CN103065813A - Preparing method and application of super capacitor electrode - Google Patents
Preparing method and application of super capacitor electrode Download PDFInfo
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- CN103065813A CN103065813A CN2012105572402A CN201210557240A CN103065813A CN 103065813 A CN103065813 A CN 103065813A CN 2012105572402 A CN2012105572402 A CN 2012105572402A CN 201210557240 A CN201210557240 A CN 201210557240A CN 103065813 A CN103065813 A CN 103065813A
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Abstract
The invention provides a preparing method of a super capacitor electrode. The method comprises the steps of preparing graphene oxide dispersion liquid with certain mass concentration; immersing an elastic three-dimensional cellular material into the graphene oxide dispersion liquid, then taking out the elastic three-dimensional cellular material for centrifugation, and further immersing the elastic three-dimensional cellular material into a graphene oxide reductive agent to obtain a three-dimensional cellular material modified by reduced grapheme at a certain temperature; immersing the three-dimensional cellular material modified by the reduced grapheme into divalent manganese solution and septivalency manganese solution in sequence, and then washing the three-dimensional cellular material for several times with deionized water to obtain the final super capacitor electrode. The super capacitor electrode prepared with the method has the advantages of being good in power density and energy density, good in cycling stability, low in cost, simple in preparing method, and suitable for commercialized production.
Description
Technical field
The invention belongs to the ultracapacitor field, relate in particular to a kind of preparation method and application thereof of electrode of super capacitor.
Background technology
In today that the energy source height consumes, earth fossil fuel is petered out, has scientist to foretell that tellurian oil will be exhausted after about 50 years, and the mankind must seek the reproducible energy.Solar energy and wind energy are inexhaustible, are desirable alternative energy sources.Yet how these step energy quick storage also can be discharged again fast is a difficult problem always, although the energy density of traditional chemical cell is very high, but power density is lower, and it is long to discharge and recharge the time, is difficult to solve the storage difficult problem of intermittent energy.Ultracapacitor is that a class of in recent years high speed development newly can energy storage material, has very high power density, quite long useful life, discharge and recharge rapidly, be the desirable storage medium of the batch (-type) energy.Each state all spares no effort ultracapacitor is carried out research and development at present.
According to the mode of charge storage, ultracapacitor can be divided into two kinds, and a kind of is to form electric double layer on electricity level surface to come stored energy, and another kind is based on the Quick Oxidation reduction reaction and comes stored energy.The former electrode material normal operation high conductivity and the material with carbon element of specific area, such traditional electrode of super capacitor normal operation active carbon material, although cost compare is cheap, poorly conductive, specific area is little, and power density and energy density are all lower.Recent years, the carbon nano-tube of scientist's usefulness high conductivity and high-ratio surface and Graphene have improved power density and the energy density of ultracapacitor greatly as electrode material.Reported such as U.S.'s " science " (Science,, 335 phases, 1326 pages in 2012) a kind ofly to prepare electrode of super capacitor with the laser reduction Graphene, the conductivity of electrode is up to 1738Scm
-1, far above active carbon (10 ~ 100Scm
-1) surface area also reaches 1520m
2G
-1, suitable (1000 ~ 2000m with activated carbon
2G
-1).Yet this class capacitor is subject to specific area, and energy density is not high, and the theoretical capacitance of grapheme material also only has 550F/g.Therefore, another kind of fake capacitance ultracapacitor based on metal oxide is subject to extensive concern.The energy density of this class capacitor is very high, and such as the about 1300F/g of theoretical electric capacity of manganese dioxide, far above double electric layers supercapacitor, but the power density of fake capacitance is very low.
