CN105609324A - Preparation method and application of N-P-dopted carbon fiber/graphene/bacterial cellulose conducting film material - Google Patents
Preparation method and application of N-P-dopted carbon fiber/graphene/bacterial cellulose conducting film material Download PDFInfo
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- CN105609324A CN105609324A CN201510990816.8A CN201510990816A CN105609324A CN 105609324 A CN105609324 A CN 105609324A CN 201510990816 A CN201510990816 A CN 201510990816A CN 105609324 A CN105609324 A CN 105609324A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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 N-P-dopted carbon fiber/graphene/bacterial cellulose conducting film material. The invention relates to a preparation method and application of a flexible electrode material and aims to solve the problem that a conducting film material prepared according to the existing method has poor stability, cycling performance and mechanical property. The preparation method disclosed by the invention comprises the following steps: preparing bacterial cellulose pulp; preparing N-P-dopted carbon fiber; preparing N-P-dopted carbon fiber/graphene composite dispersion liquid; carrying out vacuum filtering on bacterial cellulose pulp to form a film; and then adding the N-P-dopted carbon fiber/graphene composite dispersion liquid and further carrying out vacuum filtration to form a film; and finally drying in vacuum. The N-P-dopted carbon fiber/graphene/bacterial cellulose conducting film material is applied to a supercapacitor. The N-P-dopted carbon fiber/graphene/bacterial cellulose conducting film material can load high active matter mass in unit area, can be synthesized simply, has controllable electrical conductivity and good rate capability, can be put into large-scale production and can be used for preparing a symmetric supercapacitor with high capacitive character. The invention belongs to the technical field of nanomaterial.
Description
Technical field
The present invention relates to a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material preparation method andApplication.
Background technology
Ultracapacitor combines the advantage of battery and conventional dielectric capacitor, and its energy density and power density have been filled up electricityBlank between pond and conventional dielectric capacitor. Material with carbon element has good cyclicity as the electrode material of ultracapacitorCan, high stability, the hetero atoms such as nitrogen, phosphorus, oxygen, sulphur that adulterate in carbon fiber can effectively improve the electrification of carbon fiberLearn performance and material surface performance.
Along with development flexible, flexible electronic device, the flexible electrode material that exploitation has bending stability has become at presentThe important directions of energy storage area research. But existing flexible electrode material complicated process of preparation, cost are high, do not possess good steadyQualitative, cycle performance and mechanical property. Therefore, a low cost for Bian, effectively, simple, environmental protection, be applicable to scaleThe preparation method who produces prepares high performance flexible electrode material and is even more important.
Summary of the invention
The present invention be to solve that existing method prepares flexible electrode material do not possess good stability, cycle performance and mechanicsThe problem of performance, provide a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material preparation method andApplication.
The preparation method of a kind of nitrogen phosphorus doping of the present invention carbon fiber/graphite alkene/bacteria cellulose flexible electrode material, by following stepSuddenly carry out:
One, bacteria cellulose is immersed in to deionized water for ultrasonic washing, is then dispersed in deionized water, then shiftsStir to refiner high speed, obtain substrate bacteria cellulose slurry;
Two, separately get bacteria cellulose and be immersed in deionized water for ultrasonic washing, freeze drying, obtains dry bacteria cellulose;Dry bacteria cellulose is immersed in dopant solution, and ultrasonic processing after stirring, then freeze drying, obtain bacterial fibersElement presoma, is placed in the carbonization of tube furnace Pintsch process by bacteria cellulose presoma, obtains the carbon fiber of nitrogen phosphorus doping; ItsMiddle dopant solution is the mixed solution of urea and ammonium dihydrogen phosphate (ADP);
Three, the carbon fiber of nitrogen phosphorus doping is mixed with Graphene, then add surfactant, be dispersed in deionized water, superAfter sonication, transfer to refiner high speed and stir, obtain homodisperse nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquid;
Four, by bacteria cellulose slurry vacuum filtration film forming for substrate, then add nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquidContinue suction filtration film forming, then be placed in vacuum drying chamber and be dried, make nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria celluloseFlexible electrode material;
Wherein nitrogen phosphorus doping carbon fiber and Graphene in nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialMass ratio be (20～2): 1; Nitrogen phosphorus doping carbon in nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialThe mass ratio of fiber and bacteria cellulose substrate is (0.1～1): 1; Dry bacteria cellulose and the matter of urea in step 2Amount is than being (0.3～10): 1; Dry bacteria cellulose and the mass ratio of ammonium dihydrogen phosphate (ADP) are (0.3～10): 1.
