CN102222565B - Carbon-based composite electrode material and preparation method thereof, and application of the carbon-based composite electrode material to super capacitor - Google Patents
Carbon-based composite electrode material and preparation method thereof, and application of the carbon-based composite electrode material to super capacitor Download PDFInfo
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Abstract
The invention relates to a carbon-based composite electrode material and a preparation method thereof, and application of the carbon-based composite electrode material to a super capacitor. The electrode material contains a conductive polymer and a carbon-based material. The conductive polymer is attached to a surface of the carbon-based material in a manner of a nanowire array of a conductive polymer, wherein the arrangement of the nanowire array of the conductive polymer is in a good order; besides, a diameter of the nanowire of the nanowire array of the conductive polymer is 40 to 100 nm and a length of the nanowire is 100 to 1500 nm. The carbon-based composite electrode material provide in the invention has a large specific surface area, so that an active area of a conductive polymer is substantially improved and thus high capacitance can be obtained; besides, the carbon-based composite electrode material provide in the invention has a highly ordered nano structure, so that a transmission path of an electrolyte ion is reduced and an internal resistance of an electrode is also reduced; therefore, the ion in an electrode material can be diffused and transmitted conveniently, and thus high power density can be obtained.
Description
Technical field
The present invention relates to a kind of carbon-based composite electrode material and preparation method thereof and the application in ultracapacitor.
Background technology
Ultracapacitor, is called again electrochemical capacitor, is a kind of novel energy memory element with advantages such as high power density, high-energy-density, the wide temperature scope of application and long circulation lifes.According to the difference of energy storage mechanism, ultracapacitor can be divided into double electric layer capacitor and fake capacitance device.The electrode material of double electric layer capacitor is take the material with carbon element of high-specific surface area as main, dependence be that the separation of charge of electrode and electrolyte interface forms electric double layer and carrys out stored charge.The electrode material of fake capacitance device comprises metal oxide and conducting polymer, dependence be that electrode active material fast reversible redox reaction occurs carrys out stored charge.For double electric layer capacitor, its capacitance is proportional to electrode and electrolytical interface size, and therefore the performance of electrode is subject to the restriction of material with carbon element specific area.Be 1000m for specific area at present
2g
-1activated carbon, it can reach 150Fg than electric capacity
-1, the leeway that specific area further improves is little.Especially, along with the raising of specific area, the conductance of material with carbon element can decline, and this can affect the performance of capacitor to a great extent.Compared with double electric layer capacitor, fake capacitance device has higher ratio capacitance, for example dry oxidation ruthenium (RuO
2) and ruthenium-oxide hydrate (RuO
2nH
2o) ratio capacitance has reached respectively 385Fg
-1and 920Fg
-1, but the high costs constraints of noble metal its extensive use in business.Comparatively speaking, conducting polymer have advantages of cheap, conductivity is high and can be synthetic in several ways.
The more conducting polymer of research comprises polypyrrole, polyaniline, polythiophene and poly-ethylenedioxy thiophene etc. at present, but these conducting polymers are all the electrode materials based on film or unordered nano wire, compared with the capacitance of its capacitance and theoretical prediction, there is larger gap.On 2008 " JACS " the 10th phase 2942-2943 page, report employing " a step co-electrodeposition method is prepared manganese dioxide and poly-ethylenedioxy thiophene co-axial nano line and the application in a stored energy " literary composition, in literary composition, adopt aluminium oxide to prepare nano-wire array as template by electrochemical means, in supercapacitor applications, embody good charge transport properties.But adopt template synthesis nano-wire array, process is loaded down with trivial details, and also can damage nano-wire array in the time dissolving template.
In addition, conductive polymer electrodes material can be accompanied by the doping-dedoping to ion in the time discharging and recharging, this causes the volume of polymer to expand-shrink, thereby polymeric material generation stress rupture is reduced to the capacity of polymer, affects the cyclical stability of polymer electrode.
Summary of the invention
The imperfect shortcoming of cyclical stability that the deficiency that process is loaded down with trivial details when overcoming above-mentioned template synthesis electrode material, template is easily damaged and polymer electrode material discharge and recharge, the invention provides that a kind of technique is simple, with low cost, the carbon-based composite electrode material of charge and discharge cycles good stability and the application in ultracapacitor thereof.