Therefore, scientist begin one's study electric double layer and the compound ultracapacitor of fake capacitance prepare high-performance super capacitor in conjunction with the high power density of electric double layer and the high-energy-density of fake capacitance.That generally to be high by conductivity, that specific area is high material with carbon element have a polymeric material of fake capacitance character with metal oxide and some to this class material is compound.The carbon nano-tube that material with carbon element is good take conductivity, specific area is high and Graphene be as main, and the fake capacitance material is take the manganese dioxide of cheapness as main, yet this class composite material mostly is pulverulence, is difficult to its pattern, size and homogeneity on electrode material of control.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 is modified nonwoven fabrics and sponge electrode, fake capacitance material in the load of the surface uniform of these self-supporting electrodes again, obtain power density and can density larger electrode of super capacitor all." nanometer wall bulletin " (Nano letter such as American Chemical Society, 2011,11 phases, 5165 pages) reported the hybrid supercapacitor electrode that a seed supports, the first step of kind electrode preparation be with carbon nanotube adsorption at the three-dimensional netted conductive electrode that the sponge skeleton forms, use again the method for electro-deposition, at the conduction three-dimensional network skeleton manganese dioxide of growing, capacitor produced energy density is up to 31Wh/kg, and energy density is higher (63kW/kg) also.Yet, although the conductivity of the carbon nano-tube that kind electrode adopts is very high, but price is high, and the surfactant in preparation process also is difficult to remove, residual surfactant also reduces the conductivity of carbon nano-tube, adopt in addition electro-deposition very harsh to requirement for experiment condition in the method for conduction three-dimensional network skeleton growth manganese dioxide, be difficult to realize large-scale production.
Therefore, adopt cheap raw material, the manganese dioxide material with carbon element hybrid supercapacitor of preparing the self-supporting of high-energy-density and power density with method simple and easy to control still is the target of whole world science unremitting pursue.
Summary of the invention
In view of this, it is a kind of with low cost that the technical problem to be solved in the present invention is to provide, preparation is simple, be easy to the Graphene that industry changes into product/manganese dioxide hybrid supercapacitor electrode material, wherein high conductive three-dimensional reduced graphene network is very helpful to improving power density, there is the manganese dioxide of fake capacitance character compound with having excellence again, can greatly improves again the energy density of capacitor.
In order to realize purpose of the present invention, the invention provides a kind of preparation method of electrode of super capacitor, may further comprise the steps:
A) the graphene oxide dispersion liquid of preparation certain mass concentration;
B) the elasticity three-dimensional porous material is immersed in the step a) gained graphene oxide dispersion liquid, centrifugal after taking out, be immersed in again graphene oxide also in the original reagent, at a certain temperature reduction obtains the three-dimensional porous material that reduced graphene is modified;
C) three-dimensional porous material of the reduced graphene of step b) gained being modified successively is immersed in bivalent manganese solution and the septivalency manganese solution, with washed with de-ionized water for several times, obtains final electrode of super capacitor again.
Preferably, the mass concentration of graphene oxide described in the step a) is 1mg/ml ~ 10mg/ml.
Preferably, the three-dimensional porous material of elasticity described in the step b) is polyester sponge or foam rubber.
Preferably, the aperture of the elasticity three-dimensional porous material described in the step b) is between 20 μ m ~ 500 μ m.
Preferably, the centrifugal rotational speed described in the step b) is 200rpm ~ 6000rpm, and centrifugation time is 1min ~ 10min.
Preferably, going back original reagent described in the step b) is hydroiodic acid solution, sodium borohydride solution, wherein one or more of hydrazine hydrate solution, 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 the step b) is 25 ° of C ~ 100 ° C.
Preferably, the solution of bivalent manganese described in the step c) is manganese acetate solution, manganese nitrate solution, a kind of in manganese chloride solution and the 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, the ratio of divalent manganesetion and septivalency manganese ion molar concentration is 1:1 ~ 2:1 in the solution of bivalent manganese described in the step c) and the septivalency manganese solution.
Further, the invention provides the application of electrode of super capacitor in ultracapacitor of described method preparation.