The application of doping carbon fiber/Graphene/bacteria cellulose flexible electrode material of the present invention refers to and is applied to ultracapacitorIn.
Bacteria cellulose is to obtain by the fermentation of microorganism, aboundresources, environmental friendliness, and it has hyperfine netted knotStructure, Pintsch process can retain the carbon skeleton network structure of porous. Bacteria cellulose contains a large amount of hydroxyls, has goodHydrophily, the loose structure of its microcosmic makes it have high-strength absorbing simultaneously, can absorb in a large number and contain other heteroatomic waterSolution, the carbon fiber of Pintsch process preparation doping. Bacteria cellulose has high-crystallinity, high-purity, high mechanical properties, doesFor flexible substrates has good mechanical property and stability, bacteria cellulose and material with carbon element have good associativity simultaneously. StoneChina ink alkene has very high electric conductivity, can further improve the electric conductivity of flexible electrode material.
Beneficial effect of the present invention:
1, bacteria cellulose aboundresources, with low cost, utilizes its microstructure to prepare doping carbon fiber by direct carbonization.Bacteria cellulose has excellent mechanical characteristic, and Young's modulus can reach 10Mpa, and after hot-pressing processing, Young's modulus can reach30Mpa, as flexible substrates carrying active substance, the doping carbon fiber/Graphene/bacteria cellulose flexible electrode makingMaterial mechanical performance excellence, can be prepared into ultracapacitor self-supporting flexible electrode;
2, after carbon fiber introducing hetero-atoms, can be better and membrane material form hydrogen bond, cycle performance increases; Application is mixedAssorted carbon fiber/graphite alkene/bacteria cellulose flexible electrode material is made ultracapacitor, after circulation 20000 circles, and specific capacityAlmost do not decline, cycle performance excellence.
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.
Brief description of the drawings
The scanning electricity of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material that Fig. 1 obtains for embodiment 1Mirror photo;
Fig. 2 is preparing with nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material that embodiment 1 obtainsCyclic voltammetry curve under the different scanning speed of working electrode in 6M potassium hydroxide electrolyte; Wherein a is 20mV/s,B is 50mV/s, and c is 100mV/s;
Fig. 3 is preparing with nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material that embodiment 1 obtainsWorking electrode, is assembled into the circulation volt under the different scanning speed of symmetry ultracapacitor in 6M potassium hydroxide electrolytePeace curve; Wherein a is 20mV/s, and b is 50mV/s, and c is 100mV/s.
Fig. 4 is the bending property of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material of making of embodiment 1Resolution chart;
Fig. 5 is preparing with nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material that embodiment 2 obtainsCyclic voltammetry curve under the different scanning speed of working electrode in 6M potassium hydroxide electrolyte; Wherein a is 20mV/s,B is 50mV/s, and c is 100mV/s;
Fig. 6 is preparing with nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material that embodiment 2 obtainsWorking electrode, is assembled into the circulation volt under the different scanning speed of symmetry ultracapacitor in 6M potassium hydroxide electrolytePeace curve; Wherein a is 20mV/s, and b is 50mV/s, and c is 100mV/s.
