CN103065813B - The preparation method of electrode of super capacitor and application thereof - Google Patents
The preparation method of electrode of super capacitor and application thereof Download PDFInfo
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Abstract
The invention provides a kind of preparation method of electrode of super capacitor, comprise the following steps: graphene oxide dispersion a) preparing certain mass concentration; B) resilient three-dimensional porous material is immersed in step a) gained graphene oxide dispersion, centrifugal after taking out, then be immersed in graphene oxide also in original reagent, reduction at a certain temperature obtains the three-dimensional porous material that reduced graphene is modified; C) three-dimensional porous material that the reduced graphene of step b) gained is modified successively is immersed in bivalent manganese solution and septivalency manganese solution, then with washed with de-ionized water several, obtains final electrode of super capacitor.Electrode of super capacitor prepared by the present invention has excellent power density and energy density, and good cycling stability is with low cost, and preparation method is simple, is easy to commercially produce.
Description
Technical field
The invention belongs to ultracapacitor field, particularly relate to a kind of preparation method and application thereof of electrode of super capacitor.
Background technology
In today that energy source height consumes, earth fossil fuel is petered out, and tellurian oil will be exhausted after about 50 years to have scientist to foretell, the mankind must find the reproducible energy.Solar energy and wind energy inexhaustible, be desirable alternative energy source.How but by these step energy quick storage and to discharge fast be again a difficult problem always, although the energy density of traditional chemical cell is very high, but power density is lower, and the discharge and recharge time is long, is difficult to the storage difficult problem solving intermittent energy.Ultracapacitor is a class newly energy energy storage material of high speed development in recent years, and have very high power density, quite long useful life, discharge and recharge rapidly, are the desirable storage mediums of intermittent energy.Current each state all spares no effort to carry out research and development to ultracapacitor.
According to the mode of charge storage, ultracapacitor can be divided into two kinds, and one forms electric double layer on the surface in electric level to carry out stored energy, and another kind carrys out stored energy based on Quick Oxidation reduction reaction.The former electrode material generally uses the material with carbon element of high conductivity and specific area, such traditional electrode of super capacitor generally uses active carbon material, although cost compare is cheap, and poorly conductive, specific area is little, and power density and energy density are all lower.Recent years, the carbon nano-tube of scientist's high conductivity and high-ratio surface and Graphene, as electrode material, substantially increase power density and the energy density of ultracapacitor.Such as U.S.'s " science " (Science, 335 phases, 1326 pages in 2012) reports one laser reduction Graphene to prepare electrode of super capacitor, and the conductivity of electrode is up to 1738Scm
-1, far above active carbon (10 ~ 100Scm
-1) surface area also reaches 1520m
2g
-1, with activated carbon quite (1000 ~ 2000m
2g
-1).But this kind of capacitor is limited to specific area, energy density is not high, and the theoretical capacity of grapheme material also only has 550F/g.Therefore, the another kind of fake capacitance ultracapacitor based on metal oxide is subject to extensive concern.The energy density of this kind of capacitor is very high, and the theoretical electric capacity of such as manganese dioxide is about 1300F/g, and far above double electric layers supercapacitor, but the power density of fake capacitance is very low.
Therefore, scientist begins one's study the ultracapacitor of electric double layer and fake capacitance compound, prepares high-performance super capacitor in conjunction with the high power density of electric double layer and the high-energy-density of fake capacitance.This kind of material is generally high by conductivity, that specific area is high material with carbon element has fake capacitance character polymeric material compound with metal oxide and some.The carbon nano-tube that material with carbon element is good based on conductivity, specific area is high and Graphene, fake capacitance material is based on the manganese dioxide of cheapness, but this kind of composite material is mostly pulverulence, is difficult to control its pattern, size and homogeneity on electrode material.In order to address this problem, scientist develops the three-dimensional porous material with carbon element electrode of self-supporting recently, material with carbon element modifies nonwoven fabrics and sponge electrode, then in the load of the surface uniform of these self-supporting electrodes fake capacitance material, obtain power density and can all larger electrode of super capacitor of density." nanometer bulletin " (Nanoletter of such as American Chemical Society, 2011,11 phases, 5165 pages) report one seed support hybrid supercapacitor electrode, the first step prepared by this electrode is three-dimensional netted conductive electrode carbon nanotube adsorption formed on sponge skeleton, then uses the method for electro-deposition, and conducting three-dimensional network skeleton grows manganese dioxide, capacitor produced energy density is up to 31Wh/kg, and energy density is higher (63kW/kg) also.But, although the conductivity of the carbon nano-tube that this electrode adopts is very high, but price is high, and the surfactant in preparation process is also difficult to removing, residual surfactant also reduces the conductivity of carbon nano-tube, adopt electro-deposition on conducting three-dimensional network skeleton, grow the method for manganese dioxide in addition very harsh to requirement for experiment condition, be difficult to realize large-scale production.
