CN105118688B - A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material - Google Patents

A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material Download PDF

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CN105118688B
CN105118688B CN201510566811.2A CN201510566811A CN105118688B CN 105118688 B CN105118688 B CN 105118688B CN 201510566811 A CN201510566811 A CN 201510566811A CN 105118688 B CN105118688 B CN 105118688B
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bacteria cellulose
activated carbon
carbon fiber
graphene
graphene film
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CN105118688A (en
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袁国辉
刘荣
马丽娜
张芳平
黎恩源
张法宁
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Liaoning science and Technology Co., Ltd.
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Harbin Institute of Technology
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film 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/graphene film 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 bacteria cellulose/activated carbon fiber/graphene film material and its Using
Technical field
The present invention relates to a kind of preparation method and applications of membrane material.
Background technology
Traditional energy sources is increasingly depleted, stimulates people to look for the alternative energy and effective energy storage Device, and ultracapacitor has high power density and higher energy density, applied to hybrid electric vehicle, electric car, portable The important field such as formula electronic equipment, enjoys people to favor always.
For today's society to the rapid growth of flexible, flexible equipment energy storage demand, it is of future generation inexpensive, soft that people are badly in need of research and development Soft, flexible ultracapacitor, and electrode material is most important part.But existing flexible electrode material preparation technology Complicated, cost height, does not possess good stability and mechanical property.Therefore, using one it is simple, effectively, environmental protection, suitable for rule The preparation method of modelling production prepares high performance flexible electrode material and is even more important.
The content of the invention
It is high the invention aims to solve existing flexible electrode material preparation technology complexity, cost, do not possess good Stability and mechanical property the problem of, there is provided a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material And its application.
A kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material of the present invention, enters as follows OK:
First, by bacteria cellulose shear it is blocking be immersed in supersound washing in deionized water, then carried out with after liquid nitrogen frozen 15~30h is freeze-dried, obtains standby bacteria cellulose;
2nd, standby bacteria cellulose is placed in tube furnace and carries out high temperature pyrolysis, produce activated carbon fiber, then to activity Surfactant is added in carbon fiber, redisperse in deionized water, obtains activated carbon fiber dispersion liquid;
3rd, bacteria cellulose is sheared into blocking rear immersion supersound washing in deionized water, is subsequently placed in deionized water, Stirring makes it be uniformly dispersed, and is then transferred in refiner and stirs, obtains bacteria cellulose slurry;
4th, surfactant is added into the graphene of acidifying, be then dispersed in deionized water, obtain graphene dispersion Liquid;Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fiber be uniformly dispersed, and obtains To composite dispersion liquid;
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made;Wherein The mass ratio of bacteria cellulose and the activated carbon fiber of step 2 is in bacteria cellulose/activated carbon fiber/graphene film material (15~1.5):1;Bacteria cellulose and the stone being acidified in step 4 in bacteria cellulose/activated carbon fiber/graphene film material The mass ratio of black alkene is 1:(0.02~0.2).
The application of bacteria cellulose/activated carbon fiber/graphene film material of the present invention refers to as application of electrode in super In capacitor.
Activated carbon fiber has good chemical stability, electric conductivity and fake capacitance energy storage characteristic, it is considered to be Yi Zhongji Potential electrode material for super capacitor.Bacteria cellulose, its film have hyperfine network structure, thin after cracking Fungin can make carbon nano-fiber, gained activated carbon fiber function admirable.
Bacteria cellulose is obtained by the fermentation of microorganism, its function admirable, aboundresources, environment-friendly, film With hyperfine network structure, high-crystallinity, high-purity, high mechanical properties, as a kind of emerging environmentally friendly material into For the focus of domestic and international Material Field research, bacteria cellulose contains substantial amounts of hydroxyl, has good hydrophily, with other water Hydrogenbond easily occurs for the macromolecule of dissolubility, thus bacteria cellulose has natural advantage as composite.
The unique two-dimensional structure of graphene and outstanding physical property, there is its application in ultracapacitor very big Potentiality.Graphene has substantial amounts of interlayer structure compared with traditional porous carbon materials, causes it to have big specific surface area Very high electric conductivity, so as to turn into the more promising electrode material of capacitor.