According to an aspect of the present invention, the invention provides a kind of carbon-based composite electrode material, this electrode material contains conducting polymer and carbon-based material, and wherein, described conducting polymer is attached on the surface of described carbon-based material with the form of conductive polymer nanometer linear array.
A preferred embodiment of the invention, wherein, take the total amount of described carbon-based composite electrode material as benchmark, the content of described conductive polymer nanometer linear array is 5-95 % by weight, the content of described carbon-based material is 5-95 % by weight.
According to another kind of preferred implementation of the present invention, wherein, take the total amount of described carbon-based composite electrode material as benchmark, the content of described conductive polymer nanometer linear array is 10-50 % by weight, and the content of described carbon-based material is 50-90 % by weight.
According to another kind of preferred implementation of the present invention, wherein, described conductive polymer nanometer linear array neat and orderly.
According to another kind of preferred implementation of the present invention, wherein, the diameter of the nano wire of described conductive polymer nanometer linear array is 40-100nm, and the length of nano wire is 100-1500nm.
According to another kind of preferred implementation of the present invention, wherein, the diameter of the nano wire of described conductive polymer nanometer linear array is 50-80nm, and the length of nano wire is 150nm-1000nm.
According to another kind of preferred implementation of the present invention, wherein, described conducting polymer is one or more in polyaniline, polypyrrole, polythiophene and poly-ethylenedioxy thiophene.
According to another kind of preferred implementation of the present invention, wherein, described carbon-based material is that thickness is that film material or the particle diameter of 0.01-1 millimeter is the granular material of 0.01-1 micron.
According to another kind of preferred implementation of the present invention, wherein, described carbon-based material is one or more in Graphene, graphene oxide, carbon nano-tube, carbon paper and carbon cloth.
According to another aspect of the present invention, the invention provides a kind of preparation method of carbon-based composite electrode material, the method is non-template electrochemical method, described non-template electrochemical method comprises take membranaceous carbon-based material as work electrode, take platinized platinum as to electrode, take saturated calomel electrode as reference electrode, take the aqueous solution that contains conducting polymer monomer and dopant as electrolyte, generate conductive polymer nanometer linear array at carbon-based material surface in situ.
A preferred embodiment of the invention, wherein, contains 0.01-1molL in electrolyte described in non-template electrochemical method
-1conducting polymer monomer and 0.1-2molL
-1dopant.
According to another kind of preferred implementation of the present invention, wherein, the current density adopting in described non-template electrochemical method is 0.01-1mAcm
-2, be 0.5-3 hour conduction time, the temperature of electrolyte is 20-40 ℃.
According to another aspect of the present invention, the invention provides a kind of preparation method of carbon-based composite electrode material, the method is without templated chemistry method, describedly comprise carbon-based material particle is scattered in the reaction solution that contains conducting polymer monomer, dopant and oxidant without templated chemistry method, at the temperature of-10 ℃ to 20 ℃, stirring reaction 1-48 hour, generates conductive polymer nanometer linear array at carbon-based material surface in situ.
A preferred embodiment of the invention, wherein, without containing 0.01-0.1molL in reaction solution described in templated chemistry method
-1conducting polymer monomer, 0.1-2molL
-1dopant and 0.005-1.5molL
-1oxidant, the reaction time is 24-48 hour, reaction temperature is-10 ℃ to 15 ℃.
According to another kind of preferred implementation of the present invention, wherein, be ammonium persulfate or iron chloride without oxidant described in templated chemistry method.
According to another kind of preferred implementation of the present invention, wherein, described conducting polymer monomer is aniline monomer; Described dopant is one or more in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid.
According to a further aspect of the invention, the invention provides the application of described carbon-based composite electrode material in ultracapacitor.
Carbon-based composite electrode material provided by the invention has following significant advantage: (1) this carbon-based composite electrode material has higher specific area, has greatly improved the active area of conducting polymer, can obtain thus higher capacitance.Table 1 has shown that current density is 1Ag
-1time, Graphene electrodes material and deposit the capacitance values comparing result of the combination electrode after polyaniline nano linear array by electrochemical method on graphene film.(2) carbon-based material that this combination electrode material is deposited on high-specific surface area by conductive polymer nanometer linear array is formed, and has the nanostructure of high-sequential.This ordered structure can reduce the transmission path of electrolyte ion, reduces the internal resistance of electrode, is conducive to diffusion and the transmission of ion in electrode material, can make ultracapacitor obtain higher power density.(3) this conducting polymer composite material, owing to having the array nanostructure of high-sequential, is added carbon-based material itself and is had high stability, so this electrode material has good charge and discharge cycles stability.(4) electrode material described herein is on the conducting polymer and carbon-based material basis based on cheap, prepares combination electrode material by the one-step method without template, and its preparation technology is simple and with low cost.