Therefore, adopt cheap raw material, the manganese dioxide material with carbon element hybrid supercapacitor preparing the self-supporting of high-energy-density and power density by method simple and easy to control is still the target of whole world science unremitting pursue.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of with low cost, preparation is simple, be easy to Graphene/manganese dioxide hybrid supercapacitor electrode material that industry changes into product, wherein high conductive three-dimensional reduced graphene network is very helpful to raising power density, again with having the manganese dioxide compound that excellence has fake capacitance character, the energy density of capacitor greatly can be improved again.
In order to realize object of the present invention, the invention provides a kind of preparation method of electrode of super capacitor, comprising the following steps:
A) graphene oxide dispersion of certain mass concentration is prepared;
B) resilient three-dimensional porous material is immersed in step a) gained graphene oxide dispersion, centrifugal after taking out, then be immersed in graphene oxide also in original reagent, reduction at a certain temperature obtains the three-dimensional porous material that reduced graphene is modified;
C) three-dimensional porous material that the reduced graphene of step b) gained is modified successively is immersed in bivalent manganese solution and septivalency manganese solution, then with washed with de-ionized water several, obtains final electrode of super capacitor.
Preferably, the mass concentration of graphene oxide described in step a) is 1mg/ml ~ 10mg/ml.
Preferably, the porous material of resilient three-dimensional described in step b) is polyester sponge or foam rubber.
Preferably, the aperture of the resilient three-dimensional porous material described in step b) is between 20 μm ~ 500 μm.
Preferably, the centrifugal rotational speed described in step b) is 200rpm ~ 6000rpm, and centrifugation time is 1min ~ 10min.
Preferably, going back original reagent described in step b) is hydroiodic acid solution, sodium borohydride solution, hydrazine hydrate solution wherein one or more, wherein, the concentration of described hydroiodic acid solution is 10wt% ~ 100wt%, the concentration of sodium borohydride solution is 0.51wt% ~ 55wt%, and the concentration of hydrazine hydrate solution is 0.2wt% ~ 15wt%.
Preferably, reduction reaction temperature described in step b) is 25 ° of C ~ 100 ° C.
Preferably, the solution of bivalent manganese described in step c) is manganese acetate solution, manganese nitrate solution, one in manganese chloride solution and manganese sulfate solution, the concentration of described bivalent manganese solution is 4mM ~ 50mM, described septivalency manganese solution is liquor potassic permanganate, and the concentration of described liquor potassic permanganate is 2mM ~ 30mM.
Preferably, in the solution of bivalent manganese described in step c) and septivalency manganese solution, the ratio of divalent manganesetion and septivalency manganese ion molar concentration is 1:1 ~ 2:1.
Further, the invention provides the application of electrode of super capacitor in ultracapacitor prepared by described method.
