CN105140042B - A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/CNT membrane material - Google Patents

Abstract

A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/CNT membrane material, the present invention relates to a kind of preparation method and applications of membrane material, the invention aims to solve, existing flexible electrode material preparation technology is complicated, cost is high, do not possess the problem of good stability and mechanical property, method is：Standby bacteria cellulose is prepared, prepares activated carbon fiber dispersion liquid；Prepare bacteria cellulose slurry；Composite dispersion liquid is prepared, bacteria cellulose slurry is filtered by vacuum film forming, composite dispersion liquid is then added and continues to filter drying, bacteria cellulose/activated carbon fiber/CNT membrane material is made, the materials application is in ultracapacitor.The present invention is produced on a large scale, and preparation technology is simple, cost is low, conducting membrane material stability and mechanical property are good, and being prepared into ultracapacitor has good capacitive character.The invention belongs to technical field of nano material.

Description

A kind of preparation method of bacterial cellulose/activated carbon fiber/carbon nanotube membrane material and its application

technical field

The invention relates to a preparation method and application of a membrane material.

Background technique

Traditional energy sources are increasingly depleted, stimulating people to look for alternative energy sources and efficient energy storage devices, and supercapacitors have high power density and high energy density, and are used in hybrid electric vehicles, electric vehicles, portable electronic devices and other important fields have always been favored by people.

In today's society, the demand for energy storage of flexible and bendable devices is rapidly increasing, and people urgently need to develop the next generation of cheap, soft and bendable supercapacitors, and electrode materials are the most important components. However, the preparation process of existing flexible electrode materials is complicated, the cost is high, and they do not have good stability and mechanical properties. Therefore, it is particularly important to use a simple, effective, environmentally friendly preparation method suitable for large-scale production to prepare high-performance flexible electrode materials.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a bacterial cellulose/activated carbon fiber/carbon nanotube film material and to solve the problems of complex preparation process, high cost, and lack of good stability and mechanical properties of the existing flexible electrode materials. its application.

A kind of preparation method of bacterial cellulose/activated carbon fiber/carbon nanotube film material of the present invention, carry out as follows:

1. Cut bacterial cellulose into pieces and soak in deionized water for ultrasonic washing, then freeze with liquid nitrogen and freeze-dry for 15-30 hours to obtain spare bacterial cellulose;

2. Place the spare bacterial cellulose in a tube furnace for high-temperature pyrolysis to obtain activated carbon fibers, then add a surfactant to the activated carbon fibers, and then disperse them in deionized water to obtain an activated carbon fiber dispersion;

3. Cut the bacterial cellulose into pieces, soak it in deionized water and ultrasonically wash it, then place it in deionized water, stir to make it evenly dispersed, and then transfer it to a homogenizer for stirring to obtain a bacterial cellulose slurry;

4. Add a surfactant to the acidified carbon nanotubes, and then disperse them in deionized water to obtain a carbon nanotube dispersion; add the carbon nanotube dispersion to the activated carbon fiber dispersion, and stir to make the carbon nanotubes and activated carbon fibers Disperse evenly to obtain a composite material dispersion;

5. Vacuum filter the bacterial cellulose slurry in step 3 to form a film, then add the composite material dispersion to continue to filter to form a film, and then put it in a vacuum drying oven for drying to make bacterial cellulose/activated carbon fiber/carbon nano Bacteria cellulose/activated carbon fiber/carbon nanotube membrane material wherein the mass ratio of bacterial cellulose and the activated carbon fiber of step 2 is (15～1.5):1; Bacterial cellulose/activated carbon fiber/carbon nanotube membrane The mass ratio of the bacterial cellulose in the material to the acidified carbon nanotubes in step 4 is 1: (0.02-0.2).

The application of the bacterial cellulose/activated carbon fiber/carbon nanotube film material of the present invention refers to being used as an electrode in a supercapacitor.

Activated carbon fiber has good chemical stability, electrical conductivity, and pseudocapacitive energy storage properties, and is considered to be a promising electrode material for supercapacitors. Bacterial cellulose, whose film has an ultra-fine network structure, the bacterial cellulose after pyrolysis can be used to make nano-carbon fibers, and the obtained activated carbon fibers have excellent performance.

Bacterial cellulose is obtained through the fermentation of microorganisms. It has excellent performance, abundant resources, and is environmentally friendly. The film has an ultra-fine network structure, high crystallinity, high purity, and high mechanical strength. As an emerging environmentally friendly material, it has become The research hotspot in the field of materials at home and abroad, bacterial cellulose contains a large number of hydroxyl groups, has good hydrophilicity, and is prone to hydrogen bonding with other water-soluble polymers, so bacterial cellulose has natural advantages as a composite material.

