270 DEG C of 2 ~ 4 DEG C/min, again with the ramp to 390 DEG C of 0.3 ~ 0.5 DEG C/min, then with the ramp to 700 of 2 ~ 4 DEG C/min DEG C ~ 1100 DEG C, keep 2 ~ 4h, 400 DEG C are cooled to again with the speed of 3 ~ 5 DEG C/min, finally naturally cool to room temperature again, namely complete.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the method for the high temperature degradation described in step 2 is: bacteria cellulose for subsequent use is placed in porcelain boat, then puts into tube furnace; Argon gas or nitrogen 6h is passed in tube furnace; and using argon gas or nitrogen as protection gas; again by tube furnace with the ramp to 270 DEG C of 4 DEG C/min; again with the ramp to 390 DEG C of 0.3 DEG C/min; then with the ramp to 900 DEG C of 4 DEG C/min, keep 2h, then be cooled to 400 DEG C with the speed of 5 DEG C/min; finally naturally cool to room temperature again, namely complete that other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the activated carbon fiber described in step 2 and the mass ratio of surfactant are 1:(0.3 ~ 3).Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in the refiner described in step 3 stir refer under the condition of stir speed (S.S.) 10000rpm ~ 15000rpm, in refiner, stir 5min.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the carbon nano-tube of the acidifying described in step 4 and the mass ratio of surfactant are (0.5 ~ 0.8): 1.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: described surfactant is neopelex.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the preparation method of the carbon nano-tube of the acidifying described in step 4 be by carbon nano-tube in concentration be 64% nitric acid in ultrasonic process 24h, spend deionized water, suction filtration is dry.Other is identical with one of embodiment one to nine.
Embodiment 11: the application of present embodiment bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material refers to as application of electrode in ultracapacitor.
Beneficial effect of the present invention is verified by following examples:
The preparation method of embodiment 1, the present embodiment bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, carries out as follows:
One, bacteria cellulose is cut into block and be immersed in deionized water for ultrasonic washing 10h, and each hour changes deionized water, transfer to the dry 20h of freeze drier after liquid nitrogen frozen, obtain bacteria cellulose for subsequent use;
Two, bacteria cellulose for subsequent use is placed in porcelain boat, then puts into tube furnace; In tube furnace, pass into nitrogen except oxygen 6h, and as protection gas, first by tube furnace with the ramp to 270 DEG C of 4 DEG C/min, the ramp to 390 DEG C of 0.3 DEG C/min afterwards, then with the ramp to 900 DEG C of 4 DEG C/min, keeps 2h; Be cooled to 400 DEG C with the speed of 5 DEG C/min again, be finally naturally down to room temperature again, obtain activated carbon fiber, then in 25mg activated carbon fiber, add 7.5mg neopelex, be redispersed in deionized water, obtain activated carbon fiber dispersion liquid;
Three, deionized water for ultrasonic washing 10h is immersed in after 10g bacteria cellulose being cut into block, and each hour replacing deionized water, then deionized water is placed in, stirring makes it be uniformly dispersed, transfer to again in refiner with the speed of 12000 turns per minute, stir 5min, obtain bacteria cellulose slurry;
Four, in the carbon nano-tube of 0.008g acidifying, add 0.01g neopelex, then disperse in deionized water, to obtain carbon nano tube dispersion liquid; Carbon nano tube dispersion liquid is joined in activated carbon fiber dispersion liquid, stir and carbon nano-tube and activated carbon fiber are uniformly dispersed, obtain composite material dispersion liquid;
Five, by the bacteria cellulose slurry vacuum filtration film forming of step 3, then add composite material dispersion liquid and continue suction filtration film forming, then put into vacuum drying chamber and carry out drying, make bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material.
After vacuum filtration and vacuumize, in bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, the quality of bacteria cellulose is 0.3g.
The photo of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material prepared by the present embodiment as shown in Figure 1.
Bacteria cellulose/activated carbon fiber/carbon nano-tube the membrane material of acquisition is cut into 1.5cm × 2cm rectangle, directly be used as ultracapacitor work electrode, platinized platinum, as to electrode, with mercury/mercuric oxide electrode for reference electrode, tests the capacitance characteristic of self-supporting flexible membrane material electrode material.Test specimens product are labeled as BC-ACF-CNT-1.
Electrode prepared by the bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material obtained the present embodiment carries out the cyclic voltammetric performance test without sweep speed in 6M potassium hydroxide electrolyte, and result is see Fig. 2.Demonstrate difference in figure and sweep the activated carbon fiber of speed at scanning potential region-0.9 ~ 0.2V, all there is the CV curve of accurate rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material obtained the present embodiment carries out constant current charge-discharge performance test in 6M potassium hydroxide electrolyte, and result is see Fig. 3.As shown in Figure 3, curve table reveals good triangle, and different multiplying lower curve all has good symmetry.Maximum area ratio capacitance reaches 0.59F/cm
2.As Fig. 5, the ac impedance spectroscopy of electrode is by the semicircle of high frequency region, and the straight line of low frequency range and the transitional region between semicircle and straight line formed.
