CN105355450B - A kind of preparation method and applications of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material - Google Patents

A kind of preparation method and applications of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Download PDF

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CN105355450B
CN105355450B CN201510990574.2A CN201510990574A CN105355450B CN 105355450 B CN105355450 B CN 105355450B CN 201510990574 A CN201510990574 A CN 201510990574A CN 105355450 B CN105355450 B CN 105355450B
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nitrogen
bacteria cellulose
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carbon fiber
graphene
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CN105355450A (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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Abstract

A kind of preparation method and applications of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material, the present invention relates to a kind of preparation method and applications of membrane material, do not possess the problem of good stability, cycle performance and mechanical property the present invention is to solve existing method preparation flexible electrode material, method is:Prepare bacteria cellulose slurry;Prepare bacteria cellulose graphene composite material, prepare polypyrrole coated bacteria cellulose graphene composite material, high temperature cabonization prepares nitrogen-doped carbon fiber/nitrogen-doped graphene composite, prepare nitrogen-doped carbon fiber/nitrogen-doped graphene dispersion liquid, bacteria cellulose slurry is filtered by vacuum film forming, then add dispersion liquid to continue to filter film forming, vacuum drying, that is, complete;The present invention is low to equipment corrosion, cost is low, is produced on a large scale, and membrane material cycle performance and mechanical property are good, and being prepared into symmetry ultracapacitor has good capacitive character.The invention belongs to technical field of nano material.

Description

A kind of preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Method and its application
Technical field
The present invention relates to a kind of preparation method of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material and It is applied.
Background technology
Ultracapacitor combines the advantage of battery and conventional dielectric capacitor, and its energy density and power density are filled up Blank between battery and conventional dielectric capacitor.Carbon material has good follow as the electrode material of ultracapacitor Ring performance, high stability, the hetero atom such as doping nitrogen, phosphorus, oxygen, sulphur can effectively improve the electrification of carbon material in carbon material Learn performance and material surface performance.
With the development of flexible, flexible electronic device, flexible electrode material of the exploitation with bending stability has turned into The important directions of energy storage area research at present.But existing flexible electrode material preparation technology is complicated, cost is high, does not possess good Stability, cycle performance and mechanical property.Therefore, using a low cost, it is effective, simple and environmentally-friendly, suitable for large-scale production Preparation method prepare high performance flexible electrode material and be even more important.
The content of the invention
The present invention is to solve existing method prepare flexible electrode material do not possess good stability, cycle performance and The problem of mechanical property, there is provided a kind of preparation method of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material and It is applied.
A kind of preparation method of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present invention is by following Step is carried out:
First, bacteria cellulose is soaked into supersound washing in deionized water, then it is dispersed in deionized water, then turn The stirring of refiner high speed is moved on to, obtains bacteria cellulose slurry;By graphene oxide ultrasonic disperse in deionized water, obtain Graphene dispersing solution;Graphene dispersing solution is added into bacteria cellulose slurry, it is stirring while adding, obtain mixed liquor A;
2nd, take pyrrole monomer scattered in deionized water, stirring makes it be uniformly dispersed, and mixed liquor A is added into pyrroles point It is stirring while adding in dispersion liquid, obtain mixed liquid B;
3rd, by oxidant dissolving in deionized water, oxidizing agent solution is obtained;Oxidizing agent solution is added drop-wise to mixed liquid B In, in-situ oxidizing-polymerizing generation polypyrrole coated bacteria cellulose graphene composite material, filtering, solid formation is freeze-dried, Presoma is made;Presoma is cracked as tube furnace high temperature and is carbonized, it is compound to obtain nitrogen-doped carbon fiber/nitrogen-doped graphene Material;By nitrogen-doped carbon fiber/nitrogen-doped graphene composite and surfactant ultrasonic disperse in deionized water, obtain Dispersion liquid C;
4th, bacteria cellulose is soaked into supersound washing in deionized water, then it is dispersed in deionized water, then turn Move on to refiner high-speed stirred, obtain substrate bacteria cellulose slurry, by substrate with bacteria cellulose slurry be filtered by vacuum into Film, then add dispersion liquid C and continue to filter film forming, then be placed in vacuum drying chamber and be dried, nitrogen-doped carbon fiber/nitrogen is made Doped graphene/bacteria cellulose membrane material;
Wherein described oxidant is ammonium persulfate;Nitrogen-doped carbon fiber/nitrogen-doped graphene composite in step 3 The mass ratio of middle 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;Nitrogen-doped carbon is fine in nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material made from step 4 The gross mass of peacekeeping nitrogen-doped graphene and the mass ratio of bacteria cellulose are (0.1~1):1.
