CN102558857A - Grapheme/polyaniline nanometer fibrous composite material, preparation method thereof and application on super-capacitor - Google Patents
Grapheme/polyaniline nanometer fibrous composite material, preparation method thereof and application on super-capacitor Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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- 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
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- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a grapheme/polyaniline nanometer fibrous composite material, a preparation method thereof, the application of the composite material serving as an electrode material on a super-capacitor and a preparation method of the super-capacitor. The composite material is obtained by connecting a grapheme oxide obtained after functionalized processing and a conducting polymer through amide groups in a chemical-bond mode, the electricity conducting performance is improved by reducing the composite material, and the composite material has high electric capacity by combining the stable characteristic of an inherent structure. The invention further relates to the super-capacitor, the super-capacitor comprises a first electrode, a second electrode, a first current collector, a second current collector, a membrane and a electrolytic solution, and the first electrode and the second electrode consist of the grapheme/polyaniline nanometer fibrous composite material, wherein the grapheme/polyaniline nanometer fibrous composite material comprises grapheme and the conducting polymer which are connected through the amide groups in the chemical-bond mode.
Description
Technical field
The present invention relates to a kind of graphene oxide/polyaniline nano fiber matrix material and preparation method thereof, and use of preparation and the application of this material as the electrode materials of ultracapacitor.
Background technology
Ultracapacitor (Supercapacitors); Also be electrochemical capacitor (Electrochemical capacitors); It is a kind of energy density and the power density novel energy-storing device between traditional capacitor and battery; Characteristics such as but it has the high fast charging and discharging of energy density height, power density, have extended cycle life, instantaneous high-current discharge and environmentally safe are novel energy-storing, the energy-efficient equipments that grows up over past ten years.
In the prior art, conductive polymers has been widely used in the electrode materials of ultracapacitor.Conducting polymer materials has the advantage that internal resistance is little, specific storage is big, specific storage normally absorbent charcoal material 2-3 doubly.But conducting polymer materials is when the electrode material for super capacitor, and it discharges and recharges poor stability, and after the discharging and recharging repeatedly, its electrical capacity keeps rate variance.Therefore, thus it is a new research direction that conducting polymer materials is carried out compound its stability of improving.
Graphene is a kind of type material with better electroconductibility, has had the people to carry out Graphene and conductive polymers compound to improve the electroconductibility of conducting polymer materials in the prior art.Document " Supercapacitor Based on Flexible Graphene/Polyaniline Nanofiber Composite Films; Qiong Wu et al.; ACS NANO, Vol.4, No.4; 1963-1970; 2010 " has disclosed a kind of graphene oxide/polyaniline nano fiber matrix material that is used for electrode of super capacitor, and this graphene oxide/polyaniline nano fiber matrix material obtains through Graphene and conductive polymers polyaniline are mixed through physical method, and this graphene/polyaniline matrix material is applied to the electrode of ultracapacitor.Yet it is simple compound that the document only adopts physical method to carry out Graphene and polyaniline, makes between these two kinds of materials only to combine through Van der Waals force, thereby the cyclical stability of the graphene/polyaniline matrix material that is obtained can't be guaranteed.Be embodied under the current density of 0.3A/g, its electrical capacity reaches 210F/g, but after 800 times big current cycle discharged and recharged, its capacitance loss rate was 21%.And the long-time high-power cyclical stability that discharges and recharges of ultracapacitor is an important index.
People such as Hao Qingli are in the CN1015227202A China's Mainland publication application of application on April 24th, 2009, and it carries out in-situ polymerization through aniline is added drop-wise in Graphene solution, thereby obtains the graphene/polyaniline matrix material.Yet it is simple compound that the document only adopts physical method to carry out Graphene and polyaniline, combines through Van der Waals force between these two kinds of materials, thereby the stability of the graphene/polyaniline matrix material that is obtained can't be guaranteed; In the China's Mainland publication application of people such as Liu Jianhua in April, 2011 application, it directly passes through formylation reaction and bond connected with graphene oxide and conductive polymers; Because when it directly carries out Wei Er David Smail-Haake formylation reaction with graphene oxide;, hydroxyl in the graphene oxide has influence on the conductivity of graphene oxide/conducting polymer composite material with being replaced by chlorine; In addition; Contain oxy radicals such as epoxy and ehter bond on the graphene oxide of this moment, influence the electroconductibility of final matrix material, thereby make the electrical capacity of matrix material less.
Summary of the invention
In view of this; The necessary a kind of graphene/polyaniline nano-fiber composite material and preparation method thereof that provides; Through improving the conductivity of graphene oxide; And utilize its carboxylic group to carry out functionalization, thus react and carry out chemical bond and be connected with amino on the conductive polymers polyaniline, improve the stability of material; Reduction synthetic graphene oxide/polyaniline nano fiber matrix material obtains the good graphene oxide of electroconductibility/polyaniline nano fiber matrix material; This graphene oxide/polyaniline nano fiber matrix material is applied to ultracapacitor, makes this ultracapacitor have higher capacity and better charge and discharge cycles stability.
It is a kind of through stronger graphene/polyaniline nano-fiber composite material of reductive bonding force and preparation method thereof that the present invention provides; Be characterized in that said graphene/polyaniline nanofiber conducting polymer composite material is to carry out functionalization through graphene oxide, acid chloride groups that has on the graphene oxide and the amino on the polyaniline nano fiber react and obtain; Graphene oxide through with VR reagent Wei Er David Smail-Haake formylation reaction takes place by functionalization; Graphene oxide through after the functionalization is connected through chemical bond through amide group with conductive polymers; Improved the structural stability of graphene oxide/polyaniline nano fiber; Conductive polymers is wrapped up by Graphene on microcosmic; Present network-like structure on the whole, showing as high-capacitance conservation rate under big ultracapacitor electrical capacity and 500 the high current charge-discharge circulations on the electrochemistry.Be reduced through other oxy radicals except that amide group on the reductive graphene/polyaniline nano-fiber composite material; And the structure of Graphene becomes smooth regular shape by the curling shape of the preceding wave of reduction; The conductivity that this has all improved the graphene/polyaniline nano-fiber composite material has better improved matrix material and has been applied to electrical capacity and electrical capacity conservation rate under the long-time charging and discharging state on the ultracapacitor.
