CN105118688A - Preparation and application of bacterial cellulose/active carbon fiber/graphene film material - Google Patents
Preparation and application of bacterial cellulose/active carbon fiber/graphene film material Download PDFInfo
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- CN105118688A CN105118688A CN201510566811.2A CN201510566811A CN105118688A CN 105118688 A CN105118688 A CN 105118688A CN 201510566811 A CN201510566811 A CN 201510566811A CN 105118688 A CN105118688 A CN 105118688A
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- bacteria cellulose
- activated carbon
- film material
- graphene
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920002749 Bacterial cellulose Polymers 0.000 title abstract 6
- 239000005016 bacterial cellulose Substances 0.000 title abstract 6
- 229920000049 Carbon (fiber) Polymers 0.000 title abstract 4
- 239000004917 carbon fiber Substances 0.000 title abstract 4
- 239000006185 dispersion Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 241000894006 Bacteria Species 0.000 claims description 121
- 229920002678 cellulose Polymers 0.000 claims description 69
- 239000001913 cellulose Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 15
- 239000003990 capacitor Substances 0.000 abstract description 11
- 239000002086 nanomaterial Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 36
- 239000003792 electrolyte Substances 0.000 description 12
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 229940101209 mercuric oxide Drugs 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910000474 mercury oxide Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method and application of a bacterial cellulose/active carbon fiber/graphene film material. The objective of the invention is to solve the problems of complex preparation process, high cost, poor stability and mechanical properties of existing flexible electrode materials. The method includes the following steps that: spare bacterial cellulose is prepared, and activate carbon fiber dispersion is prepared; bacterial cellulose slurry is prepared; and composite material dispersion is prepared, and vacuum filtration is performed on the bacterial cellulose slurry, so that a film can be formed, and the composite material dispersion is added, and vacuum filtration and drying are performed, and as a result, the bacterial cellulose/active carbon fiber/graphene film material can be obtained. The film material is applied to super capacitors. The film material prepared by the invention can be mass produced, and has the advantages of simple preparation process, low cost, high stability and excellent mechanical properties. A super capacitor apparatus adopting the film material has an excellent capacitive characteristic. The invention belongs to the nano material technical field.
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/graphene film material is provided.
The preparation method of a kind of bacteria cellulose/activated carbon fiber/graphene film 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 Graphene of acidifying, add surfactant, then disperse in deionized water, to obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and Graphene 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/graphene film material; Wherein in bacteria cellulose/activated carbon fiber/graphene film 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/graphene film material, in bacteria cellulose and step 4, the mass ratio of the Graphene of acidifying 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 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.
The two-dimensional structure of Graphene uniqueness and outstanding physical property, make its application in ultracapacitor have great potentiality.Graphene has a large amount of interlayer structures compared with traditional porous carbon materials, causes it to have large specific area and very high conductivity, thus becomes the more promising electrode material of capacitor.
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/graphene film material prepared by embodiment 1;
Cyclic voltammetry curve under the different scanning speed of the work electrode prepared with bacteria cellulose/activated carbon fiber/graphene film material that Fig. 2 obtains for embodiment 1 in 6M potassium hydroxide electrolyte; Wherein a is 5mV/s, b be 10mV/s, c be 20mV/s, d is 50mV/s;
The constant current charge-discharge curve of work electrode in 6M potassium hydroxide electrolyte prepared with bacteria cellulose/activated carbon fiber/graphene film 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;
The AC impedance spectrogram of the work electrode with bacteria cellulose/activated carbon fiber/graphene film 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/graphene film material that Fig. 5 obtains for embodiment 2 in 6M potassium hydroxide electrolyte; Wherein a is 5mV/s, b be 10mV/s, c is 20mV/s;
The constant current charge-discharge curve of work electrode in 6M potassium hydroxide electrolyte prepared with bacteria cellulose/activated carbon fiber/graphene film 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;
Cyclic voltammetry curve under the different scanning speed of the work electrode prepared with bacteria cellulose/activated carbon fiber/graphene film material that Fig. 7 obtains for embodiment 3 in 6M potassium hydroxide electrolyte; Wherein a is 5mV/s, b be 10mV/s, c is 20mV/s;
The constant current charge-discharge curve of work electrode in 6M potassium hydroxide electrolyte prepared with bacteria cellulose/activated carbon fiber/graphene film material that Fig. 8 obtains for embodiment 3; Wherein a is 1mA/cm
2, b is 2mA/cm
2, c is 5mA/cm
2, d is 10mA/cm
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/graphene film 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, 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 Graphene of acidifying, add surfactant, then disperse in deionized water, to obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and Graphene 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/graphene film material; Wherein in bacteria cellulose/activated carbon fiber/graphene film 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/graphene film material, in bacteria cellulose and step 4, the mass ratio of the Graphene 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.