Detailed description of the invention
Detailed description of the invention one: a kind of nitrogen phosphorus doping of present embodiment carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialPreparation method, carry out according to the following steps:
One, bacteria cellulose is immersed in to deionized water for ultrasonic washing, is then dispersed in deionized water, then shiftsStir to refiner high speed, obtain substrate bacteria cellulose slurry;
Two, separately get bacteria cellulose and be immersed in deionized water for ultrasonic washing, freeze drying, obtains dry bacteria cellulose;Dry bacteria cellulose is immersed in dopant solution, and ultrasonic processing after stirring, then freeze drying, obtain bacterial fibersElement presoma, is placed in the carbonization of tube furnace Pintsch process by bacteria cellulose presoma, obtains the carbon fiber of nitrogen phosphorus doping; ItsMiddle dopant solution is the mixed solution of urea and ammonium dihydrogen phosphate (ADP);
Three, the carbon fiber of nitrogen phosphorus doping is mixed with Graphene, then add surfactant, be dispersed in deionized water, superAfter sonication, transfer to refiner high speed and stir, obtain homodisperse nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquid;
Four, by bacteria cellulose slurry vacuum filtration film forming for substrate, then add nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquidContinue suction filtration film forming, then be placed in vacuum drying chamber and be dried, make nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria celluloseFlexible electrode material;
Wherein nitrogen phosphorus doping carbon fiber and Graphene in nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialMass ratio be (20～2): 1; Nitrogen phosphorus doping carbon in nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialThe mass ratio of fiber and bacteria cellulose substrate is (0.1～1): 1; Dry bacteria cellulose and the matter of urea in step 2Amount is than being (0.3～10): 1; Dry bacteria cellulose and the mass ratio of ammonium dihydrogen phosphate (ADP) are (0.3～10): 1.
Bacteria cellulose is to obtain by the fermentation of microorganism, aboundresources, environmental friendliness, and it has hyperfine netted knotStructure, Pintsch process can retain the carbon skeleton network structure of porous. Bacteria cellulose contains a large amount of hydroxyls, has goodHydrophily, the loose structure of its microcosmic makes it have high-strength absorbing simultaneously, can absorb in a large number and contain other heteroatomic waterSolution, the carbon fiber of Pintsch process preparation doping. Bacteria cellulose has high-crystallinity, high-purity, high mechanical properties, doesFor flexible substrates has good mechanical property and stability, bacteria cellulose and material with carbon element have good associativity simultaneously. StoneChina ink alkene has very high electric conductivity, can further improve the electric conductivity of flexible electrode material.
Bacteria cellulose described in present embodiment step 1 and step 2 is bacteria cellulose bulk goods or membrane material.
The beneficial effect of present embodiment:
1, bacteria cellulose aboundresources, with low cost, utilizes its microstructure to prepare doping carbon fiber by direct carbonization.Bacteria cellulose has excellent mechanical characteristic, and Young's modulus can reach 10Mpa, and after hot-pressing processing, Young's modulus can reach30Mpa, as flexible substrates carrying active substance, the doping carbon fiber/Graphene/bacteria cellulose flexible electrode makingMaterial mechanical performance excellence, can be prepared into ultracapacitor self-supporting flexible electrode;
2, after carbon fiber introducing hetero-atoms, can be better and membrane material form hydrogen bond, cycle performance increases; Application is mixedAssorted carbon fiber/graphite alkene/bacteria cellulose flexible electrode material is made ultracapacitor, after circulation 20000 circles, and specific capacityAlmost do not decline, cycle performance excellence.
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.
Detailed description of the invention two: present embodiment is different from detailed description of the invention one: described ultrasonic power is1000w, frequency is 30KHz. Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is different from detailed description of the invention one or two: ultrasonic the washing described in step 1The condition of washing is ultrasonic time 1～10h. Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is different from one of detailed description of the invention one to three: the height described in step 2The carbonization of anneal crack solution is to be to react 1～4h under 600～900 DEG C of conditions in temperature. Other and one of detailed description of the invention one to three phaseWith.
Detailed description of the invention five: present embodiment is different from one of detailed description of the invention one to four: the stone described in step 3The mass ratio of China ink alkene and surfactant is 1:(0.2～5). Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is different from one of detailed description of the invention one to five: the table described in step 3Surface-active agent is lauryl sodium sulfate. Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment is different from one of detailed description of the invention one to six: step 1 and step 3The speed of described high-speed stirred is 8000～15000r/min, mixing time 3-30min. Other and detailed description of the invention oneTo one of six identical.