The preparation method of embodiment 2, the present embodiment bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, carries out as follows:
One, bacteria cellulose is cut into block and be immersed in deionized water for ultrasonic washing 10h, and each hour changes deionized water, transfer to the dry 20h of freeze drier after liquid nitrogen frozen, obtain bacteria cellulose for subsequent use;
Two, bacteria cellulose for subsequent use is placed in porcelain boat, then puts into tube furnace; In tube furnace, pass into nitrogen except oxygen 6h, and as protection gas, first by tube furnace with the ramp to 270 DEG C of 4 DEG C/min, the ramp to 390 DEG C of 0.3 DEG C/min afterwards, then with the ramp to 800 DEG C of 4 DEG C/min, keeps 2h; Be cooled to 400 DEG C with the speed of 5 DEG C/min again, be finally naturally down to room temperature again, obtain activated carbon fiber, then in 50mg activated carbon fiber, add 15mg neopelex, be redispersed in deionized water, obtain activated carbon fiber dispersion liquid;
Three, deionized water for ultrasonic washing 10h is immersed in after 10g bacteria cellulose being cut into block, and each hour replacing deionized water, then deionized water is placed in, stirring makes it be uniformly dispersed, transfer to again in refiner with the speed of 12000 turns per minute, stir 5min, obtain bacteria cellulose slurry;
Four, in the carbon nano-tube of 0.015g acidifying, add 0.03g neopelex, then disperse in deionized water, to obtain carbon nano tube dispersion liquid; Carbon nano tube dispersion liquid is joined in activated carbon fiber dispersion liquid, stir and carbon nano-tube and activated carbon fiber are uniformly dispersed, obtain composite material dispersion liquid;
Five, by the bacteria cellulose slurry vacuum filtration film forming of step 3, then add composite material dispersion liquid and continue suction filtration film forming, then put into vacuum drying chamber and carry out drying, make bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material.
After vacuum filtration and vacuumize, in bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, the quality of bacteria cellulose is 0.3g.
Bacteria cellulose/activated carbon fiber/carbon nano-tube the membrane material of acquisition is cut into 1.5cm × 2cm rectangle, directly be used as ultracapacitor work electrode, platinized platinum, as to electrode, with mercury/mercuric oxide electrode for reference electrode, tests the capacitance characteristic of self-supporting flexible membrane material electrode material.Test specimens product are labeled as BC-ACF-CNT-2.
Electrode prepared by the bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material obtained the present embodiment carries out the cyclic voltammetric performance test without sweep speed in potassium hydroxide electrolyte, and result is see Fig. 5.Demonstrate difference in figure and sweep the activated carbon fiber of speed at scanning potential region-0.9 ~ 0.2V, all there is the CV curve of accurate rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material obtained the present embodiment carries out constant current charge-discharge performance test in potassium hydroxide electrolyte, and result is see Fig. 6.As shown in Figure 6, curve table reveals good triangle, and different multiplying lower curve all has good symmetry.Maximum area ratio capacitance reaches 1.33F/cm
2.As Fig. 7, the ac impedance spectroscopy of electrode is by the semicircle of high frequency region, and the straight line of low frequency range and the transitional region between semicircle and straight line formed.The work electrode prepared with bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that embodiment 1 ~ 2 obtains in 6M potassium hydroxide electrolyte according to the ratio capacitance curve of constant current charge-discharge curve calculation gained as shown in Figure 8, as shown in Figure 8, the ratio capacitance of BC-ACF-CNT-1 0.59F/cm respectively
2, 0.54F/cm
2, 0.51F/cm
2, 0.50F/cm
2, 0.48F/cm
2; The ratio capacitance 1.33F/cm respectively of BC-ACF-CNT-2
2, 1.32F/cm
2, 1.22F/cm
2, 1.19F/cm
2, 1.09F/cm
2.
The bacteria cellulose of embodiment 1 ~ 2 is commercially available prod.Embodiment 1 ~ 2 utilizes the characteristic such as the hyperfine network configuration of bacteria cellulose and excellent mechanical property, as base load nano active material, can be prepared into ultracapacitor self-supporting self-supporting flexible electrode; The direct Pintsch process of the hyperfine network configuration of bacteria cellulose is utilized to prepare activated carbon fiber; Be produced on a large scale, preparation technology be simple, energy-conservation, reaction condition is gentle, toxicity is little, cheaper starting materials is easy to get that cost is low, membrane material stability and mechanical property good; Directly be used as electrode of super capacitor and there is good capacitive character.
