CN105355450A - Preparation method and application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacterial cellulose membrane material - Google Patents

Preparation method and application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacterial cellulose membrane material Download PDF

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CN105355450A
CN105355450A CN201510990574.2A CN201510990574A CN105355450A CN 105355450 A CN105355450 A CN 105355450A CN 201510990574 A CN201510990574 A CN 201510990574A CN 105355450 A CN105355450 A CN 105355450A
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nitrogen
carbon fiber
doped
bacteria cellulose
membrane material
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CN105355450B (en
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黄玉东
马丽娜
刘荣
刘丽
王芳
黎俊
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Harbin Institute of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/34Carbon-based characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/40Fibres
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • 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

The invention discloses a preparation method and an application of a nitrogen-doped carbon fiber/nitrogen-doped graphene/bacterial cellulose membrane material, relates to a preparation method and an application of a membrane material and aims to solve the problem that a flexible electrode material prepared with a conventional method does not have good stability, cycle performance and mechanical properties. The method comprises the following steps: preparing bacterial cellulose pulp; preparing a bacterial cellulose and graphene composite; preparing a polypyrrole coated bacterial cellulose and graphene composite; preparing a nitrogen-doped carbon fiber/nitrogen-doped graphene composite through high-temperature carbonization; preparing a nitrogen-doped carbon fiber/nitrogen-doped graphene dispersing agent; performing vacuum pumping filtration on the bacterial cellulose pulp for membrane forming, adding the dispersing agent for continuous pumping filtration for membrane forming, and performing vacuum drying for finishing. The membrane material has low equipment corrosion, low cost, good cycle performance and good mechanical properties and can realize scale production, and a symmetrical supercapacitor prepared from the membrane material has the good capacitive character. The invention belongs to the technical field of nanomaterials.

Description

A kind of preparation method of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material and application thereof
Technical field
The present invention relates to preparation method and the application thereof of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material.
Background technology
Ultracapacitor combines the advantage of battery and conventional dielectric capacitor, and its energy density and power density have filled up the blank between battery and conventional dielectric capacitor.Material with carbon element has good cycle performance, high stability as the electrode material of ultracapacitor, and the hetero-atoms such as nitrogen, phosphorus, oxygen, sulphur that adulterate in material with carbon element effectively can improve chemical property and the material surface performance of material with carbon element.
Along with development that is flexible, flexible electronic device, exploitation has the important directions that the flexible electrode material bending stability has become current energy storage area research.But existing flexible electrode material complicated process of preparation, cost are high, do not possess good stability, cycle performance and mechanical property.Therefore, a Bian low cost, effectively, simple, 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 present invention will solve the problem not possessing good stability, cycle performance and mechanical property that existing method prepares flexible electrode material, provides preparation method and the application thereof of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material.
The preparation method of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present invention carries out according to the following steps:
One, bacteria cellulose is immersed in deionized water for ultrasonic washing, then in deionized water dispersed, then transfer to the stirring of refiner high speed, obtain bacteria cellulose slurry; By graphene oxide ultrasonic disperse in deionized water, graphene dispersing solution is obtained; In bacteria cellulose slurry, add graphene dispersing solution, limit edged stirs, and obtains mixed liquor A;
Two, get pyrrole monomer dispersion in deionized water, stir and make it be uniformly dispersed, mixed liquor A joined in pyrroles's dispersion liquid, limit edged stirs, and obtains mixed liquid B;
Three, oxidant is dissolved in deionized water, obtain oxidizing agent solution; Be added drop-wise to by oxidizing agent solution in mixed liquid B, in-situ oxidizing-polymerizing generates polypyrrole coated bacteria cellulose graphene composite material, filters, by solid formation freeze drying, and obtained presoma; By presoma as Pintsch process carbonization in tube furnace, obtain nitrogen-doped carbon fiber/nitrogen-doped graphene composite material; By nitrogen-doped carbon fiber/nitrogen-doped graphene composite material and surfactant ultrasonic disperse in deionized water, dispersion liquid C is obtained;
Four, bacteria cellulose is immersed in deionized water for ultrasonic washing, then in deionized water dispersed, transfer to refiner high-speed stirred again, obtain substrate bacteria cellulose slurry, by substrate bacteria cellulose slurry vacuum filtration film forming, then add dispersion liquid C and continue suction filtration film forming, then be placed in vacuum drying chamber and carry out drying, make nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material;
Wherein said oxidant is ammonium persulfate; In step 3, in nitrogen-doped carbon fiber/nitrogen-doped graphene composite material, the mass ratio of nitrogen-doped carbon fiber and nitrogen-doped graphene is (2 ~ 20): 1; The mol ratio of pyrrole monomer and oxidant is (0.2 ~ 6): 1; In nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that step 4 obtains, nitrogen-doped carbon fiber and the gross mass of nitrogen-doped graphene and the mass ratio of bacteria cellulose are (0.1 ~ 1): 1.