The present invention using it is a kind of it is inexpensive, it is environmentally friendly and can scale preparation method, pass through vacuum filtration, prepare Go out membrane material and capacitor is assembled into this.Structure shows membrane material good mechanical performance, has good capacitive properties and excellent Good recycling.Therefore, application of this membrane material in ultracapacitor has wide commercial promise.
Beneficial effects of the present invention:(1) spies such as the hyperfine network structure of bacteria cellulose and excellent mechanical property are utilized Property, as base load nano active material, ultracapacitor self-supporting self-supporting flexible electrode can be prepared into;(2) it is sharp Activated carbon fiber is prepared with the direct Pintsch process of the hyperfine network structure of bacteria cellulose;(3) it is produced on a large scale, preparation technology Simply, energy-conservation, reaction condition be gentle, small toxicity, and raw material cost cheap and easy to get is low, membrane material stability and mechanical property are good;(4) Directly being used as electrode of super capacitor has good capacitive character.
Brief description of the drawings
Fig. 1 is the photo of bacteria cellulose/activated carbon fiber/graphene film material prepared by embodiment 1;
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 2 is obtained by embodiment 1 Cyclic voltammetry curve under different scanning speed of the pole in 6M potassium hydroxide electrolytes;Wherein a is 5mV/s, b 10mV/s, c For 20mV/s, d 50mV/s;
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 3 is obtained by embodiment 1 Constant current charge-discharge curve of the pole in 6M potassium hydroxide electrolytes;Wherein a is 1mA/cm2, b 2mA/cm2, c 5mA/cm2, D is 10mA/cm2
Fig. 4 is the work prepared with bacteria cellulose/activated carbon fiber/graphene film material obtained in embodiment 1 The AC impedance spectroscopy of electrode;
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 5 is obtained by embodiment 2 Cyclic voltammetry curve under different scanning speed of the pole in 6M potassium hydroxide electrolytes;Wherein a is 5mV/s, b 10mV/s, c For 20mV/s;
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 6 is obtained by embodiment 2 Constant current charge-discharge curve of the pole in 6M potassium hydroxide electrolytes;Wherein a is 1mA/cm2, b 2mA/cm2, c 5mA/cm2, D is 10mA/cm2
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 7 is obtained by embodiment 3 Cyclic voltammetry curve under different scanning speed of the pole in 6M potassium hydroxide electrolytes;Wherein a is 5mV/s, b 10mV/s, c For 20mV/s;
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 8 is obtained by embodiment 3 Constant current charge-discharge curve of the pole in 6M potassium hydroxide electrolytes;Wherein a is 1mA/cm2, b 2mA/cm2, c 5mA/cm2, D is 10mA/cm2
Embodiment
Technical solution of the present invention is not limited to the embodiment of act set forth below, in addition to each embodiment it Between any combination.
Embodiment one:A kind of preparation of bacteria cellulose/activated carbon fiber/graphene film material of present embodiment Method, carry out as follows:
First, by bacteria cellulose shear it is blocking be immersed in supersound washing in deionized water, then carried out with after liquid nitrogen frozen 15~30h is freeze-dried, obtains standby bacteria cellulose;
2nd, standby bacteria cellulose is placed in tube furnace and carries out high temperature pyrolysis, produce activated carbon fiber, then to activity Surfactant is added in carbon fiber, redisperse in deionized water, obtains activated carbon fiber dispersion liquid;
3rd, the blocking rear immersion supersound washing in deionized water of bacteria cellulose shearing is got, is subsequently placed in deionized water In, stirring makes it be uniformly dispersed, and is then transferred in refiner and stirs, obtains bacteria cellulose slurry;
4th, surfactant is added into the graphene of acidifying, be then dispersed in deionized water, obtain graphene dispersion Liquid;Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fiber be uniformly dispersed, and obtains To composite dispersion liquid;
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made;Wherein The mass ratio of bacteria cellulose and the activated carbon fiber of step 2 is in bacteria cellulose/activated carbon fiber/graphene film material (15~1.5):1;Bacteria cellulose and the stone being acidified in step 4 in bacteria cellulose/activated carbon fiber/graphene film material The mass ratio of black alkene is 1:(0.02~0.2).