Bacteria cellulose is obtained by the fermentation of microorganism, and aboundresources, environment-friendly, it has superfinishing fine mesh Structure, high water retention property and good biological degradability, led in food industry, nano material, biology sensor, photoelectric device etc. Applied in domain.The loose structure of bacteria cellulose and containing substantial amounts of hydroxyl, effectively can form hydrogen with pyrrole monomer Key, prepare the covered fiber material of uniform in-situ polymerization.Bacteria cellulose has high-crystallinity, high-purity, high machinery simultaneously Intensity.
Graphene has big specific surface area and very high electric conductivity, so as to turn into the more promising electrode material of capacitor Material.
The application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present invention refers to applied to super In capacitor.
Beneficial effects of the present invention:
1st, bacteria cellulose aboundresources, cost are cheap, using its microstructure can direct carbonization prepare doping carbon fiber, It is preferably dispersed using graphene oxide, it is supported on bacteria cellulose, high temperature causes graphene oxide to be converted into reduction graphite Alkene, while complete the carbon fiber and graphite alkene that a step prepares N doping.Bacteria cellulose has excellent mechanical characteristic, Young mould Amount is up to 10Mpa, and after hot-pressing processing, Young's modulus is obtained as flexible substrates carrying active substance up to 30Mpa Carbon fiber and graphite alkene/bacteria cellulose flexible electrode material excellent in mechanical performance is adulterated, ultracapacitor can be prepared into and used from branch Support flexible electrode;
2nd, the shortcomings that pure carbon material hydrophily is poor limits its application in ultracapacitor.In carbon nanomaterial Doping N hetero atoms can significantly change the surface texture of material, strengthen its hydrophily, modulation its pore passage structure, improve material Electron transfer rate, dramatically increase capacitance characteristic.Simultaneously after carbon fiber introducing hetero-atoms, can preferably with membrane material shape Into hydrogen bond, cycle performance increase;Super electricity is made using nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material After container, after the circle of circulation 20000, specific capacity does not decline, and cycle performance is excellent.
3rd, preparation technology is simple, is produced on a large scale;
4th, being directly used as electrode of super capacitor has good capacitive character.
Brief description of the drawings
The scanning for nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that Fig. 1 is obtained by embodiment 1 Electromicroscopic photograph;
Fig. 2 is prepared by what embodiment 1 obtained with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Different scanning speed of the working electrode in 6M potassium hydroxide electrolytes under cyclic voltammetry curve;Wherein a is 20mV/s, b For 50mV/s, c 100mV/s;
Fig. 3 is prepared by what embodiment 1 obtained with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Working electrode, be assembled under different scanning speed of the symmetry ultracapacitor in 6M potassium hydroxide electrolytes circulation volt Pacify curve;Wherein a is 20mV/s, b 50mV/s, c 100mV/s;
Fig. 4 is the bendability of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material made from embodiment 1 Can test chart;
Fig. 5 is prepared by what embodiment 2 obtained with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Different scanning speed of the working electrode in 6M potassium hydroxide electrolytes under cyclic voltammetry curve;Wherein a is 20mV/s, b For 50mV/s, c 100mV/s;
Fig. 6 is prepared by what embodiment 2 obtained with nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Working electrode, be assembled under different scanning speed of the symmetry ultracapacitor in 6M potassium hydroxide electrolytes circulation volt Pacify curve;Wherein a is 20mV/s, b 50mV/s, c 100mV/s.