Bacteria cellulose is obtained by the fermentation of microbe, aboundresources, environmental friendliness, and it has hyperfine network structure, high water retention property and good biological degradability, in food industry, nano material, biology sensor, the fields such as photoelectric device obtain application.The loose structure of bacteria cellulose and containing a large amount of hydroxyls, can effectively and pyrrole monomer form hydrogen bond, prepare the covered fiber material of uniform in-situ polymerization.Bacteria cellulose has high-crystallinity, high-purity, high mechanical properties simultaneously.
Graphene has large specific area and very high conductivity, thus becomes the more promising electrode material of capacitor.
Nitrogen-doped carbon fiber/nitrogen-doped graphene/the application of bacteria cellulose membrane material of the present invention refers to and is applied in ultracapacitor.
Beneficial effect of the present invention:
1, bacteria cellulose aboundresources, with low cost, utilize its microstructure can prepare doping carbon fiber by direct carbonization, utilize graphene oxide better dispersed, load is on bacteria cellulose, high temperature makes graphene oxide be converted into reduced graphene, completes the carbon fiber and graphite alkene that a step prepares N doping simultaneously.Bacteria cellulose has excellent mechanical characteristic, Young's modulus can reach 10Mpa, after hot-pressing processing, Young's modulus can reach 30Mpa, as flexible substrates carrying active substance, obtained doping carbon graphite fiber alkene/bacteria cellulose flexible electrode material excellent in mechanical performance, can be prepared into ultracapacitor self-supporting flexible electrode;
2, the shortcoming that pure material with carbon element hydrophily is poor limits its application in ultracapacitor.The N hetero-atom that adulterates in carbon nanomaterial significantly can change the surface texture of material, strengthens its hydrophily, its pore passage structure of modulation, improve the electron transfer rate of material, significantly increases capacitance characteristic.Simultaneously after carbon fiber introducing hetero-atoms, can better and membrane material form hydrogen bond, cycle performance increase; Application nitrogen-doped carbon is after fiber/nitrogen-doped graphene/ultracapacitor made by bacteria cellulose membrane material, and after circulation 20000, specific capacity does not decline, and cycle performance is excellent.
3, preparation technology is simple, is produced on a large scale;
4, be directly used as electrode of super capacitor and there is good capacitive character.
Accompanying drawing explanation
The stereoscan photograph of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that Fig. 1 obtains for embodiment 1;
Cyclic voltammetry curve under the different scanning speed of the work electrode prepared with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that Fig. 2 obtains for embodiment 1 in 6M potassium hydroxide electrolyte; Wherein a is 20mV/s, b be 50mV/s, c is 100mV/s;
The work electrode prepared with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that Fig. 3 obtains for embodiment 1, is assembled into the cyclic voltammetry curve under the different scanning speed of symmetry ultracapacitor in 6M potassium hydroxide electrolyte; Wherein a is 20mV/s, b be 50mV/s, c is 100mV/s;
Fig. 4 is the bending property resolution chart of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that embodiment 1 obtains;
Cyclic voltammetry curve under the different scanning speed of the work electrode prepared with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that Fig. 5 obtains for embodiment 2 in 6M potassium hydroxide electrolyte; Wherein a is 20mV/s, b be 50mV/s, c is 100mV/s;
The work electrode prepared with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that Fig. 6 obtains for embodiment 2, is assembled into the cyclic voltammetry curve under the different scanning speed of symmetry ultracapacitor in 6M potassium hydroxide electrolyte; Wherein a is 20mV/s, b be 50mV/s, c is 100mV/s.