Claims (10)
1. a preparation method for bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, is characterized in that the method is carried out as follows:
One, bacteria cellulose is cut into block and be immersed in deionized water for ultrasonic washing, then carry out freeze drying 15 ~ 30h with after liquid nitrogen frozen, obtain bacteria cellulose for subsequent use;
Two, bacteria cellulose for subsequent use is placed in tube furnace and carries out high temperature pyrolysis, obtain activated carbon fiber, then in activated carbon fiber, add surfactant, be redispersed in deionized water, obtain activated carbon fiber dispersion liquid;
Three, separately get and after bacteria cellulose cuts into block, to be immersed in deionized water for ultrasonic washing, be then placed in deionized water, stir and make it be uniformly dispersed, then transfer in refiner and stir, obtain bacteria cellulose slurry;
Four, in the carbon nano-tube of acidifying, add surfactant, then disperse in deionized water, to obtain carbon nano tube dispersion liquid; Carbon nano tube dispersion liquid is joined in activated carbon fiber dispersion liquid, stir and carbon nano-tube and activated carbon fiber are uniformly dispersed, obtain composite material dispersion liquid;
Five, by the bacteria cellulose slurry vacuum filtration film forming of step 3, then add composite material dispersion liquid and continue suction filtration film forming, then put into vacuum drying chamber and carry out drying, make bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material; Wherein in bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, the mass ratio of the activated carbon fiber of bacteria cellulose and step 2 is (15 ~ 1.5): 1; In bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material, in bacteria cellulose and step 4, the mass ratio of the carbon nano-tube of acidifying is 1:(0.02 ~ 0.2).
2. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, is characterized in that described bacteria cellulose is bacteria cellulose leftover pieces.
3. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, is characterized in that the condition of the supersound washing described in step one and step 3 is ultrasonic time 10h, and each hour changes deionized water.
4. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, is characterized in that the method for the high temperature degradation described in step 2 is: bacteria cellulose for subsequent use is placed in porcelain boat, then puts into tube furnace; Argon gas or nitrogen 3 ~ 8h is passed in tube furnace, and using argon gas or nitrogen as protection gas; Again by tube furnace with the ramp to 270 DEG C of 2 ~ 4 DEG C/min, again with the ramp to 390 DEG C of 0.3 ~ 0.5 DEG C/min, then with the ramp to 700 of 2 ~ 4 DEG C/min DEG C ~ 1100 DEG C, keep 2 ~ 4h, 400 DEG C are cooled to again with the speed of 3 ~ 5 DEG C/min, finally naturally cool to room temperature again, namely complete.
5. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, is characterized in that the mass ratio of activated carbon fiber described in step 2 and surfactant is 1:(0.3 ~ 3).
6. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, it is characterized in that stirring in the refiner described in step 3 referring under the condition of stir speed (S.S.) 10000rpm ~ 15000rpm, in refiner, stir 5min.
7. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, is characterized in that the carbon nano-tube of the acidifying described in step 4 and the mass ratio of surfactant are (0.5 ~ 0.8): 1.
8. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1,5 or 7, is characterized in that described surfactant is neopelex.
9. the preparation method of a kind of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material according to claim 1, it is characterized in that the preparation method of the carbon nano-tube of the acidifying described in step 4 be by carbon nano-tube in concentration be 64% nitric acid in ultrasonic process 24h, spend deionized water, suction filtration is dry.
10. the application of bacteria cellulose/activated carbon fiber/carbon nano-tube membrane material that obtains of preparation method as claimed in claim 1, is characterized in that this conducting membrane material as application of electrode in ultracapacitor.
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| CN105957729A (en) * | 2016-05-18 | 2016-09-21 | 哈尔滨万鑫石墨谷科技有限公司 | Super capacitor flexible electrode, preparation method thereof and super capacitor |
| CN105977046A (en) * | 2016-07-28 | 2016-09-28 | 北京化工大学 | Integrated supercapacitor and manufacturing method thereof |
| CN106905562A (en) * | 2017-03-20 | 2017-06-30 | 江南大学 | A kind of bacteria cellulose in situ/functionalized multi-wall carbonnanotubes membrane material and preparation method thereof |
| CN108390012A (en) * | 2018-01-23 | 2018-08-10 | 柔电（武汉）科技有限公司 | A kind of preparation method of flexibility pole piece |
| CN108496233A (en) * | 2016-01-29 | 2018-09-04 | 日本贵弥功株式会社 | Electrode uses the capacitor of electrode and the manufacturing method of electrode |
| CN108912375A (en) * | 2018-05-31 | 2018-11-30 | 江南大学 | The oriented growth nanogold bacteria cellulose/compound film method of carbon pipe |
| CN113788965A (en) * | 2021-09-14 | 2021-12-14 | 大连理工大学 | Bacterial cellulose modified bucky paper and preparation method and application thereof |
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