Embodiment
Embodiment one:A kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of present embodiment The preparation method of material is carried out according to the following steps:
First, bacteria cellulose is soaked into supersound washing in deionized water, then it is dispersed in deionized water, then turn The stirring of refiner high speed is moved on to, obtains bacteria cellulose slurry;By graphene oxide ultrasonic disperse in deionized water, obtain Graphene dispersing solution;Graphene dispersing solution is added into bacteria cellulose slurry, it is stirring while adding, obtain mixed liquor A;
2nd, take pyrrole monomer scattered in deionized water, stirring makes it be uniformly dispersed, and mixed liquor A is added into pyrroles point It is stirring while adding in dispersion liquid, obtain mixed liquid B;
3rd, by oxidant dissolving in deionized water, oxidizing agent solution is obtained;Oxidizing agent solution is added drop-wise to mixed liquid B In, in-situ oxidizing-polymerizing generation polypyrrole coated bacteria cellulose graphene composite material, filtering, solid formation is freeze-dried, Presoma is made;Presoma is cracked as tube furnace high temperature and is carbonized, it is compound to obtain nitrogen-doped carbon fiber/nitrogen-doped graphene Material;By nitrogen-doped carbon fiber/nitrogen-doped graphene composite and surfactant ultrasonic disperse in deionized water, obtain Dispersion liquid C;
4th, bacteria cellulose is soaked into supersound washing in deionized water, then it is dispersed in deionized water, then turn Move on to refiner high-speed stirred, obtain substrate bacteria cellulose slurry, by substrate with bacteria cellulose slurry be filtered by vacuum into Film, then add dispersion liquid C and continue to filter film forming, then be placed in vacuum drying chamber and be dried, nitrogen-doped carbon fiber/nitrogen is made Doped graphene/bacteria cellulose membrane material;
Wherein described oxidant is ammonium persulfate;Nitrogen-doped carbon fiber/nitrogen-doped graphene composite in step 3 The mass ratio of middle 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;Nitrogen-doped carbon is fine in nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material made from step 4 The gross mass of peacekeeping nitrogen-doped graphene and the mass ratio of bacteria cellulose are (0.1~1):1.
Bacteria cellulose described in present embodiment step 1 and step 4 is bacteria cellulose bulk goods.
Bacteria cellulose is obtained by the fermentation of microorganism, and aboundresources, environment-friendly, it has superfinishing fine mesh Structure, high water retention property and good biological degradability, led in food industry, nano material, biology sensor, photoelectric device etc. Applied in domain.The loose structure of bacteria cellulose and containing substantial amounts of hydroxyl, effectively can form hydrogen with pyrrole monomer Key, prepare the covered fiber material of uniform in-situ polymerization.Bacteria cellulose has high-crystallinity, high-purity, high machinery simultaneously Intensity.
Graphene has big specific surface area and very high electric conductivity, so as to turn into the more promising electrode material of capacitor Material.
The beneficial effect of present embodiment:
1st, bacteria cellulose aboundresources, cost are cheap, using its microstructure can direct carbonization prepare doping carbon fiber, It is preferably dispersed using graphene oxide, it is supported on bacteria cellulose, high temperature causes graphene oxide to be converted into reduction graphite Alkene, while complete the carbon fiber and graphite alkene that a step prepares N doping.Bacteria cellulose has excellent mechanical characteristic, Young mould Amount is up to 10Mpa, and after hot-pressing processing, Young's modulus is obtained as flexible substrates carrying active substance up to 30Mpa Carbon fiber and graphite alkene/bacteria cellulose flexible electrode material excellent in mechanical performance is adulterated, ultracapacitor can be prepared into and used from branch Support flexible electrode;
2nd, the shortcomings that pure carbon material hydrophily is poor limits its application in ultracapacitor.In carbon nanomaterial Doping N hetero atoms can significantly change the surface texture of material, strengthen its hydrophily, modulation its pore passage structure, improve material Electron transfer rate, dramatically increase capacitance characteristic.Simultaneously after carbon fiber introducing hetero-atoms, can preferably with membrane material shape Into hydrogen bond, cycle performance increase;Super electricity is made using nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material After container, after the circle of circulation 20000, specific capacity does not decline, and cycle performance is excellent..
3rd, preparation technology is simple, is produced on a large scale;
4th, being directly used as electrode of super capacitor has good capacitive character.
Embodiment two:Present embodiment is unlike embodiment one:Described ultrasonic power is 1000w, frequency are 30KHz.It is other identical with embodiment one.
Embodiment three:Present embodiment is unlike embodiment one or two:Step 1 and step 4 The condition of described supersound washing is 1~10h of ultrasonic time.It is other identical with embodiment one or two.
Embodiment four:Unlike one of present embodiment and embodiment one to three:Described in step 3 Nitrogen-doped carbon fiber/nitrogen-doped graphene composite and surfactant mass ratio be 1:(0.2~5).Other and tool One of body embodiment one to three is identical.
