CN102496481A - Graphene/polypyrrole nanotube composite material, super capacitor with graphene/polypyrrole nanotube composite material as electrode, and methods for preparing graphene/polypyrrole nanotube composite material and super capacitor - Google Patents
Graphene/polypyrrole nanotube composite material, super capacitor with graphene/polypyrrole nanotube composite material as electrode, and methods for preparing graphene/polypyrrole nanotube composite material and super capacitor Download PDFInfo
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Abstract
The invention relates to a graphene/polypyrrole nanotube composite material, a method for preparing the graphene/polypyrrole nanotube composite material, and a super capacitor with the graphene/polypyrrole nanotube composite material. The graphene/polypyrrole nanotube composite material is obtained by performing chemical bond connection on graphene which is functionalized and a polypyrrole nanotube through an amide group. The graphene/polypyrrole nanotube composite material is microcosmically characterized in that: the polypyrrole nanotube is coated by the graphene. The whole graphene/polypyrrole nanotube composite material has a meshed structure. The graphene/polypyrrole nanotube composite material has the characteristic of stable structure.
Description
Technical field
The present invention relates to a kind of Graphene/polypyrrole nanometer tube composite materials and preparation method thereof, and a kind of be the ultracapacitor and preparation method thereof of electrode with it.
Background technology
Graphene (Graphene) is a kind of novel two dimensional surface nano material that the Geim of University of Manchester in 2004 finds.Desirable single-layer graphene has the specific area (2630m of super large
2/ g), thickness is merely 0.35nm, has good electrical conductivity, light transmission and thermal conductivity, and have high hardness, and be very potential energy storage material.Wherein.Good electrical conductivity is the peculiar property that other bigger serface carbonaceous materials are difficult to have, and is indicating that Graphene is likely the electrode material that performance is splendid.The edge of the graphene oxide that obtains through the method for graphite being carried out chemical oxidation or surface have epoxide group, hydroxyl or carboxyl and exist, and this just provides convenience for the chemical modification of Graphene.
The polypyrrole nanotube is widely used in a lot of organic assemblies.In order to improve or expand the performance of these devices, the polypyrrole nanotube often is prepared to and is nano material.At the polypyrrole nano-tube material and Graphene carries out compound and assembling becomes in the application of ultracapacitor,, cause the poor stability that discharges and recharges of ultracapacitor because the adhesion between polypyrrole nanotube and the Graphene is poor.Therefore, thereby using Graphene that the polypyrrole nano-tube material is carried out compound its character of improving, is a new research direction.
Before document and patent application in, existing people obtains Graphene/Pt/Polypyrrole composite material through polypyrrole and Graphene are combined.Yet; These methods all are only to adopt the method for physical mixed to carry out simple compound Graphene and polypyrrole; Combine through Van der Waals force between these two kinds of materials, thereby the stability of the graphene/polyaniline pyrroles composite material that is obtained can't be guaranteed.And polypyrrole wherein is main with nanofiber, and its surface area is limited, makes its capacitance receive certain restriction.
Summary of the invention
The present invention provides the stronger Graphene of the adhesion between a kind of Graphene and the polypyrrole nanotube/polypyrrole nanometer tube composite materials and preparation method thereof, and with its electrode material as a kind of ultracapacitor.
Be characterized in:
Said Graphene/polypyrrole nanometer tube composite materials is to react through the amino on acid chloride groups on the Graphene and the polypyrrole nanotube to obtain; Graphene carries out chemical bond with the polypyrrole nanotube through amide group and is connected; Graphene/polypyrrole nanometer tube composite materials is wrapped up by Graphene for the polypyrrole nanotube on microcosmic, presents network-like structure on the whole.
This ultracapacitor comprises: one first electrode, one second electrode, one first collector body, one second collector body, a barrier film, an and electrolytic solution; Said first electrode is arranged on said first collector body; Said second electrode is arranged on said second collector body; Said first electrode and second electrode are provided with relatively and through said barrier film at interval; Said first electrode, second electrode, first collector body, second collector body, and barrier film all be arranged in the said electrolytic solution, said first electrode and second electrode are made up of one Graphene/polypyrrole nanometer tube composite materials.