The two-dimensional structure of Graphene uniqueness and outstanding physical property, make its application in ultracapacitor have great potentiality.Graphene has a large amount of interlayer structures compared with traditional porous carbon materials, causes it to have large specific area and very high conductivity, thus becomes the more promising electrode material of capacitor.
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 Graphene of the acidifying described in step 4 and the mass ratio of surfactant are 1:(0.25 ~ 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 Graphene of the acidifying described in step 4 be by Graphene 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/graphene film 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/graphene film 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 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 Graphene of 0.01g acidifying, add 0.01g neopelex, then disperse in deionized water, to obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and Graphene 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/graphene film material.
After vacuum filtration and vacuumize, in bacteria cellulose/activated carbon fiber/graphene film material, the quality of bacteria cellulose is 0.3g.
The photo of bacteria cellulose/activated carbon fiber/graphene film material prepared by the present embodiment as shown in Figure 1.
Bacteria cellulose/activated carbon fiber/graphene film the 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-CN-1.
Electrode prepared by the bacteria cellulose/activated carbon fiber/graphene film 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/graphene film 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 1.15F/cm
2, quality is about 237F/g than electric capacity.As Fig. 4, in high frequency region, the distortion semi arch representing electrode material charge-transfer resistance is all very little with the x-axis intercept representing electrode material internal resistance, is the straight line near y-axis, shows the impedance operator that the electric capacity of electrode material is intrinsic in low frequency range.
The preparation method of embodiment 2, the present embodiment bacteria cellulose/activated carbon fiber/graphene film 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 100mg activated carbon fiber, add 30mg 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 Graphene of 0.02g acidifying, add 0.005g neopelex, then disperse in deionized water, to obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and Graphene 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/graphene film material.
After vacuum filtration and vacuumize, in bacteria cellulose/activated carbon fiber/graphene film material, the quality of bacteria cellulose is 0.3g.
Bacteria cellulose/activated carbon fiber/graphene film the 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-CN-2.
Electrode prepared by the bacteria cellulose/activated carbon fiber/graphene film 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/graphene film 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 2.12F/cm
2, quality is about 212F/g than electric capacity.
The preparation method of embodiment 3, the present embodiment bacteria cellulose/activated carbon fiber/graphene film 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 Graphene of 0.006g acidifying, add 0.006g neopelex, then disperse in deionized water, to obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and Graphene 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/graphene film material.
After vacuum filtration and vacuumize, in bacteria cellulose/activated carbon fiber/graphene film material, the quality of bacteria cellulose is 0.3g.
Bacteria cellulose/activated carbon fiber/graphene film the 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-CN-3.
Electrode prepared by the bacteria cellulose/activated carbon fiber/graphene film 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. 7.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/graphene film material obtained the present embodiment carries out constant current charge-discharge performance test in potassium hydroxide electrolyte, and result is see Fig. 8.As shown in Figure 8, curve table reveals good triangle, and different multiplying lower curve all has good symmetry.Maximum area ratio capacitance reaches 0.65F/cm
2, quality is about 252F/g than electric capacity.
Embodiment 1 ~ 3 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/graphene film 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 Graphene of acidifying, add surfactant, then disperse in deionized water, to obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and Graphene 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/graphene film material; Wherein in bacteria cellulose/activated carbon fiber/graphene film 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/graphene film material, in bacteria cellulose and step 4, the mass ratio of the Graphene of acidifying is 1:(0.02 ~ 0.2).
2. the preparation method of a kind of bacteria cellulose/activated carbon fiber/graphene film 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/graphene film 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/graphene film 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 of min, finally naturally cool to room temperature again, namely complete.
5. the preparation method of a kind of bacteria cellulose/activated carbon fiber/graphene film 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/graphene film 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/graphene film material according to claim 1, is characterized in that the Graphene of the acidifying described in step 4 and the mass ratio of surfactant are 1:(0.25 ~ 1).
8. the preparation method of a kind of bacteria cellulose/activated carbon fiber/graphene film 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/graphene film material according to claim 1, it is characterized in that the preparation method of the Graphene of the acidifying described in step 4 be by Graphene 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/graphene film 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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