Embodiment five:Unlike one of present embodiment and embodiment one to four:Described surface Activating agent is lauryl sodium sulfate.It is other identical with one of embodiment one to four.
Embodiment six:Unlike one of present embodiment and embodiment one to five:Described in step 3 Described Pintsch process carbonization be 600~900 DEG C in temperature under the conditions of crack 1~4h.Other and embodiment one It is identical to five May Day.
Embodiment eight:Unlike one of present embodiment and embodiment one to seven:Described in step 4 The speed of high-speed stirred be 8000~15000r/min, 3~30min of mixing time.Other and embodiment one to seven One of it is identical.
Embodiment nine:Present embodiment nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material Using refer to be applied to ultracapacitor in.
Embodiment ten:Present embodiment is unlike embodiment nine:The membrane material is as negative pole material Material is applied in ultracapacitor or the membrane material is assembled into symmetry ultracapacitor with two panels.Other and specific embodiment party Formula nine is identical.
Beneficial effects of the present invention are verified by following examples:
Embodiment 1:A kind of preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present embodiment Method is carried out according to the following steps:
First, the commercially available bacteria cellulose bulk goodses of 20g are soaked into supersound washing 5h in deionized water, be then dispersed in In deionized water, it is then transferred in refiner and 10min is stirred with 12000r/min speed, obtain bacteria cellulose slurry;Will 20mg graphene oxides ultrasonic disperse in deionized water, obtains graphene dispersing solution;Stone is added into bacteria cellulose slurry Black alkene dispersion liquid, it is stirring while adding, obtain mixed liquor A;
2nd, take 0.5mL pyrrole monomers scattered in deionized water, stirring makes it be uniformly dispersed, and mixed liquor A is added into pyrrole Cough up in dispersion liquid, it is stirring while adding, obtain mixed liquid B;
3rd, by the dissolving of 1.68g ammonium persulfates in deionized water, ammonium persulfate solution is obtained;Ammonium persulfate solution is dripped It is added in mixed liquid B, in-situ oxidizing-polymerizing generation polypyrrole coated bacteria cellulose graphene composite material, filtering, by solid phase Thing is freeze-dried 6h, and presoma is made;By presoma as fine in 900 DEG C of cracking carbonization 2h, acquisition nitrogen-doped carbon in tube furnace Dimension/nitrogen-doped graphene composite;Take 0.04g nitrogen-doped carbons fiber/nitrogen-doped graphene composite and 0.02g dodecanes Base sodium sulphate ultrasonic disperse in deionized water, obtains dispersion liquid C;
4th, the commercially available bacteria cellulose bulk goodses of 5g are soaked into supersound washing 5h in deionized water, be then dispersed in In deionized water, it is then transferred in refiner and 10min is stirred with 12000r/min speed, obtain substrate and starched with bacteria cellulose Material, substrate is filtered by vacuum film forming with bacteria cellulose slurry, then adds dispersion liquid C and continue to filter film forming, then be placed in vacuum It is dried in drying box, nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is made;
Nitrogen-doped carbon fiber/the nitrogen-doped graphene obtained after step 4 is filtered by vacuum and is dried in vacuo/bacterium is fine The quality for tieing up bacteria cellulose substrate in plain membrane material is 150mg.
Obtained nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose film material cutting is grown into 2cm × 1.5cm It is square, 1, be directly used as ultracapacitor working electrode, platinized platinum is used as to electrode, using mercury/mercuric oxide electrode as reference electrode, is surveyed Try the capacitance characteristic of self-supporting flexible membrane electrode material.Test sample is labeled as N-CNF-1.2nd, it is two panels 2cm × 1.5cm is rectangular Shape nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is assembled into symmetry ultracapacitor, and test is flexible The capacitance characteristic of ultracapacitor.Test sample is labeled as D-N-CNF-1.
The membrane material obtained to the present embodiment is tested.Nitrogen-doped carbon fiber and graphene are tight as seen from Figure 1 Close combination, and it is dispersed.The different nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose films for sweeping speed are shown in Fig. 2 The scanning potential window of material is -0.8~0.2V.With the increase of sweep speed, CV curves are respectively provided with quasi- rectangular shape, show Preferable high rate performance is shown.Show that the potential window that symmetry ultracapacitor difference sweeps speed is 0~1V in Fig. 3.