Embodiment
Embodiment one: the preparation method of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of present embodiment carries out according to the following steps:
One, bacteria cellulose is immersed in deionized water for ultrasonic washing, then in deionized water dispersed, then transfer to the stirring of refiner high speed, obtain bacteria cellulose slurry; By graphene oxide ultrasonic disperse in deionized water, graphene dispersing solution is obtained; In bacteria cellulose slurry, add graphene dispersing solution, limit edged stirs, and obtains mixed liquor A;
Two, get pyrrole monomer dispersion in deionized water, stir and make it be uniformly dispersed, mixed liquor A joined in pyrroles's dispersion liquid, limit edged stirs, and obtains mixed liquid B;
Three, oxidant is dissolved in deionized water, obtain oxidizing agent solution; Be added drop-wise to by oxidizing agent solution in mixed liquid B, in-situ oxidizing-polymerizing generates polypyrrole coated bacteria cellulose graphene composite material, filters, by solid formation freeze drying, and obtained presoma; By presoma as Pintsch process carbonization in tube furnace, obtain nitrogen-doped carbon fiber/nitrogen-doped graphene composite material; By nitrogen-doped carbon fiber/nitrogen-doped graphene composite material and surfactant ultrasonic disperse in deionized water, dispersion liquid C is obtained;
Four, bacteria cellulose is immersed in deionized water for ultrasonic washing, then in deionized water dispersed, transfer to refiner high-speed stirred again, obtain substrate bacteria cellulose slurry, by substrate bacteria cellulose slurry vacuum filtration film forming, then add dispersion liquid C and continue suction filtration film forming, then be placed in vacuum drying chamber and carry out drying, make nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material;
Wherein said oxidant is ammonium persulfate; In step 3, in nitrogen-doped carbon fiber/nitrogen-doped graphene composite material, the mass ratio of nitrogen-doped carbon fiber and nitrogen-doped graphene is (2 ~ 20): 1; The mol ratio of pyrrole monomer and oxidant is (0.2 ~ 6): 1; In nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that step 4 obtains, nitrogen-doped carbon fiber and the gross mass of nitrogen-doped graphene and the mass ratio of bacteria cellulose are (0.1 ~ 1): 1.
Present embodiment step one and the bacteria cellulose described in step 4 are bacteria cellulose bulk goods.
Bacteria cellulose is obtained by the fermentation of microbe, aboundresources, environmental friendliness, and it has hyperfine network structure, high water retention property and good biological degradability, in food industry, nano material, biology sensor, the fields such as photoelectric device obtain application.The loose structure of bacteria cellulose and containing a large amount of hydroxyls, can effectively and pyrrole monomer form hydrogen bond, prepare the covered fiber material of uniform in-situ polymerization.Bacteria cellulose has high-crystallinity, high-purity, high mechanical properties simultaneously.
Graphene has large specific area and very high conductivity, thus becomes the more promising electrode material of capacitor.
The beneficial effect of present embodiment:
1, bacteria cellulose aboundresources, with low cost, utilize its microstructure can prepare doping carbon fiber by direct carbonization, utilize graphene oxide better dispersed, load is on bacteria cellulose, high temperature makes graphene oxide be converted into reduced graphene, completes the carbon fiber and graphite alkene that a step prepares N doping simultaneously.Bacteria cellulose has excellent mechanical characteristic, Young's modulus can reach 10Mpa, after hot-pressing processing, Young's modulus can reach 30Mpa, as flexible substrates carrying active substance, obtained doping carbon graphite fiber alkene/bacteria cellulose flexible electrode material excellent in mechanical performance, can be prepared into ultracapacitor self-supporting flexible electrode;
2, the shortcoming that pure material with carbon element hydrophily is poor limits its application in ultracapacitor.The N hetero-atom that adulterates in carbon nanomaterial significantly can change the surface texture of material, strengthens its hydrophily, its pore passage structure of modulation, improve the electron transfer rate of material, significantly increases capacitance characteristic.Simultaneously after carbon fiber introducing hetero-atoms, can better and membrane material form hydrogen bond, cycle performance increase; Application nitrogen-doped carbon is after fiber/nitrogen-doped graphene/ultracapacitor made by bacteria cellulose membrane material, and after circulation 20000, specific capacity does not decline, and cycle performance is excellent.。
3, preparation technology is simple, is produced on a large scale;
4, be directly used as electrode of super capacitor and there is good capacitive character.