Carbon nanotubes have attracted much attention due to their unique structures, chemical properties, thermal properties, and electrical properties. Its applications have been involved in many aspects such as nanoelectronic devices, catalyst supports, hydrogen storage materials and composite materials. It has broad prospects when it is combined with other carbon materials and used in supercapacitors.

The invention utilizes a low-cost, environmentally friendly and scalable preparation method to prepare membrane materials through vacuum filtration and assemble them into capacitors. The structure shows that the membrane material has excellent mechanical properties, good capacitive properties and excellent recyclability. Therefore, the application of this film material in supercapacitors has broad commercial prospects.

Beneficial effects of the present invention: (1) Utilize the superfine network structure and excellent mechanical properties of bacterial cellulose, and use it as a substrate to load nano-active substances, which can be prepared into self-supporting self-supporting flexible electrodes for supercapacitors; (2) Activated carbon fiber is prepared by direct pyrolysis of bacterial cellulose ultra-fine network structure; (3) large-scale production, simple preparation process, energy saving, mild reaction conditions, low toxicity, cheap and easy-to-obtain raw materials, low cost, membrane material stability and mechanical properties Good; (4) directly used as supercapacitor electrode has good capacitance.

Description of drawings

Fig. 1 is the photo of the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material that embodiment 1 prepares;

Fig. 2 is the cyclic voltammetry curve under the different scanning speeds of the working electrode that Fig. 2 obtains with bacterial cellulose/activated carbon fiber/carbon nanotube film material preparation in 6M potassium hydroxide electrolyte that embodiment 1; Wherein a is 10mV/ s, b is 20mV/s, c is 50mV/s;

Fig. 3 is the galvanostatic charge-discharge curve in 6M potassium hydroxide electrolyte of the working electrode prepared with bacterial cellulose/activated carbon fiber/carbon nanotube film material obtained in Example 1; wherein a is 1mA/cm ² , b 2mA/cm ² , c is 5mA/cm ² , d is 10mA/cm ² , e is 15mA/cm ² ;

Fig. 4 is the AC impedance spectrogram of the working electrode prepared with bacterial cellulose/activated carbon fiber/carbon nanotube membrane material obtained in embodiment 1;

Fig. 5 is the cyclic voltammetry curve under the different scanning speeds of the working electrode that Fig. 5 obtains with bacterial cellulose/activated carbon fiber/carbon nanotube film material preparation in 6M potassium hydroxide electrolyte that embodiment 2; Wherein a is 10mV/ s, b is 30mV/s, c is 50mV/s;

Figure 6 is the galvanostatic charge-discharge curve of the working electrode prepared in Example 2 in 6M potassium hydroxide electrolyte with bacterial cellulose/activated carbon fiber/carbon nanotube film material; wherein a is 1mA/cm ² , b 2mA/cm ² , c is 5mA/cm ² , d is 10mA/cm ² , e is 15mA/cm ² ;

Fig. 7 is the AC impedance spectrogram of the working electrode prepared with bacterial cellulose/activated carbon fiber/carbon nanotube membrane material obtained in embodiment 2;

Fig. 8 is the specific capacitance curve calculated according to the galvanostatic charge-discharge curve of the working electrode prepared by the bacterial cellulose/activated carbon fiber/carbon nanotube film material obtained in Examples 1-2 in 6M potassium hydroxide electrolyte, wherein a is BC-ACF-CNT-1, b is BC-ACF-CNT-2.

detailed description

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific embodiment one: the preparation method of a kind of bacterial cellulose/activated carbon fiber/carbon nanotube membrane material of this embodiment, carries out as follows:

1. Cut bacterial cellulose into pieces and soak in deionized water for ultrasonic washing, then freeze with liquid nitrogen and freeze-dry for 15-30 hours to obtain spare bacterial cellulose;

2. Place the spare bacterial cellulose in a tube furnace for high-temperature pyrolysis to obtain activated carbon fibers, then add a surfactant to the activated carbon fibers, and then disperse them in deionized water to obtain an activated carbon fiber dispersion;

3. Cut the bacterial cellulose into pieces, soak it in deionized water and ultrasonically wash it, then place it in deionized water, stir to make it evenly dispersed, and then transfer it to a homogenizer for stirring to obtain a bacterial cellulose slurry;