Beneficial effect of the present invention is as follows:
The electrode of super capacitor adopting said method to prepare, has micron-sized loose structure, is conducive to ion and forms electric double layer on electrode of super capacitor surface, greatly reduce the internal resistance of capacitor, improve the power density of capacitor.The realization of this micron of network adopts price and cheap polymeric sponges thereof to make skeleton, three-dimensional reduced graphene network is prepared by the method for simple solution impregnation, with synthesize compared with three-dimensional grapheme network in nickel foam by the method for chemical gaseous phase product, the cost of polyester sponge will be significantly less than nickel foam, in preparation process, energy consumption of the present invention is also much smaller than chemical gaseous phase product, and electrode of super capacitor of the present invention has good flexibility.Compared with carbon nano-tube/poly ester sponge electrode of super capacitor, the cost of carbon nano-tube is far above graphene oxide.And carbon nano-tube is difficult to dispersion, need to use a large amount of surfactants, when carbon nanotube adsorption is in sponge, need a large amount of water to go to rinse, this not only wastes a large amount of water sources, also brings environmental pollution.The hummers method preparation of the graphene oxide employing classics that the present invention is used, the method is with strong oxidizer oxidized graphite flake or graphite powder, obtain expanded graphite, again except deionization obtains graphene oxide, adopt reducing agent reduction or high-temperature heating can be reduced into the good reduced graphene of conductivity.Compared with chemical vapour deposition (CVD), the method, not by spatial limitation, can become to produce on a large scale, and graphene oxide exists in form of an aqueous solutions, is easy to modify in various substrate, easy to use.The amount of the graphene oxide that the present invention is simultaneously used is also extremely low.The present invention only adopts simple solwution method in a word, utilize cheap polyester sponge, graphene oxide, bivalent manganese reagent that can be water-soluble and potassium permanganate are raw material, prepare electrode of super capacitor, its energy density can reach 8.34Wh/kg, power density can reach 94kW/kg, and useful life is more than 10000 times.
Accompanying drawing explanation
The stereoscan photograph of the polyester sponge that Fig. 1 provides for the embodiment of the present invention 1 and embodiment 2;
The stereoscan photograph of the nano silver wire that Fig. 2 provides for the embodiment of the present invention 1 and embodiment 2;
One of volt-ampere electro-chemical test figure of the polyester sponge that Fig. 3 modifies for the reduced graphene that the embodiment of the present invention 1 provides;
The volt-ampere electro-chemical test figure bis-of the polyester sponge that Fig. 4 modifies for the reduced graphene that the embodiment of the present invention 1 provides;
The electron scanning micrograph of the electrode of super capacitor that Fig. 5 provides for the embodiment of the present invention 1;
One of volt-ampere electro-chemical test figure of the electrode of super capacitor that Fig. 6 provides for the embodiment of the present invention 1;
The volt-ampere electro-chemical test figure bis-of the electrode of super capacitor that Fig. 7 provides for the embodiment of the present invention 1;
The cycle life resolution chart of the electrode of super capacitor that Fig. 8 provides for the embodiment of the present invention 1.
Embodiment
The present invention is introduced in detail below in conjunction with accompanying drawing and embodiment thereof.But protection orientation of the present invention is not limited to following instance, should comprise the full content in claims.
The invention provides a kind of preparation method of electrode of super capacitor, comprise the following steps:
A) graphene oxide dispersion of certain mass concentration is prepared;
B) resilient three-dimensional porous material is immersed in step a) gained graphene oxide dispersion, centrifugal after taking out, then be immersed in graphene oxide also in original reagent, reduction at a certain temperature obtains the three-dimensional porous material that reduced graphene is modified;
C) three-dimensional porous material that the reduced graphene of step b) gained is modified successively is immersed in bivalent manganese solution and septivalency manganese solution, then with washed with de-ionized water several, obtains final electrode of super capacitor.
The present invention using resilient three-dimensional porous material as skeleton, then in the uniform absorption in skeleton surface graphene oxide, in the solution with reproducibility, reduction obtains reducing the three-dimensional porous material that graphite is modified.The three-dimensional porous material modified by reduced graphene is successively immersed in bivalent manganese solution and septivalency manganese solution, divalent manganesetion and septivalency manganese ion generation redox reaction, the three-dimensional porous material skeleton that reduced graphene is modified generates petal-like manganese dioxide particle, then washes away manganese dioxide particle unnecessary in cavity with deionized water and namely obtain final electrode of super capacitor.
The present invention's graphene oxide used is that business is bought or existing configuration, prepares graphene oxide as adopted Hummers method.In its concentration of demarcation, prepare certain density graphene oxide dispersion.According to the present invention, the mass concentration of described graphene oxide dispersion is preferably 1 ~ 10mg/ml, is more preferably 2.5 ~ 8mg/ml.
After preparing graphene oxide dispersion, resilient three-dimensional porous material is immersed in graphene oxide dispersion, take out also centrifugal under certain rotating speed, then be immersed in and go back in original reagent, reduction at a certain temperature obtains the three-dimensional porous material that reduced graphene is modified.