Embodiment two: present embodiment and embodiment one unlike: described ultrasonic power is 1000w, and frequency is 30KHz.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are ultrasonic time 1 ~ 10h unlike the condition of the supersound washing described in: step one and step 4.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the nitrogen-doped carbon fiber/nitrogen-doped graphene composite material described in step 3 and the mass ratio of surfactant are 1:(0.2 ~ 5).Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: described surfactant is lauryl sodium sulfate.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the described Pintsch process carbonization described in step 3 is cracking 1 ~ 4h under temperature is 600 ~ 900 DEG C of conditions.Other is identical for May Day with embodiment one to five.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the speed of the high-speed stirred described in step 4 is 8000 ~ 15000r/min, mixing time 3 ~ 30min.Other is identical with one of embodiment one to seven.
Embodiment nine: the fiber/nitrogen-doped graphene/application of bacteria cellulose membrane material of present embodiment nitrogen-doped carbon refers to and is applied in ultracapacitor.
Embodiment ten: present embodiment and embodiment nine to be applied in ultracapacitor or with this membrane material of two panels as negative material unlike: this membrane material and to be assembled into symmetry ultracapacitor.Other is identical with embodiment nine.
Beneficial effect of the present invention is verified by following examples:
Embodiment 1: the preparation method of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present embodiment carries out according to the following steps:
One, commercially available for 20g bacteria cellulose bulk goods is immersed in deionized water for ultrasonic washing 5h, then in deionized water dispersed, then transfer in refiner with the speed of 12000r/min stir 10min, obtain bacteria cellulose slurry; By 20mg graphene oxide ultrasonic disperse in deionized water, graphene dispersing solution is obtained; In bacteria cellulose slurry, add graphene dispersing solution, limit edged stirs, and obtains mixed liquor A;
Two, get the dispersion of 0.5mL pyrrole monomer in deionized water, stir and make it be uniformly dispersed, mixed liquor A joined in pyrroles's dispersion liquid, limit edged stirs, and obtains mixed liquid B;
Three, 1.68g ammonium persulfate is dissolved in deionized water, obtain ammonium persulfate solution; Be added drop-wise to by ammonium persulfate solution in mixed liquid B, in-situ oxidizing-polymerizing generates polypyrrole coated bacteria cellulose graphene composite material, filters, by solid formation freeze drying 6h, and obtained presoma; By presoma as in tube furnace at 900 DEG C of cracking carbonization 2h, obtain nitrogen-doped carbon fiber/nitrogen-doped graphene composite material; Get 0.04g nitrogen-doped carbon fiber/nitrogen-doped graphene composite material and 0.02g lauryl sodium sulfate ultrasonic disperse in deionized water, obtain dispersion liquid C;
Four, commercially available for 5g bacteria cellulose bulk goods is immersed in deionized water for ultrasonic washing 5h, then in deionized water dispersed, transfer to again in refiner and stir 10min with the speed of 12000r/min, obtain substrate bacteria cellulose slurry, by substrate bacteria cellulose slurry vacuum filtration film forming, then add dispersion liquid C and continue suction filtration film forming, then be placed in vacuum drying chamber and carry out drying, make nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material;
In the nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material obtained after step 4 vacuum filtration and vacuumize, the quality of bacteria cellulose substrate is 150mg.
Obtained nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is cut into 2cm × 1.5cm rectangle, 1, directly ultracapacitor work electrode is used as, platinized platinum is as to electrode, with mercury/mercuric oxide electrode for reference electrode, the capacitance characteristic of test self-supporting flexible membrane electrode material.Test specimens product are labeled as N-CNF-1.2, two panels 2cm × 1.5cm rectangle nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is assembled into symmetry ultracapacitor, tests the capacitance characteristic of flexible ultracapacitor.Test specimens product are labeled as D-N-CNF-1.