Beneficial effect of the present invention is as follows:
Adopt the electrode of super capacitor of said method preparation, have micron-sized loose structure, be conducive to ion and form electric double layer on the electrode of super capacitor surface, greatly reduce the internal resistance of capacitor, improve the power density of capacitor.The realization of this micron network is to adopt price and cheap polymerization sponge thereof to make skeleton, prepare three-dimensional reduced graphene network with the method for simple solution impregnation, compare at the synthetic three-dimensional grapheme network of nickel foam with the method with the 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 the chemical gaseous phase product, and electrode of super capacitor of the present invention has good flexibility.Compare 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 be difficult to disperse, and needs to use a large amount of surfactants, when carbon nanotube adsorption in sponge, need a large amount of water go flushing, this not only wastes a large amount of water sources, also brings environmental pollution.The used graphene oxide of the present invention adopts classical hummers method preparation, the method is with strong oxidizer oxidized graphite flake or graphite powder, obtain expanded graphite, obtain graphene oxide except deionization again, adopt reducing agent reduction or high-temperature heating can be reduced into the good reduced graphene of conductivity.Compare with chemical vapour deposition (CVD), the method is not subjected to spatial limitation, can be on a large scale become to produce, and graphene oxide is that form with the aqueous solution exists, and is easy to modify to various substrates, and is easy to use.The amount of the graphene oxide that simultaneously the present invention is 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.
Description of drawings
The stereoscan photograph of the nano silver wire that Fig. 1 provides for the embodiment of the invention 1 and embodiment 2;
The stereoscan photograph of the polyester sponge that Fig. 2 provides for the embodiment of the invention 1 and embodiment 2;
The electron scanning micrograph of the conductive polyester sponge that Fig. 3 provides for the embodiment of the invention 1;
The electron scanning micrograph of the elastic conductor that Fig. 4 provides for the embodiment of the invention 1;
The high multiple electron scanning micrograph of the conductive polyester sponge that Fig. 5 provides for the embodiment of the invention 1;
The high multiple electron scanning micrograph of the conductive polyester sponge that Fig. 6 provides for the embodiment of the invention 2.
Two of the volt-ampere electro-chemical test figure of the electrode of super capacitor that Fig. 7 provides for the embodiment of the invention 1;
The cycle life resolution chart of the electrode of super capacitor that Fig. 8 provides for the embodiment of the invention 1.
Embodiment
Introduce in detail the present invention below in conjunction with accompanying drawing and embodiment thereof.But protection of the present invention orientation 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, may further comprise the steps:
A) the graphene oxide dispersion liquid of preparation certain mass concentration;
B) the elasticity three-dimensional porous material is immersed in the step a) gained graphene oxide dispersion liquid, centrifugal after taking out, be immersed in again graphene oxide also in the original reagent, at a certain temperature reduction obtains the three-dimensional porous material that reduced graphene is modified;
C) three-dimensional porous material of the reduced graphene of step b) gained being modified successively is immersed in bivalent manganese solution and the septivalency manganese solution, with washed with de-ionized water for several times, obtains final electrode of super capacitor again.
The present invention with the elasticity three-dimensional porous material as skeleton, graphene oxide in the uniformly absorption of skeleton surface again, reduction obtains reducing the three-dimensional porous material that graphite is modified in having the solution of reproducibility.The three-dimensional porous material that reduced graphene is modified successively is immersed in bivalent manganese solution and the septivalency manganese solution, divalent manganesetion and septivalency manganese ion generation redox reaction, the three-dimensional porous material skeleton of modifying at reduced graphene generates petal-like manganese dioxide particle, namely obtains final electrode of super capacitor with manganese dioxide particle unnecessary in the deionized water flush away cavity again.
The used graphene oxide of the present invention is commercial the purchase or existing configuration, prepares graphene oxide as adopting the Hummers method.Demarcating its concentration, prepare certain density graphene oxide dispersion liquid.According to the present invention, the mass concentration of described graphene oxide dispersion liquid is preferably 1 ~ 10mg/ml, more preferably 2.5 ~ 8mg/ml.
After preparing the graphene oxide dispersion liquid, the elasticity three-dimensional porous material is immersed in the graphene oxide dispersion liquid, taking-up is also centrifugal under certain rotating speed, is immersed in and goes back in the original reagent, and at a certain temperature reduction obtains the three-dimensional porous material that reduced graphene is modified.
