CN102222565A - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000007772 electrode material Substances 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title abstract description 10
- 239000003990 capacitor Substances 0.000 title description 12
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 80
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 48
- 239000002070 nanowire Substances 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 60
- 229920000767 polyaniline Polymers 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 44
- 239000002322 conducting polymer Substances 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 239000002019 doping agent Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002848 electrochemical method Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001311 chemical methods and process Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
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- XWURZHGKODQZMK-UHFFFAOYSA-N O.[Ru]=O Chemical compound O.[Ru]=O XWURZHGKODQZMK-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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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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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明涉及一种碳基复合电极材料及其制备方法和在超级电容器中的应用，该电极材料含有导电聚合物和碳基材料，其中，所述导电聚合物以导电聚合物纳米线阵列的形式附着在所述碳基材料的表面上，所述导电聚合物纳米线阵列的排列整齐有序，所述导电聚合物纳米线阵列的纳米线的直径为40-100nm，纳米线的长度为100-1500nm。本发明提供的碳基复合电极材料具有较高的比表面积和高度有序的纳米结构，大大提高了导电聚合物的活性面积和降低电解液离子的传输路径，减小电极的内阻，有利于离子在电极材料中的扩散与传输，由此可以获得较高的电容容量和功率密度。
The invention relates to a carbon-based composite electrode material and its preparation method and application in supercapacitors. The electrode material contains a conductive polymer and a carbon-based material, wherein the conductive polymer is in the form of a conductive polymer nanowire array Attached to the surface of the carbon-based material, the arrangement of the conductive polymer nanowire array is orderly, the diameter of the nanowire of the conductive polymer nanowire array is 40-100 nm, and the length of the nanowire is 100-100 nm. 1500nm. The carbon-based composite electrode material provided by the invention has a relatively high specific surface area and a highly ordered nanostructure, which greatly increases the active area of the conductive polymer and reduces the transmission path of the electrolyte ions, reduces the internal resistance of the electrode, and is beneficial to Diffusion and transmission of ions in the electrode material, which can obtain higher capacitance capacity and power density.
Description
Technical field
The present invention relates to a kind of carbon back combination electrode material and preparation method thereof and the application in ultracapacitor.
Background technology
Ultracapacitor is called electrochemical capacitor again, 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 based on the material with carbon element of high-specific surface area, dependence be that the separation of charge of electrode and electrolyte interface forms electric double layer and comes stored charge.The electrode material of fake capacitance device then comprises metal oxide and conducting polymer, dependence be that electrode active material reversible redox reaction takes place fast comes stored charge.For double electric layer capacitor, its capacitance is proportional to electrode and electrolytical interface size, so the performance of electrode is subjected 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 descend, and this can influence the performance of capacitor to a great extent.Compare with double electric layer capacitor, the fake capacitance device then has higher ratio capacitance, for example dry oxidation ruthenium (RuO
2) and ruthenium-oxide hydrate (RuO
2NH
2O) ratio capacitance has reached 385Fg respectively
-1And 920Fg
-1, but the high costs constraints of noble metal its extensive use in commerce.Comparatively speaking, conducting polymer then have cheap, conductivity is high and the advantage that can synthesize in several ways.
The more conducting polymer of research comprises polypyrrole, polyaniline, polythiophene and poly-enedioxy thiophene etc. at present, but these conducting polymers all are based on the electrode material of film or unordered nano wire, its capacitance is compared with the capacitance of theoretical prediction, has bigger gap.Reporting employing " a step co-electrodeposition method prepares manganese dioxide and poly-enedioxy thiophene co-axial nano line and the application in a energy storage " literary composition on " JACS " the 10th phase in 2008 2942-2943 page or leaf, adopt aluminium oxide to prepare nano-wire array by electrochemical means in the literary composition, in supercapacitor applications, embody good charge transport properties as template.But adopt template to prepare nano-wire array, process is loaded down with trivial details, and also can damage nano-wire array when the dissolving template.
In addition, the conductive polymer electrodes material can be accompanied by the doping-dedoping to ion when discharging and recharging, this causes the volume of polymer to expand-shrink, thereby polymeric material generation stress rupture is reduced the capacity of polymer, the cyclical stability of impact polymer electrode.