Detailed description of the invention eight: present embodiment is different from one of detailed description of the invention one to seven: stirring described in step 2Mixing rear ultrasonic processing refers to and stirs ultrasonic processing 0.5h after 1～2h. Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment is different from one of detailed description of the invention one to eight: ultrasonic place in step 3The time of reason is 2h. Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material shouldBe applied in ultracapacitor with referring to.
Detailed description of the invention 11: present embodiment is different from detailed description of the invention ten: this flexible electrode material is as negativeUtmost point material is applied in ultracapacitor or with two these flexible electrode material and is assembled into symmetry ultracapacitor. Other withDetailed description of the invention ten is identical.
Verify beneficial effect of the present invention by following examples:
Embodiment 1: the preparation side of a kind of nitrogen phosphorus doping of the present embodiment carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialMethod, carry out according to the following steps:
One, commercially available 5g bacteria cellulose bulk goods is immersed in to deionized water for ultrasonic washing 5h deacidification, then dispersedIn deionized water, then transfer to the speed stirring 10min with 10000r/min in refiner, obtain substrate bacterial fibersElement slurry;
Two, separately get the commercially available bacteria cellulose of 60g and be immersed in deionized water for ultrasonic washing 4h deacidification, freeze drying, obtainsDry bacteria cellulose; Bacteria cellulose dry 1g is immersed in to the mixed solution of 100ml urea and ammonium dihydrogen phosphate (ADP)In, ultrasonic processing 0.5h after stirring 1h, then freeze drying, obtain bacteria cellulose presoma, by bacteria cellulose forerunnerBody is placed in tube furnace cracking 2h at 900 DEG C, obtains the carbon fiber of nitrogen phosphorus doping; The mixing of its urea and ammonium dihydrogen phosphate (ADP)In solution, the concentration of urea is that the concentration of 5mg/mL, ammonium dihydrogen phosphate (ADP) is 5mg/mL;
Three, the carbon fiber of 40mg nitrogen phosphorus doping is mixed with 10mg Graphene, then adds 30mg lauryl sodium sulfate,Be dispersed in 100mL deionized water, after ultrasonic processing 2h, transfer in refiner and stir 10min with 10000r/min, obtainObtain homodisperse nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquid;
Four, by bacteria cellulose slurry vacuum filtration film forming for substrate, then add nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquidContinue suction filtration film forming, then be placed in vacuum drying chamber and be dried, make nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria celluloseFlexible electrode material;
The nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexibility obtaining after step 4 vacuum filtration and vacuum dryingIn electrode material, the quality of bacteria cellulose substrate is 150mg.
The nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material making is cut into 2cm × 1.5cm rectangularShape, 1, directly as ultracapacitor working electrode, platinized platinum is as to electrode, taking mercury/mercuric oxide electrode as reference electrode,The capacitance characteristic of test flexible electrode material. Test specimens product are labeled as NP-CNF-1. 2, by rectangular two 2cm × 1.5cmShape membrane material is assembled into symmetry ultracapacitor, tests the capacitance characteristic of flexible ultracapacitor. Test specimens product are labeled asD-NP-CNF-1。
Obtained flexible electrode material is tested. The doping carbon fiber tool that as seen from Figure 1 prepared by bacteria celluloseThere is meticulous network structure, disperse with graphene uniform simultaneously. In Fig. 2, demonstrate difference and sweep the scanning of fast doping carbon fiberPotential window is-0.8～0.2V. Along with the increase of sweep speed, CV curve all has the shape of accurate rectangle, has shown betterHigh rate performance. In Fig. 3, demonstrating symmetry ultracapacitor difference, to sweep fast potential window be 0～1V. Fig. 4 is this realityExecute the bending property resolution chart of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material that example makes, from Fig. 4In can find out that this material has good flexible performance, can 180 degree turn back.