4. Add a surfactant to the acidified carbon nanotubes, and then disperse them in deionized water to obtain a carbon nanotube dispersion; add the carbon nanotube dispersion to the activated carbon fiber dispersion, and stir to make the carbon nanotubes and activated carbon fibers Disperse evenly to obtain a composite material dispersion;

5. Vacuum filter the bacterial cellulose slurry in step 3 to form a film, then add the composite material dispersion to continue to filter to form a film, and then put it in a vacuum drying oven for drying to make bacterial cellulose/activated carbon fiber/carbon nano Bacteria cellulose/activated carbon fiber/carbon nanotube membrane material wherein the mass ratio of bacterial cellulose and the activated carbon fiber of step 2 is (15～1.5):1; Bacterial cellulose/activated carbon fiber/carbon nanotube membrane The mass ratio of the bacterial cellulose in the material to the acidified carbon nanotubes in step 4 is 1: (0.02-0.2).

Activated carbon fiber has good chemical stability, electrical conductivity, and pseudocapacitive energy storage properties, and is considered to be a promising electrode material for supercapacitors. Bacterial cellulose, whose film has an ultra-fine network structure, the bacterial cellulose after pyrolysis can be used to make nano-carbon fibers, and the obtained activated carbon fibers have excellent performance.

Bacterial cellulose is obtained through the fermentation of microorganisms. It has excellent performance, abundant resources, and is environmentally friendly. The film has an ultra-fine network structure, high crystallinity, high purity, and high mechanical strength. As an emerging environmentally friendly material, it has become The research hotspot in the field of materials at home and abroad, bacterial cellulose contains a large number of hydroxyl groups, has good hydrophilicity, and is prone to hydrogen bonding with other water-soluble polymers, so bacterial cellulose has natural advantages as a composite material.

Carbon nanotubes have attracted much attention due to their unique structures, chemical properties, thermal properties, and electrical properties. Its applications have been involved in many aspects such as nanoelectronic devices, catalyst supports, hydrogen storage materials and composite materials. It has broad prospects when it is combined with other carbon materials and used in supercapacitors.

In this embodiment, a low-cost, environmentally friendly and scalable preparation method is used to prepare membrane materials through vacuum filtration and assemble them into capacitors. The structure shows that the membrane material has excellent mechanical properties, good capacitive properties and excellent recyclability. Therefore, the application of this film material in supercapacitors has broad commercial prospects.

Beneficial effects of this embodiment: (1) Utilizing the ultrafine network structure and excellent mechanical properties of bacterial cellulose, and using it as a substrate to load nano-active substances, it can be prepared as a self-supporting self-supporting flexible electrode for supercapacitors; (2 )Using the superfine network structure of bacterial cellulose to directly pyrolyze activated carbon fibers to prepare activated carbon fibers; (3) large-scale production, simple preparation process, energy saving, mild reaction conditions, low toxicity, cheap raw materials and low cost, stability and mechanical properties of membrane materials Good performance; (4) directly used as supercapacitor electrode has good capacitance.

In this embodiment, the freeze-drying is carried out in a freeze-drying machine, and the bacterial cellulose is a commercially available product.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the bacterial cellulose is bacterial cellulose leftovers. Others are the same as in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the condition of the ultrasonic cleaning in step 1 is ultrasonic time of 10 hours, and the deionized water is replaced every hour. Others are the same as in the first or second embodiment.

Specific embodiment four: the difference between this embodiment and one of the specific embodiments one to three is: the method of high-temperature degradation described in step two is: the spare bacterial cellulose is placed in a porcelain boat, and then put into a tube furnace; Put argon or nitrogen into the tube furnace for 3-8 hours, and use argon or nitrogen as a protective gas; then raise the temperature of the tube furnace to 270 °C at a rate of 2-4 °C/min, and then increase the temperature at a rate of 0.3-0.5 °C/min. Raise the temperature to 390°C at a rate of 2-4°C/min, then raise the temperature to 700°C-1100°C at a rate of 2-4°C/min, keep it for 2-4 hours, then cool down to 400°C at a rate of 3-5°C/min, and finally cool down naturally to room temperature and done. Others are the same as those in the first to third specific embodiments.