Summary of the invention
In order to overcome the imperfect shortcoming of cyclical stability that process was loaded down with trivial details, template easily is damaged when above-mentioned template prepared electrode material deficiency and polymer electrode material discharge and recharge, the invention provides that a kind of technology is simple, with low cost, the carbon back combination 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 back combination electrode material, this electrode material contains conducting polymer and carbon-based material, wherein, and on the surface of form attached to described carbon-based material of described conducting polymer with the conductive polymer nanometer linear array.
A preferred embodiment of the invention wherein, is a benchmark with the total amount of described carbon back combination electrode material, and the content of described conductive polymer nanometer linear array is 5-95 weight %, and the content of described carbon-based material is 5-95 weight %.
According to another kind of preferred implementation of the present invention, wherein, be benchmark with the total amount of described carbon back combination electrode material, the content of described conductive polymer nanometer linear array is 10-50 weight %, the content of described carbon-based material is 50-90 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 the poly-enedioxy thiophene.
According to another kind of preferred implementation of the present invention, wherein, described carbon-based material is that thickness is that the 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 the carbon cloth.
According to another aspect of the present invention, the invention provides a kind of preparation method of carbon back combination electrode material, this method is the non-template electrochemical method, described non-template electrochemical method comprises that with membranaceous carbon-based material be work electrode, with platinized platinum is to electrode, with the saturated calomel electrode is reference electrode, is electrolyte with the aqueous solution that contains conducting polymer monomer and dopant, generates the conductive polymer nanometer linear array at the carbon-based material surface in situ.
A preferred embodiment of the invention wherein, contains 0.01-1molL in the electrolyte described in the 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 that adopts in the 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 back combination electrode material, this method is no templated chemistry method, described no templated chemistry method comprises the carbon-based material Dispersion of Particles in the reaction solution that contains conducting polymer monomer, dopant and oxidant, under-10 ℃ to 20 ℃ temperature, stirring reaction 1-48 hour, generate the conductive polymer nanometer linear array at the carbon-based material surface in situ.
A preferred embodiment of the invention wherein, contains 0.01-0.1molL in the reaction solution described in the no 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, oxidant is ammonium persulfate or iron chloride described in the no templated chemistry method.
According to another kind of preferred implementation of the present invention, wherein, described conducting polymer monomer is an aniline monomer; Described dopant is one or more in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and the camphorsulfonic acid.
According to a further aspect of the invention, the invention provides the application of described carbon back combination electrode material in ultracapacitor.
Carbon back combination electrode material provided by the invention has following significant advantage: (1) this carbon back combination electrode material has higher specific surface area, has improved the active area of conducting polymer greatly, can obtain higher capacitance thus.Table 1 has shown that current density is 1Ag
-1The time, Graphene electrodes material and the capacitance values comparing result by the combination electrode of electrochemical method after deposition polyaniline nano linear array on the graphene film.(2) this combination electrode material is made up of the carbon-based material that the conductive polymer nanometer linear array is deposited on high-specific surface area, has the nanostructure of high-sequential.This ordered structure can reduce the transmission path of electrolyte ion, reduces the internal resistance of electrode, helps diffusion and the transmission of ion in electrode material, can make ultracapacitor obtain higher power density.(3) this conducting polymer composite material is added carbon-based material itself and is had high stability, so this electrode material has charge and discharge cycles stability preferably owing to have the array nanostructure of high-sequential.(4) electrode material described herein is based on the cheap conducting polymer and carbon-based material basis, and the one-step method by no template prepares combination electrode material, 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 |
Description of drawings
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 invention 1 obtains on graphene film.
Fig. 2 represents to adopt the polyaniline nano linear array that the method for the embodiment of the invention 3 prepares and the electron micrograph of graphene combination electrode material.
Fig. 3 represents to adopt the polyaniline nano linear array that the method for the embodiment of the invention 5 prepares and the electron micrograph of graphene combination electrode material.
Fig. 4 represents to adopt the 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 the 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 the 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
Because the cyclical stability that the conductive polymer electrodes material discharges and recharges is good inadequately, therefore conductive polymers ordered nano structure and material with carbon element is compound, the synergy of the stability of performance material with carbon element and the high power capacity of conductive polymer nanometer structure can the excellent more ultracapacitor of obtained performance.Based on this discovery, the invention provides a kind of carbon back combination electrode material, this electrode material contains conducting polymer and carbon-based material, it is characterized in that, on the surface of form attached to described carbon-based material of described conducting polymer with the conductive polymer nanometer linear array.