Activated carbon fiber has good chemical stability, electric conductivity and fake capacitance energy storage characteristic, it is considered to be Yi Zhongji Potential electrode material for super capacitor.Bacteria cellulose, its film have hyperfine network structure, thin after cracking Fungin can make carbon nano-fiber, gained activated carbon fiber function admirable.
Bacteria cellulose is obtained by the fermentation of microorganism, its function admirable, aboundresources, environment-friendly, film With hyperfine network structure, high-crystallinity, high-purity, high mechanical properties, as a kind of emerging environmentally friendly material into For the focus of domestic and international Material Field research, bacteria cellulose contains substantial amounts of hydroxyl, has good hydrophily, with other water Hydrogenbond easily occurs for the macromolecule of dissolubility, thus bacteria cellulose has natural advantage as composite.
The unique two-dimensional structure of graphene and outstanding physical property, there is its application in ultracapacitor very big Potentiality.Graphene has substantial amounts of interlayer structure compared with traditional porous carbon materials, causes it to have big specific surface area Very high electric conductivity, so as to turn into the more promising electrode material of capacitor.
Present embodiment using it is a kind of it is inexpensive, it is environmentally friendly and can scale preparation method, by vacuum filtration, Prepare membrane material and capacitor is assembled into this.Structure shows membrane material good mechanical performance, has good capacitive properties With excellent recycling.Therefore, application of this membrane material in ultracapacitor has wide commercial promise.
The beneficial effect of present embodiment:(1) the hyperfine network structure of bacteria cellulose and excellent mechanical property are utilized Etc. characteristic, as base load nano active material, ultracapacitor self-supporting self-supporting flexible electrode can be prepared into; (2) activated carbon fiber is prepared using the direct Pintsch process of the hyperfine network structure of bacteria cellulose;(3) it is produced on a large scale, makes Standby technique is simple, energy-conservation, reaction condition are gentle, small toxicity, and raw material cost cheap and easy to get is low, membrane material stability and mechanical property It is good;(4) being directly used as electrode of super capacitor has good capacitive character.
Freeze-drying is carried out in freeze drier in present embodiment, and bacteria cellulose is commercially available prod.
Embodiment two:Present embodiment is unlike embodiment one:Described bacteria cellulose is Bacteria cellulose leftover pieces.It is other identical with embodiment one.
Embodiment three:Present embodiment is unlike embodiment one or two:It is super described in step 1 The condition of sound washing is ultrasonic time 10h, and each hour changes deionized water.Other and embodiment one or two-phase Together.
Embodiment four:Unlike one of present embodiment and embodiment one to three:Described in step 2 The method of high temperature degradation be:Standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace;Argon is passed through into tube furnace 3~8h of gas or nitrogen, and using argon gas or nitrogen as protection gas;Tube furnace is warming up to 270 with 2~4 DEG C/min speed again DEG C, then be warming up to 390 DEG C with 0.3~0.5 DEG C/min speed, then with 2~4 DEG C/min speed be warming up to 700 DEG C~ 1100 DEG C, 2~4h is kept, then 400 DEG C are cooled to 3~5 DEG C/min speed, room temperature is finally naturally cooled to again, that is, completes. It is other identical with one of embodiment one to three.
Embodiment five:Unlike one of present embodiment and embodiment one to four:Described in step 2 The method of high temperature degradation be:Standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace;Argon is passed through into tube furnace Gas or nitrogen 6h, and using argon gas or nitrogen as protection gas, then tube furnace is warming up to 270 DEG C with 4 DEG C/min speed, then with 0.3 DEG C/min speed is warming up to 390 DEG C, is then warming up to 900 DEG C with 4 DEG C/min speed, keeps 2h, then with 5 DEG C/min Speed be cooled to 400 DEG C, finally naturally cool to room temperature again, that is, complete other phases one of with embodiment one to four Together.
Embodiment six:Unlike one of present embodiment and embodiment one to five:Described in step 2 Activated carbon fiber and surfactant mass ratio be 1:(0.3~3).Other phases one of with embodiment one to five Together.