A kind of preparation method of ultracapacitor; May further comprise the steps: provide one Graphene/polypyrrole nanometer tube composite materials as electrode material, said Graphene/polypyrrole nanometer tube composite materials comprises Graphene and the polypyrrole nanotube that carries out the chemical bond connection through amide group; An above-mentioned Graphene/polypyrrole nanometer tube composite materials and an additive are dispersed to acquisition one Graphene/polypyrrole nanotube colloidal sol in the solvent; Remove the solvent in said Graphene/polypyrrole nanotube colloidal sol, and prepare surface that Graphene/polypyrrole nano-tube film is separately positioned on one first collector body and one second collector body to form first electrode and second electrode; With these both sides that are provided with first collector body of first electrode and are provided with second collector body interval of second electrode and are oppositely arranged on a barrier film, 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.
Employing Graphene/polypyrrole nanometer tube composite materials that this method obtained can make this ultracapacitor not only have higher capacitance as the electrode of ultracapacitor; And has a very high high current charge-discharge battery capacity conservation rate; This is because the Graphene in this Graphene/polypyrrole nanometer tube composite materials is connected through chemical bond with the polypyrrole nanotube, has very high stability.
Said is the preparation method of the ultracapacitor of electrode with Graphene/polypyrrole nanometer tube composite materials, specifically may further comprise the steps:
Step 1 prepares Graphene/polypyrrole nanometer tube composite materials
Step 2 is dispersed to acquisition one Graphene/polypyrrole nanotube colloidal sol in the solvent with an above-mentioned Graphene/polypyrrole nanometer tube composite materials and an additive.
Step 3 is removed the solvent in said Graphene/polypyrrole nanotube colloidal sol, and prepares surface that Graphene/polypyrrole nano-tube film is separately positioned on one first collector body and one second collector body to form first electrode and second electrode.
Step 4 with this first collector body that is provided with first electrode and second collector body that is provided with second electrode at interval and be oppositely arranged on the both sides of a barrier film, and in the shell of packing into.
Below will be elaborated to above-mentioned each step.
In step 1, the concrete grammar of preparation Graphene/polypyrrole nanometer tube composite materials is:
M1: a graphene oxide powder is provided;
M2: this graphene oxide is carried out functionalization with this graphene oxide of activation;
M3: a polypyrrole nanotube is provided, dissolves this polypyrrole nanotube to obtain a polypyrrole nanotube solution;
M4: mix said polypyrrole nanotube solution and said graphene oxide through functionalization, the graphene oxide generation chemical reaction that makes said polypyrrole nanotube and process functionalization is to obtain one graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution;
M5: remove solvent in said graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution to obtain graphene oxide/polypyrrole nanometer tube composite materials; It is reduced to obtain Graphene/polypyrrole nanometer tube composite materials.
In M1, the concrete preparation method of said graphene oxide is:
S1 provides a powdered graphite;
S2, this powdered graphite of oxidation processes 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 addition of said powdered graphite is confirmed according to the amount of Graphene/polypyrrole nanometer tube composite materials that final needs obtain; 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 oxidation processes is: S21, said powdered graphite evenly is dispersed in the sulfuric acid solution, and the amount of said sulfuric acid solution 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 concentrated sulfuric acids with crossing 300 purposes, 1～20 gram powdered graphite, and further stir this mixture with the said powdered graphite of even dispersion, said mixing 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; In the said sulfuric acid solution that evenly is dispersed with powdered graphite, slowly add a potassium permanganate powder to form a mixed solution; 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 mixed solution of ice bath and make its temperature be lower than 3 ℃; S23; Remove ice bath; And add a certain amount of water to said mixed solution, as can adding 100～400 ml waters (being preferably distilled water or deionized water), and heat this mixed solution and make its temperature be elevated to 90 ℃～a definite value temperature more than 100 ℃ in the scope so that powdered graphite in the mixed solution and potassium permanganate powder and sulfuric acid fully react the acquisition graphite oxide; Further, in said course of reaction, can stir said mixed solution; 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 ultrasonic Treatment and obtained the graphene oxide gel in 1～120 minute, the purpose of said ultrasonic Treatment 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 elecrtonegativity; 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; The step that is above-mentioned dissolving and filtration can be carried out repeatedly, is preferably to dissolve repeatedly and filter this graphene oxide to be no less than twice, thereby obtains comparatively pure 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 dried, and baking temperature is preferably 15～60 degrees centigrade, is preferably 12～48 hours drying time.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 diameter, see also Fig. 3, be the graphene oxide transmission electron microscope photo that is obtained.