In the present invention, be benchmark with the total amount of described carbon back combination electrode material, the content of described conductive polymer nanometer linear array is 5-95 weight %, the content of described carbon-based material is 5-95 weight %.Under the preferable case, the content of described conductive polymer nanometer linear array is 10-50 weight %, and the content of described carbon-based material is 50-90 weight %.
According to carbon back combination electrode material provided by the invention, described conductive polymer nanometer linear array neat and orderly, the capacitance of this carbon back combination electrode material is significantly improved than simple material with carbon element, reason is, be distributed in the orderly conductive polymer nanometer linear array on the 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 the diffusion and the electric transmission of ion greatly, effectively reduce the internal resistance of capacitor, even under the higher speed that discharges and recharges, also can obtain higher capacity (being higher power density) like this.
Carbon back combination electrode material provided by the invention, the diameter of the nano wire of described conductive polymer nanometer linear array are 40-100nm, and the length of nano wire is 100-1500nm.Under the 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 that covers in the conductive polymer nanometer linear array of this range scale has better capacitive property.
Have the shortcoming that process is loaded down with trivial details and template easily is damaged owing to adopting template to prepare electrode material, so the present invention adopts the non-template electrochemical method or does not have the templated chemistry method in carbon-based material surface one step formation conductive polymer nanometer linear array.Wherein, the non-template electrochemical method is to be work electrode with membranaceous carbon-based material, with platinized platinum is to electrode, with the saturated calomel electrode is reference electrode, with the aqueous solution that contains conducting polymer monomer and dopant is electrolyte, the temperature of electrolyte is 20-40 ℃, and be 0.5-3 hour conduction time, and current density is 0.01-1mAcm
-2, the conducting polymer monomer generates the conductive polymer nanometer linear array at the carbon-based material surface in situ.Under the preferable case, contain 0.01-1molL in the described electrolyte
-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 is lower in the electrolyte prescription that the present invention adopts, and adopt less current density, therefore can on described carbon-based material, generate the nano-wire array of arrangement in good order, if the excessive concentration or the current density of conducting polymer monomer are excessive, then on carbon-based material, nano-wire array can be do not generated, only some unordered nano wires can be generated.
No templated chemistry method is that Dispersion of Particles with carbon-based material is in the reaction solution that contains conducting polymer monomer, dopant, oxidant and solvent, under-10 ℃ to 20 ℃ temperature, stirring reaction 1-48 hour, generate the conductive polymer nanometer linear array at the 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 weight %.
Similarly, in above-mentioned no templated chemistry method, because the concentration of conducting polymer monomer is lower in the reaction solution that the present invention adopts, and adopt lower reaction temperature, more preferably-10 ℃, therefore can on described carbon-based material, generate the nano-wire array of arrangement in good order to 5 ℃, too high as if the concentration or the reaction temperature of conducting polymer monomer, then on carbon-based material, nano-wire array can be do not generated, only some unordered nano wires can be generated.
As seen, adopt non-template electrochemical method and no templated chemistry legal system to be equipped with in the process of 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 access a kind of the 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, and the length of nano wire is 100-1500nm.
Described conducting polymer is selected from one or more in polyaniline, polypyrrole, polythiophene and the poly-enedioxy thiophene.Described conducting polymer monomer is for forming the corresponding monomer of above-mentioned conducting polymer.More preferably, described conducting polymer monomer is an aniline monomer.Further preferably, the concentration of conducting polymer monomer is 0.01-0.1mol L in the described reaction solution of chemical method
-1
Described dopant can be selected from sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and the camphorsulfonic acid one or more.Preferably, dopant is a perchloric acid.More preferably, the concentration of described perchloric acid in reaction solution is 0.1-2molL
-1
Oxidant in the described chemical method can be ammonium persulfate or iron chloride.Preferably, the oxidant in the chemical method is an 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 the 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 the carbon cloth.More preferably, described carbon-based material is a Graphene.The BET specific area of described carbon-based material is preferably the 10-600 meters squared per gram.
This embodiment is used to illustrate the preparation method of carbon back combination electrode material of the present invention.
Concentration to 20mL is 1molL
-1HClO
4Add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure) in the aqueous solution, obtaining concentration is 0.1molL
-1Aniline monomer solution.