Embodiment seven:Unlike one of present embodiment and embodiment one to six:Described in step 3 Refiner in stir and refer under conditions of stir speed (S.S.) 10000rpm~15000rpm, 5min is stirred in refiner.Its It is identical with one of embodiment one to six.
Embodiment eight:Unlike one of present embodiment and embodiment one to seven:Described in step 4 Acidifying graphene and surfactant mass ratio be 1:(0.25~1).One of other and embodiment one to seven It is identical.
Embodiment nine:Unlike one of present embodiment and embodiment one to eight:Described surface Activating agent is neopelex.It is other identical with one of embodiment one to eight.
Embodiment ten:Unlike one of present embodiment and embodiment one to nine:Described in step 4 The preparation method of graphene of acidifying be that graphene is ultrasonically treated 24h in the nitric acid that concentration is 64%, use deionized water Washing, filter drying.It is other identical with one of embodiment one to nine.
Embodiment 11:The application of present embodiment bacteria cellulose/activated carbon fiber/graphene film material is Refer to as application of electrode in ultracapacitor.
Beneficial effects of the present invention are verified by following examples:
The preparation method of embodiment 1, the present embodiment bacteria cellulose/activated carbon fiber/graphene film material, by following step It is rapid to carry out:
First, by bacteria cellulose shear it is blocking be immersed in supersound washing 10h in deionized water, and change within each hour go from Sub- water, freeze drier is transferred to after liquid nitrogen frozen and dries 20h, obtains standby bacteria cellulose;
2nd, standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace;Nitrogen is passed through into tube furnace and removes oxygen 6h, and as protection gas, tube furnace is warming up to 270 DEG C with 4 DEG C/min speed first, afterwards 0.3 DEG C/min speed liter Then temperature is warming up to 900 DEG C to 390 DEG C with 4 DEG C/min speed, keep 2h;400 DEG C are cooled to 5 DEG C/min speed again, Finally it is down to room temperature naturally again, produces activated carbon fiber, 15mg detergent alkylate sulphurs is then added into 50mg activated carbon fibers Sour sodium, redisperse in deionized water, obtain activated carbon fiber dispersion liquid;
3rd, by the blocking rear immersion supersound washing 10h, and each hour is more in deionized water of 10g bacteria celluloses shearing Deionized water is changed, is subsequently placed in deionized water, stirring makes it be uniformly dispersed, and is then transferred in refiner with per minute 12000 The speed turned, 5min is stirred, obtains bacteria cellulose slurry;
4th, 0.01g neopelexes are added in the graphene being acidified to 0.01g, is then dispersed in deionized water In, obtain graphene dispersing solution;Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activity Carbon fiber is uniformly dispersed, and obtains composite dispersion liquid;
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made.
The bacterial fibers in bacteria cellulose/activated carbon fiber/graphene film material after vacuum filtration and vacuum drying The quality of element is 0.3g.
The photo of bacteria cellulose/activated carbon fiber/graphene film material manufactured in the present embodiment is as shown in Figure 1.
By bacteria cellulose/activated carbon fiber/graphene film material cutting of acquisition into 1.5cm × 2cm rectangles, directly As ultracapacitor working electrode, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test self-supporting is soft The capacitance characteristic of property membrane material electrode material.Test sample is labeled as BC-ACF-CN-1.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in 6M hydrogen The cyclic voltammetric performance test without sweep speed is carried out in potassium oxide electrolyte, as a result referring to Fig. 2.Show that difference is swept in figure The activated carbon fiber of speed is in scanning potential region -0.9~0.2V, all the CV curves with quasi- rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in 6M hydrogen Constant current charge-discharge performance test is carried out in potassium oxide electrolyte, as a result referring to Fig. 3.From the figure 3, it may be seen that curve is shown well Triangle, different multiplying lower curve are respectively provided with preferable symmetry.Maximum area specific capacitance reaches 1.15F/cm2, mass ratio electricity It is about 237F/g to hold.Such as Fig. 4, in high frequency region, represent the deformation semi arch of electrode material charge-transfer resistance and represent electrode X-axis intercept all very littles of material resistance, the straight line of y-axis is proximate in low frequency range, shows the intrinsic resistance of the electric capacity of electrode material Anti- characteristic.