The preparation method of said graphene/polyaniline nano-fiber composite material specifically may further comprise the steps:
Step 1: a kind of graphene oxide powder is provided,
Step 2: dissolve this graphene oxide powder, and this graphene oxide is carried out functionalization with this graphene oxide of activation,
Step 3: a polyaniline nano fiber is provided, dissolves this conductive polymers obtaining a conductive polymer solution,
Step 4: mix said conductive polymer solution and said graphene oxide through functionalization; Make said conductive polymers and process activatory graphene oxide generation chemical reaction to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution
Step 5: remove solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution obtaining graphene oxide/polyaniline nano fiber matrix material,
Step 6: said graphene oxide/polyaniline nano fiber matrix material is reduced, through separating drying treatment, obtain the graphene/polyaniline nano-fiber composite material then.
Below will be elaborated to above-mentioned each step.
In step 1, the concrete preparation method of said graphene oxide powder is:
S1 provides a powdered graphite;
S2, this powdered graphite of oxide treatment is to obtain the graphene oxide powder.
In the S1 step; Said powdered graphite is the graphite of flakey nature graphite or acidified processing; The add-on of said powdered graphite is confirmed according to the amount of graphene oxide/polyaniline nano fiber matrix material that ultimate demand obtains; The particle diameter of said powdered graphite is not limit, and is preferably to satisfy 300 mesh sieves.
In the S2 step, the detailed process of said this powdered graphite of oxide treatment is: S21, in said powdered graphite homodisperse to a sulphuric acid soln, the amount of said sulphuric acid soln is not limit, and said powdered graphite is dissolved fully get final product.Be specially, can be added to formation one mixture in 100～400 milliliters of vitriol oils with crossing 300 purposes, 1～20 gram powdered graphite, and further stir this mixture with the said powdered graphite of homodisperse, said churning time is not limit, and can be 5 minutes to 30 minutes.Further, but in the process of this stirring this mixture of ice bath too high to prevent this mixture temperature; S22; Have to said homodisperse and slowly to add a potassium permanganate powder in the sulphuric acid soln of powdered graphite to form a mixing solutions; Said adding speed was controlled through the control joining day; Be specially can in 30 minutes to 2 hours, add 5～50 grams potassium permanganate powder avoiding taking place violent intensification, and in the process that adds said potassium permanganate powder, continue this mixing solutions of ice bath and make its temperature be lower than 3 ℃; S23; Remove ice bath; And add a certain amount of water to said mixing solutions, as can adding 100～400 ml waters (being preferably zero(ppm) water or deionized water), and heat this mixing solutions and make its temperature be elevated to 90 ℃～a definite value temperature more than 100 ℃ in the scope so that powdered graphite in the mixing solutions and potassium permanganate powder and sulfuric acid fully react the acquisition graphite oxide; Further, in said reaction process, can stir said mixing solutions; S24; The dilute with water that carries out at least once filters and washs said graphite oxide; And said graphite oxide is dissolved in a pH value is in the solution between 5.5～10; Then above-mentioned solution is carried out ultrasonication and obtained the graphene oxide gel in 1～120 minute, the purpose of said ultrasonication is that the graphite oxide that is obtained among the step S23 is fully peeled off, thereby obtains graphene oxide; The purpose of regulating the pH value is that the graphene oxide lamella that step S24 is obtained presents electronegativity; Since the Coulomb repulsion effect between lamella and the lamella, thus be difficult between the graphene oxide lamella reuniting, and then make the graphene oxide in the graphene oxide solution be difficult for deposition; S25 separates said graphene oxide from said graphene oxide gel, be specially in said graphene oxide gel to add deionized water; And filter out said graphene oxide, further, can the graphene oxide that obtained be dissolved with deionized water once more; Filter then; Be that above-mentioned dissolving and filtering step can be carried out repeatedly, be preferably to dissolve repeatedly and filter this graphene oxide and be no less than twice, thereby obtain comparatively purified graphene oxide; S26 carries out drying and pulverization process to the graphene oxide after separating, and this process is specially: the graphene oxide that is obtained is carried out drying treatment, and drying temperature is preferably 15～60 degrees centigrade, is preferably 12～48 hours time of drying.Further, can grind dried graphene oxide, lapping mode is not limit, preferred ball milling method, thus obtain to have graphene oxide powder than small particle size, see also Fig. 3, be the graphene oxide transmission electron microscope photo that is obtained.
In said step 2, said graphene oxide powder can be dissolved in a certain amount of first solvent, and can further carry out dispersion treatment to this graphene oxide solution.Said first solvent can be organic solvent, like N, and dinethylformamide, DMAC N,N, THF, toluene, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, N-Methyl pyrrolidone, or dithiocarbonic anhydride etc.The add-on of said first solvent gets final product can dissolve said whole graphene oxide powder, as can be with 100～300 milligrams of graphene oxide powder dissolutions in 2～30 milliliter of first solvent.Said dispersion treatment can be uses high-speed stirring or ultrasonic dispersing to stir said graphene oxide solution, and said churning time can be 3 minutes～and 2 hours.
The said graphene oxide solution of said functionalization is specially: under a protection of inert gas and exsiccant atmosphere; In said graphene oxide solution, add VR reagent, and keep this graphene oxide solution that is mixed with chloride reagent to descend so that the two reacts at 5～90 degrees centigrade; Remove said residual chloride reagent afterwards.
Wherein, Said rare gas element can be nitrogen, helium etc., said VR reagent can be thionyl chloride, Benzoyl chloride 99min., POCl3, and phosphorus pentachloride etc. in one or more and N, dinethylformamide; The mixture of one or both in the DMAC N,N.The mass ratio of said VR reagent and said graphene oxide is preferably 2: 1～and 300: 1.This graphene oxide solution time under 5～90 degrees centigrade that is mixed with chloride reagent of said maintenance can be 10 minutes～and 120 minutes.In addition, carry out, in the process of reaction, can further stir the said graphene oxide solution that is mixed with chloride reagent for making said sufficient reacting.
The concrete mode of the said residual chloride reagent of said removal can be: under a protection of inert gas; Heat the mixture after above-mentioned reaction is accomplished, with evaporative removal wherein residual chloride reagent and other impurity except that graphene oxide verivate and graphene oxide.
In step 3, said polyaniline is nanometer fibrous, and nanometer fibrous diameter is 30～200 nanometers, and length is between 200～2000 nanometers.The mass ratio of said conductive polymers and above-mentioned graphene oxide can be 10: 1～and 1: 5, be preferably 4: 1.Further, can carry out filtration drying to said conductive polymers and handle, be specially, use 200～1000 ml deionized water to clean, and filter.Place loft drier then, drying is 20 minutes～24 hours under 25～80 degrees centigrade.
The step of the said conductive polymers of said dissolving can be: said conductive polymers is dissolved in one second solvent, and dispersion treatment obtains a conductive polymer solution.Be specially: get a certain amount of conductive polymers and be dissolved in second solvent; Wherein this second solvent can be N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, THF, toluene, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, N-Methyl pyrrolidone or dithiocarbonic anhydride, the add-on of said second solvent can dissolve said conductive polymers fully and get final product.