Comparative example:The preparation method of bacteria cellulose/activated carbon fiber/graphene film material is as follows:
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 dodecyl sulphates is then added into 50mg activated carbon fibers 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 12000r/min's Speed, 5min is stirred, obtains bacteria cellulose slurry;
4th, 10mg lauryl sodium sulfate is added in the graphene being acidified to 10mg, is then dispersed in deionized water, obtains To graphene dispersing solution;Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fine Dimension 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 300mg.
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.
N-CNF-1 and BC-ACF-CN-1 cycle performance are tested, 1, N-CNF-1 membrane materials have preferably times Rate performance, because graphene bacteria cellulose and pyrroles's in-situ polymerization so that nitrogen-doped carbon graphite fiber alkene is scattered more Uniformly.2nd, NP-CNF-1 carbon fiber doping introducing hetero-atoms so that material forms hydrogen bond, adhesion with bacteria cellulose substrate More preferably, there is more preferably cycle performance, specific capacity does not change after circulating 20000 circles.And after the circle of BC-ACF-CN-1 circulations 10000 Electrolyte has color change, and specific capacitance has a small amount of decline, and illustrates nitrogen-doped carbon fiber/N doping stone manufactured in the present embodiment Black alkene/bacteria cellulose membrane material has excellent cycle performance.3rd, one is reduced using bacteria cellulose amount in N-CNF-1 Half, obtain thinner counterdie.4th, N-CNF-1 has higher specific capacitance, carries out cyclic voltammetry to material, is swept in 20mV/s When retouching speed, specific capacitance improves 11%, by 171F/g to 190F/g.
Embodiment 2:A kind of preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material of the present embodiment Method is carried out according to the following steps:
First, the commercially available bacteria cellulose bulk goodses of 20g are soaked into supersound washing 5h in deionized water, be then dispersed in In deionized water, it is then transferred in refiner and 10min is stirred with 12000r/min speed, obtain bacteria cellulose slurry;Will 30mg graphene oxides ultrasonic disperse in deionized water, obtains graphene dispersing solution;Stone is added into bacteria cellulose slurry Black alkene dispersion liquid, it is stirring while adding, obtain mixed liquor A;
2nd, take 0.3mL pyrrole monomers scattered in deionized water, stirring makes it be uniformly dispersed, and mixed liquor A is added into pyrrole Cough up in dispersion liquid, it is stirring while adding, obtain mixed liquid B;
3rd, by the dissolving of 1g ammonium persulfates in deionized water, ammonium persulfate solution is obtained;Ammonium persulfate solution is added drop-wise to In mixed liquid B, in-situ oxidizing-polymerizing generation polypyrrole coated bacteria cellulose graphene composite material, filter, solid formation is cold Dry 10h is freezed, presoma is made;By presoma as in 900 DEG C of cracking carbonization 2h, obtained in tube furnace nitrogen-doped carbon fiber/ Nitrogen-doped graphene composite;Take 40mg nitrogen-doped carbons fiber/nitrogen-doped graphene composite and 30mg dodecyl sulphur Sour sodium ultrasonic disperse in deionized water, obtains dispersion liquid C;
4th, the commercially available bacteria cellulose bulk goodses of 5g are soaked into supersound washing 5h in deionized water, be then dispersed in In deionized water, it is then transferred in refiner and 10min is stirred with 10000r/min speed, obtain substrate and starched with bacteria cellulose Material, substrate is filtered by vacuum film forming with bacteria cellulose slurry, then adds dispersion liquid C and continue to filter film forming, then be placed in vacuum It is dried in drying box, nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is made;
Nitrogen-doped carbon fiber/the nitrogen-doped graphene obtained after step 4 is filtered by vacuum and is dried in vacuo/bacterium is fine The quality for tieing up bacteria cellulose substrate in plain membrane material is 150mg.
By nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose film material cutting into 2cm × 1.5cm rectangles, 1, Ultracapacitor working electrode is directly used as, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test is propped up certainly Support the capacitance characteristic of flexible membrane material electrode material.Test sample is labeled as N-CNF-2.2nd, by two panels 2cm × 1.5cm rectangle nitrogen Doping carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is assembled into symmetry ultracapacitor, and test is flexible super The capacitance characteristic of capacitor.Test sample is labeled as D-N-CNF-2.
The scanning potential window of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material is shown in Fig. 5 For -0.8~0.2V.With the increase of sweep speed, CV curves are respectively provided with quasi- rectangular shape, it is shown that preferably forthright again Energy.Show that the potential window that symmetry ultracapacitor difference sweeps speed is 0~1V in Fig. 6.