Table 1
| Electrode type | Than electric capacity (Fg -1) |
| Polyaniline nano linear array and |
500 |
| Graphene electrodes | 203.59 |
Accompanying drawing explanation
Fig. 1 represents to adopt the electron micrograph (amplifying 90,000 times) of the polyaniline nano linear array that the method for the embodiment of the present invention 1 obtains on graphene film.
Fig. 2 represents to adopt polyaniline nano linear array that the method for the embodiment of the present invention 3 prepares and the electron micrograph of graphene combination electrode material.
Fig. 3 represents to adopt polyaniline nano linear array that the method for the embodiment of the present invention 5 prepares and the electron micrograph of graphene combination electrode material.
Fig. 4 represents to adopt polyaniline nano linear array that method of the present invention prepares and the cyclic voltammetry curve figure of graphene composite material.
Fig. 5 represents to adopt polyaniline nano linear array that method of the present invention prepares and the capacitive property curve chart of graphene composite material.
Power density when Fig. 6 represents to adopt polyaniline nano linear array that method of the present invention prepares and graphene combination electrode material to be applied to electrode of super capacitor and the curve chart of energy density.
The curve chart of charge and discharge cycles stability when Fig. 7 represents to adopt polyaniline nano linear array that method of the present invention prepares and graphene combination electrode material to be applied to electrode of super capacitor.
Embodiment
The cyclical stability discharging and recharging due to conductive polymer electrodes material is good not, therefore by compound to conductive polymers ordered nano structure and material with carbon element, the synergy of the performance stability of material with carbon element and the high power capacity of conductive polymer nanometer structure, can obtain the ultracapacitor that performance is more excellent.Based on this discovery, the invention provides a kind of carbon-based composite electrode material, this electrode material contains conducting polymer and carbon-based material, it is characterized in that, described conducting polymer is attached on the surface of described carbon-based material with the form of conductive polymer nanometer linear array.
In the present invention, take the total amount of described carbon-based composite electrode material as benchmark, the content of described conductive polymer nanometer linear array is 5-95 % by weight, and the content of described carbon-based material is 5-95 % by weight.Under preferable case, the content of described conductive polymer nanometer linear array is 10-50 % by weight, and the content of described carbon-based material is 50-90 % by weight.
According to carbon-based composite electrode material provided by the invention, described conductive polymer nanometer linear array neat and orderly, the capacitance of this carbon-based composite electrode material is significantly improved than simple material with carbon element, reason is, be distributed in the orderly conductive polymer nanometer linear array on carbon-based material, not only can further improve the active area of conducting polymer, and the nano-wire array of this high-sequential can strengthen diffusion and the electric transmission of ion greatly, effectively reduce the internal resistance of capacitor, even if also can obtain like this higher capacity (i.e. higher power density) under the higher speed that discharges and recharges.
Carbon-based composite electrode material provided by the invention, the diameter of the nano wire of described conductive polymer nanometer linear array is 40-100nm, the length of nano wire is 100-1500nm.Under preferable case, the diameter of the nano wire of described conductive polymer nanometer linear array is 50-80nm, and the length of nano wire is 150nm-1000nm, and the electrode covering in the conductive polymer nanometer linear array of this range scale has better capacitive property.
Owing to adopting template synthesis electrode material to have the shortcoming that process is loaded down with trivial details and template is easily damaged, therefore the present invention adopts non-template electrochemical method or forms conductive polymer nanometer linear array without templated chemistry method in carbon-based material surface one step.Wherein, non-template electrochemical method is take membranaceous carbon-based material as work electrode, take platinized platinum as to electrode, take saturated calomel electrode as reference electrode, take the aqueous solution that contains conducting polymer monomer and dopant as electrolyte, the temperature of electrolyte is 20-40 ℃, and be 0.5-3 hour conduction time, and current density is 0.01-1mAcm
-2, conducting polymer monomer generates conductive polymer nanometer linear array at carbon-based material surface in situ.Under preferable case, in described electrolyte, contain 0.01-1molL
-1conducting polymer monomer and 0.1-2molL
-1the dopant aqueous solution, be 0.5-2 hour conduction time.