In step 4; The concrete grammar of the graphene oxide of said acquisition/polyaniline nano fiber matrix material preformed objects solution is: under a protection of inert gas and exsiccant atmosphere; And under 10～90 degrees centigrade temperature; Said conductive polymer solution is joined in the said process graphene oxide of functionalization, and continue to stir 15 minutes～8 hours, thereby obtain graphene oxide/polyaniline nano fiber matrix material preformed objects solution.
In step 5; At first; To resulting graphene oxide/polyaniline nano fiber matrix material preformed objects solution dilution, secondly, resulting graphene oxide/polyaniline nano fiber matrix material preformed objects solution is filtered; Again secondly, the graphene oxide/polyaniline nano fiber matrix material preformed objects that obtains is cleaned and drying treatment to filtering.
Be specially: can in resulting solution, add 50～200 milliliters acetone or 50～200 ml deionized water are diluted so that follow-up filtration; Solution with gained uses the millipore filtration of the micropore that 0.1～0.5 μ m diameter is arranged on solvent filter, to filter then; Use 100～300 milliliters deionized water to clean to the product after filtering afterwards; To the drying of carrying out through the product after cleaning, drying temperature is 10～90 ℃, obtains graphene oxide/polyaniline nano fiber matrix material preformed objects at last.
In step 6, use and graphene oxide/polyaniline nano fiber matrix material preformed objects is reduced with a kind of reductive agent.Particularly, use the Hydrazine Hydrate 80 of 50% concentration of 100ml that graphene oxide/polyaniline nano fiber composite powder is dissolved, ultrasonic 15～30min separates drying treatment then, obtains the graphene/polyaniline nano-fiber composite material.
A kind of graphene oxide powder is provided; Dissolve this graphene oxide powder obtaining a graphene oxide solution, and this graphene oxide solution is carried out functionalization with this graphene oxide of activation; One conductive polymers is provided, dissolves this conductive polymers to obtain a conductive polymer solution; Mix said conductive polymer solution and said graphene oxide solution, make said conductive polymers and process activatory graphene oxide generation chemical reaction to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution through functionalization; Remove solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution to obtain graphene oxide/polyaniline nano fiber matrix material; Graphene oxide/polyaniline nano fiber matrix material preformed objects to obtaining is reduced, and separates drying, obtains the graphene/polyaniline nano-fiber composite material.
The present invention also provides a kind of ultracapacitor 10; See also Fig. 6; This ultracapacitor 10 has flat structure, comprising: one first electrode 101, one second electrode 102, one first current collector 103, one second current collector 104, a barrier film 105, an electrolytic solution 106, an and shell 107.Said first electrode 101 is arranged on said first current collector 103, and said second electrode 102 is arranged on said second current collector 104, and said first electrode 102 and second electrode 102 are provided with relatively and at interval.Said barrier film 105 is arranged between said first electrode 101 and second electrode 102 and is provided with at interval with said first electrode 101 and second electrode 102 respectively.Said first electrode 101, second electrode 102, first current collector 103, second current collector 104, and barrier film 105 all be arranged in the said electrolytic solution 106.Said first electrode 101, second electrode 102, first current collector 103, second current collector 104, barrier film 105, and electrolytic solution 106 all be arranged in the said shell 107.Said first electrode 101 and second electrode 102 include a graphene/polyaniline nano-fiber composite material.
Said graphene/polyaniline nano-fiber composite material comprises Graphene and the conductive polymers that carries out the chemical bond connection through amide group.Be specially; This graphene/polyaniline nano-fiber composite material is to react through acid chloride groups on the graphene oxide and the amino on the conducting polymer materials to have obtained graphene oxide/polyaniline nano fiber matrix material preformed objects; Then it is reduced; After separating drying, obtain the graphene/polyaniline nano-fiber composite material.Acid chloride groups on the said graphene oxide obtains through using VR reagent that graphene oxide is carried out formylation reaction.This graphene/polyaniline nano-fiber composite material shows that on microcosmic conductive polymers is wrapped up by Graphene, presents network-like structure on the whole.Said polyaniline is nanometer fibrous, and diameter is 30～200 nanometers, and length is 200～2000 nanometers.The thickness of this first electrode 101 and second electrode 102 can be 1 micron～3 millimeters.See also Fig. 7 to Fig. 9, in the present embodiment, said electrode materials is the graphene/polyaniline matrix material, and this graphene/polyaniline matrix material comprises Graphene and the polyaniline that carries out the chemical bond connection through amide group.
Said barrier film 105 is spun glass or polymeric film, and it allows the ionogen in the electrolytic solution 106 to contact through stoping said first electrode 101 and second electrode 102.
Said electrolytic solution 106 can be the carbonic allyl ester solution of aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sulfuric acid, aqueous nitric acid, lithium perchlorate, the carbonic allyl ester solution of tetraethylammonium tetrafluoroborate or the mixed solution of above arbitrary combination.
Said shell 107 can be glass shell, stainless steel casing or polymer plastic shell.
The material of said first current collector 103 and second current collector 104 can be materials such as graphite flake, metal, and said metallic substance can be nickel, aluminium or copper etc., and in the present embodiment, this first current collector 103 and second current collector 104 are a copper sheet.The shape size of this first current collector 103 and second current collector 104 is not limit; Can change according to actual needs; During practical application, can be directly on this first current collector 103 and second current collector 104 respectively coating electrically conductive glue with said first electrode 101 and second electrode 102 of boning respectively.
See also Figure 10, the embodiment of the invention provides a kind of method for preparing above-mentioned ultracapacitor, specifically may further comprise the steps:
Step 1: provide a graphene/polyaniline nano-fiber composite material as electrode material, said graphene/polyaniline nano-fiber composite material comprises graphene oxide and the conductive polymers polyaniline nano fiber that carries out the chemical bond connection through amide group.
See also Figure 11, the preparation method of this graphene/polyaniline nano-fiber composite material may further comprise the steps:
M1: a graphene oxide powder is provided;
M2:, obtaining graphene oxide solution, and this graphene oxide is carried out functionalization with this graphene oxide of activation to this graphene oxide powder dissolution;
M3: a polyaniline nano fiber powder is provided, dissolves this polyaniline nano fiber to obtain a conductive polymer solution;
M4; Mix said conductive polymer solution and said graphene oxide solution through functionalization, the graphene oxide generation chemical reaction that makes said conductive polymers and process functionalization is to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution;
M5 removes solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution to obtain graphene oxide/polyaniline nano fiber matrix material preformed objects.