According to the present invention, described resilient three-dimensional porous material is preferably polyester sponge (the happy commerce and trade Co., Ltd of Yangzhou Dare, brand dele); The aperture of described resilient three-dimensional porous material, between 20 ~ 500 μm, is more preferably between 50 ~ 350 μm; It is described that by resilient three-dimensional porous material, the time be immersed in graphene oxide dispersion is 1 ~ 10min; Described centrifugal rotational speed is preferably 200 ~ 6000rpm, is more preferably 1000 ~ 4500rpm; Described centrifugation time is preferably 1 ~ 10min.Described original reagent of going back is hydroiodic acid solution, sodium borohydride solution, hydrazine hydrate solution one wherein, and wherein, the concentration of described hydroiodic acid solution is 10 ~ 100wt%, and the concentration of sodium borohydride solution is 0.51 ~ 55wt%, and the concentration of hydrazine hydrate solution is 0.2 ~ 15wt%.Be more preferably hydroiodic acid solution.Described reduction temperature is 25 ° of C ~ 100 ° C, is more preferably 50 ~ 85 ° of C.Affect the conductivity that one of principal element of the power density of electrode of super capacitor of the present invention is the three-dimensional porous material that reduced graphene is modified, and the height of conductivity depends on the recovery time of redox graphene.The concrete recovery time will change according to the temperature of reduction, when reduction temperature is lower, should extend the recovery time, but no longer than 3min, when reduction temperature is higher, should shorten the recovery time, but the shortlyest be no less than 30s.
After obtaining the three-dimensional porous material of reduced graphene modification, be more successively immersed in bivalent manganese solution and septivalency manganese solution by it, the concentration of described bivalent manganese solution is 4 ~ 50mM, and the concentration of described liquor potassic permanganate is 2 ~ 30mM.The time of placing in bivalent manganese solution is 1 ~ 5min, make to fill bivalent manganese solution completely in the cavity of sponge, the time of placing in septivalency manganese solution is 1 ~ 4min, septivalency manganese ion is reacted completely with divalent manganesetion, but can not place long, in case reduced graphene is by potassium permanganate solution oxide.Again with washed with de-ionized water several, obtain final electrode of super capacitor.According to the present invention, described bivalent manganese solution is preferably manganese acetate solution, manganese nitrate solution, manganese chloride solution and manganese sulfate solution one wherein, is more preferably manganese acetate solution and manganese nitrate solution one wherein; Described 7 valency manganese solutions are preferably liquor potassic permanganate.Potassium permanganate meeting redox Graphene, reduce the conductivity of reduced graphene, the three-dimensional porous material that therefore reduced graphene is modified should first be immersed in divalent manganesetion solution, then taking-up is immersed in liquor potassic permanganate.
Electrode of super capacitor prepared by the present invention, with low cost, preparation is simple, and be easy to realize suitability for industrialized production, energy density can reach 8.34Wh/kg, and power density can reach 94kW/kg, and useful life is more than 10000 times.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method to electrode of super capacitor provided by the invention is described in detail.
In following embodiment, each raw material is and buys from the market.
Embodiment 1
The graphene oxide adopting huumer method to prepare is adopted cryodesiccated method, demarcates the concentration of graphene oxide dispersion, add deionized water again according to this concentration and be adjusted to predetermined concentration 5mg/ml.Ultrasonic disperse 30min again, obtains finely dispersed graphene oxide dispersion.
Polyester sponge is cut into the pane of 1mm × 10mm × 20mm, three times are washed respectively with ethanol and water, dry in the baking oven of 100 ° of C, be immersed in above-mentioned graphene oxide dispersion again, place 1min to take out, under the rotating speed of 3000rpm, centrifugal 2min is centrifugal, reduction in the hydroiodic acid solution (concentration of hydroiodic acid solution used is 100wt%) of 85 ° of C is immersed in rapidly after taking-up, after 90s, take out and clean with a large amount of running water, use ethanol purge twice again, put into the dry 30min of baking oven of 200 ° of C, obtain reduced graphene and modify polyester sponge.