Embodiment 1~2 is in situ using bacteria cellulose and the stable bond of graphene and its hyperfine reticulated microstructure Polymerization contains heteroatomic high polymer, and direct carbonization prepares doping carbon fiber and graphite alkene, netted porous knot is remained after carbonization Structure, while the stable bond performance of material and carbon material and excellent mechanical characteristic are recycled, load and live as flexible substrates Property material, is prepared into ultracapacitor self-supporting flexible electrode;Preparation technology is simple, is produced on a large scale;Directly it is used as super Level electrode for capacitors has good capacitive character.

Claims (9)

  1. A kind of 1. preparation method of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material, it is characterised in that the party Method is carried out according to the following steps:
    First, by bacteria cellulose soak supersound washing in deionized water, then it is dispersed in deionized water, be then transferred to Refiner high speed stirs, and obtains bacteria cellulose slurry;By graphene oxide ultrasonic disperse in deionized water, aoxidized Graphene dispersing solution;Graphene oxide dispersion is added into bacteria cellulose slurry, it is stirring while adding, obtain mixed liquor A;
    2nd, take pyrrole monomer scattered in deionized water, stirring makes it be uniformly dispersed, and mixed liquor A is added into pyrroles's dispersion liquid In, it is stirring while adding, obtain mixed liquid B;
    3rd, by oxidant dissolving in deionized water, oxidizing agent solution is obtained;Oxidizing agent solution is added drop-wise in mixed liquid B, it is former Position oxidation polymerization generation polypyrrole coated bacteria cellulose oxidation graphene composite material, filtering, solid formation is freeze-dried, made Obtain presoma;Presoma is placed in the cracking carbonization of tube furnace high temperature, obtains nitrogen-doped carbon fiber/nitrogen-doped graphene composite wood Material;By nitrogen-doped carbon fiber/nitrogen-doped graphene composite and surfactant ultrasonic disperse in deionized water, divided Dispersion liquid C;
    4th, by bacteria cellulose soak supersound washing in deionized water, then it is dispersed in deionized water, be then transferred to Refiner high-speed stirred, substrate bacteria cellulose slurry is obtained, substrate is filtered by vacuum film forming with bacteria cellulose slurry, so Dispersion liquid C is added afterwards to continue to filter film forming, then is placed in vacuum drying chamber and is dried, and nitrogen-doped carbon fiber/N doping is made Graphene/bacteria cellulose membrane material;
    Wherein described oxidant is ammonium persulfate;Nitrogen in nitrogen-doped carbon fiber/nitrogen-doped graphene composite in step 3 The mass ratio for adulterating carbon fiber and nitrogen-doped graphene is (2~20):1;The mol ratio of pyrrole monomer and oxidant for (0.2~ 6):1;Nitrogen-doped carbon fiber and nitrogen in nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material made from step 4 The gross mass of doped graphene and the mass ratio of bacteria cellulose are (0.1~1):1.
  2. A kind of 2. preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 Method, it is characterised in that described ultrasonic power is 1000w, and frequency is 30KHz.
  3. A kind of 3. preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 Method, it is characterised in that the condition of the supersound washing described in step 1 and step 4 is 1~10h of ultrasonic time.
  4. A kind of 4. preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 Method, it is characterised in that the matter of nitrogen-doped carbon fiber/nitrogen-doped graphene composite and surfactant described in step 3 Amount is than being 1:(0.2~5).
  5. 5. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 or 4 Preparation method, it is characterised in that described surfactant is lauryl sodium sulfate.
  6. A kind of 6. preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 Method, it is characterised in that the Pintsch process carbonization described in step 3 is to crack 1~4h under the conditions of temperature is 600~900 DEG C.
  7. A kind of 7. preparation of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 1 Method, it is characterised in that the speed of the high-speed stirred described in step 4 is 8000~15000r/min, 3~30min of mixing time.
  8. 8. nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material that preparation method as claimed in claim 1 obtains The application of material, it is characterised in that the membrane material is applied in ultracapacitor.
  9. 9. a kind of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material according to claim 8 is answered It is applied to, it is characterised in that the membrane material as negative material in ultracapacitor or is assembled into pair with the two panels membrane material Title property ultracapacitor.
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