The membrane material that the present embodiment obtains is tested.Nitrogen-doped carbon fiber and Graphene are combined closely as seen from Figure 1, and dispersed.Demonstrating the scanning potential window of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that difference sweeps speed in Fig. 2 is-0.8 ~ 0.2V.Along with the increase of sweep speed, CV curve all has the shape of accurate rectangle, shows good high rate performance.Demonstrating the different potential window sweeping speed of symmetry ultracapacitor in Fig. 3 is 0 ~ 1V.
Comparative example: the preparation method of bacteria cellulose/activated carbon fiber/graphene film material is 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 lauryl sodium sulfate, 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 12000r/min, stir 5min, obtain bacteria cellulose slurry;
Four, in the Graphene of 10mg acidifying, add 10mg lauryl sodium sulfate, 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 300mg.
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.
The cycle performance of N-CNF-1 and BC-ACF-CN-1 is tested, 1, N-CNF-1 membrane material has better high rate performance, this is because Graphene bacteria cellulose and pyrroles's in-situ polymerization, nitrogen-doped carbon graphite fiber alkene disperseed more even.2, the carbon fiber doping introducing hetero-atoms of NP-CNF-1, make material and bacteria cellulose substrate form hydrogen bond, adhesion is better, has better cycle performance, specific capacity no change after circulation 20000 circle.And electrolyte has color to change after BC-ACF-CN-1 circulation 10000 circle, ratio capacitance has a small amount of decline, and illustrates that nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material prepared by the present embodiment has excellent cycle performance.3, use bacteria cellulose amount to decrease half in N-CNF-1, obtain thinner counterdie.4, N-CNF-1 has higher ratio capacitance, carries out cyclic voltammetry to material, and when 20mV/s sweep speed, specific capacitance improves 11%, by 171 to 190.
Embodiment 2: the preparation method of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present embodiment carries out according to the following steps:
One, commercially available for 20g bacteria cellulose bulk goods is immersed in deionized water for ultrasonic washing 5h, then in deionized water dispersed, then transfer in refiner with the speed of 12000r/min stir 10min, obtain bacteria cellulose slurry; By 30mg graphene oxide ultrasonic disperse in deionized water, graphene dispersing solution is obtained; In bacteria cellulose slurry, add graphene dispersing solution, limit edged stirs, and obtains mixed liquor A;
Two, get the dispersion of 0.3mL pyrrole monomer in deionized water, stir and make it be uniformly dispersed, mixed liquor A joined in pyrroles's dispersion liquid, limit edged stirs, and obtains mixed liquid B;
Three, 1g ammonium persulfate is dissolved in deionized water, obtain ammonium persulfate solution; Be added drop-wise to by ammonium persulfate solution in mixed liquid B, in-situ oxidizing-polymerizing generates polypyrrole coated bacteria cellulose graphene composite material, filters, by solid formation freeze drying 10h, and obtained presoma; By presoma as in tube furnace at 900 DEG C of cracking carbonization 2h, obtain nitrogen-doped carbon fiber/nitrogen-doped graphene composite material; Get 40mg nitrogen-doped carbon fiber/nitrogen-doped graphene composite material and 30mg lauryl sodium sulfate ultrasonic disperse in deionized water, obtain dispersion liquid C;
Four, commercially available for 5g bacteria cellulose bulk goods is immersed in deionized water for ultrasonic washing 5h, then in deionized water dispersed, transfer to again in refiner and stir 10min with the speed of 10000r/min, obtain substrate bacteria cellulose slurry, by substrate bacteria cellulose slurry vacuum filtration film forming, then add dispersion liquid C and continue suction filtration film forming, then be placed in vacuum drying chamber and carry out drying, make nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material;
In the nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material obtained after step 4 vacuum filtration and vacuumize, the quality of bacteria cellulose substrate is 150mg.
Nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is cut into 2cm × 1.5cm rectangle, 1, directly ultracapacitor work electrode is used as, 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 N-CNF-2.2, two panels 2cm × 1.5cm rectangle nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is assembled into symmetry ultracapacitor, tests the capacitance characteristic of flexible ultracapacitor.Test specimens product are labeled as D-N-CNF-2.