The preparation method of embodiment 2, the present embodiment bacteria cellulose/activated carbon fiber/graphene film material, by following step It is rapid to carry out:
First, by bacteria cellulose shear it is blocking be immersed in supersound washing 10h in deionized water, and change within each hour go from Sub- water, freeze drier is transferred to after liquid nitrogen frozen and dries 20h, obtains standby bacteria cellulose;
2nd, standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace;Nitrogen is passed through into tube furnace and removes oxygen 6h, and as protection gas, tube furnace is warming up to 270 DEG C with 4 DEG C/min speed first, afterwards 0.3 DEG C/min speed liter Then temperature is warming up to 800 DEG C to 390 DEG C with 4 DEG C/min speed, keep 2h;400 DEG C are cooled to 5 DEG C/min speed again, Finally it is down to room temperature naturally again, produces activated carbon fiber, 30mg detergent alkylate sulphurs is then added into 100mg activated carbon fibers Sour sodium, redisperse in deionized water, obtain activated carbon fiber dispersion liquid;
3rd, by the blocking rear immersion supersound washing 10h, and each hour is more in deionized water of 10g bacteria celluloses shearing Deionized water is changed, is subsequently placed in deionized water, stirring makes it be uniformly dispersed, and is then transferred in refiner with per minute 12000 The speed turned, 5min is stirred, obtains bacteria cellulose slurry;
4th, 0.005g neopelexes are added in the graphene being acidified to 0.02g, is then dispersed in deionized water In, obtain graphene dispersing solution;Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activity Carbon fiber is uniformly dispersed, and obtains composite dispersion liquid;
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made.
The bacterial fibers in bacteria cellulose/activated carbon fiber/graphene film material after vacuum filtration and vacuum drying The quality of element is 0.3g.
By bacteria cellulose/activated carbon fiber/graphene film material cutting of acquisition into 1.5cm × 2cm rectangles, directly As ultracapacitor working electrode, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test self-supporting is soft The capacitance characteristic of property membrane material electrode material.Test sample is labeled as BC-ACF-CN-2.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in hydrogen-oxygen Change the cyclic voltammetric performance test carried out in potassium electrolyte without sweep speed, as a result referring to Fig. 5.Show that difference sweeps speed in figure Activated carbon fiber in scanning potential region -0.9~0.2V, all CV curves with quasi- rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in hydrogen-oxygen Change and constant current charge-discharge performance test is carried out in potassium electrolyte, as a result referring to Fig. 6.It will be appreciated from fig. 6 that curve shows good three Angular, different multiplying lower curve is respectively provided with preferable symmetry.Maximum area specific capacitance reaches 2.12F/cm2, quality specific capacitance About 212F/g.
The preparation method of embodiment 3, the present embodiment bacteria cellulose/activated carbon fiber/graphene film material, by following step It is rapid to carry out:
First, by bacteria cellulose shear it is blocking be immersed in supersound washing 10h in deionized water, and change within each hour go from Sub- water, freeze drier is transferred to after liquid nitrogen frozen and dries 20h, obtains standby bacteria cellulose;
2nd, standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace;Nitrogen is passed through into tube furnace and removes oxygen 6h, and as protection gas, tube furnace is warming up to 270 DEG C with 4 DEG C/min speed first, afterwards 0.3 DEG C/min speed liter Then temperature is warming up to 900 DEG C to 390 DEG C with 4 DEG C/min speed, keep 2h;400 DEG C are cooled to 5 DEG C/min speed again, Finally it is down to room temperature naturally again, produces activated carbon fiber, 7.5mg detergent alkylate sulphurs is then added into 25mg activated carbon fibers Sour sodium, redisperse in deionized water, obtain activated carbon fiber dispersion liquid;
3rd, by the blocking rear immersion supersound washing 10h, and each hour is more in deionized water of 10g bacteria celluloses shearing Deionized water is changed, is subsequently placed in deionized water, stirring makes it be uniformly dispersed, and is then transferred in refiner with per minute 12000 The speed turned, 5min is stirred, obtains bacteria cellulose slurry;
4th, 0.006g neopelexes are added in the graphene being acidified to 0.006g, is then dispersed in deionization In water, graphene dispersing solution is obtained;Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and work Property carbon fiber is uniformly dispersed, and obtains composite dispersion liquid;
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made.