The Graphene dispersion liquid prepares through following process: at first, by the Hummers method native graphite is oxidized to graphene oxide.Its process is sodium nitrate (Chemical Reagent Co., Ltd., Sinopharm Group) mixing with the sheet native graphite (Chemical Reagent Co., Ltd., Sinopharm Group) of 5g and 2g, and adds in the 120mL concentrated sulfuric acid (98wt%, Chemical Reagent Co., Ltd., Sinopharm Group).Under condition of ice bath, stir, and slowly add the potassium permanganate of 15g, after reaction is carried out 2-3 hour,, make temperature rise to 100 ℃ and also continue reaction 30 minutes to the deionized water of this reactant liquor adding 300mL.The deionized water that further adds 100mL then in this reactant liquor to be diluting described reactant liquor, and the hydrogenperoxide steam generator (30wt%, Chemical Reagent Co., Ltd., Sinopharm Group) that the adds 15mL unreacted potassium permanganate that neutralizes.After 30 minutes, filter while hot, and wash 3-5 time repeatedly with deionized water.Under 60 ℃ temperature, vacuumize 72 hours promptly obtains dry graphene oxide then.Graphene oxide with drying is scattered in the deionized water then, makes the concentration of graphene oxide be about 1mg mL
-1, the power that adopts 80W in ultrasonic disperser evenly disperses graphene oxide the ultrasonic dispersion of this dispersion liquid 30min.The gained dispersion liquid at the centrifugal graphene oxide particle of not peeled off fully (particle of not peeled off fully is attached on the inwall of centrifuge) of removing under the condition of 5000r/min, is obtained the graphene oxide dispersion liquid of black.Still in ultrasonic disperser, adopt the power of 80W then and (30w%, Aldrich), the concentration that makes hydrazine hydrate is 0.1mol L add the reducing agent hydrazine hydrate under 30-80 ℃ the temperature in this dispersion liquid
-1, after reduction reaction was carried out 6 hours, the centrifugal Graphene subparticle of removing a small amount of reunion in the gained reaction solution under the condition of 10000r/min obtained uniform black Graphene dispersion liquid.
Under 25 ℃ temperature, graphene film (10 * the 30mm that obtains with this Graphene dispersion liquid suction filtration, 0.02mm) as work electrode, with Pt sheet (15 * 30mm, 0.2mm) as to electrode, as reference electrode, be electrolyte with above-mentioned aniline monomer solution with saturated calomel electrode, adopt the method for constant current, current density is 0.01mAcm
-2, switched on 1 hour, in the polyaniline nano linear array (seeing electromicroscopic photograph shown in Figure 1) of surface deposition one deck green of work electrode.Can estimate by the Electronic Speculum picture to obtain that the about 50nm of the diameter of polyaniline nano-line, length are about 400nm.Obtain conductive polymer nanometer linear array of the present invention and graphene combination electrode material thus, the proportion of Graphene in combination electrode material is 85 weight %.
This embodiment is used to illustrate the preparation method of combination electrode material of the present invention.
Concentration to 20mL is 1.5molL
-1HClO
4Add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure) in the aqueous solution, obtaining concentration is 0.1molL
-1Aniline monomer solution.
Under 25 ℃ temperature, with commercial carbon paper (10 * 30mm, 0.19mm, toray company, Toray carbon paper) and as work electrode, with Pt sheet (15 * 30mm, 0.2mm) as to electrode, as reference electrode, be electrolyte with above-mentioned aniline monomer solution with saturated calomel electrode, adopt the method for constant current, current density is 0.01mAcm
-2, switched on 2 hours, in the polyaniline nano linear array (can see) of surface deposition one deck green of work electrode by ESEM.Can estimate by the Electronic Speculum picture to obtain that the about 50nm of the diameter of polyaniline nano-line, length are about 500nm, obtain conductive polymer nanometer linear array of the present invention and carbon paper combination electrode material thus.The proportion of carbon paper in combination electrode material is 95 weight %.
Embodiment 3
This embodiment is used to illustrate the preparation method of carbon back combination electrode material of the present invention.
Concentration to 20mL is 1molL
-1HClO
4Add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure) in the aqueous solution, making its concentration is 0.05molL
-1To wherein adding the graphene oxide dispersion soln that 9mL concentration is 1mg/mL (making according to embodiment 1 described method), add the oxidant ammonium persulfate then again, making its concentration is 0.034molL
-1Under-10 ℃ temperature, stirring reaction 24 hours.Reaction back isolated by filtration solid sample, and be 0.1molL with concentration
-1HClO
4Solution obtains the polyaniline and the graphene oxide combination electrode material of deposition one deck polyaniline nano linear array on the graphene oxide surface with this sample washing three times (each 5mL).Can estimate by the Electronic Speculum picture to obtain that the diameter of polyaniline nano-line is about 50nm, length is about 200nm.The proportion of graphene oxide in combination electrode material is 27 weight %.