In M2, the said graphene oxide of said functionalization is specially: in said graphene oxide, add chloride reagent, and keep the mixture of this graphene oxide and chloride reagent to descend so that the two reacts at 25～90 degrees centigrade; Remove said residual chloride reagent afterwards.
Wherein, said inert gas can be nitrogen, helium etc., said chloride reagent can be thionyl chloride, chlorobenzoyl chloride, POCl3, and phosphorus pentachloride etc. in one or more.The mass ratio of said chloride reagent and said graphene oxide is preferably 2: 1～and 300: 1.The time of mixture under 25～90 degrees centigrade of this graphene oxide of said maintenance and chloride reagent can be 10 minutes～and 120 minutes.In addition, can fully carry out, in the process of reaction, can further stir the mixture of said graphene oxide and chloride reagent for making said reaction.
The concrete mode of the said residual chloride reagent of said removal can be: under an inert gas shielding; Heat the mixture after above-mentioned reaction is accomplished, with evaporative removal wherein residual chloride reagent and other impurity except that graphene oxide derivative and graphene oxide.
In M3, the concrete preparation method of said polypyrrole nanotube is: with oxidant and pyrroles in solvent with 5: 1-1: 10 mixed in molar ratio, stirred 100～3000 minutes down at 10～90 degrees centigrade, remove solvent subsequently.Wherein, said oxidant can be one or more in ammonium persulfate, ferric trichloride, hydrogen peroxide, the vanadic oxide etc.Further, can carry out filtration drying to said polypyrrole nanotube and handle, be specially, use 200～1000 ml deionized water to clean, and filter.Place drying box then, drying is 20 minutes～24 hours under 25～80 degrees centigrade.The mass ratio of said polypyrrole nanotube and above-mentioned graphene oxide can be 10: 1～and 1: 5, as 1.5: 1.
The step of the said polypyrrole nanotube of said dissolving can be: said polypyrrole nanotube is dissolved in the solvent, and dispersion treatment obtains a polypyrrole nanotube solution.Be specially: get a certain amount of polypyrrole nanotube and be dissolved in the solvent; Wherein this solvent can be N; Dinethylformamide, N; N-dimethylacetylamide, oxolane, toluene, carrene, chloroform, monochlorethane, dichloroethanes, N-methyl pyrrolidone or carbon disulfide, the addition of said second solvent can dissolve said polypyrrole nanotube fully and get final product.
In M4; The concrete grammar of the graphene oxide of said acquisition/polypyrrole nanometer tube composite materials preformed objects solution is: under 10～90 degrees centigrade temperature; Said polypyrrole nanotube solution is joined said through in the graphene oxide of functionalization; And continue to stir 15 minutes～180 minutes, thereby obtain graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution.
In M5; At first; To resulting graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution dilution, secondly, resulting graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution is filtered; Again secondly, the graphene oxide/polypyrrole nanometer tube composite materials preformed objects that obtains is cleaned and dried to filtering.Then, use reducing agent that it is reduced to obtain Graphene/polypyrrole nanometer tube composite materials.
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 miillpore filter 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, baking temperature is 10～90 ℃, obtains graphene oxide/polypyrrole nanometer tube composite materials at last.In said graphene oxide/polypyrrole nanometer tube composite materials, add reducing agent and leave standstill 1～48h, wherein reducing agent can be one or more in hydrazine hydrate, sodium sulfite, the frerrous chloride.The mass ratio of said graphene oxide/polypyrrole nanometer tube composite materials and said reducing agent can be 1: 1000～and 10: 1; With the Graphene that is obtained/polypyrrole nanometer tube composite materials filtration, drying.