According to the present invention, described elasticity three-dimensional porous material is preferably polyester sponge (the happy commerce and trade of Yangzhou Dare Co., Ltd, brand dele); The aperture of described elasticity three-dimensional porous material is between 20 ~ 500 μ m, more preferably between 50 ~ 350 μ m; The described time that the elasticity three-dimensional porous material is immersed in the graphene oxide dispersion liquid is 1 ~ 10min; Described centrifugal rotational speed is preferably 200 ~ 6000rpm, more preferably 1000 ~ 4500rpm; Described centrifugation time is preferably 1 ~ 10min.The described original reagent of going back is wherein a kind of of hydroiodic acid solution, sodium borohydride solution, hydrazine hydrate solution, 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%.Hydroiodic acid solution more preferably.Described reduction temperature is 25 ° of C ~ 100 ° C, more preferably 50 ~ 85 ° of C.One of the principal element that affects the power density of electrode of super capacitor of the present invention is the conductivity of the three-dimensional porous material modified of reduced graphene, 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, and when reduction temperature is low, should prolongs the recovery time, but no longer than 3min, when reduction temperature is higher, should shorten the recovery time, but the shortest 30s that is no less than.
After obtaining the three-dimensional porous material of reduced graphene modification, it successively is immersed in bivalent manganese solution and the septivalency manganese solution, the concentration of described bivalent manganese solution is 4 ~ 50mM again, and the concentration of described liquor potassic permanganate is 2 ~ 30mM.The time of placing in bivalent manganese solution is 1 ~ 5min, so that fill bivalent manganese solution in the cavity of sponge fully, the time of placing in the septivalency manganese solution is 1 ~ 4min, so that the septivalency manganese ion reacts completely with divalent manganesetion, but can not place long, in case reduced graphene is by the potassium permanganate solution oxide.With washed with de-ionized water for several times, obtain final electrode of super capacitor again.According to the present invention, described bivalent manganese solution is preferably manganese acetate solution, manganese nitrate solution, wherein a kind of of manganese chloride solution and manganese sulfate solution, more preferably wherein a kind of of manganese acetate solution and manganese nitrate solution; Described 7 valency manganese solutions are preferably liquor potassic permanganate.Potassium permanganate can redox Graphene, reduce the conductivity of reduced graphene, so the three-dimensional porous material that reduced graphene is modified should be immersed in first in the divalent manganesetion solution, take out again and be immersed in the liquor potassic permanganate.
The electrode of super capacitor of the present invention's preparation, with low cost, preparation is simple, is easy to realize suitability for industrialized production, and 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 specify the present invention, below in conjunction with embodiment the preparation method of electrode of super capacitor provided by the invention is described in detail.
Below among each embodiment each raw material be from the market and buy.
With adopting the graphene oxide of huumer method preparation to adopt cryodesiccated method, demarcate the concentration of graphene oxide dispersion liquid, add again deionized water according to this concentration and be adjusted to predetermined concentration 5mg/ml.Ultrasonic dispersion 30min obtains finely dispersed graphene oxide dispersion liquid again.
The polyester sponge is cut into the pane of 1mm * 10mm * 20mm, wash respectively three times with ethanol and water, dry in the baking oven of 100 ° of C, again it is immersed in the above-mentioned graphene oxide dispersion liquid, placing 1min takes out, centrifugal 2min is centrifugal under the rotating speed of 3000rpm, be immersed in rapidly the middle reduction of hydroiodic acid solution (concentration of used hydroiodic acid solution is 100wt%) of 85 ° of C after the taking-up, behind the 90s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 30min of baking oven of 200 ° of C, obtain reduced graphene and modify the polyester sponge.