Specific embodiment five: the difference between this embodiment and one of the specific embodiments one to four is: the method of high-temperature degradation described in step two is: the spare bacterial cellulose is placed in a porcelain boat, and then put into a tube furnace; Put argon or nitrogen into the tube furnace for 6 hours, and use argon or nitrogen as a protective gas, then raise the temperature of the tube furnace to 270 °C at a rate of 4 °C/min, and then raise the temperature to 390 °C at a rate of 0.3 °C/min ℃, then raise the temperature to 900°C at a rate of 4°C/min, keep it for 2h, then cool down to 400°C at a rate of 5°C/min, and finally cool down to room temperature naturally, that is to say, complete the same process as one of the specific embodiments 1 to 4. .

Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is that the mass ratio of the activated carbon fiber to the surfactant in step 2 is 1:(0.3-3). Others are the same as one of the specific embodiments 1 to 5.

Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that the stirring in the homogenizer described in step 3 refers to stirring in the homogenizer for 5 minutes at a stirring rate of 10,000 rpm to 15,000 rpm. Others are the same as one of the specific embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that the mass ratio of the acidified carbon nanotubes to the surfactant in step 4 is (0.5-0.8):1. Others are the same as one of the specific embodiments 1 to 7.

Embodiment 9: This embodiment is different from Embodiment 1 to Embodiment 8 in that: the surfactant is sodium dodecylbenzenesulfonate. Others are the same as one of the specific embodiments 1 to 8.

Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that: the preparation method of the acidified carbon nanotubes described in step 4 is to ultrasonically treat the carbon nanotubes in 64% nitric acid for 24 hours, Wash with deionized water, filter and dry. Others are the same as one of the specific embodiments 1 to 9.

Embodiment 11: The application of bacterial cellulose/activated carbon fiber/carbon nanotube film material in this embodiment refers to the application as an electrode in a supercapacitor.

Verify the beneficial effects of the present invention through the following examples:

Embodiment 1, the preparation method of bacterial cellulose/activated carbon fiber/carbon nanotube film material of the present embodiment, carry out as follows:

1. Cut bacterial cellulose into pieces and soak in deionized water for ultrasonic washing for 10 hours, and replace the deionized water every hour, freeze in liquid nitrogen and transfer to a freeze dryer to dry for 20 hours to obtain spare bacterial cellulose;

2. Put the spare bacterial cellulose in the porcelain boat, and then put it into the tube furnace; pass nitrogen gas into the tube furnace to remove oxygen for 6 hours, and use it as a protective gas, first raise the temperature of the tube furnace at a rate of 4°C/min to 270°C, then raised to 390°C at a rate of 0.3°C/min, then raised to 900°C at a rate of 4°C/min, and kept for 2 hours; then cooled to 400°C at a rate of 5°C/min, and finally dropped to At room temperature, activated carbon fibers are obtained, and then 7.5 mg of sodium dodecylbenzenesulfonate is added to 25 mg of activated carbon fibers, and then dispersed in deionized water to obtain an activated carbon fiber dispersion;

3. Cut 10g of bacterial cellulose into pieces, soak in deionized water and ultrasonically wash for 10 hours, and replace the deionized water every hour, then place in deionized water, stir to disperse evenly, and then transfer to a homogenizer Stir for 5 minutes at a speed of 12000 revolutions per minute to obtain a bacterial cellulose slurry;

4. Add 0.01g sodium dodecylbenzene sulfonate to 0.008g acidified carbon nanotubes, and then disperse in deionized water to obtain a carbon nanotube dispersion; add the carbon nanotube dispersion to the activated carbon fiber dispersion , stirring to disperse the carbon nanotubes and activated carbon fibers evenly to obtain a composite material dispersion;

5. Vacuum filter the bacterial cellulose slurry in step 3 to form a film, then add the composite material dispersion to continue to filter to form a film, and then put it in a vacuum drying oven for drying to make bacterial cellulose/activated carbon fiber/carbon nano tube membrane material.

After vacuum filtration and vacuum drying, the mass of the bacterial cellulose in the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material was 0.3 g.

The photo of bacterial cellulose/activated carbon fiber/carbon nanotube membrane material prepared in this embodiment is shown in Figure 1.

The obtained bacterial cellulose/activated carbon fiber/carbon nanotube film material was cut into a 1.5cm×2cm rectangle, which was directly used as the working electrode of the supercapacitor, the platinum sheet was used as the counter electrode, and the mercury/mercury oxide electrode was used as the reference electrode. Capacitive properties of supporting flexible membrane electrode materials. The test sample was labeled BC-ACF-CNT-1.

Cyclic voltammetry performance tests at different scan speeds were performed on the electrode prepared from the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material obtained in this example in a 6M potassium hydroxide electrolyte, and the results are shown in FIG. 2 . The figure shows that activated carbon fibers with different scanning speeds have quasi-rectangular CV curves in the scanning potential range of -0.9 to 0.2V.