In above-mentioned electrochemical method, because the concentration of conducting polymer monomer in the electrolyte prescription of the present invention's employing is lower, and adopt less current density, therefore can on described carbon-based material, generate the nano-wire array of arrangement in good order, if excessive concentration or the current density of conducting polymer monomer are excessive, on carbon-based material, can not generate nano-wire array, only can generate some unordered nano wires.
That the particle of carbon-based material is scattered in the reaction solution that contains conducting polymer monomer, dopant, oxidant and solvent without templated chemistry method, at the temperature of-10 ℃ to 20 ℃, stirring reaction 1-48 hour, generates conductive polymer nanometer linear array at carbon-based material surface in situ.Preferably, the reaction temperature of chemical method is-10 ℃ to 15 ℃, and the reaction time is 24-48 hour.The weight ratio of carbon-based material and reaction solution is 1-70 % by weight.
Similarly, above-mentioned without templated chemistry method in, because the concentration of conducting polymer monomer in the reaction solution of the present invention's employing is lower, and adopt lower reaction temperature, more preferably-10 ℃ to 5 ℃, therefore can on described carbon-based material, generate the nano-wire array of arrangement in good order, if the concentration of conducting polymer monomer or reaction temperature are too high, on carbon-based material, can not generate nano-wire array, only can generate some unordered nano wires.
Visible, adopt non-template electrochemical method and without templated chemistry legal system in the process for the combination electrode material of conductive polymer nanometer linear array and carbon-based material in the present invention, because the present invention has adopted special formula and preparation technology, therefore can obtain a kind of have orderly conductive polymer nanometer linear array and the combination electrode material of carbon-based material, and the diameter that makes the nano wire of described conductive polymer nanometer linear array is 40-100nm, the length of nano wire is 100-1500nm.
Described conducting polymer is selected from one or more in polyaniline, polypyrrole, polythiophene and poly-ethylenedioxy thiophene.Described conducting polymer monomer is the corresponding monomer that forms above-mentioned conducting polymer.More preferably, described conducting polymer monomer is aniline monomer.Further preferably, described in chemical method, in reaction solution, the concentration of conducting polymer monomer is 0.01-0.1mol L
-1.
Described dopant can be selected from sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid one or more.Preferably, dopant is perchloric acid.More preferably, the concentration of described perchloric acid in reaction solution is 0.1-2molL
-1.
Oxidant in described chemical method can be ammonium persulfate or iron chloride.Preferably, the oxidant in chemical method is ammonium persulfate.The concentration of described ammonium persulfate in reaction solution is 0.005-1.5mol L
-1.
Described solvent is preferably water.
Described carbon-based material is that thickness is that film material or the particle diameter of 0.01-1 millimeter is the granular material of 0.01-2 micron.Preferably, described carbon-based material is selected from one or more in Graphene (graphene), graphene oxide (graphene oxide), carbon nano-tube, carbon paper and carbon cloth.More preferably, described carbon-based material is Graphene.The BET specific area of described carbon-based material is preferably 10-600 meters squared per gram.
Embodiment 1
This embodiment is for illustrating the preparation method of carbon-based composite electrode material of the present invention.
Be 1molL to the concentration of 20mL
-1hClO
4in the aqueous solution, add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure), obtaining concentration is 0.1molL
-1aniline monomer solution.
Graphene dispersing solution is prepared through following process: first, by Hummers method, native graphite is oxidized to graphene oxide.Its process is that the sodium nitrate (Chemical Reagent Co., Ltd., Sinopharm Group) of the sheet native graphite (Chemical Reagent Co., Ltd., Sinopharm Group) of 5g and 2g is mixed, and add (98wt%, Chemical Reagent Co., Ltd., Sinopharm Group) in the 120mL concentrated sulfuric acid.Under condition of ice bath, stir, and slowly add the potassium permanganate of 15g, reaction is carried out, after 2-3 hour, adding the deionized water of 300mL to this reactant liquor, makes temperature rise to 100 ℃ and also continues reaction 30 minutes.Then further in this reactant liquor, add the deionized water of 100mL to dilute described reactant liquor, and add the hydrogenperoxide steam generator (30wt%, Chemical Reagent Co., Ltd., Sinopharm Group) of 15mL to neutralize unreacted potassium permanganate.After 30 minutes, filter while hot, and repeatedly rinse 3-5 time with deionized water.Then at the temperature of 60 ℃, vacuumize 72 hours, obtains dry graphene oxide.Then dry graphene oxide is scattered in deionized water, makes the concentration of graphene oxide be about 1mg mL
-1, in ultrasonic disperser, adopt the power of 80W by ultrasonic this dispersion liquid dispersion 30min, make graphene oxide dispersed.By gained dispersion liquid centrifugal graphene oxide particle (particle of not peeled off is completely attached on the inwall of centrifuge) of not peeled off completely of removing under the condition of 5000r/min, obtain the graphene oxide dispersion liquid of black.Then still in ultrasonic disperser, adopt the power of 80W and in this dispersion liquid, add reducing agent hydrazine hydrate (30w%, Aldrich) at the temperature of 30-80 ℃, the concentration that makes hydrazine hydrate is 0.1mol L
-1, when reduction reaction was carried out after 6 hours, under the condition of 10000r/min, the centrifugal Graphene subparticle of removing a small amount of reunion in gained reaction solution, obtains uniform black graphene dispersing solution.
