CN103258656A - Method for preparing electrodes of super capacitor based on nickel foam and products thereof - Google Patents
Method for preparing electrodes of super capacitor based on nickel foam and products thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing electrodes of a dissymmetric super capacitor based on nickel foam. The method comprises the steps: washing the nickel foam, soaking the nickel foam into a graphene oxide aqueous solution to obtain nickel foam in which graphene oxide deposits, serving the nickel foam in which the graphene oxide deposits as precursor materials, and respectively adopting a three-electrode method for preparaing a positive electrode and a negative electrode of the dissymmetric super capacitor, wherein the positive electrode is composed of composite materials of graphene, a carbon nanometer tube and the nickel foam, and the negative electrode is composed of composite materials of graphene, manganese dioxide and the nickel foam. The invention further discloses some other methods for preparing the electrodes of the super capacitor based on the similar principle, and products which correspond to the methods. By means of the methods and the products, respective high-ratio capacitance characteristics of the composite materials are fully played, and energy density of the super capacitor is improved. In addition, usage of various combined reagents can be avoided, and accordingly large-batch industrial production is conducted in a mode of convenient control, low cost and low energy consumption.
Description
Technical field
The invention belongs to the ultracapacitor technical field, more specifically, relate to preparation method of a kind of electrode of super capacitor based on nickel foam and products thereof.
Background technology
Ultracapacitor is high energy, the green energy-storing device of a kind of performance between battery and traditional capacitor, because advantages such as it have the power density height, the speed that discharges and recharges is fast, have extended cycle life and operating temperature range is wide, thereby obtained to use widely in a plurality of fields such as electric automobile, communication, E-consumers.Difference according to energy storage mechanism, ultracapacitor can be divided into double electric layer capacitor and pseudo capacitance device, wherein double electric layer capacitor is to utilize the interfacial electric double layer electric capacity that forms between electrode and the electrolyte to come stored energy, the pseudo capacitance device is on electrode surface or the body two dimension or accurate two-dimensional space in mutually, carry out underpotential deposition by electrode active material, make it carry out energy by the Faradic electricity charge transfer reaction and store.In addition, in order to obtain high energy density and power density simultaneously, the novel ultracapacitor of having designed a kind of comprehensive above two class ultracapacitor advantages also is asymmetric ultracapacitor, one utmost point of this asymmetric ultracapacitor adopts double layer electrodes, and another utmost point adopts the pseudo capacitance electrode.
One of key factor that determines above-mentioned ultracapacitor performance is the electrode material that it adopts.The electrode of double electric layer capacitor adopts porous carbon material and the compound thereof of high-specific surface area usually at present, and the electrode material of pseudo capacitance device adopts metal oxide or conducting polymer usually.For example, a kind of electrode material of porous charcoal super capacitor and preparation method thereof is disclosed among the CN200910243306.9, wherein by adopt zinc chloride as template agent and catalyst, fructose as presoma, it is dissolved in behind the deionized water oil bath stirs, calcining obtains the porous charcoal super capacitor material thus under protective atmosphere then; A kind of C/V based on Faraday pseudo-capacitance is disclosed among the CN200710074617.8
2O
5The preparation method of super capacitor film electrode is principle with vanadium metal and hydrogen peroxide wherein, is equipped with vanadium colloidal sol by the liquid phase reactor legal system earlier, stirs at the adding conductive carbon material then, finally forms C/V by czochralski method on the stainless steel foil surface
2O
5Super capacitor film electrode.