M6 reduces to said graphene oxide/polyaniline nano fiber matrix material preformed objects, separates, and drying treatment obtains the graphene/polyaniline nano-fiber composite material.
Below will be elaborated to above-mentioned each step.
In step M1, the concrete preparation method of said graphene oxide powder is:
S1 provides a powdered graphite;
S2, this powdered graphite of oxide treatment is to obtain the graphene oxide powder.
In the S1 step; Said powdered graphite is the graphite of flakey nature graphite or acidified processing; The add-on of said powdered graphite is confirmed according to the amount of graphene oxide/polyaniline nano fiber matrix material that ultimate demand obtains; The particle diameter of said powdered graphite is not limit, and is preferably to satisfy 300 mesh sieves.
In the S2 step, the detailed process of said this powdered graphite of oxide treatment is: S21, in said powdered graphite homodisperse to a sulphuric acid soln, the amount of said sulphuric acid soln is not limit, and said powdered graphite is dissolved fully get final product.Be specially, can be added to formation one mixture in 100～400ml vitriol oil with crossing 300 purposes, 1～20g powdered graphite, and further stir this mixture with the said powdered graphite of homodisperse, said churning time is not limit, and can be 5min to 30 minute.Further, but in the process of this stirring this mixture of ice bath too high to prevent this mixture temperature; S22; Have to said homodisperse and slowly to add a potassium permanganate powder in the sulphuric acid soln of powdered graphite to form a mixing solutions; Said adding speed was controlled through the control joining day; Be specially the potassium permanganate powder that can in 30 minutes to 2 hours, add 5～50g avoiding taking place violent intensification, and in the process that adds said potassium permanganate powder, continue this mixing solutions of ice bath and make its temperature be lower than 3 ℃; S23; Remove ice bath, and add a certain amount of water, as adding 100～400ml water (being preferably zero(ppm) water or deionized water) to said mixing solutions; And heat this mixing solutions and make its temperature be elevated to 90 ℃～a definite value temperature more than 100 ℃ in the scope so that powdered graphite in the mixing solutions and potassium permanganate powder and sulfuric acid fully react the acquisition graphite oxide; Under this definite value temperature, keep a scheduled time, be preferably 0.5～2h, further; In said reaction process, can stir said mixing solutions, at room temperature leave standstill 12～120h afterwards; S24; Carry out dilute with water filtration at least once and dissolve said mixing solutions to control the pH value between 5.5～10; Then above-mentioned gained mixing solutions is carried out ultrasonication 1～120min and obtain the graphene oxide gel, the purpose of said ultrasonication is that the graphite oxide that is obtained among the step S23 is fully peeled off, thereby obtains graphene oxide; The purpose of regulating the pH value is that the graphene oxide lamella that step S24 is obtained presents electronegativity; Since the Coulomb repulsion effect between lamella and the lamella, thus be difficult between the graphene oxide lamella reuniting, and then make the graphene oxide in the graphene oxide solution be difficult for deposition; S25 separates said graphene oxide from said graphene oxide gel, be specially in said graphene oxide gel to add deionized water; And filter out said graphene oxide, further, can the graphene oxide that obtained be dissolved with deionized water once more; Filter then; Be that above-mentioned dissolving and filtering step can be carried out repeatedly, be preferably to dissolve repeatedly and filter this graphene oxide and be no less than twice, thereby obtain comparatively purified graphene oxide; S26 carries out drying and pulverization process to the graphene oxide after separating, and this process is specially: the graphene oxide that is obtained is carried out drying treatment, and drying temperature is preferably 15～60 degrees centigrade, is preferably 12～48 hours time of drying.Further, can grind dried graphene oxide, lapping mode is not limit, preferred ball milling method, thus obtain to have graphene oxide powder than small particle size.
In said M2, said graphene oxide powder is dissolved in a certain amount of first solvent, and can further carry out dispersion treatment to this graphene oxide solution.Said first solvent can be organic solvent, like N, and dinethylformamide, DMAC N,N, THF, toluene, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, N-Methyl pyrrolidone, or dithiocarbonic anhydride etc.The add-on of said first solvent gets final product can dissolve said whole graphene oxide powder, as can be with 100～300 milligrams graphene oxide powder dissolution in 2～30 milliliter of first solvent.Said dispersion treatment can be uses high-speed stirring or ultrasonic dispersing to stir said graphene oxide solution, and said churning time can be 3 minutes～and 2 hours.
The said graphene oxide solution of said functionalization is specially: under a protection of inert gas and exsiccant atmosphere; In said graphene oxide solution, add VR reagent, and keep this graphene oxide solution that is mixed with chloride reagent to descend so that the two reacts at 5～90 degrees centigrade; Remove said residual chloride reagent afterwards.
Wherein, Said rare gas element can be nitrogen, helium etc., said VR reagent can be thionyl chloride, Benzoyl chloride 99min., POCl3, and phosphorus pentachloride etc. in one or more and N, dinethylformamide; The mixture of one or both in the DMAC N,N.The mass ratio of said VR reagent and said graphene oxide is preferably 2: 1～and 300: 1.This graphene oxide solution time under 5～90 degrees centigrade that is mixed with chloride reagent of said maintenance can be 10 minutes～and 120 minutes.In addition, can fully carry out, in the process of reaction, can further stir the said graphene oxide solution that is mixed with chloride reagent for making said reaction.
The concrete mode of the said residual chloride reagent of said removal can be: under a protection of inert gas; Heat the mixture after above-mentioned reaction is accomplished, with evaporative removal wherein residual chloride reagent and other impurity except that graphene oxide verivate and graphene oxide.
In M3, said polyaniline is nanometer fibrous, and nanometer fibrous diameter is 30～200 nanometers, and length is between 200～2000 nanometers.The mass ratio of said conductive polymers and above-mentioned graphene oxide can be 10: 1～and 1: 5, be preferably 4: 1.Further, can carry out filtration drying to said conductive polymers and handle, be specially, use 200～1000 ml deionized water to clean, and filter.Place loft drier then, drying is 20 minutes～24 hours under 25～80 degrees centigrade.
The step of the said conductive polymers of said dissolving can be: said conductive polymers is dissolved in one second solvent, and dispersion treatment obtains a conductive polymer solution.Be specially: get a certain amount of conductive polymers and be dissolved in second solvent; Wherein this second solvent can be N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, THF, toluene, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, N-Methyl pyrrolidone or dithiocarbonic anhydride, the add-on of said second solvent can dissolve said conductive polymers fully and get final product.