Embodiment 4
This embodiment is used to illustrate the preparation method of carbon back combination electrode material of the present invention.
Concentration to 20mL is 1molL
-1HClO
4Add aniline monomer (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure) in the aqueous solution, making its concentration is 0.01molL
-1Put into commercial carbon paper (10 * 30mm, 0.19mm, toray company, the Toray carbon paper) small pieces of three cuttings in this solution, and then add the oxidant ammonium persulfate, making its concentration is 0.0067molL
-1Under 0-5 ℃ temperature, stirring reaction 24 hours.Reaction back isolated by filtration solid sample, and be 0.1molL with concentration
-1HClO
4Solution obtains the polyaniline and the carbon paper combination electrode material of deposition one deck polyaniline nano linear array on the carbon paper surface with this sample washing three times (each 20mL).Can estimate by the Electronic Speculum picture to obtain that the diameter of polyaniline nano-line is about 50nm, length is about 150nm.The proportion of carbon paper in combination electrode material is 5 weight %.
Embodiment 5
Method according to embodiment 1 prepares polyaniline nano linear array and graphene combination electrode, and different is that current density is 0.08mAcm
-2, the about 70nm of the diameter of the nano wire that obtains, length are about the polyaniline nano linear array of 400nm, but occur the unordered nano wire of part on nano-wire array.
Embodiment 6
Method according to embodiment 1 prepares polyaniline nano linear array and graphene combination electrode material, and different is, the reaction time is 20min, obtains the polyaniline nano linear array that the about 50nm of nanowire diameter, length are about 100nm on the Graphene surface.
Embodiment 7
Method according to embodiment 3 prepares polyaniline nano linear array and graphene oxide combination electrode material, and different is that aniline monomer concentration is 0.12molL
-1, on the 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, more unordered nano wire occurs.
Embodiment 8
Method according to embodiment 3 prepares polyaniline nano linear array and graphene oxide combination electrode, different is, but reaction temperature is 40 ℃, obtaining nanowire diameter on the graphene oxide surface is polyaniline and the graphene oxide combination electrode material that 50nm, length are about 200nm, but the arrangement of nano wire is more unordered in the nano-wire array.
Comparative Examples 1
Method according to embodiment 1 prepares polyaniline and graphene combination electrode material, and different is that current density is 2mAcm
-2, the result has formed the unordered polyaniline nano-line (diameter is 100-200nm) of one deck on the surface of Graphene, do 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 invention 1 deposits on graphene film.Fig. 2 represents to adopt the polyaniline nano linear array that the method for the embodiment of the invention 3 prepares and the electron micrograph of graphene combination electrode material.On Fig. 1 and Fig. 2 as can be seen, polyaniline nano linear array neat and orderly on grapheme material.
Fig. 3 represents to adopt the polyaniline nano linear array that the method for the embodiment of the invention 5 prepares and the electron micrograph of graphene combination electrode material.As can be seen, in the polyaniline nano linear array that forms on grapheme material, some unordered polyaniline nano-lines have been scattered from Fig. 3.
From embodiment 5 results,, be to occur the unordered nano wire of part in the resulting polyaniline nano linear array though the current density that adopts in the reaction big (in the scope that the present invention allows) also can generate nano-wire array on the Graphene surface; From the result of embodiment 6, because the reaction time is too short, the length of resulting polyaniline nano linear array is shorter; From the result of embodiment 7, because the unordered nano wire of part also appears in the concentration of aniline monomer big (in the scope that the present invention allows) in the electrolyte in the resulting polyaniline nano linear array; From the result of embodiment 8, because reaction temperature higher (in the scope that the present invention allows) still can obtain nano-wire array, the arrangement that is nano wire in the resulting polyaniline nano linear array is more unordered.And Comparative Examples 1 adopts the method for prior art, therefore the combination electrode material that can't obtain having the polyaniline nano linear array.
Performance test
The conductive polymer nanometer linear array for preparing by cyclic voltammetry test implementation example 1 and the cyclic voltammetric characteristic (see figure 4) of 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 (see figure 5) of graphene combination electrode material.