For asymmetric ultracapacitor, its electrode system mainly comprises raw material of wood-charcoal material/metal oxide system, conducting polymer/raw material of wood-charcoal material system and lithium titanium oxygen compound/active carbon (AC) system etc.Wherein for raw material of wood-charcoal material/metal oxide system, the most typical example is the anodal RuO of employing
2, negative pole adopts active carbon, and electrolyte adopts H
2SO
4, the specific capacity of prepared hybrid super capacitor can reach 770F/g, and specific energy reaches 2617Wh/kg.But because the cost costliness of ruthenium makes application be subjected to bigger restriction, for this reason, synthetic RuO
2With the composite material of other metal oxides to reduce RuO
2Consumption or seek other metal oxides and replace rare precious metals etc. and become the hot research in recent years place.For example, a kind of hybrid super capacitor and manufacture method thereof are disclosed among the CN200910113946.8, the anodal double-layer capacitor material with carbon element that adopts wherein, its mix with graphite powder afterwards the adding ptfe emulsion then filling in nickel foam; Negative pole adopts hydrogen bearing alloy sheet, the nickel oxide with pseudo-capacitance characteristic or manganese dioxide, and perhaps the composite material made of material with carbon element and nickel oxide or manganese dioxide is assembled in this way and namely got hybrid super capacitor.In addition, asymmetric ultracapacitor of a kind of manganese dioxide and preparation method thereof is disclosed among the CN201210142685.4, wherein with manganese dioxide or manganese dioxide/absorbent charcoal composite material as positive active material, a kind of as negative electrode active material with in asphalt based active carbon, activated carbon fiber, carbon nano-tube or the Graphene mixes it respectively then to be coated in behind conductive electrode, the binding agent and makes both positive and negative polarity on the nickel foam thus.
Yet, studies show that, in the process of preparation electrode of super capacitor, often need to mix acetylene black or electrically conductive graphite at present as conductive agent, mix polytetrafluoroethylene, Kynoar or similar material simultaneously as binding agent, so not only make complicated process of preparationization, cost uprises, but also can have influence on the performance of electrode material self; On the other hand, along with the rise of electric automobile and hybrid electric vehicle, keeping improving the research focus that energy density is just becoming present ultracapacitor under high-power, the long-life prerequisite of ultracapacitor.In order to obtain the more good ultracapacitor of combination property, satisfy new technology and frontier to its application requirements that improves day by day, seek well behaved other composite materials and substitute above-mentioned electrode material, just becoming the technical problem that association area is needed solution badly.
Summary of the invention
Above defective or improvement demand at prior art, the invention provides preparation method of a kind of electrode of super capacitor based on nickel foam and products thereof, its purpose is to design by the compound type to electrode material, can give full play to these materials high specific capacitance feature separately, further improve the energy density of ultracapacitor; In addition, by adopting the mode of water system electrolyte assembling, can avoid the use of various groups of agent, mutually should be able to so that control, mode low-cost, low energy consumption makes electrode and ultracapacitor product, possess environmental protection simultaneously and be suitable for characteristics such as mass industrialized production.
According to a first aspect of the present invention, a kind of preparation method of the asymmetric electrode of super capacitor based on nickel foam is provided, it is characterized in that this method comprises the following steps:
(a) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(b) be persursor material with the nickel foam that deposits graphene oxide, make the both positive and negative polarity of asymmetric ultracapacitor respectively, its process is specially:
(b1) adopt three-electrode method that described persursor material is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way; The foam nickel electrode that then this is deposited Graphene is dipped in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml～2mg/ml and takes out dry, make the nickel foam that deposits carbon nano-tube and Graphene simultaneously thus, and with its negative pole as asymmetric ultracapacitor;
(b2) adopt three-electrode method that described persursor material is carried out the cyclic voltammetric electrochemical deposition, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration is that the manganese acetate aqueous solution of 0.1mol/L～1mol/L is as electrolyte, make the nickel foam that deposits manganese dioxide and Graphene simultaneously in this way, and with its positive pole as asymmetric ultracapacitor.
According to a second aspect of the present invention, a kind of preparation method of the electrode of super capacitor based on nickel foam is provided, it is characterized in that this method comprises the following steps:
(i) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(ii) adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration is that the sulfate solution of 0.1mol/L～1mol/L is as electrolyte, make the nickel foam that deposits Graphene in this way, and with its electrode as ultracapacitor.
According to a third aspect of the present invention, a kind of preparation method of the electrode of super capacitor based on nickel foam is provided, it is characterized in that this method comprises the following steps:
(A) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(B) adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way;
(C) nickel foam that this is deposited Graphene is dipped in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml～2mg/ml and takes out dry, make the nickel foam that deposits Graphene and carbon nano-tube simultaneously thus, and with its electrode as ultracapacitor.
According to a fourth aspect of the present invention, a kind of preparation method of the electrode of super capacitor based on nickel foam is provided, it is characterized in that this method comprises the following steps:
(I) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(II) adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the cyclic voltammetric electrochemical deposition, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration is that the manganese acetate aqueous solution of 0.1mol/L～1mol/L is as electrolyte, make the nickel foam that deposits Graphene and manganese dioxide simultaneously in this way, and with its electrode as ultracapacitor.