In step M4; The concrete grammar of the graphene oxide of said acquisition/polyaniline nano fiber matrix material preformed objects solution is: under a protection of inert gas and exsiccant atmosphere; And under 10～90 degrees centigrade temperature; Said conductive polymer solution is joined in the said process graphene oxide of functionalization, and continue to stir 15 minutes～8 hours, thereby obtain graphene oxide/polyaniline nano fiber matrix material preformed objects solution.
In step M5; At first; To resulting graphene oxide/polyaniline nano fiber matrix material preformed objects solution dilution, secondly, resulting graphene oxide/polyaniline nano fiber matrix material preformed objects solution is filtered; Again secondly, the graphene oxide/polyaniline nano fiber matrix material preformed objects that obtains is cleaned and drying treatment to filtering.
Be specially: can in resulting solution, add 50～200 milliliters acetone or 50～200 ml deionized water are diluted so that follow-up filtration; Solution with gained uses the millipore filtration of the micropore that 0.1～0.5 μ m diameter is arranged on solvent filter, to filter then; Use 100～300 milliliters deionized water to clean to the product after filtering afterwards; To the drying of carrying out through the product after cleaning, drying temperature is 10～90 ℃, obtains graphene oxide/polyaniline nano fiber matrix material at last.
In step M6, at first use the graphene oxide/polyaniline nano fiber matrix material preformed objects of Hydrazine Hydrate 80 dissolving 1g of 50% concentration of 100ml, behind the supersound process 15min, to separate, drying obtains the graphene/polyaniline nano-fiber composite material.
A kind of graphene oxide powder is provided; Dissolve this graphene oxide powder obtaining a graphene oxide solution, and this graphene oxide solution is carried out functionalization with this graphene oxide of activation; One conductive polymers is provided, dissolves this conductive polymers to obtain a conductive polymer solution; Mix said conductive polymer solution and said graphene oxide solution, make said conductive polymers and process activatory graphene oxide generation chemical reaction to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution through functionalization; Remove solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution to obtain graphene oxide/polyaniline nano fiber matrix material preformed objects; Reduce said graphene oxide/polyaniline nano fiber matrix material preformed objects, separate drying treatment, obtain the graphene/polyaniline nano-fiber composite material.
Step 2: an above-mentioned graphene/polyaniline nano-fiber composite material and an additive are dispersed to acquisition one Graphene/conductive polymers colloidal sol in the solvent.
In this step 2, said solvent can be selected water, organic solvent etc. for use.Said water is preferably zero(ppm) water or deionized water, and said organic solvent can be ethanol, acetone or pyrrolidone etc.Said additive can be nafion, pvdf, tetrafluoroethylene, carbon nanotube or its mixture, and the mass ratio of said additive and said graphene/polyaniline nano-fiber composite material is 25: 1～200: 1.Said additive act as cohesiveness and the shape hold facility that increases the graphene/polyaniline nano-fiber composite material, make with step 3 in current collector have stronger bonding force, and avoid being come off by the electrolytic solution swelling.Said dispersion treatment can adopt methods such as ultrasonic dispersing, high-strength mechanical stirring or magnetic agitation.Adopt magnetic agitation after 5 minutes in the present embodiment, used ultrasonic dispersing 15～30 minutes.
Step 3 is removed the solvent in said Graphene/conductive polymers colloidal sol, and prepares surface that Graphene/conducting polymer thin film is separately positioned on one first current collector and one second current collector to form first electrode and second electrode.
The preparation process of this Graphene/conducting polymer thin film can be: pour above-mentioned Graphene/conductive polymers colloidal sol into one and be placed with in the solvent filter of teflon membrane filter; Obtain one Graphene/conducting polymer thin film through peeling off teflon membrane filter behind the suction filtration of certain hour, afterwards this Graphene/conducting polymer thin film directly or through a conductive adhesive is bonded to the surperficial and dry to obtain first electrode and second electrode of said first current collector and one second current collector; Perhaps said Graphene/conductive polymers colloidal sol is coated in the surface of first current collector and second current collector respectively; Remove the solvent in said Graphene/conductive polymers colloidal sol afterwards; Thereby obtain to be laid on said first current collector respectively and to be laid on first electrode and second electrode on said second current collector, be specially and make said solvent evaporates through the mode of seasoning or low-temperature heat.In addition, can finalize the design and handle said Graphene/conducting polymer thin film, as adopt the said Graphene/conducting polymer thin film of a dull and stereotyped compacting, thereby make this Graphene/conducting polymer thin film have comparatively level and smooth surface.
The material of this first current collector and second current collector can be graphite, metal etc.In the present embodiment, this first current collector and second current collector are copper sheet.The shape size of this first current collector and second current collector is not limit, and can change according to actual needs.
Step 4, with this first current collector that is provided with first electrode and second current collector that is provided with second electrode at interval and be oppositely arranged on membranous both sides, and in the shell of packing into.
Use barrier film to be provided with at interval at this first electrode and second electrode, and this barrier film is arranged between said first electrode and second electrode at interval.Present embodiment uses non-woven fabrics as barrier film.
Step 5 provides an electrolytic solution, and this electrolytic solution is injected into above-mentioned shell, and encapsulation makes a ultracapacitor..
This electrolytic solution injects into this shell, and during the first above-mentioned electrode, second electrode, first current collector, second current collector and barrier film all were arranged in this electrolyte solution, the encapsulation process of whole ultracapacitor was all carried out in being full of the rare gas element loft drier.See also Figure 11, be the charging and discharging curve figure of present embodiment ultracapacitor, among the figure, use current density to find that as the 0.3A/g test electrical capacity under this current density of graphene/polyaniline matrix material is 660F/g.
It is thus clear that; The electrode that the employing graphene/polyaniline nano-fiber composite material that present method obtained is used for ultracapacitor can make this ultracapacitor not only have higher electrical capacity; And has a very high high current charge-discharge cell container conservation rate; This is because the Graphene in this Shi Moxi conductive polymers is connected through chemical bond with conductive polymers, has very high stability.
In addition; For the application of graphene/polyaniline nano-fiber composite material in ultracapacitor; Employing Graphene/conducting polymer composite material that present method obtained can make this ultracapacitor not only have higher electrical capacity as the electrode of ultracapacitor; And has a very high high current charge-discharge cell container conservation rate; This is because the Graphene in this graphene/polyaniline nano-fiber composite material is connected through chemical bond with conductive polymers, has very high stability.