In step 2, above-mentioned Graphene/polypyrrole nanometer tube composite materials and an additive be dispersed to the concrete grammar that obtains one Graphene/conducting polymer colloidal sol in the solvent be:
In this step, said solvent can be selected water, organic solvent etc. for use.Said water is preferably distilled water or deionized water, and said organic solvent can be ethanol, acetone or pyrrolidones etc.Said additive can be nafion, Kynoar, tetrafluoroethene, CNT or its mixture, and the mass ratio of said additive and said Graphene/conducting polymer composite material is 25: 1～200: 1.The caking property that act as increase Graphene/polypyrrole nanometer tube composite materials and the shape hold facility of said additive, make with step 3 in collector body have stronger adhesion, and avoid being come off by the electrolyte 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.
In step 3, remove the solvent in said Graphene/conducting polymer colloidal sol, and prepare surface that Graphene/polypyrrole nano-tube film is separately positioned on one first collector body and one second collector body to form first electrode and second electrode.
The preparation process of this Graphene/polypyrrole nano-tube film can be: pour above-mentioned Graphene/polypyrrole nanotube colloidal sol into one and be placed with in the solvent filter of teflon membrane filter; Obtain one Graphene/polypyrrole nano-tube film through peeling off teflon membrane filter behind the suction filtration of certain hour, afterwards this Graphene/polypyrrole nano-tube film directly or through a conductive adhesive is bonded to the surperficial and dry to obtain first electrode and second electrode of said first collector body and one second collector body; Perhaps said Graphene/polypyrrole nanotube colloidal sol is coated in the surface of first collector body and second collector body respectively; Remove the solvent in said Graphene/polypyrrole nanotube colloidal sol afterwards; Thereby obtain to be laid on said first collector body respectively and to be laid on first electrode and second electrode on said second collector body, be specially and make said solvent evaporates through the mode of air dry or low-temperature heat.In addition, can finalize the design and handle said Graphene/polypyrrole nano-tube film, as adopt the said Graphene/conducting polymer thin film of a dull and stereotyped compacting, thereby make this Graphene/polypyrrole nano-tube film have comparatively level and smooth surface.
The material of this first collector body and second collector body can be graphite, metal etc.In the present embodiment, this first collector body and second collector body are copper sheet.The shape size of this first collector body and second collector body is not limit, and can change according to actual needs.
In 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.Present embodiment uses nonwoven fabrics as barrier film.
In step 5; This electrolytic solution is injected into this shell; During the first above-mentioned electrode, second electrode, first collector body, second collector body 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 inert gas drying box.
The present invention provides a kind of graphene oxide powder and it is reduced to Graphene; This Graphene is carried out functionalization with this Graphene of activation; One polypyrrole nanotube is provided, dissolves this polypyrrole nanotube to obtain a polypyrrole nanotube solution; Mix said polypyrrole nanotube solution and said Graphene through functionalization, make said polypyrrole nanotube and through the Graphene generation chemical reaction of overactivation to obtain one Graphene/polypyrrole nanometer tube composite materials preformed objects solution; Remove solvent in said Graphene/polypyrrole nanometer tube composite materials preformed objects solution to obtain Graphene/polypyrrole nanometer tube composite materials.Then, use the electrode material of this Composite Preparation ultracapacitor, and its encapsulation is obtained ultracapacitor.
The invention has the advantages that: the electrode that employing Graphene/polypyrrole nanometer tube composite materials that this method obtained is used for ultracapacitor can make this ultracapacitor not only have higher capacitance; And has a very high high current charge-discharge battery capacity conservation rate; This is because Graphene and the polypyrrole nanotube in this Graphene/polypyrrole nanometer tube composite materials is to carry out substitution reaction through the acid chloride groups of grapheme material and amino on the polypyrrole nanotube Graphene is connected with the polypyrrole nanotube, has very high stability.