The electrode prepared from the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material obtained in this example was tested for constant current charge and discharge performance in a 6M potassium hydroxide electrolyte, and the results are shown in FIG. 3 . It can be seen from Figure 3 that the curves show a good triangle shape, and the curves have good symmetry under different magnifications. The maximum area specific capacitance reaches 0.59F/cm ² . As shown in Figure 5, the AC impedance spectrum of the electrode consists of a semicircle in the high frequency region, a straight line in the low frequency region, and a transition region between the semicircle and the straight line.

Embodiment 2, the preparation method of bacterial cellulose/activated carbon fiber/carbon nanotube membrane material of the present embodiment, carry out as follows:

1. Cut bacterial cellulose into pieces and soak in deionized water for ultrasonic washing for 10 hours, and replace the deionized water every hour, freeze in liquid nitrogen and transfer to a freeze dryer to dry for 20 hours to obtain spare bacterial cellulose;

2. Put the spare bacterial cellulose in the porcelain boat, and then put it into the tube furnace; pass nitrogen gas into the tube furnace to remove oxygen for 6 hours, and use it as a protective gas, first raise the temperature of the tube furnace at a rate of 4°C/min to 270°C, then raised to 390°C at a rate of 0.3°C/min, then raised to 800°C at a rate of 4°C/min, and kept for 2 hours; then cooled to 400°C at a rate of 5°C/min, and finally dropped to At room temperature, activated carbon fibers are obtained, then 15 mg of sodium dodecylbenzenesulfonate is added to 50 mg of activated carbon fibers, and then dispersed in deionized water to obtain an activated carbon fiber dispersion;

3. Cut 10g of bacterial cellulose into pieces, soak in deionized water and ultrasonically wash for 10 hours, and replace the deionized water every hour, then place in deionized water, stir to disperse evenly, and then transfer to a homogenizer Stir for 5 minutes at a speed of 12000 revolutions per minute to obtain a bacterial cellulose slurry;

4. Add 0.03g sodium dodecylbenzenesulfonate to 0.015g acidified carbon nanotubes, then disperse in deionized water to obtain a carbon nanotube dispersion; add the carbon nanotube dispersion to the activated carbon fiber dispersion , stirring to disperse the carbon nanotubes and activated carbon fibers evenly to obtain a composite material dispersion;

5. Vacuum filter the bacterial cellulose slurry in step 3 to form a film, then add the composite material dispersion to continue to filter to form a film, and then put it in a vacuum drying oven for drying to make bacterial cellulose/activated carbon fiber/carbon nano tube membrane material.

After vacuum filtration and vacuum drying, the mass of the bacterial cellulose in the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material was 0.3 g.

The obtained bacterial cellulose/activated carbon fiber/carbon nanotube film material was cut into a 1.5cm×2cm rectangle, which was directly used as the working electrode of the supercapacitor, the platinum sheet was used as the counter electrode, and the mercury/mercury oxide electrode was used as the reference electrode. Capacitive properties of supporting flexible membrane electrode materials. The test sample was labeled BC-ACF-CNT-2.

Cyclic voltammetry performance tests at different scan speeds were performed on the electrode prepared from the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material obtained in this example in a potassium hydroxide electrolyte, and the results are shown in FIG. 5 . The figure shows that activated carbon fibers with different scanning speeds have quasi-rectangular CV curves in the scanning potential range of -0.9 to 0.2V.

The electrode prepared from the bacterial cellulose/activated carbon fiber/carbon nanotube membrane material obtained in this example was subjected to a constant current charge and discharge performance test in a potassium hydroxide electrolyte solution, and the results are shown in FIG. 6 . It can be seen from Figure 6 that the curves show a good triangle, and the curves have good symmetry under different magnifications. The maximum area specific capacitance reaches 1.33F/cm ² . As shown in Figure 7, the AC impedance spectrum of the electrode consists of a semicircle in the high frequency region, a straight line in the low frequency region, and a transition region between the semicircle and the straight line. The working electrode prepared by the bacterial cellulose/activated carbon fiber/carbon nanotube film material obtained in Examples 1-2 is calculated according to the constant current charge-discharge curve in the 6M potassium hydroxide electrolyte, and the specific capacitance curve is shown in Figure 8 , it can be seen from Figure 8 that the specific capacitance of BC-ACF-CNT-1 is 0.59F/cm ² , 0.54F/cm ² , 0.51F/cm ² , 0.50F/cm ² , 0.48F/cm ² ; BC-ACF -The specific capacitance of CNT-2 is 1.33F/cm ² , 1.32F/cm ² , 1.22F/cm ² , 1.19F/cm ² , and 1.09F/cm ² .