The invention has the advantages that: graphene oxide/polyaniline nano fiber matrix material is reduced; The smooth structure of graphene oxide; Improved the conductivity of Graphene and graphene oxide/polyaniline nano fiber matrix material; Chemically Graphene is connected with conducting polymer materials through chemical bond; Promptly carry out substitution reaction and make being connected of Graphene and conductive polymers through the acid chloride groups of graphene oxide material and amino on the conducting polymer materials; Thereby make the graphene/polyaniline nano-fiber composite material Stability Analysis of Structures of acquisition, the electric capacity conservation rate after electrical capacity and the big electric current that has improved the graphene/polyaniline nano-fiber composite material repeatedly circulates.
Description of drawings
Fig. 1 is a graphene/polyaniline nano-fiber composite material preparing method's of the present invention schema.
Fig. 2 is a graphene/polyaniline nano-fiber composite material preparing method's of the present invention process synoptic diagram.
Fig. 3 is the electron scanning micrograph of the graphene oxide/polyaniline nano fiber matrix material prepolymer of the embodiment of the invention 1 preparation.
Fig. 4 is the transmission electron microscope photo of the graphene oxide/polyaniline nano fiber matrix material prepolymer of the embodiment of the invention 1 preparation.
Fig. 5 is the electron scanning micrograph of the graphene/polyaniline nano-fiber composite material of the embodiment of the invention 1 preparation.
Fig. 6 is the transmission electron microscope photo of the graphene/polyaniline nano-fiber composite material of the embodiment of the invention 1 preparation.
Fig. 7 is the graphene/polyaniline nano-fiber composite material structural formula that the embodiment of the invention provides.
Fig. 8 is the structural representation of the ultracapacitor that provides of the embodiment of the invention.
Fig. 9 is preparing method's schema of the ultracapacitor that provides of the embodiment of the invention.
Figure 10 is that the graphene/polyaniline nano-fiber composite material that the embodiment of the invention provides is cyclic voltammetric (CV) the test curve figure under the sweep velocity at 100mV/s in quality; Wherein, the graphene/polyaniline nano composite material that P-G1 and P-G2 are among the embodiment to be provided, wherein, in the preparation process in P-G1 and P-G2, the graphene oxide of adding and the weight ratio of polyaniline were respectively 30: 70 and 6: 94; P-GO1 and P-GO2 are two kinds of contrast materials, and it is the presoma of P-G1 and P-G2, and it is not for passing through reductive graphene oxide/polyaniline composite material; Wherein, in the process of preparation P-GO1 and P-GO2, the weight ratio of graphene oxide and polyaniline was respectively 30: 70 and 6: 94; PANI is pure polyaniline material.GO is without reductive graphene oxide material; Re-GO is the graphene oxide material through partial reduction.
Figure 11 is that the graphene/polyaniline nano-fiber composite material that the embodiment of the invention provides is 1.25 * 10 in quality
-5During g, with the electric current test curve comparison diagram under the charge and discharge cycles under the continuous current of 0.3A/g; Wherein, the graphene/polyaniline nano composite material that P-G1 and P-G2 are among the embodiment to be provided, wherein, in the preparation process in P-G1 and P-G2, the graphene oxide of adding and the weight ratio of polyaniline were respectively 30: 70 and 6: 94; P-GO1 and P-GO2 are two kinds of contrast materials, and it is the presoma of P-G1 and P-G2, and it is not for passing through reductive graphene oxide/polyaniline composite material; Wherein, in the process of preparation P-GO1 and P-GO2, the weight ratio of graphene oxide and polyaniline was respectively 30: 70 and 6: 94; PANI is pure polyaniline material; GO is without reductive graphene oxide material; Re-GO is the graphene oxide material through partial reduction.
Figure 12 is that the graphene/polyaniline nano-fiber composite material that the embodiment of the invention provides is 1.25 * 10 in quality
-5During g, with the electric current test curve contrast under 200 charge and discharge cycles under the continuous current of 3A/g; Wherein, the graphene/polyaniline nano composite material that P-G1 and P-G2 are among the embodiment to be provided, wherein, in the preparation process in P-G1 and P-G2, the graphene oxide of adding and the weight ratio of polyaniline were respectively 30: 70 and 6: 94; P-GO1 and P-GO2 are two kinds of contrast materials, and it is the presoma of P-G1 and P-G2, and it is not for passing through reductive graphene oxide/polyaniline composite material; Wherein, in the process of preparation P-GO1 and P-GO2, the weight ratio of graphene oxide and polyaniline was respectively 30: 70 and 6: 94; PANI is pure polyaniline material; GO is without reductive graphene oxide material; Re-GO is the graphene oxide material through partial reduction.
Embodiment
To combine accompanying drawing and embodiment that the present invention is done further detailed description below.
Embodiment 1
Step 1: a graphene oxide powder is provided; That is: 5 gram flakey nature graphite are distributed to formation one mixture in 100 milliliters of vitriol oils, stir this mixture in this process high speed; In 1 hour, in said mixture, add 10 gram potassium permanganate powder, continue this mixture that is mixed with potassium permanganate of ice bath and be no more than 3 ℃ to keep its temperature; After potassium permanganate adds completion; Remove ice bath and the slow deionized water that adds 400 milliliters; Afterwards solution is heated; Make solution temperature be elevated to 100 ℃, under this temperature of 100 ℃, kept 1 hour, thereby make powdered graphite and potassium permanganate powder and sulfuric acid fully react the formation graphite oxide; After reaction finishes, diluting, filter and wash said graphite oxide, is 5% Na then with concentration
2CO
3Solution joins in the graphite oxide and stirs becomes uniform solution, is 5% Na through the concentration that adds
2CO
3The pH value to 6 of the amount regulator solution of solution, and this solution carried out supersound process, the treatment time is 30 minutes, thereby obtains the graphene oxide gel; From said graphene oxide gel, filter out said graphene oxide and this graphene oxide of vacuum-drying, drying temperature is 40 ℃, and be 6 hours time of drying; 200 milligrams above-mentioned graphene oxide powder is carried out ball milling, and the powder behind the ball milling is crossed 325 mesh sieves;
Step 2: this graphene oxide is dissolved, obtaining a graphene oxide solution, and this graphene oxide solution is carried out functionalization with this graphene oxide of activation; Be specially: get exsiccant graphene oxide powder 100mg, add VR reagent, promptly contain 1mlN; The solution of dinethylformamide and 20ml thionyl chloride adds in the said graphene oxide; And this graphene oxide solution that is mixed with thionyl chloride of oil bath heating kept 8 hours down at 25 ℃, so that graphene oxide and thionyl chloride react, thus the activation graphene oxide; In reaction process, use drying tube that waterproofing protection is carried out in the reaction outlet; The thionyl chloride that evaporative removal is remaining;
Step 3 a: polyaniline nano fiber is provided, dissolves this conductive polymers to obtain a conductive polymer solution; That is: 400 milligrams of polyaniline fibers are dissolved to 25 milliliters of N, in the N-2 NMF and stir, supersound process 5 minutes is to obtain the uniform conductive polymers soln then;
Step 4: mix said conductive polymer solution and said graphene oxide through functionalization, the graphene oxide generation chemical reaction that makes said conductive polymers and process functionalization is to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution; That is: the conductive polymer solution with gained joins through in the graphene oxide solution after the chloride, stirs 2 hours down at 15 ℃ afterwards, thereby obtains graphene oxide/polyaniline nano fiber matrix material preformed objects solution;
Step 5: remove solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution to obtain graphene oxide/polyaniline nano fiber matrix material preformed objects.That is: use 200 milliliters acetone or 200 ml deionized water to dilute resulting graphene oxide/polyaniline nano fiber matrix material preformed objects solution; And the graphene oxide/polyaniline nano fiber matrix material preformed objects solution that will pass through dilution uses the millipore filtration of 0.22 μ m micropore on solvent filter, to filter, afterwards the graphene oxide after the cleaning and filtering/polyaniline nano fiber matrix material; Dry said graphene oxide/polyaniline nano fiber matrix material preformed objects.