Description of drawings
Fig. 1 is Graphene of the present invention/polypyrrole nanometer tube composite materials preparation method's a flow chart;
Fig. 2 is Graphene of the present invention/polypyrrole nanometer tube composite materials preparation method's a process sketch map;
Fig. 3 is the transmission electron microscope photo of the Graphene that provides of the embodiment of the invention 1;
Fig. 4 is the electron scanning micrograph of the Graphene/polypyrrole nanometer tube composite materials of the embodiment of the invention 1 preparation;
Fig. 5 is the transmission electron microscope photo of the Graphene/polypyrrole nanometer tube composite materials of the embodiment of the invention 1 preparation;
Fig. 6 is the cyclic voltammetry curve of the Graphene/polypyrrole nanometer tube composite materials of the embodiment of the invention 1 preparation;
Fig. 7 is the charging and discharging curve of the Graphene/polypyrrole nanometer tube composite materials of the embodiment of the invention 1 preparation.
Embodiment
To combine accompanying drawing and embodiment that the present invention is done further detailed description below.
Embodiment 1
Step 1 provides a graphene oxide powder and it is reduced to Graphene; That is: 5 gram flakey nature graphite are distributed to formation one mixture in 100 milliliters of concentrated sulfuric acids, 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 sonicated, the processing 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 vacuumize, baking temperature is 40 ℃, and be 6 hours drying time; 100 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 carried out functionalization with this graphene oxide of activation; Be specially: thionyl chloride is added in the said graphene oxide; And this graphene oxide that is mixed with thionyl chloride of oil bath heating at 50 ℃ so that graphene oxide and thionyl chloride react; Thereby activation graphene oxide; In course of reaction, use drying tube that waterproofing protection is carried out in the reaction outlet, duration of the reaction is 2 hours; Under nitrogen protection, the thionyl chloride that evaporative removal is remaining;
Step 3: a polypyrrole nanotube is provided, dissolves this polypyrrole nanotube to obtain a polypyrrole nanotube solution; Be specially: get 1.82 gram methyl oranges and be dissolved in 240 ml deionized water, add 1.4 gram ferric trichloride powder and 900 microgram pyrroles; Stirred 24 hours, and from liquid, leached and dry polypyrrole nanotube.
Get 400 milligrams of polypyrrole nanotubes and be dissolved in 25 milliliters of carrene and stir, sonicated 5 minutes is to obtain uniform polypyrrole nanotube solution then;
Step 4: mix said polypyrrole nanotube solution and said graphene oxide through functionalization, the graphene oxide generation chemical reaction that makes said polypyrrole nanotube and process functionalization is to obtain one graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution; That is: the polypyrrole nanotube solution with gained joins through in the graphene oxide after the chloride, stirs 1 hour down at 25 ℃ afterwards, thereby obtains graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution;
Step 5: remove solvent in said graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution to obtain graphene oxide/polypyrrole nanometer tube composite materials.That is: use 200 milliliters acetone or 200 ml deionized water to dilute resulting graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution; And the graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution that will pass through dilution uses the miillpore filter of 0.22 μ m micropore on solvent filter, to filter, afterwards the graphene oxide after the cleaning and filtering/polypyrrole nanometer tube composite materials; Dry said graphene oxide/polypyrrole nanometer tube composite materials.In this 100 milligrams of graphene oxides/polypyrrole nanometer tube composite materials, add 20 milliliters of hydrazine hydrates, left standstill 24 hours, suction filtration is also dry.
Embodiment 2
Step 1:
The first, a graphene oxide powder is provided and it is reduced to Graphene; That is: 5 gram flakey nature graphite are distributed to formation one mixture in 100 milliliters of concentrated sulfuric acids, 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 sonicated, the processing 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 vacuumize, baking temperature is 40 ℃, and be 6 hours drying time; 100 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 carried out functionalization with this graphene oxide of activation; Be specially: thionyl chloride is added in the said graphene oxide; And this graphene oxide that is mixed with thionyl chloride of oil bath heating at 50 ℃ so that graphene oxide and thionyl chloride react; Thereby activation graphene oxide; In course of reaction, use drying tube that waterproofing protection is carried out in the reaction outlet, duration of the reaction is 2 hours; Under nitrogen protection, the thionyl chloride that evaporative removal is remaining;
The the 3rd: a polypyrrole nanotube is provided, dissolves this polypyrrole nanotube to obtain a polypyrrole nanotube solution; Be specially: get 1.82 gram methyl oranges and be dissolved in 240 ml deionized water, add 1.4 gram ferric trichloride powder and 900 microgram pyrroles; Stirred 24 hours, and from liquid, leached and dry polypyrrole nanotube.