Field emission scanning electron microscope observation is carried out to the polyester sponge that the present embodiment provides, result is see Fig. 1, the stereoscan photograph of the polyester sponge that Fig. 1 adopts for the embodiment of the present invention 1 and embodiment 2, as shown in Figure 1, the pore size of polyester sponge of the present invention is at 100 ~ 300 μm.Carry out field emission scanning electron microscope observation to the polyester sponge of the reduced graphene modification that the present embodiment provides, result is see Fig. 2, and from 2, nano silver wire is formed as micron order three-dimensional net structure on polyester sponge skeleton; A volt-ampere telephony test is carried out to the polyester sponge of the reduced graphene modification that the present embodiment provides, result is see Fig. 3 and Fig. 4, from Fig. 3 and Fig. 4, the polyester sponge that reduced graphene is modified does the electrode of micro-ultracapacitor can at very wide operating at voltages, and under the voltage scan rate of 200V/s, CV curve still keeps good rectangular characteristic, represents that the polyester sponge that reduced graphene is modified has very high power density.
The three-dimensional porous material that reduced graphene is modified first is immersed in 6.9mmol/LMn (CH
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 4.7mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, obtain final electrode of super capacitor.
Field emission scanning electron microscope observation is carried out to the electrode of super capacitor that the present embodiment provides, result is see Fig. 5, the stereoscan photograph of the electrode of super capacitor that Fig. 5 provides for the present embodiment 1, as shown in Figure 5, on the surface of polyester sponge skeleton that the evengranular load of manganese dioxide is modified at graphene oxide.Cyclic voltammetry test is carried out to the electrode of super capacitor that the present embodiment 1 provides, result see Fig. 6 and Fig. 7, from Fig. 6 and Fig. 7, this electrode is under the voltage scan rate of 2V/s, CV curve still keeps good rectangle, illustrates that capacitance characteristic is good, has very high power density.Cycle life test is carried out to the electrode of super capacitor that the present embodiment 1 provides, result is see Fig. 7, as seen from Figure 7, under the voltage surface sweeping speed of 5V/s, circulate after 10000 times, capacity retention is more than 90%, illustrates that the electrode of super capacitor that the present embodiment 1 provides has very long useful life.
Embodiment 2
The graphene oxide adopting huumer method to prepare is adopted cryodesiccated method, demarcates the concentration of graphene oxide dispersion, add deionized water again according to this concentration and be adjusted to predetermined concentration 3.8mg/ml.Ultrasonic disperse 30min again, obtains finely dispersed graphene oxide dispersion.
Polyester sponge is cut into the pane (pore size of polyester sponge used is at 100 ~ 300 μm) of 1mm × 10mm × 20mm, three times are washed respectively with ethanol and water, dry in the baking oven of 100 ° of C, be immersed in above-mentioned graphene oxide dispersion again, place 3min to take out, under the rotating speed of 2500rpm, centrifugal 3min is centrifugal, reduction in the hydroiodic acid solution (concentration of hydroiodic acid solution used is 100wt%) of 90 ° of C is immersed in rapidly after taking-up, after 30s, take out and clean with a large amount of running water, use ethanol purge twice again, put into the dry 30min of baking oven of 200 ° of C, obtain reduced graphene and modify polyester sponge.
The three-dimensional porous material that reduced graphene is modified first is immersed in 30mmol/LMn (CH
3cOO)
24H
2in the aqueous solution of O, place 4min, then taking-up is immersed in 20mmol/LKMnO
4the aqueous solution in, place after 2min and take out, then with washed with de-ionized water for several times, obtain final electrode of super capacitor and repeat the electrode that above step 3 time obtains ultracapacitor.Number of repetition is more, and the content of manganese dioxide is higher, and electric capacity is larger, but power density can reduce, and therefore, needs the number of times determining repetition according to the required energy density of practical application and power density.
Embodiment 3
The graphene oxide adopting huumer method to prepare is adopted cryodesiccated method, demarcates the concentration of graphene oxide dispersion, add deionized water again according to this concentration and be adjusted to predetermined concentration 1mg/ml, 4mg/ml, 8mg/ml, 10mg/ml.Ultrasonic disperse 30min again, obtains finely dispersed graphene oxide dispersion.