Step 6: graphene oxide/polyaniline nano fiber matrix material preformed objects that the Hydrazine Hydrate 80 of 50% concentration of use 200ml dissolves said 1g; After UW is peeled off and is disperseed 10min; Spinning, drying obtains the graphene/polyaniline nano-fiber composite material.
Embodiment 2
Step 1:
The first, 5 gram flakey nature graphite are distributed to formation one mixture in 230 milliliters of vitriol oils, stir this mixture in this process high speed; In 1 hour, in said mixture, add 30 gram potassium permanganate powder, continue this mixture that is mixed with potassium permanganate of ice bath and be no more than 3 ℃ to keep its temperature; After potassium permanganate adds completion; Remove ice bath and the slow deionized water that adds 400 milliliters; Afterwards solution is heated; Make solution temperature be elevated to 100 ℃, under this temperature of 100 ℃, kept 1 hour, thereby make powdered graphite and potassium permanganate powder and sulfuric acid fully react the formation graphite oxide; After reaction finishes, dilute, filter and wash said graphite oxide, then graphite oxide is used water dissolution; Adding concentration then and be 5% Na2CO3 solution, to make its pH value be 6; And this solution carried out supersound process, the treatment time is 30 minutes, thereby obtains the graphene oxide gel; From said graphene oxide gel, filter out said graphene oxide and this graphene oxide of vacuum-drying, drying temperature is 40 ℃, and be 6 hours time of drying; 200 milligrams above-mentioned graphene oxide powder is carried out ball milling, and the powder behind the ball milling is crossed 325 mesh sieves;
Second: this graphene oxide is dissolved, obtain a graphene oxide solution, and this graphene oxide solution is carried out functionalization with this graphene oxide of activation; Be specially: get the graphene oxide powder 100mg after the dried partial reduction, add VR reagent, promptly contain 1mlN; The solution of dinethylformamide and 20ml thionyl chloride adds in the said graphene oxide; And this graphene oxide solution that is mixed with thionyl chloride of oil bath heating kept 8 hours down at 25 ℃, so that graphene oxide and thionyl chloride react, thus the activation graphene oxide; In reaction process, use drying tube that waterproofing protection is carried out in the reaction outlet; The thionyl chloride that evaporative removal is remaining;
The the 3rd: a polyaniline nano fiber is provided, dissolves this conductive polymers to obtain a conductive polymer solution; That is: 400 milligrams of polyaniline fibers are dissolved to 25 milliliters of N, in the N-2 NMF and stir, supersound process 5 minutes is to obtain the uniform conductive polymers soln then;
The 4th: mix said conductive polymer solution and said graphene oxide solution through functionalization, the graphene oxide generation chemical reaction that makes said conductive polymers and process functionalization is to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution; That is: the conductive polymer solution with gained joins through in the graphene oxide solution after the chloride, stirs 2 hours down at 15 ℃ afterwards, thereby obtains graphene oxide/polyaniline nano fiber matrix material preformed objects solution;
The the 5th: remove solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution to obtain graphene oxide/polyaniline nano fiber matrix material.That is: use 200 milliliters acetone or 200 ml deionized water to dilute resulting graphene oxide/polyaniline nano fiber matrix material preformed objects solution; And the graphene oxide/polyaniline nano fiber matrix material preformed objects solution that will pass through dilution uses the millipore filtration of 0.22 μ m micropore on solvent filter, to filter, afterwards the graphene oxide after the cleaning and filtering/polyaniline nano fiber matrix material; Dry said graphene oxide/polyaniline nano fiber matrix material.
The 6th: after graphene oxide/polyaniline nano fiber matrix material preformed objects that the Hydrazine Hydrate 80 of 50% concentration of use 200ml dissolves said 1g, UW are peeled off and are disperseed 10min, spinning, drying obtains the graphene/polyaniline nano-fiber composite material.
Step 2: 10g graphene/polyaniline nano-fiber composite material is joined in the 50ml deionized water, add 5% nafion of 100 microlitres, UW separates, and the time is 15 minutes.Obtain the water-sol of one graphene oxide/polyaniline nano fiber matrix material.
Step 3: remove the solvent in said Graphene/conductive polymers colloidal sol, and prepare surface that Graphene/conducting polymer thin film is separately positioned on one first current collector and one second current collector to form first electrode and second electrode.Be specially: pour above-mentioned Graphene/conductive polymers colloidal sol into one at twice and be placed with in the solvent filter of teflon membrane filter; Behind suction filtration, peel off teflon membrane filter and obtain one Graphene/conducting polymer thin film, afterwards this Graphene/conducting polymer thin film directly is bonded to the copper sheet surface of a diameter 50mm and dry to obtain first electrode and second electrode;
Step 4: use barrier film to be provided with at interval at this first electrode and second electrode, and this barrier film is arranged between said first electrode and second electrode at interval, and in the vinyon shell of packing into.Present embodiment uses non-woven fabrics as barrier film.
Step 5 as electrolytic solution, is injected into above-mentioned shell with this electrolytic solution with the 2M vitriolic aqueous solution, and encapsulation makes a ultracapacitor.The encapsulation process of whole ultracapacitor is all carried out in being full of the rare gas element loft drier.
See also Fig. 7, be the charging and discharging curve figure of present embodiment ultracapacitor, among the figure, use current density to find that as the 0.3A/g test electrical capacity under this current density of graphene/polyaniline nano-fiber composite material is 285F/g.