Comparative example: the preparation method of bacteria cellulose/activated carbon fiber/graphene film material is as follows:
One, bacteria cellulose is cut into piece and be immersed in deionized water for ultrasonic washing 10h, and each hour changed deionizationWater, transfers 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 to porcelain boat, then puts into tube furnace; In tube furnace, pass into nitrogen except oxygen 6h,And as protection gas, first tube furnace is warming up to 270 DEG C with the speed of 4 DEG C/min, afterwards the speed liter of 0.3 DEG C/minTemperature, to 390 DEG C, is then warming up to 900 DEG C with the speed of 4 DEG C/min, keeps 2h; Be cooled to the speed of 5 DEG C/min again400 DEG C, be finally naturally down to again room temperature, obtain activated carbon fiber, then in 50mg activated carbon fiber, add 15mg tenDialkyl benzene sulfonic acids sodium, then be dispersed in deionized water, activated carbon fiber dispersion liquid obtained;
Three, 10g bacteria cellulose is cut into and be immersed in deionized water for ultrasonic washing 10h after piece, and each hour changed and goIonized water, is then placed in deionized water, stirs it is uniformly dispersed, then transfer to the speed with 12000r/min in refinerDegree, stirs 5min, obtains bacteria cellulose slurry;
Four, in the Graphene of 10mg acidifying, add 10mg neopelex, be then dispersed in deionized water,Obtain graphene dispersing solution; Graphene dispersing solution is joined in activated carbon fiber dispersion liquid, stir and make Graphene and activated carbonFiber dispersion is even, obtains composite dispersion liquid;
Five,, by the bacteria cellulose slurry vacuum filtration film forming of step 3, then add composite dispersion liquid to continue suction filtration and becomeFilm, then put into vacuum drying chamber and be dried, bacteria cellulose/activated carbon fiber/graphene film material made.
Bacteria cellulose in bacteria cellulose/activated carbon fiber after vacuum filtration and vacuum drying/graphene film materialQuality is 300mg.
Bacteria cellulose/the activated carbon fiber of acquisition/graphene film material is cut into 1.5cm × 2cm rectangle, is directly used asUltracapacitor working electrode, platinized platinum, as to electrode, taking mercury/mercuric oxide electrode as reference electrode, is tested self-supporting flexibilityThe capacitance characteristic of film material electrode material. Test specimens product are labeled as BC-ACF-CN-1.
Cycle performance to NP-CNF-1 and BC-ACF-CN-1 is tested, and 1, NP-CNF-1 membrane material has moreGood high rate performance, this is because Graphene has better electric conductivity compared with bacteria cellulose base carbon fibre, andIn NP-CNF-1 experiment, adopt the mode of high-speed stirred, NP-CNF is mixed with graphene uniform. 2, D-NP-CNF-1Carbon fiber doping introducing hetero-atoms, make material and bacteria cellulose substrate formation hydrogen bond, adhesion is better, has betterCycle performance, circulation 20000 circle after specific capacity almost do not decline. And electricity after BC-ACF-CN-1 circulation 10000 circlesSeparating liquid has change color, has a small amount of decline than electric capacity, and doping carbon fiber/Graphene/bacterium fibre prepared by the present embodiment is describedTie up plain flexible electrode material and there is excellent cycle performance. In 3, NP-CNF-1, use bacteria cellulose amount to subtract and be a half,Obtain thinner counterdie. 4, NP-CNF-1 has higher ratio electric capacity, material is carried out to cyclic voltammetry, at 20mV/sWhen sweep speed, specific capacitance has improved 12.8%, by 171 to 197.
The preparation side of embodiment 2, a kind of nitrogen phosphorus doping of the present embodiment carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialMethod, carry out according to the following steps:
One, commercially available 5g bacteria cellulose bulk goods is immersed in to deionized water for ultrasonic washing 5h deacidification, then dispersedIn deionized water, then transfer to the speed stirring 15min with 10000r/min in refiner, obtain substrate bacterial fibersElement slurry;
Two, separately get commercially available 60g bacteria cellulose and be immersed in deionized water for ultrasonic washing 4h deacidification, freeze drying, obtainsDry bacteria cellulose; Bacteria cellulose dry 1g is immersed in to the mixed solution of 100ml urea and ammonium dihydrogen phosphate (ADP)In, ultrasonic processing 0.5h after stirring 1h, then freeze drying, obtain bacteria cellulose presoma, by bacteria cellulose forerunnerBody is placed in tube furnace cracking 2h at 900 DEG C, obtains the carbon fiber of nitrogen phosphorus doping; The mixing of its urea and ammonium dihydrogen phosphate (ADP)In solution, the concentration of urea is that the concentration of 3mg/mL, ammonium dihydrogen phosphate (ADP) is 3mg/mL;
Three, the carbon fiber of 40mg nitrogen phosphorus doping is mixed with 8mg Graphene, then adds 24mg lauryl sodium sulfate,Be dispersed in 100mL deionized water, the speed with 10000r/min in refiner of transferring to after ultrasonic processing 2h stirs15min, obtains homodisperse nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquid;
Four, by bacteria cellulose slurry vacuum filtration film forming for substrate, then add nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquidContinue suction filtration film forming, then be placed in vacuum drying chamber and be dried, make nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria celluloseFlexible electrode material;
The nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexibility obtaining after step 4 vacuum filtration and vacuum dryingIn electrode material, the quality of bacteria cellulose substrate is 150mg.
The nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material making is cut into 2cm × 1.5cm rectangularShape, 1, directly as ultracapacitor working electrode, platinized platinum is as to electrode, taking mercury/mercuric oxide electrode as reference electrode,The capacitance characteristic of test flexible electrode material. Test specimens product are labeled as NP-CNF-2. 2, by rectangular two 2cm × 1.5cmShape membrane material is assembled into symmetry ultracapacitor, tests the capacitance characteristic of flexible ultracapacitor. Test specimens product are labeled asD-NP-CNF-2。
In Fig. 5, demonstrating difference, to sweep the scanning potential window of fast doping carbon fiber be-0.8～0.2V. Along with sweep speedIncrease, CV curve all has the shape of accurate rectangle, has shown good high rate performance. In Fig. 6, demonstrate symmetry superIt is 0～1V that capacitor difference is swept fast potential window.
In embodiment 1～2, ultrasonic ultrasonic power used is 1000w, and frequency is 30KHz.
Known by above embodiment, embodiment 1～2 utilizes the microstructure direct carbonization of bacteria cellulose to prepare doping carbonFiber, has retained the network structure of superfinishing refinement after carbonization, simultaneously material and the stable bond performance of material with carbon element and the power of excellenceLearn characteristic, as flexible substrates carrying active substance, be prepared into ultracapacitor flexible electrode; Preparation technology is simple,Be produced on a large scale; Directly be used as electrode of super capacitor and there is good capacitive character and cycle performance.
Claims (9)
1. a preparation method for nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material, is characterized in that thisMethod is carried out according to the following steps:
One, bacteria cellulose is immersed in to deionized water for ultrasonic washing, is then dispersed in deionized water, then shiftsStir to refiner high speed, obtain substrate bacteria cellulose slurry;
Two, separately get bacteria cellulose and be immersed in deionized water for ultrasonic washing, freeze drying, obtains dry bacteria cellulose;Dry bacteria cellulose is immersed in dopant solution, and ultrasonic processing after stirring, then freeze drying, obtain bacterial fibersElement presoma, is placed in the carbonization of tube furnace Pintsch process by bacteria cellulose presoma, obtains the carbon fiber of nitrogen phosphorus doping; ItsMiddle dopant solution is the mixed solution of urea and ammonium dihydrogen phosphate (ADP);
Three, the carbon fiber of nitrogen phosphorus doping is mixed with Graphene, then add surfactant, be dispersed in deionized water, superAfter sonication, transfer to refiner high speed and stir, obtain homodisperse nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquid;
Four, by bacteria cellulose slurry vacuum filtration film forming for substrate, then add nitrogen phosphorus doping carbon fiber and graphite alkene dispersion liquidContinue suction filtration film forming, then be placed in vacuum drying chamber and be dried, make nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose softProperty electrode material;
Wherein nitrogen phosphorus doping carbon fiber and Graphene in nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialMass ratio is (20～2): 1; Nitrogen phosphorus doping carbon fiber in nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode materialWith the mass ratio of bacteria cellulose substrate be (0.1～1): 1; Dry bacteria cellulose and the mass ratio of urea in step 2For (0.3～10): 1; Dry bacteria cellulose and the mass ratio of ammonium dihydrogen phosphate (ADP) are (0.3～10): 1.