Polyester sponge is cut into the pane (pore size of polyester sponge used is at 100 ~ 300 μm) of 1mm × 10mm × 20mm, get four these panes, three times are washed respectively with ethanol and water, dry in the baking oven of 100 ° of C, carry out according to the following steps respectively again: a) be immersed in the graphene oxide dispersion of above-mentioned 1mg/ml, place 5min to take out, under the rotating speed of 1000rpm, centrifugal 5min is centrifugal, reduction in the hydroiodic acid solution (concentration of hydroiodic acid solution used is 100wt%) of 70 ° of C is immersed in all rapidly after taking-up, after 120s, take out and clean with a large amount of running water, use ethanol purge twice again, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.B) be immersed in the graphene oxide dispersion of above-mentioned 4mg/ml, place 5mins to take out, under the rotating speed of 2000rpm, centrifugal 5min is centrifugal, be immersed in all rapidly after taking-up in the hydroiodic acid solution of 70 ° of C and reduce, after 120s, take out and clean with a large amount of running water, then using ethanol purge twice, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.C) be immersed in the graphene oxide dispersion of above-mentioned 8mg/ml, place 5min to take out, under the rotating speed of 3500rpm, centrifugal 5min is centrifugal, be immersed in all rapidly after taking-up in the hydroiodic acid solution of 70 ° of C and reduce, after 120s, take out and clean with a large amount of running water, then using ethanol purge twice, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.D) be immersed in the graphene oxide dispersion of above-mentioned 10mg/ml, place 5min to take out, under the rotating speed of 4500rpm, centrifugal 5min is centrifugal, be immersed in all rapidly after taking-up in the hydroiodic acid solution of 70 ° of C and reduce, after 120s, take out and clean with a large amount of running water, then using ethanol purge twice, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.
Do electro-chemical test respectively to the polyester sponge that above-mentioned four reduced graphenes are modified, test result refers to table 1:
The polyester sponge Electrochemical results that table 1 four reduced graphenes are modified
| Sample number into spectrum | a | b | c | d |
| Ratio capacitance (F/g) | 36 | 86 | 68 | 43 |
| Power density (kW/kg) | 35 | 98 | 140 | 204 |
The three-dimensional porous material that above-mentioned four reduced graphenes are modified is clicked step process respectively: be immersed in 22mmol/LMn (CH
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 15mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, then repeat the electrode that above step 1 time obtains ultracapacitor.
Carry out electro-chemical test respectively to above-mentioned electrode of super capacitor, test result is see table 2:
Table 2 electrode of super capacitor Electrochemical results
| Sample number into spectrum | a | b | c | d |
| Ratio capacitance (F/g) | 160 | 240 | 225 | 210 |
| Power density (kW/kg) | 12 | 36 | 48 | 53 |
The power density of the electrode of super capacitor of gained of the present invention is determined by the amount of reduced graphene on polyester sponge skeleton, and the amount of reduced graphene is larger, and conductivity is better, and power density is larger.And the ratio capacitance of electrode of super capacitor provided by the invention is not only relevant with its conductivity, also relevant with the specific area of reduced graphene, the amount of reduced graphene is larger, and specific area is less, and ratio capacitance is less.
Embodiment 4
The graphene oxide adopting huumer method to prepare is adopted cryodesiccated method, demarcates the concentration of graphene oxide dispersion, add deionized water again according to this concentration and be adjusted to predetermined concentration 6.5mg/ml.Ultrasonic disperse 30min again, obtains finely dispersed graphene oxide dispersion.
Polyester sponge is cut into the pane (pore size of polyester sponge used is at 100 ~ 300 μm) of 1mm × 10mm × 20mm, get four these pane ethanol and water washes three times respectively, dry in the baking oven of 100 ° of C, be immersed in respectively again in above-mentioned graphene oxide dispersion, place 10min to take out, under the rotating speed of 2500rpm, centrifugal 3min is centrifugal, reduction in the hydroiodic acid solution (concentration of hydroiodic acid solution used is 100wt%) of 50 ° of C is immersed in rapidly after taking-up, after 300s, take out and clean with a large amount of running water, use ethanol purge twice again, put into the dry 60min of baking oven of 180 ° of C, obtain four pieces of reduced graphenes and modify polyester sponge.