The bacterial fibers in bacteria cellulose/activated carbon fiber/graphene film material after vacuum filtration and vacuum drying The quality of element is 0.3g.
By bacteria cellulose/activated carbon fiber/graphene film material cutting of acquisition into 1.5cm × 2cm rectangles, directly As ultracapacitor working electrode, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test self-supporting is soft The capacitance characteristic of property membrane material electrode material.Test sample is labeled as BC-ACF-CN-3.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in 6M hydrogen The cyclic voltammetric performance test without sweep speed is carried out in potassium oxide electrolyte, as a result referring to Fig. 7.Show that difference is swept in figure The activated carbon fiber of speed is in scanning potential region -0.9~0.2V, all the CV curves with quasi- rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in hydrogen-oxygen Change and constant current charge-discharge performance test is carried out in potassium electrolyte, as a result referring to Fig. 8.As shown in Figure 8, curve shows good three Angular, different multiplying lower curve is respectively provided with preferable symmetry.Maximum area specific capacitance reaches 0.65F/cm2, quality specific capacitance About 252F/g.
Embodiment 1~3 is using characteristics such as the hyperfine network structure of bacteria cellulose and excellent mechanical properties, as base Bed load nano active material, ultracapacitor self-supporting self-supporting flexible electrode can be prepared into;Surpassed using bacteria cellulose The direct Pintsch process of fine network structure prepares activated carbon fiber;It is produced on a large scale, preparation technology is simple, energy-conservation, reaction bar Part is gentle, small toxicity, and raw material cost cheap and easy to get is low, membrane material stability and mechanical property are good;Directly it is used as ultracapacitor Electrode has good capacitive character.

Claims (9)

1. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material, it is characterised in that this method is by as follows 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 graphene of acidifying, be then dispersed in deionized water, obtain graphene dispersing solution; Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fiber be uniformly dispersed, and obtains 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/graphene film material is made;Wherein bacterium In cellulose/activated carbon fiber/graphene film material the mass ratio of bacteria cellulose and the activated carbon fiber of step 2 for (15~ 1.5):1;The graphene being acidified in bacteria cellulose/activated carbon fiber/graphene film material in bacteria cellulose and step 4 Mass ratio is 1:(0.02~0.2);The method of wherein high temperature pyrolysis is:Standby bacteria cellulose is placed in porcelain boat, Ran Houfang Enter 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 by tube furnace with 2 ~4 DEG C/min speed is warming up to 270 DEG C, then is warming up to 390 DEG C with 0.3~0.5 DEG C/min speed, then with 2~4 DEG C/ Min speed is warming up to 700 DEG C~1100 DEG C, keeps 2~4h, then is cooled to 400 DEG C with 3~5 DEG C of min speed, again finally Room temperature is naturally cooled to, that is, is completed.
2. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its It is characterised by that described bacteria cellulose is bacteria cellulose leftover pieces.
3. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its The condition for the supersound washing being characterised by described in step 1 and step 3 is ultrasonic time 10h, and change within each hour go from Sub- water.
4. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its The activated carbon fiber and the mass ratio of surfactant being characterised by described in step 2 are 1:(0.3~3).
5. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its It is characterised by the refiner described in step 3 that stirring refers under conditions of stir speed (S.S.) 10000rpm~15000rpm, even 5min is stirred in pulp grinder.
6. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its The graphene for the acidifying being characterised by described in step 4 and the mass ratio of surfactant are 1:(0.25~1).
A kind of 7. preparation side of bacteria cellulose/activated carbon fiber/graphene film 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/graphene film material according to claim 1, its The preparation method of the graphene for the acidifying being characterised by described in step 4 be by graphene in the nitric acid that concentration is 64% it is ultrasonic 24h is handled, is washed with deionized, filters drying.
9. bacteria cellulose/activated carbon fiber/graphene film material that preparation method as claimed in claim 1 obtains is answered With, it is characterised in that the bacteria cellulose/activated carbon fiber/graphene film material is as application of electrode in ultracapacitor.
CN201510566811.2A 2015-09-08 2015-09-08 A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material Active CN105118688B (en)

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