As further preferably, for the operation of above-mentioned cleaning nickel foam, its detailed process is for to clean nickel foam successively with glacial acetic acid, acetone, ethanol and deionized water, and scavenging period is 5～30 minutes.
As further preferably, for above-mentioned nickel foam is dipped into the operation of graphite oxide aqueous solution, its system temperature is controlled as 40 ℃～80 ℃ scope.
As further preferably, carry out the operation of constant voltage electrochemical reduction for above-mentioned employing three-electrode method, reduction potential is set to-1.5V～+ 1.0V, the recovery time was set to 200 seconds～800 seconds.
As further preferably, carry out the operation of cyclic voltammetric electrochemical deposition for above-mentioned employing three-electrode method, potential region is set to-1.5V～+ 1.4V, to sweep speed and be 50mV/s, the circulation number of turns is 1～3 circle.
According to a fifth aspect of the present invention, the asymmetric ultracapacitor product that adopts above-mentioned both positive and negative polarity assembling to make also is provided, give superimposed by solid electrolyte between two electrodes of this asymmetric ultracapacitor and separate with barrier film, described electrolyte is made of the mixed liquor of polyacrylic acid potassium and potassium chloride, and described barrier film is selected from polypropylene screen, glass fibre or kraft capacitor paper etc.
As further preferably, under the test condition of electrochemistry constant current charge-discharge, the ratio electric capacity of described asymmetric ultracapacitor is 37.2F/g～69.4F/g, and energy density is 18.2wh/kg～31.8wh/kg.
According to a sixth aspect of the present invention, also provide a kind of ultracapacitor that adopts above-mentioned electrode assembling to make to reach the purposes of aspects such as emergent back-up source at the power supply of electric automobile, hybrid vehicle, pulsed electron device.
In general, the above technical scheme of conceiving by the present invention compared with prior art mainly possesses following technological merit:
1, designs by the compound type to electrode material, can give full play to these materials advantage separately, and the electrode for capacitors of acquisition high specific capacitance and high-energy-density, wherein nickel foam is convenient to and the compound electrode material of making of other materials as collector, and is easy to press process; Graphene itself possesses excellent electricity, mechanical property and high-specific surface area, and when with itself and carbon nano-tube or transition metal oxide is compound when making electrode, test shows can significantly improve the energy density of the capacitive property of ultracapacitor;
2, owing to adopt the mode of water system electrolyte assembling, the use of various groups of agent be can avoid, should be able to electrode and corresponding ultracapacitor product be made in mode low-cost, low energy consumption mutually;
3, by the selection to the positive and negative pole material of asymmetric ultracapacitor, can make the electric capacity of two electrode materials be more or less the same to realize good coupling, and in asymmetric ultracapacitor the best capacitance characteristic of performance; In addition, the mixed liquor by adopting polyacrylic acid potassium and potassium chloride can be convenient to realize the assembling of ultracapacitor, and obtain high-energy-density as electrolyte;
4, according to process of the present invention be convenient to control, the preparation efficiency height, can effectively reduce cost of material and energy consumption, and can not produce environmental pollution, thereby be particularly suited for large batch of suitability for industrialized production purposes.
Description of drawings
Fig. 1 is the scanning electron microscope diagram sheet that deposits the nickel foam of graphene oxide for demonstration;
Fig. 2 is for the scanning electron microscope diagram sheet that shows the nickel foam that deposits Graphene and carbon nano-tube simultaneously;
Fig. 3 is the scanning electron microscope diagram sheet that deposits the nickel foam of Graphene and manganese dioxide for demonstration;
Fig. 4 is the cyclic voltammogram of foam nickel electrode under different scanning rates that deposits Graphene;
Fig. 5 is the foam nickel electrode (shown in the dotted line) that deposits Graphene and deposits Graphene and the foam nickel electrode of carbon nano-tube (shown in the solid line) discharges and recharges schematic diagram when current density is 1A/g;
Fig. 6 is the foam nickel electrode (shown in the dotted line) that deposits Graphene and carbon nano-tube simultaneously and the cyclic voltammogram of foam nickel electrode (shown in the solid line) when sweep speed is 50mV/s that deposit Graphene and manganese dioxide simultaneously;
Fig. 7 sweeps cyclic voltammogram under the speed according to the prepared asymmetric ultracapacitor of the present invention in difference;
Fig. 8 is for the optical photograph that shows according to the prepared asymmetric ultracapacitor of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.In addition, below in each execution mode of described the present invention involved technical characterictic just can not make up mutually as long as constitute conflict each other.