The three-dimensional porous material that above-mentioned four pieces of reduced graphenes are modified is carried out respectively according to the following steps: a) be immersed in 5mmol/LMn (CH
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 5mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, repeating a step 1 time and obtaining the electrode of ultracapacitor.B) 5mmol/LMn (CH is immersed in
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 6mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, repeating b step and obtaining for 1 time the electrode of ultracapacitor.C) 5mmol/LMn (CH is immersed in
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 7.35mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, repeating step c and obtaining for 1 time the electrode of ultracapacitor.D) 5mmol/LMn (CH is immersed in
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 9mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, repeating Step d and obtaining for 1 time the electrode of ultracapacitor.E) 5mmol/LMn (CH is immersed in
3cOO)
24H
2in the aqueous solution of O, place 1min, then taking-up is immersed in 10mmol/LKMnO
4the aqueous solution in, place after 1min and take out, then with washed with de-ionized water for several times, repeating step e and obtaining for 1 time the electrode of ultracapacitor.
Carry out electrochemical analysis to the electrode of super capacitor of the present embodiment gained, analysis result is see table 3:
Table 3 electrode of super capacitor electrochemical analysis result
The electric capacity of electrode of super capacitor provided by the present invention is made up of electric double layer capacitance and fake capacitance, and manganese dioxide is fake capacitance part, and in the present invention, manganese dioxide is reacted by bivalent manganese and potassium permanganate to generate.Potassium permanganate has strong oxidation to reduced graphene, can reduce the conductivity of reduced graphene, and therefore the present invention adopts and first immerses bivalent manganese solution, then immerses in permanganic acid valency solution, and the time of immersing high violent acid value solution can not be oversize.The molar concentration comparison manganese dioxide of bivalent manganese solution and liquor potassic permanganate has a great impact at the deposition on electrode of super capacitor surface.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a preparation method for electrode of super capacitor, comprises the following steps:
A) graphene oxide dispersion of certain mass concentration is prepared;
B) resilient three-dimensional porous material is immersed in step a) in gained graphene oxide dispersion, centrifugal after taking out, then be immersed in graphene oxide also in original reagent, reduction at a certain temperature obtains the three-dimensional porous material that reduced graphene is modified;
C) by step b) three-dimensional porous material modified of the reduced graphene of gained is successively immersed in bivalent manganese solution and septivalency manganese solution, then with washed with de-ionized water for several times, obtain final electrode of super capacitor; The aperture of described resilient three-dimensional porous material is between 20 ~ 500 μm.
2. preparation method according to claim 1, is characterized in that, step a) described in the mass concentration of graphene oxide at 1 ~ 10mg/ml.
3. preparation method according to claim 1, is characterized in that, step b) described in resilient three-dimensional porous material be polyester sponge or foam rubber.
4. preparation method according to claim 1, is characterized in that, step b) described in centrifugal rotational speed be 200 ~ 6000rpm, centrifugation time is 1 ~ 10min.
5. preparation method according to claim 1, it is characterized in that, step b) described in go back original reagent be hydroiodic acid solution, sodium borohydride solution, hydrazine hydrate solution wherein one or more, wherein, the concentration of described hydroiodic acid solution is 10 ~ 100wt%, the concentration of sodium borohydride solution is 0.51 ~ 55wt%, and the concentration of hydrazine hydrate solution is 0.2 ~ 15wt%.
6. preparation method according to claim 1, is characterized in that, step b) described in reduction temperature be 25 DEG C ~ 100 DEG C.
7. preparation method according to claim 1, is characterized in that, step c) described in bivalent manganese solution be one in manganese acetate solution, manganese nitrate solution, manganese chloride solution or manganese sulfate solution, the concentration of described bivalent manganese solution is 4 ~ 50mM; Described septivalency manganese solution is liquor potassic permanganate, and the concentration of described liquor potassic permanganate is 2 ~ 30mM.
8. preparation method according to claim 1, is characterized in that, step c) described in bivalent manganese solution and septivalency manganese solution the ratio of divalent manganesetion and septivalency manganese ion molar concentration be 1:1 ~ 2:1.
9. the application of electrode of super capacitor in ultracapacitor that described in claim 1 ~ 8 any one prepared by method.
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