2. the system of a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 1Preparation Method, is characterized in that described ultrasonic power is 1000w, and frequency is 30KHz.
3. the system of a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 1Preparation Method, is characterized in that the condition of the supersound washing described in step 1 and step 2 is ultrasonic time 1～10h.
4. the system of a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 1Preparation Method, is characterized in that the Pintsch process carbonization described in step 2 is to be to react 1～4h under 600～900 DEG C of conditions in temperature.
5. the system of a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 1Preparation Method, is characterized in that Graphene described in step 3 and the mass ratio of surfactant are 1:(0.2～5).
6. a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 1 or 5Preparation method, it is characterized in that the surfactant described in step 3 is lauryl sodium sulfate.
7. the system of a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 1Preparation Method, is characterized in that the speed of the high-speed stirred described in step 1 and step 3 is 8000～15000r/min, mixing time3-30min。
8. nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode that preparation method as claimed in claim 1 obtainsThe application of material, is characterized in that this flexible electrode material is applied in ultracapacitor.
9. answering of a kind of nitrogen phosphorus doping carbon fiber/graphite alkene/bacteria cellulose flexible electrode material according to claim 8With, it is characterized in that this flexible electrode material is applied in ultracapacitor or with two these flexible electrodes as negative materialMaterial is assembled into symmetry ultracapacitor.
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| CN106099055A (en) * | 2016-06-20 | 2016-11-09 | 三峡大学 | A kind of preparation method of nitrogen-phosphor codoping flexibility carbon-fiber film negative material |
| CN106129359A (en) * | 2016-07-15 | 2016-11-16 | 天津大学 | A kind of red phosphorus carbonization Bacterial cellulose flexible composite and preparation method |
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| CN106129359A (en) * | 2016-07-15 | 2016-11-16 | 天津大学 | A kind of red phosphorus carbonization Bacterial cellulose flexible composite and preparation method |
| CN106129359B (en) * | 2016-07-15 | 2019-02-22 | 天津大学 | A kind of red phosphorus-carbonization bacteria cellulose flexible composite and preparation method |
| CN106229157A (en) * | 2016-08-17 | 2016-12-14 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of polyatom co-doped nano carbon fiber and one one step preparation method and purposes |
| CN106299385B (en) * | 2016-08-26 | 2019-04-12 | 南京理工大学 | N doping carbonization bacterial cellulose loaded nanometer platinum electrode material and preparation method thereof |
| CN106299385A (en) * | 2016-08-26 | 2017-01-04 | 南京理工大学 | N doping carbonization bacterial cellulose loaded nanometer platinum electrode material and preparation method thereof |
| CN108281635A (en) * | 2018-01-26 | 2018-07-13 | 北京化工大学 | A kind of nitrogen P elements codope carbon material and its preparation method and application |
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| CN108658067B (en) * | 2018-06-20 | 2020-07-17 | 河北大学 | Phosphorus-nitrogen co-doped carbon material and preparation method and application thereof |
| CN108658067A (en) * | 2018-06-20 | 2018-10-16 | 河北大学 | A kind of nitrogen co-doped carbon material of phosphorus and preparation method thereof and purposes |
| CN109449006A (en) * | 2018-09-30 | 2019-03-08 | 湘潭大学 | A kind of preparation process of phosphorus nitrogen-doped graphene porous carbon composite |
| CN110289179A (en) * | 2019-05-29 | 2019-09-27 | 南京源恒能源科技有限公司 | Reactive metal oxides-carbonization bacteria cellulose electrode material preparation method |
| CN110581267A (en) * | 2019-09-16 | 2019-12-17 | 哈尔滨工业大学 | nano-cellulose-silicon-graphite micron sheet flexible electrode material and preparation method and application thereof |
| CN112695342A (en) * | 2020-12-28 | 2021-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cobalt/nitrogen-doped graphene and carbon nanofiber composite material, product and application thereof |
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| CN114743809B (en) * | 2022-04-29 | 2023-08-18 | 武夷学院 | Preparation method of cellulose nanofiber membrane-based flexible electrode material |
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