The polyester sponge that present embodiment is provided carries out the field emission scanning electron microscope observation, the result is referring to Fig. 1, Fig. 1 is the stereoscan photograph of the embodiment of the invention 1 and the embodiment 2 polyester sponge of adopting, and as shown in Figure 1, the pore size of polyester sponge of the present invention is at 100 ~ 300 μ m.The polyester sponge that the reduced graphene that present embodiment is provided is modified carries out field emission scanning electron microscope to be observed, and the result is referring to Fig. 2, and by 2 as can be known, nano silver wire forms the micron order three-dimensional net structure at polyester sponge skeleton; The polyester sponge that the reduced graphene that present embodiment is provided is modified carries out a volt-ampere telephony test, the result is referring to Fig. 3 and Fig. 4, by Fig. 3 and Fig. 4 as can be known, the polyester sponge that reduced graphene is modified is cooked the electrode of little ultracapacitor and can work under very wide voltage, and under the voltage scanning speed of 200V/s, the CV curve still keeps good rectangular characteristic, and the polyester sponge that the expression reduced graphene is modified has very high power density.
The three-dimensional porous material that reduced graphene is modified is immersed in first 6.9mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 4.7mmol/LKMnO
4The aqueous solution in, take out after placing 1min, with washed with de-ionized water for several times, obtain final electrode of super capacitor again.
The electrode of super capacitor that present embodiment is provided carries out the field emission scanning electron microscope observation, the result is referring to Fig. 5, the stereoscan photograph of the electrode of super capacitor that Fig. 5 provides for present embodiment 1, as shown in Figure 5, on the evengranular surface that loads on the polyester sponge skeleton that graphene oxide modifies of manganese dioxide.The electrode of super capacitor that present embodiment 1 is provided carries out the cyclic voltammetry test, and the result is referring to Fig. 6 and Fig. 7, by Fig. 6 and Fig. 7 as can be known, this electrode is under the voltage scanning speed of 2V/s, the CV curve still keeps good rectangle, illustrates that capacitance characteristic is good, has very high power density.The electrode of super capacitor that present embodiment 1 is provided carries out the cycle life test, the result is referring to Fig. 7, as seen from Figure 7, under the voltage surface sweeping speed of 5V/s, circulate after 10000 times, the electric capacity conservation rate is more than 90%, illustrates that the electrode of super capacitor that present embodiment 1 provides has very long useful life.
With adopting the graphene oxide of huumer method preparation to adopt cryodesiccated method, demarcate the concentration of graphene oxide dispersion liquid, add again deionized water according to this concentration and be adjusted to predetermined concentration 3.8mg/ml.Ultrasonic dispersion 30min obtains finely dispersed graphene oxide dispersion liquid again.
The polyester sponge is cut into the pane (pore size of used polyester sponge is at 100 ~ 300 μ m) of 1mm * 10mm * 20mm, wash respectively three times with ethanol and water, dry in the baking oven of 100 ° of C, again it is immersed in the above-mentioned graphene oxide dispersion liquid, placing 3min takes out, centrifugal 3min is centrifugal under the rotating speed of 2500rpm, be immersed in rapidly the middle reduction of hydroiodic acid solution (concentration of used hydroiodic acid solution is 100wt%) of 90 ° of C after the taking-up, behind the 30s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 30min of baking oven of 200 ° of C, obtain reduced graphene and modify the polyester sponge.
The three-dimensional porous material that reduced graphene is modified is immersed in first 30mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 4min, take out again and be immersed in 20mmol/LKMnO
4The aqueous solution in, take out after placing 2min, again 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, however power density can reduce, therefore, need to determine the number of times that repeats according to the required energy density of practical application and power density.
Embodiment 3
With adopting the graphene oxide of huumer method preparation to adopt cryodesiccated method, demarcate the concentration of graphene oxide dispersion liquid, add again deionized water according to this concentration and be adjusted to predetermined concentration 1mg/ml, 4mg/ml, 8mg/ml, 10mg/ml.Ultrasonic dispersion 30min obtains finely dispersed graphene oxide dispersion liquid again.