At the temperature of 25 ℃, graphene film (10 × the 30mm obtaining with this graphene dispersing solution suction filtration, 0.02mm) as work electrode, with Pt sheet (15 × 30mm, 0.2mm) conduct is to electrode, using saturated calomel electrode as reference electrode, take above-mentioned aniline monomer solution as electrolyte, the method that adopts constant current, current density is 0.01mAcm
-2, switch on 1 hour, in the polyaniline nano linear array (electromicroscopic photograph as shown in Figure 1) of surface deposition one deck green of work electrode.Can be estimated and be obtained by Electronic Speculum picture, the diameter 50nm of polyaniline nano-line, length are about 400nm.Obtain thus conductive polymer nanometer linear array of the present invention and graphene combination electrode material, the proportion of Graphene in combination electrode material is 85 % by weight.
Embodiment 2
This embodiment is for illustrating the preparation method of combination electrode material of the present invention.
Be 1.5molL to the concentration of 20mL
-1hClO
4in the aqueous solution, add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure), obtaining concentration is 0.1molL
-1aniline monomer solution.
At the temperature of 25 ℃, with business carbon paper (10 × 30mm, 0.19mm, toray company, Toray carbon paper) as work electrode, with Pt sheet (15 × 30mm, 0.2mm) conduct is to electrode, using saturated calomel electrode as reference electrode, take above-mentioned aniline monomer solution as electrolyte, the method that adopts constant current, current density is 0.01mAcm
-2, switch on 2 hours, in the polyaniline nano linear array (can see by ESEM) of surface deposition one deck green of work electrode.Can be estimated and be obtained by Electronic Speculum picture, the diameter 50nm of polyaniline nano-line, length are about 500nm, obtain thus conductive polymer nanometer linear array of the present invention and carbon paper combination electrode material.The proportion of carbon paper in combination electrode material is 95 % by weight.
Embodiment 3
This embodiment is for illustrating the preparation method of carbon-based composite electrode material of the present invention.
Be 1molL to the concentration of 20mL
-1hClO
4in the aqueous solution, add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure), making its concentration is 0.05molL
-1.Adding wherein 9mL concentration is the graphene oxide dispersion soln (making according to the method described in embodiment 1) of 1mg/mL again, then adds oxidant ammonium persulfate, and making its concentration is 0.034molL
-1.At the temperature of-10 ℃, stirring reaction 24 hours.Reaction after isolated by filtration solid sample, and with concentration be 0.1molL
-1hClO
4solution, by this sample washing three times (each 5mL), obtains depositing polyaniline and the graphene oxide composite electrode material of one deck polyaniline nano linear array on graphene oxide surface.Can be estimated and be obtained by Electronic Speculum picture, the diameter of polyaniline nano-line is about 50nm, length is about 200nm.The proportion of graphene oxide in combination electrode material is 27 % by weight.
Embodiment 4
This embodiment is for illustrating the preparation method of carbon-based composite electrode material of the present invention.
Be 1molL to the concentration of 20mL
-1hClO
4in the aqueous solution, add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure), making its concentration is 0.01molL
-1.In this solution, put into business carbon paper (10 × 30mm, 0.19mm, toray company, the Toray carbon paper) small pieces of three cuttings, and then add oxidant ammonium persulfate, making its concentration is 0.0067molL
-1.At the temperature of 0-5 ℃, stirring reaction 24 hours.Reaction after isolated by filtration solid sample, and with concentration be 0.1molL
-1hClO
4solution, by this sample washing three times (each 20mL), obtains depositing polyaniline and the carbon paper combination electrode material of one deck polyaniline nano linear array on carbon paper surface.Can be estimated and be obtained by Electronic Speculum picture, the diameter of polyaniline nano-line is about 50nm, length is about 150nm.The proportion of carbon paper in combination electrode material is 5 % by weight.