As previously mentioned, at existing deficiency in all kinds of electrode of super capacitor preparation process of prior art, study by electrode composite material and preparation technology thereof to ultracapacitor among the present invention, the preparation method of multiple novel electrode of super capacitor is provided, correspondingly, can give full play to these composite materials high specific capacitance feature separately, further improve the energy density of ultracapacitor; In addition, by adopting the mode of water system electrolyte assembling, can avoid the use of various groups of agent, mutually should be able to so that control, mode low-cost, low energy consumption makes electrode and ultracapacitor product.
Particularly, for the electrode production process of asymmetric ultracapacitor, preparation method proposed by the invention mainly comprises the following steps:
At first, nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
Be persursor material with the nickel foam that deposits graphene oxide then, make the both positive and negative polarity of asymmetric ultracapacitor respectively, its process is specially:
Adopt three-electrode method that described persursor material is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way; The foam nickel electrode that then this is deposited Graphene is dipped in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml～2mg/ml and takes out dry, make the nickel foam that deposits carbon nano-tube and Graphene simultaneously thus, and with its negative pole as asymmetric ultracapacitor;
Meanwhile, adopt three-electrode method that described persursor material is carried out the cyclic voltammetric electrochemical deposition, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the manganese acetate aqueous solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits manganese dioxide and Graphene simultaneously in this way, and with its positive pole as asymmetric ultracapacitor.
At last, can obtain final asymmetric ultracapacitor product thus with assembling by the mixed liquor by polyacrylic acid potassium and the potassium chloride solid electrolyte that constitutes and the barrier film that is selected from polypropylene screen, glass fibre or kraft capacitor paper etc. by said method or the prepared both positive and negative polarity of other suitable modes.
For the electrode of double electric layer capacitor or pseudo capacitance device, its electrode material can be made of Graphene/nickel foam, Graphene/carbon nano-tube/nickel foam or Graphene/manganese dioxide/nickel foam respectively, and this depends on particular type and the energy storage mechanism thereof of ultracapacitor.
Correspondingly, its preparation method can adopt following steps:
Scheme one:
At first, nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
Then, adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way, and with its electrode as ultracapacitor.
Scheme two:
At first, nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
Then, adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way;
At last, be dipped into this foam nickel electrode that deposits Graphene in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml～2mg/ml and the taking-up drying, make the nickel foam that deposits Graphene and carbon nano-tube simultaneously thus, and with its electrode as ultracapacitor.
Scheme three:
At first, nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
Then, adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the cyclic voltammetric electrochemical deposition, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the manganese acetate aqueous solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene and manganese dioxide simultaneously in this way, and with its electrode as ultracapacitor.
To provide specific embodiments more of the present invention below, in order to further explain mechanism of the present invention and preparation process, the reagent that wherein adopts and raw material all can obtain from commercial channels.
Embodiment 1
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 5mg/mL, system temperature control is at 80 degree.Take out the nickel foam drying after about 10 minutes and get final product, its scanning electron microscope diagram sheet can be participated in accompanying drawing 1.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, and reduction potential is-1.5V that the recovery time is 600s, namely makes the foam nickel electrode that deposits Graphene.In this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the metabisulfite solution of 0.5mol/L.Then, it is in the 1mg/mL carbon nano-tube dispersion liquid that the nickel foam that deposits Graphene that makes is dipped into concentration, take out dry then immediately, this immersion-dry run is carried out 2 times, namely make the nickel foam negative pole that deposits carbon nano-tube and Graphene, its concrete scanning electron microscope diagram sheet can be referring to accompanying drawing 2.
The nickel foam that deposits graphene oxide is carried out cyclic voltammetric electrochemical deposition manganese dioxide and redox graphene with three-electrode method, potential region is-1.5V, sweep speed and be 50mV/s, the circulation number of turns is 1 circle, namely makes the foam nickel electrode that deposits manganese dioxide and Graphene.In this process, be work electrode with the described nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, manganese acetate solution with 0.5mol/L is electrolyte, namely make positive pole after the drying, its concrete scanning electron microscope diagram sheet can be referring to accompanying drawing 3.