See also Fig. 4 to Fig. 6, in the present embodiment, said graphene/polyaniline nano-fiber composite material is the graphene/polyaniline matrix material, and this graphene/polyaniline matrix material comprises Graphene and the polyaniline that carries out the chemical bond connection through amide group.
Claims (10)
1. the preparation method of a graphene/polyaniline nano-fiber composite material, this method may further comprise the steps:
A kind of graphene oxide powder is provided,
Dissolve this graphene oxide powder obtaining a graphene oxide solution, and this graphene oxide solution carried out functionalization with this graphene oxide of activation,
One polyaniline nano fiber is provided, dissolves this conductive polymers obtaining a conductive polymer solution,
Mix said conductive polymer solution and said graphene oxide solution through functionalization; Make said conductive polymers and process activatory graphene oxide generation chemical reaction to obtain one graphene oxide/polyaniline nano fiber matrix material preformed objects solution
Remove solvent in said graphene oxide/polyaniline nano fiber matrix material preformed objects solution obtaining graphene oxide/polyaniline nano fiber matrix material preformed objects powder,
Reduce this graphene oxide/polyaniline nano fiber matrix material, separate drying treatment and obtain a graphene/polyaniline nano-fiber composite material.
2. the preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 1; It is characterized in that; The said graphene oxide of said functionalization may further comprise the steps: under a protection of inert gas and exsiccant atmosphere; In said graphene oxide, be mixed into VR reagent and carry out Wei Er David Smail-Haake formylation reaction; And keep this graphene oxide solution that is mixed with VR reagent to descend so that graphene oxide dissolves and chloride reagent reacts at 5～90 degrees centigrade, remove said residual chloride reagent afterwards.
3. the preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 1 is characterized in that, said polyaniline is nanometer fibrous, and diameter is 30～200 nanometers, and length is between 200～2000 nanometers.
The preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 1; It is characterized in that; The preparation method of said graphene oxide/polyaniline nano fiber matrix material preformed objects solution is: under a protection of inert gas and exsiccant atmosphere; And under 5～90 degrees centigrade temperature; Said conductive polymer solution is joined in the said process graphene oxide solution of functionalization, and continue to stir 15 minutes～8 hours, thereby obtain graphene oxide/polyaniline nano fiber matrix material preformed objects solution;
The preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 1 is characterized in that:
The mass ratio of said polyaniline nano fiber and above-mentioned graphene oxide can be 10: 1～and 1: 5;
Said graphene oxide/polyaniline nano fiber matrix material is to react through acid chloride groups on the graphene oxide and the amino on the conductive polymers to obtain.
4. the preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 2; It is characterized in that; Said VR reagent be thionyl chloride, Benzoyl chloride 99min., POCl3, and phosphorus pentachloride etc. in one or more and N, the mixture of dinethylformamide.
The mass ratio of said VR reagent and said graphene oxide is 2: 1～300: 1;
Said VR reagent constitute N, the mass ratio of dinethylformamide and chloride reagent is 1: 100～1: 300;
5. the preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 1 is characterized in that, graphene oxide/polyaniline nano fiber matrix material preformed objects is reduced the used original reagent of going back be: hydrazine; The Hydrazine Hydrate 80 of 50%～80% concentration; Dimethylhydrazine, one or both in the unsymmetric dimethyl hydrazine etc., or Peng Qinghuana; Phenol, one or both in the terepthaloyl moietie etc.
6. the preparation method of graphene/polyaniline nano-fiber composite material as claimed in claim 1; It is characterized in that, be 2000: 1～50: 1 to graphene oxide/original reagent of going back used when polyaniline nano fiber matrix material preformed objects is carried out partial reduction with graphene oxide/polyaniline nano fiber matrix material preformed objects powder weight ratio.
7. the invention still further relates to a kind of ultracapacitor; Comprise: one first electrode, one second electrode, one first current collector, one second current collector, a barrier film, an and electrolytic solution; Said first electrode is arranged on said first current collector; Said second electrode is arranged on said second current collector; Said first electrode and second electrode are provided with relatively and through said barrier film at interval, said first electrode, second electrode, first current collector, second current collector, and barrier film all be arranged in the said electrolytic solution, said first electrode and second electrode are made up of a graphene/polyaniline nano-fiber composite material; It is characterized in that said graphene/polyaniline nano-fiber composite material comprises Graphene and the polyaniline nano fiber that carries out the chemical bond connection through amide group; The preparation method of graphene/polyaniline nano-fiber composite material defers to according to claim 1 step and carries out.
8. ultracapacitor as claimed in claim 7 is characterized in that: said graphene/polyaniline nano-fiber composite material is to react through acid chloride groups on the graphene oxide and the amino on the conductive polymers to obtain; The preparation method of graphene/polyaniline nano-fiber composite material defers to according to claim 1 step and carries out.
A kind of preparation method of ultracapacitor may further comprise the steps:
Provide a graphene/polyaniline nano-fiber composite material as electrode material, said graphene/polyaniline nano-fiber composite material comprises Graphene and the conductive polymers that carries out the chemical bond connection through amide group;
An above-mentioned graphene/polyaniline nano-fiber composite material and an additive are dispersed to acquisition one graphene/polyaniline nanofiber colloidal sol in the solvent;
Remove the solvent in the said graphene/polyaniline nanofiber colloidal sol, and prepare surface that graphene/polyaniline nano-fiber composite material film is separately positioned on one first current collector and one second current collector to form first electrode and second electrode;
With this first current collector that is provided with first electrode and second current collector that is provided with second electrode at interval and be oppositely arranged on membranous both sides, and in the shell of packing into;
One electrolytic solution is provided, this electrolytic solution is injected into above-mentioned shell, encapsulation makes a ultracapacitor.
9. the preparation method of ultracapacitor as claimed in claim 7; It is characterized in that; Said first solvent is an organic solvent; This organic solvent is N, dinethylformamide, DMAC N,N, THF, toluene, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, N-Methyl pyrrolidone or dithiocarbonic anhydride.
10. like the preparation method of the said ultracapacitor of claim 7, it is characterized in that said polyaniline is nanometer fibrous, diameter is 30～200 nanometers, and length is between 200～2000 nanometers; Its characteristic also is, the mass ratio of said conductive polymers and above-mentioned graphene oxide can be 10: 1～and 1: 5; Its characteristic also is; Said additive is nafion, pvdf, tetrafluoroethylene, carbon nanotube or its mixture; The mass ratio of said additive and said graphene/polyaniline nano-fiber composite material is 25: 1～200: 1, and said solvent is water or organic solvent.
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