Embodiment 5
Prepare polyaniline nano linear array and graphene combination electrode according to the method for embodiment 1, different, current density is 0.08mAcm
-2, the diameter 70nm of the nano wire obtaining, the polyaniline nano linear array that length is about 400nm, but on nano-wire array, there is the nano wire that part is unordered.
Embodiment 6
Prepare polyaniline nano linear array and graphene combination electrode material according to the method for embodiment 1, different, the reaction time is 20min, obtains the polyaniline nano linear array that the about 50nm of nanowire diameter, length are about 100nm on Graphene surface.
Embodiment 7
Prepare polyaniline nano linear array and graphene oxide composite electrode material according to the method for embodiment 3, different, aniline monomer concentration is 0.12molL
-1, on graphene oxide surface, obtain the polyaniline nano linear array that the about 50nm of nanowire diameter, length are about 200nm, but on nano-wire array, occur more unordered nano wire.
Embodiment 8
Prepare polyaniline nano linear array and graphene oxide combination electrode according to the method for embodiment 3, different is, but reaction temperature is 40 ℃, on graphene oxide surface, obtaining nanowire diameter is polyaniline and the graphene oxide composite electrode material that 50nm, length are about 200nm, but in nano-wire array, the arrangement of nano wire is more unordered.
Comparative example 1
Prepare polyaniline and graphene combination electrode material according to the method for embodiment 1, different, current density is 2mAcm
-2, result has formed the unordered polyaniline nano-line (diameter is 100-200nm) of one deck on the surface of Graphene, does not generate orderly polyaniline nano linear array.
Fig. 1 represents to adopt the electron micrograph (amplifying 90,000 times) of the polyaniline nano linear array that the method for the embodiment of the present invention 1 deposits on graphene film.Fig. 2 represents to adopt polyaniline nano linear array that the method for the embodiment of the present invention 3 prepares and the electron micrograph of graphene combination electrode material.From Fig. 1 and Fig. 2, can find out neat and orderly on grapheme material of polyaniline nano linear array.
Fig. 3 represents to adopt polyaniline nano linear array that the method for the embodiment of the present invention 5 prepares and the electron micrograph of graphene combination electrode material.From Fig. 3, can find out, in the polyaniline nano linear array forming on grapheme material, some unordered polyaniline nano-lines have been scattered.
From embodiment 5 results, although the current density adopting in reaction large (in the scope allowing in the present invention), also can on Graphene surface, generate nano-wire array, be to occur the nano wire that part is unordered in obtained polyaniline nano linear array; From the result of embodiment 6, because the reaction time is too short, the length of the polyaniline nano linear array obtaining is shorter; From the result of embodiment 7, due to the concentration large (in the scope allowing in the present invention) of aniline monomer in electrolyte, in the polyaniline nano linear array obtaining, also there is the nano wire that part is unordered; From the result of embodiment 8, due to reaction temperature higher (in the scope allowing in the present invention), still can obtain nano-wire array, be in obtained polyaniline nano linear array the arrangement of nano wire more unordered.And comparative example 1 adopts the method for prior art, therefore cannot obtain having the combination electrode material of polyaniline nano linear array.
Performance test
The cyclic voltammetric characteristic (seeing Fig. 4) of the conductive polymer nanometer linear array preparing by cyclic voltammetry test implementation example 1 and graphene combination electrode material; Method by constant current charge-discharge (selects that current density is respectively 0.1,0.5,1,1.5,2,3A g
-1, voltage is for-0.2 to 0.8V) and the conductive polymer nanometer linear array that test implementation example 1 prepares and the capacitive property of graphene combination electrode material (seeing Fig. 5).
As can be seen from Figure 4, compared with simple Graphene electrodes material, polyaniline nano linear array provided by the invention and graphene combination electrode material show good cyclic voltammetry curve, and the area that this cyclic voltammetry curve comprises is larger, show that the capacitance of electrode material is higher.