The bacterial cellulose of Examples 1-2 is a commercially available product. Examples 1-2 utilize the characteristics of bacterial cellulose ultrafine network structure and excellent mechanical properties, and use this as a substrate to load nano-active substances, which can be prepared as self-supporting self-supporting flexible electrodes for supercapacitors; using bacterial cellulose ultrafine network Activated carbon fiber is prepared by direct pyrolysis of the structure; large-scale production is possible, the preparation process is simple, energy-saving, mild reaction conditions, low toxicity, cheap and easy to obtain raw materials, low cost, good stability and mechanical properties of membrane materials; directly used as supercapacitor electrodes has great Good capacitance.

Claims (9)

1. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material, it is characterised in that this method is by such as Lower step is carried out：

First, by bacteria cellulose shear it is blocking be immersed in supersound washing in deionized water, then with being freezed after liquid nitrogen frozen 15~30h is dried, obtains standby bacteria cellulose；

2nd, standby bacteria cellulose is placed in tube furnace and carries out high temperature pyrolysis, produce activated carbon fiber, it is then fine to activated carbon Surfactant is added in dimension, redisperse in deionized water, obtains activated carbon fiber dispersion liquid；

3rd, it is another to take the blocking rear immersion supersound washing in deionized water of bacteria cellulose shearing, it is subsequently placed in deionized water, stirs Mixing makes it be uniformly dispersed, and is then transferred in refiner and stirs, and obtains bacteria cellulose slurry；

4th, surfactant is added into the CNT of acidifying, be then dispersed in deionized water, obtained CNT and disperse Liquid；Carbon nano tube dispersion liquid is added in activated carbon fiber dispersion liquid, stirring makes CNT and activated carbon fiber scattered equal It is even, obtain composite dispersion liquid；

5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then add composite dispersion liquid continue to filter into Film, place into vacuum drying chamber and be dried, bacteria cellulose/activated carbon fiber/CNT membrane material is made；It is wherein thin The mass ratio of bacteria cellulose and the activated carbon fiber of step 2 is in fungin/activated carbon fiber/CNT membrane material (15~1.5):1；It is acidified in bacteria cellulose/activated carbon fiber/CNT membrane material in bacteria cellulose and step 4 The mass ratio of CNT is 1:(0.02~0.2)；The method of wherein high temperature pyrolysis is：Standby bacteria cellulose is placed in porcelain boat In, it is then placed in tube furnace；3~8h of argon gas or nitrogen is passed through into tube furnace, and using argon gas or nitrogen as protection gas；Again will Tube furnace is warming up to 270 DEG C with 2~4 DEG C/min speed, then is warming up to 390 DEG C with 0.3~0.5 DEG C/min speed, then 700 DEG C~1100 DEG C are warming up to 2~4 DEG C/min speed, keeps 2~4h, then 400 are cooled to 3~5 DEG C/min speed DEG C, room temperature is finally naturally cooled to again, that is, is completed.

2. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1, It is characterized in that described bacteria cellulose is bacteria cellulose leftover pieces.

3. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1, It is characterized in that the condition of the supersound washing described in step 1 and step 3 is ultrasonic time 10h, and changes within each hour and go Ionized water.

4. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1, It is characterized in that the mass ratio of the activated carbon fiber and surfactant described in step 2 is 1:(0.3~3).

5. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1, Refer to it is characterized in that being stirred in refiner described in step 3 under conditions of stir speed (S.S.) 10000rpm~15000rpm, 5min is stirred in refiner.

6. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1, It is characterized in that the CNT of acidifying and the mass ratio of surfactant described in step 4 are (0.5~0.8):1.

A kind of 7. preparation of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1,4 or 6 Method, it is characterised in that described surfactant is neopelex.

8. a kind of preparation method of bacteria cellulose/activated carbon fiber/CNT membrane material according to claim 1, It is characterized in that the nitric acid that it is 64% in concentration by CNT that the preparation method of the CNT of acidifying described in step 4, which is, Middle supersound process 24h, is washed with deionized, and filters drying.

9. bacteria cellulose/activated carbon fiber/CNT membrane material that preparation method as claimed in claim 1 obtains is answered With, it is characterised in that the bacteria cellulose/activated carbon fiber/CNT membrane material is as application of electrode in ultracapacitor In.