The polyester sponge is cut into the pane (pore size of used polyester sponge is at 100 ~ 300 μ m) of 1mm * 10mm * 20mm, get four these panes, wash respectively three times with ethanol and water, dry in the baking oven of 100 ° of C, carry out according to the following steps respectively again: a) it is immersed in the graphene oxide dispersion liquid of above-mentioned 1mg/ml, placing 5min takes out, centrifugal 5min is centrifugal under the rotating speed of 1000rpm, all be immersed in rapidly the middle reduction of hydroiodic acid solution (concentration of used hydroiodic acid solution is 100wt%) of 70 ° of C after the taking-up, behind the 120s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.B) it is immersed in the graphene oxide dispersion liquid of above-mentioned 4mg/ml, placing 5mins takes out, centrifugal 5min is centrifugal under the rotating speed of 2000rpm, all be immersed in rapidly after the taking-up in the hydroiodic acid solution of 70 ° of C and reduce, behind the 120s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.C) it is immersed in the graphene oxide dispersion liquid of above-mentioned 8mg/ml, placing 5min takes out, centrifugal 5min is centrifugal under the rotating speed of 3500rpm, all be immersed in rapidly after the taking-up in the hydroiodic acid solution of 70 ° of C and reduce, behind the 120s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.D) it is immersed in the graphene oxide dispersion liquid of above-mentioned 10mg/ml, placing 5min takes out, centrifugal 5min is centrifugal under the rotating speed of 4500rpm, all be immersed in rapidly after the taking-up in the hydroiodic acid solution of 70 ° of C and reduce, behind the 120s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 30min of baking oven of 200 ° of C, obtain the polyester sponge that reduced graphene is modified.
The polyester sponge that above-mentioned four reduced graphenes are modified is cooked respectively electro-chemical test, and test result sees also table 1:
The polyester sponge Electrochemical results that four reduced graphenes of table 1 are modified
| Sample number into spectrum | a | b | c | d |
| Than electric capacity (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 clicks respectively step process: be immersed in 22mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 15mmol/LKMnO
4The aqueous solution in, take out after placing 1min, again with washed with de-ionized water for several times, repeat again the electrode that above step 1 time obtains ultracapacitor.
Above-mentioned electrode of super capacitor is carried out respectively electro-chemical test, and test result is referring to table 2:
Table 2 electrode of super capacitor Electrochemical results
| Sample number into spectrum | a | b | c | d |
| Than electric capacity (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 to determine that by the amount of reduced graphene on the polyester sponge skeleton amount of reduced graphene is larger, and conductivity is better, and power density is larger.And the ratio electric capacity of electrode of super capacitor provided by the invention is not only relevant with its conductivity, and is also relevant with the specific area of reduced graphene, and the amount of reduced graphene is larger, and specific area is less, and is less than electric capacity.
Embodiment 4
With adopting the graphene oxide of huumer method preparation to adopt cryodesiccated method, demarcate the concentration of graphene oxide dispersion liquid, add again deionized water according to this concentration and be adjusted to predetermined concentration 6.5mg/ml.Ultrasonic dispersion 30min obtains finely dispersed graphene oxide dispersion liquid again.
The polyester sponge is cut into the pane (pore size of used polyester sponge is at 100 ~ 300 μ m) of 1mm * 10mm * 20mm, getting four these panes washes respectively three times with ethanol and water, dry in the baking oven of 100 ° of C, respectively it is immersed in the above-mentioned graphene oxide dispersion liquid again, placing 10min takes out, centrifugal 3min is centrifugal under the rotating speed of 2500rpm, be immersed in rapidly the middle reduction of hydroiodic acid solution (concentration of used hydroiodic acid solution is 100wt%) of 50 ° of C after the taking-up, behind the 300s, take out and clean with a large amount of running water, clean twice with ethanol again, put into the dry 60min of baking oven of 180 ° of C, obtain four reduced graphenes and modify the polyester sponge.