As can be seen from Figure 5, polyaniline nano linear array provided by the invention and graphene combination electrode show excellent electrochemistry capacitance performance.Under identical current density, the ratio electric capacity of polyaniline nano linear array provided by the invention and graphene combination electrode is much larger than the ratio electric capacity of simple Graphene electrodes.This is that carbon-based material not only can be contributed electric double layer capacity, but also has higher specific area, thereby has improved the active area of conducting polymer, can obtain thus higher ratio electric capacity because in this composite material.
Application examples
According to method described in embodiment 1, respectively using the composite material of grapheme material and polyaniline nano linear array and Graphene as electrode material, according to electrode material: conductive carbon powder (Super P, Beijing reagent company): the part by weight of PTFE (Aldrich company)=85: 10: 5 adds gained mixture in the ethanol (Aldrich company) of 5-10ml, ultrasonic dispersion 15min under the power of 200w, the baking oven of then putting into temperature and be 60 ℃ dries 2 hours.Then products therefrom is rolled into thickness and be the thin slice of 150 microns, this thin slice is pressed on stainless (steel) wire as work electrode with the pressure of 12MPa.Two work electrodes that adopt above-mentioned electrode material to make are assembled into respectively to two Swagelok
tMin instrument (Swagelok company, the U.S.).Method by constant current charge-discharge (selects that current density is respectively 0.1,0.5,1,1.5,2,3Ag
-1, voltage is-0.2 to 0.8V), power density, energy density and cyclical stability (seeing respectively Fig. 6 and Fig. 7) when testing respectively above-mentioned two kinds of electrode materials and being applied to electrode of super capacitor.
As can be seen from Figure 6, adopt combination electrode provided by the invention can make capacitor in thering is higher energy density, (curve is more in the upper right corner also to have higher power density, its power density and energy density are higher), can not obtain higher power density because of off-energy density.Its reason is, the nanostructure of the high-sequential on combination electrode can reduce the transmission path of electrolyte ion, reduce the internal resistance of electrode, be conducive to diffusion and the transmission of ion in electrode material, thereby can make ultracapacitor obtain higher power density.As can be seen from Figure 7, combination electrode provided by the invention has good charge and discharge cycles stability, and this is the result that the nanowire array structure of the high-sequential that has due to composite material and high stability that carbon-based material itself has bring.
Claims (10)
1. a carbon-based composite electrode material, this electrode material contains conducting polymer and carbon-based material, wherein, described conducting polymer is attached to the form of conductive polymer nanometer linear array on the surface of described carbon-based material, described conducting polymer is one or more in polyaniline, polythiophene and poly-ethylenedioxy thiophene, described carbon-based material is that particle diameter is the granular material of 0.01-2 micron, the content of described conductive polymer nanometer linear array is 10-50 % by weight, and the content of described carbon-based material is 50-90 % by weight.
2. carbon-based composite electrode material according to claim 1, wherein, described conductive polymer nanometer linear array neat and orderly.
3. carbon-based composite electrode material according to claim 1 and 2, wherein, the diameter of the nano wire of described conductive polymer nanometer linear array is 40-100nm, the length of nano wire is 100-1500nm.
4. carbon-based composite electrode material according to claim 3, wherein, the diameter of the nano wire of described conductive polymer nanometer linear array is 50-80nm, the length of nano wire is 150nm-1000nm.
5. carbon-based composite electrode material according to claim 1, wherein, described carbon-based material is one or more in Graphene and graphene oxide.
6. the preparation method of carbon-based composite electrode material described in a claim 1, the method is without templated chemistry method, describedly comprise carbon-based material particle is scattered in the reaction solution that contains conducting polymer monomer, dopant and oxidant without templated chemistry method, at the temperature of-10 ℃ to 20 ℃, stirring reaction 1-48 hour, generates conductive polymer nanometer linear array at carbon-based material surface in situ.
7. method according to claim 6, wherein, contains 0.01-0.1molL in described reaction solution
-1conducting polymer monomer, 0.1-2molL
-1dopant and 0.005-1.5molL
-1oxidant, the reaction time is 24-48 hour, reaction temperature is-10 ℃ to 15 ℃.
8. method according to claim 6, wherein, described oxidant is ammonium persulfate or iron chloride.
9. according to the method described in claim 6 or 7, wherein, described conducting polymer monomer is aniline monomer; Described dopant is one or more in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid.
10. the application of the carbon-based composite electrode material described in any one in ultracapacitor in claim 1-5.
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