As can be seen from Figure 4, compare with simple Graphene electrodes material, polyaniline nano linear array provided by the invention and graphene combination electrode material show cyclic voltammetry curve preferably, and the area that this cyclic voltammetry curve comprises is big more, show that the capacitance of electrode material is high more.
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 the electric double layer capacity, but also has higher specific surface area, thereby has improved the active area of conducting polymer, can obtain higher ratio electric capacity thus because in this composite material.
Application examples
According to embodiment 1 described method, respectively with 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 the gained mixture in the ethanol (Aldrich company) of 5-10ml, ultrasonic dispersion 15min under the power of 200w puts into temperature and is 60 ℃ baking oven baking 2 hours then.Then products therefrom is rolled into thickness and be 150 microns thin slice, this thin slice is pressed on the 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 two Swagelok respectively
TMIn the 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 Fig. 6 and Fig. 7 respectively) when testing above-mentioned two kinds of electrode materials respectively 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 when having high energy density, (curve is in the upper right corner more also to have higher power density, its power density and energy density are high more), promptly 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, help 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 charge and discharge cycles stability preferably, and this is the result that the nano-wire array structure of the high-sequential that has owing to composite material and high stability that carbon-based material itself has bring.
Claims (17)
1. carbon back combination electrode material, this electrode material contains conducting polymer and carbon-based material, wherein, on the surface of form attached to described carbon-based material of described conducting polymer with the conductive polymer nanometer linear array.
2. carbon back combination electrode material according to claim 1 wherein, is a benchmark with the total amount of described carbon back combination electrode material, and the content of described conductive polymer nanometer linear array is 5-95 weight %, and the content of described carbon-based material is 5-95 weight %.
3. carbon back combination electrode material according to claim 2 wherein, is a benchmark with the total amount of described carbon back combination electrode material, and the content of described conductive polymer nanometer linear array is 10-50 weight %, and the content of described carbon-based material is 50-90 weight %.
4. carbon back combination electrode material according to claim 1, wherein, described conductive polymer nanometer linear array neat and orderly.
5. according to any described carbon back combination electrode material among the claim 1-4, 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.
6. carbon back combination electrode material according to claim 5, 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.
7. carbon back combination electrode material according to claim 5, wherein, described conducting polymer is one or more in polyaniline, polypyrrole, polythiophene and the poly-enedioxy thiophene.
8. carbon back combination electrode material according to claim 1, wherein, described carbon-based material is that thickness is that the film material or the particle diameter of 0.01-1 millimeter is the granular material of 0.01-1 micron.
9. carbon back combination electrode material according to claim 8, wherein, described carbon-based material is one or more in Graphene, graphene oxide, carbon nano-tube, carbon paper and the carbon cloth.
10. the preparation method of a carbon back combination electrode material, this method is the non-template electrochemical method, described non-template electrochemical method comprises that with membranaceous carbon-based material be work electrode, with platinized platinum is to electrode, with the saturated calomel electrode is reference electrode, with the aqueous solution that contains conducting polymer monomer and dopant is electrolyte, generates the conductive polymer nanometer linear array at the carbon-based material surface in situ.
11. method according to claim 10 wherein, contains 0.01-1molL in the described electrolyte
-1Conducting polymer monomer and 0.1-2molL
-1Dopant.
12. method according to claim 10, wherein, the current density that adopts in the described non-template electrochemical method is 0.01-1mAcm
-2, be 0.5-3 hour conduction time, the temperature of electrolyte is 20-40 ℃.
13. the preparation method of a carbon back combination electrode material, this method is no templated chemistry method, described no templated chemistry method comprises the carbon-based material Dispersion of Particles in the reaction solution that contains conducting polymer monomer, dopant and oxidant, under-10 ℃ to 20 ℃ temperature, stirring reaction 1-48 hour, generate the conductive polymer nanometer linear array at the carbon-based material surface in situ.
14. method according to claim 13 wherein, contains 0.01-0.1molL in the 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 ℃.
15. method according to claim 13, wherein, described oxidant is ammonium persulfate or iron chloride.
16. according to claim 10,11,13 or 14 described methods, wherein, described conducting polymer monomer is an aniline monomer; Described dopant is one or more in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and the camphorsulfonic acid.
17. the application of any described carbon back combination electrode material in ultracapacitor among the claim 1-9.
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