The scanning potential window demonstrating nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material in Fig. 5 is-0.8 ~ 0.2V.Along with the increase of sweep speed, CV curve all has the shape of accurate rectangle, shows good high rate performance.Demonstrating the different potential window sweeping speed of symmetry ultracapacitor in Fig. 6 is 0 ~ 1V.
Embodiment 1 ~ 2 utilizes the stable bond of bacteria cellulose and Graphene and hyperfine reticulated microstructure in-situ polymerization thereof to contain heteroatomic high polymer, direct carbonization prepares doping carbon graphite fiber alkene, netted loose structure is remained after carbonization, recycle material and the stable bond performance of material with carbon element and the mechanical characteristic of excellence simultaneously, as flexible substrates carrying active substance, be prepared into ultracapacitor self-supporting flexible electrode; Preparation technology is simple, is produced on a large scale; Directly be used as electrode of super capacitor and there is good capacitive character.

Claims (9)

1. a preparation method for nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material, is characterized in that the method is carried out according to the following steps:
One, bacteria cellulose is immersed in deionized water for ultrasonic washing, then in deionized water dispersed, then transfer to the stirring of refiner high speed, obtain bacteria cellulose slurry; By graphene oxide ultrasonic disperse in deionized water, graphene dispersing solution is obtained; In bacteria cellulose slurry, add graphene dispersing solution, limit edged stirs, and obtains mixed liquor A;
Two, get pyrrole monomer dispersion in deionized water, stir and make it be uniformly dispersed, mixed liquor A joined in pyrroles's dispersion liquid, limit edged stirs, and obtains mixed liquid B;
Three, oxidant is dissolved in deionized water, obtain oxidizing agent solution; Be added drop-wise to by oxidizing agent solution in mixed liquid B, in-situ oxidizing-polymerizing generates polypyrrole coated bacteria cellulose graphene composite material, filters, by solid formation freeze drying, and obtained presoma; By presoma as Pintsch process carbonization in tube furnace, obtain nitrogen-doped carbon fiber/nitrogen-doped graphene composite material; By nitrogen-doped carbon fiber/nitrogen-doped graphene composite material and surfactant ultrasonic disperse in deionized water, dispersion liquid C is obtained;
Four, bacteria cellulose is immersed in deionized water for ultrasonic washing, then in deionized water dispersed, transfer to refiner high-speed stirred again, obtain substrate bacteria cellulose slurry, by substrate bacteria cellulose slurry vacuum filtration film forming, then add dispersion liquid C and continue suction filtration film forming, then be placed in vacuum drying chamber and carry out drying, make nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material;
Wherein said oxidant is ammonium persulfate; In step 3, in nitrogen-doped carbon fiber/nitrogen-doped graphene composite material, the mass ratio of nitrogen-doped carbon fiber and nitrogen-doped graphene is (2 ~ 20): 1; The mol ratio of pyrrole monomer and oxidant is (0.2 ~ 6): 1; In nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that step 4 obtains, nitrogen-doped carbon fiber and the gross mass of nitrogen-doped graphene and the mass ratio of bacteria cellulose are (0.1 ~ 1): 1.
2. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1, it is characterized in that described ultrasonic frequency be ultrasonic power is 1000w, frequency is 30KHz.
3. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1, is characterized in that the condition of the supersound washing described in step one and step 4 is ultrasonic time 1 ~ 10h.
4. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1, is characterized in that the mass ratio of nitrogen-doped carbon fiber/nitrogen-doped graphene composite material described in step 3 and surfactant is 1:(0.2 ~ 5).
5. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 or 4, is characterized in that described surfactant is lauryl sodium sulfate.
6. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1, is characterized in that the described Pintsch process carbonization described in step 3 is cracking 1 ~ 4h under temperature is 600 ~ 900 DEG C of conditions.
7. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1, is characterized in that the speed of the high-speed stirred described in step 4 is 8000 ~ 15000r/min, mixing time 3 ~ 30min.
8. the application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that obtains of preparation method as claimed in claim 1, is characterized in that this membrane material is applied in ultracapacitor.
9. the application of a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 8, is characterized in that this membrane material is applied in ultracapacitor or with this membrane material of two panels as negative material and is assembled into symmetry ultracapacitor.
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