Get 400 milligrams of polypyrrole nanotubes and be dissolved in 25 milliliters of carrene and stir, sonicated 5 minutes is to obtain uniform polypyrrole nanotube solution then;
The 4th: mix said polypyrrole nanotube solution and said graphene oxide through functionalization, the graphene oxide generation chemical reaction that makes said polypyrrole nanotube and process functionalization is to obtain one graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution; That is: the polypyrrole nanotube solution with gained joins through in the graphene oxide after the chloride, stirs 1 hour down at 25 ℃ afterwards, thereby obtains graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution;
The the 5th: remove solvent in said graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution to obtain graphene oxide/polypyrrole nanometer tube composite materials.That is: use 200 milliliters acetone or 200 ml deionized water to dilute resulting graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution; And the graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution that will pass through dilution uses the miillpore filter of 0.22 μ m micropore on solvent filter, to filter, afterwards the graphene oxide after the cleaning and filtering/polypyrrole nanometer tube composite materials; Dry said graphene oxide/polypyrrole nanometer tube composite materials.In this 100 milligrams of graphene oxides/polypyrrole nanometer tube composite materials, add 20 milliliters of hydrazine hydrates, left standstill 24 hours, suction filtration is also dry.
Step 2Above-mentioned Graphene/polypyrrole nanometer tube composite materials and additive nafion be dispersed to obtain Graphene/polypyrrole nanotube colloidal sol in the acetone.
Step 3Remove the solvent in said Graphene/polypyrrole nanotube colloidal sol, and prepare surface that Graphene/polypyrrole nano-tube film is separately positioned on one first collector body and one second collector body to form first electrode and second electrode.
Step 4 uses 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 nonwoven fabrics as barrier film.
Step 5One electrolytic solution is provided, this electrolytic solution is injected into above-mentioned shell, encapsulation makes a ultracapacitor.This electrolytic solution injects into this shell, and during the first above-mentioned electrode, second electrode, first collector body, second collector body 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 inert gas drying box.
Claims (8)
1. ultracapacitor; Comprise: one first electrode, one second electrode, one first collector body, one second collector body, a barrier film, an and electrolytic solution; Said first electrode is arranged on said first collector body; Said second electrode is arranged on said second collector body; Said first electrode and second electrode are provided with relatively and through said barrier film at interval; Said first electrode, second electrode, first collector body, second collector body, and barrier film all be arranged in the said electrolytic solution, said first electrode and second electrode are formed, it is characterized in that by one Graphene/polypyrrole nanometer tube composite materials; Graphene in said Graphene/polypyrrole nanometer tube composite materials carries out chemical bond with the polypyrrole nanotube through amide group and is connected, and described Graphene/polypyrrole nanometer tube composite materials obtains through its preformed objects graphene oxide/polypyrrole nanometer tube composite materials is carried out electronation.
2. Graphene as claimed in claim 1/polypyrrole nanometer tube composite materials is characterized in that its preparation method may further comprise the steps:
A kind of graphene oxide powder is provided,
This graphene oxide is carried out functionalization with this graphene oxide of activation,
The polypyrrole nanotube is provided, dissolves this polypyrrole nanotube obtaining a polypyrrole nanotube solution,
Mix said polypyrrole nanotube solution and said graphene oxide through functionalization; Make said polypyrrole nanotube and through the graphene oxide generation chemical reaction of overactivation to obtain one graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution
Remove solvent in said graphene oxide/Pt/Polypyrrole composite material preformed objects solution obtaining graphene oxide/polypyrrole nanometer tube composite materials, and with its reduction to obtain Graphene/polypyrrole nanometer tube composite materials
3. Graphene as claimed in claim 2/polypyrrole nanometer tube composite materials is characterized in that, the graphene oxide powder among the said preparation method prepares through following steps:
With particle diameter was that 300 mesh sieve powdered graphites evenly are dispersed in the sulfuric acid solution,
In the said sulfuric acid solution that evenly is dispersed with powdered graphite, add a potassium permanganate powder gradually forming a mixed solution,
Add entry to said mixed solution, and heat this mixed solution make its temperature be elevated to 90 ℃～100 ℃ so that graphite in the mixed solution and potassium permanganate powder and sulfuric acid powder react forming graphite oxide,
Dilution, filter and wash said graphite oxide, and this graphite oxide is dissolved in a pH value is in the solution between 5.5～10, and sonicated said be dissolved with graphite oxide and pH value be 5.5～10 solution with acquisition graphene oxide gel,
From said graphite oxide gel, isolate graphene oxide, and the graphene oxide after separating is carried out dried obtain the graphene oxide powder.