The three-dimensional porous material that above-mentioned four reduced graphenes are modified carries out respectively according to the following steps: a) be immersed in 5mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 5mmol/LKMnO
4The aqueous solution in, take out after placing 1min, again with washed with de-ionized water for several times, repeating a step 1 and time obtaining the electrode of ultracapacitor.B) be immersed in 5mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 6mmol/LKMnO
4The aqueous solution in, take out after placing 1min, again with washed with de-ionized water for several times, repeating b step 1 and time obtaining the electrode of ultracapacitor.C) be immersed in 5mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 7.35mmol/LKMnO
4The aqueous solution in, take out after placing 1min, again with washed with de-ionized water for several times, repeating c step 1 and time obtaining the electrode of ultracapacitor.D) be immersed in 5mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 9mmol/LKMnO
4The aqueous solution in, take out after placing 1min, again with washed with de-ionized water for several times, repeating d step 1 and time obtaining the electrode of ultracapacitor.E) be immersed in 5mmol/LMn (CH
3COO)
24H
2In the aqueous solution of O, place 1min, take out again and be immersed in 10mmol/LKMnO
4The aqueous solution in, take out after placing 1min, again with washed with de-ionized water for several times, repeating e step 1 and time obtaining the electrode of ultracapacitor.
Electrode of super capacitor to the present embodiment gained carries out electrochemical analysis, and analysis result is referring to 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 comprised of electric double layer capacitance and fake capacitance, and manganese dioxide is the fake capacitance part, and in the present invention, manganese dioxide is to be generated by bivalent manganese and potassium permanganate reaction.Potassium permanganate has strong oxidation to reduced graphene, can reduce the conductivity of reduced graphene, so the present invention adopts and to immerse first bivalent manganese solution, immerse again in the permanganic acid valency solution, and immerse time of high violent acid value solution can not be oversize.The molar concentration of bivalent manganese solution and liquor potassic permanganate is compared the deposition of manganese dioxide on the electrode of super capacitor surface and is had a great impact.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (10)
1. the preparation method of an electrode of super capacitor may further comprise the steps:
A) the graphene oxide dispersion liquid of preparation certain mass concentration;
B) the elasticity three-dimensional porous material is immersed in the step a) gained graphene oxide dispersion liquid, centrifugal after taking out, be immersed in again graphene oxide also in the original reagent, at a certain temperature reduction obtains the three-dimensional porous material that reduced graphene is modified;
C) three-dimensional porous material of the reduced graphene of step b) gained being modified successively is immersed in bivalent manganese solution and the septivalency manganese solution, with washed with de-ionized water for several times, obtains final electrode of super capacitor again.
2. preparation method according to claim 1 is characterized in that, the mass concentration of graphene oxide described in the step a) is at 1 ~ 10mg/ml.
3. preparation method according to claim 1 is characterized in that, the three-dimensional porous material of elasticity described in the step b) is polyester sponge or foam rubber.
4. preparation method according to claim 1 is characterized in that, the aperture of the elasticity three-dimensional porous material described in the step b) is between 20 ~ 500 μ m.
5. preparation method according to claim 1 is characterized in that, the centrifugal rotational speed described in the step b) is 200 ~ 6000rpm, and centrifugation time is 1 ~ 10min.
6. preparation method according to claim 1, it is characterized in that, going back original reagent described in the step b) is hydroiodic acid solution, sodium borohydride solution, wherein one or more of hydrazine hydrate solution, 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%.
7. preparation method according to claim 1 is characterized in that, reduction temperature described in the step b) is 25 ° of C ~ 100 ° C.
8. preparation method according to claim 1 is characterized in that, the solution of bivalent manganese described in the step c) is a kind of in manganese acetate solution, manganese nitrate solution, manganese chloride solution or the manganese sulfate solution, and 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.
9. preparation method according to claim 1 is characterized in that, divalent manganesetion is 1:1 ~ 2:1 with the ratio of septivalency manganese ion molar concentration in the solution of bivalent manganese described in the step c) and the septivalency manganese solution.
10. the application of electrode of super capacitor in ultracapacitor of the described method preparation of claim 1 ~ 9 any one.
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