4. Graphene as claimed in claim 2/polypyrrole nanometer tube composite materials; It is characterized in that; The said graphene oxide of functionalization among the said preparation method may further comprise the steps: in said graphene oxide, be mixed into chloride reagent; And keep the mixture of this graphene oxide and chloride reagent to descend so that graphene oxide and chloride reagent react at 25～90 degrees centigrade, remove said residual chloride reagent afterwards; Wherein, said chloride reagent be thionyl chloride, chlorobenzoyl chloride, POCl3, and phosphorus pentachloride etc. in one or more, the mass ratio of said chloride reagent and said graphene oxide is 2: 1～300: 1.
5. Graphene as claimed in claim 2/polypyrrole nanometer tube composite materials; It is characterized in that; The preparation method of the polypyrrole nanotube among the said preparation method is: with oxidant and pyrroles in solvent with 5: 1-1: 10 mixed in molar ratio; Stirred 100～3000 minutes down at 10～90 degrees centigrade, remove solvent subsequently.Wherein, said oxidant can be one or more in ammonium persulfate, ferric trichloride, hydrogen peroxide, the vanadic oxide etc.; Its characteristic also is, the mass ratio of said polypyrrole nanotube and above-mentioned graphene oxide can be 10: 1～and 1: 5.
6. Graphene as claimed in claim 2/polypyrrole nanometer tube composite materials; It is characterized in that; The preparation method of said graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution is: under 10～90 degrees centigrade temperature; Said polypyrrole nanotube solution is joined in the said process Graphene of functionalization, and continue to stir 15 minutes～180 minutes, thereby obtain graphene oxide/polypyrrole nanometer tube composite materials preformed objects solution; Said use reducing agent reduces said graphene oxide/polypyrrole nanometer tube composite materials, and wherein reducing agent can be one or more in hydrazine hydrate, sodium sulfite, the frerrous chloride.The mass ratio of said graphene oxide/polypyrrole nanometer tube composite materials and said reducing agent can be 1: 1000～and 10: 1.
7. Graphene as claimed in claim 2/polypyrrole nanometer tube composite materials is characterized in that: prepared graphene/polypyrrole nanometer tube composite materials is wrapped up by Graphene for the polypyrrole nanotube on microcosmic, presents network-like structure on the whole; Its characteristic is that also said Graphene/polypyrrole nanometer tube composite materials is to react through the amino on acid chloride groups on the Graphene and the polypyrrole nanotube to obtain.
8. ultracapacitor as claimed in claim 1 is characterized in that, this preparation method may further comprise the steps:
Provide one Graphene/polypyrrole nanometer tube composite materials as electrode material, said Graphene/polypyrrole nanometer tube composite materials comprises Graphene and the polypyrrole nanotube that carries out the chemical bond connection through amide group;
An above-mentioned Graphene/polypyrrole nanometer tube composite materials and an additive are dispersed to acquisition one Graphene/polypyrrole nanotube colloidal sol in the solvent;
Remove the solvent in said Graphene/polypyrrole nanotube colloidal sol, and prepare surface that Graphene/polypyrrole nano-tube film is separately positioned on one first collector body and one second collector body to form first electrode and second electrode;
With these both sides that are provided with first collector body of first electrode and are provided with second collector body interval of second electrode and are oppositely arranged on a barrier film, 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.
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