Get and take out behind the certain hour in the mixed solution that two above-mentioned positive poles that make and negative pole be dipped into the polyacrylic acid potassium of debita spissitudo and potassium chloride and be bonded together, middlely separate with the barrier film that is selected from polypropylene screen, glass fibre or kraft capacitor paper.Treat that the moisture evaporation in the polyacrylic acid potassium encapsulates after fully, namely makes required asymmetric ultracapacitor product (specifically referring to Fig. 8)
Embodiment 2
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 1mg/mL, system temperature control is at 40 degree.Taking out the nickel foam drying after about 30 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, and reduction potential is-1.0V that the recovery time is 800s, namely makes the foam nickel electrode that deposits Graphene.In this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the metabisulfite solution of 1mol/L.Then, it is in the 0.2mg/mL carbon nano-tube dispersion liquid that the nickel foam that deposits Graphene that makes is dipped into concentration, takes out drying then immediately, and this immersion-dry run is carried out 2 times, namely makes the foam nickel electrode that deposits carbon nano-tube and Graphene.
The nickel foam that deposits graphene oxide is carried out cyclic voltammetric electrochemical deposition manganese dioxide and redox graphene with three-electrode method, potential region is-1.0V, sweep speed and be 50mV/s, the circulation number of turns is 2 circles, namely makes the foam nickel electrode that deposits manganese dioxide and Graphene.In this process, be work electrode with the described nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the manganese acetate solution of 1mol/L, namely make positive pole after the drying.
Get and take out behind the certain hour in the mixed solution that two above-mentioned positive poles that make and negative pole be dipped into the polyacrylic acid potassium of debita spissitudo and potassium chloride and be bonded together, middlely separate with the barrier film that is selected from polypropylene screen, glass fibre or kraft capacitor paper.Treat that the moisture evaporation in the polyacrylic acid potassium encapsulates after fully, namely makes required asymmetric ultracapacitor product.
Embodiment 3
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 10mg/mL, system temperature control is at 60 degree.Taking out the nickel foam drying after about 15 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, and reduction potential is 1.0V, and the recovery time is 200s, namely makes the foam nickel electrode that deposits Graphene.In this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the metabisulfite solution of 0.1mol/L.Then, it is in the 2mg/mL carbon nano-tube dispersion liquid that the nickel foam that deposits Graphene that makes is dipped into concentration, takes out drying then immediately, and this immersion-dry run is carried out 3 times, namely makes the foam nickel electrode that deposits carbon nano-tube and Graphene.
The nickel foam that deposits graphene oxide is carried out cyclic voltammetric electrochemical deposition manganese dioxide and redox graphene with three-electrode method, potential region is 1.4V, sweep speed and be 50mV/s, the circulation number of turns is 3 circles, namely makes the foam nickel electrode that deposits manganese dioxide and Graphene.In this process, be work electrode with the described nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the manganese acetate solution of 0.1mol/L, namely make positive pole after the drying.
Get and take out behind the certain hour in the mixed solution that two above-mentioned positive poles that make and negative pole be dipped into the polyacrylic acid potassium of debita spissitudo and potassium chloride and be bonded together, middlely separate with the barrier film that is selected from polypropylene screen, glass fibre or kraft capacitor paper.Treat that the moisture evaporation in the polyacrylic acid potassium encapsulates after fully, namely makes required asymmetric ultracapacitor product.
Embodiment 4
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 5mg/mL, system temperature control is at 80 degree.Taking out the nickel foam drying after about 5 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, in this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, being reference electrode with the saturated calomel electrode, is electrolyte with the metabisulfite solution of 0.3mol/L.Reduction potential is-1.5V that the recovery time is 200s, namely makes the foam nickel electrode that deposits Graphene.
Embodiment 5
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 10mg/mL, system temperature control is at 80 degree.Taking out the nickel foam drying after about 5 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, in this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, being reference electrode with the saturated calomel electrode, is electrolyte with the metabisulfite solution of 1mol/L.Reduction potential is-1.0V that the recovery time is 400s, namely makes the foam nickel electrode that deposits Graphene.
Embodiment 6
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 1mg/mL, system temperature control is at 40 degree.Taking out the nickel foam drying after about 30 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, in this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, being reference electrode with the saturated calomel electrode, is electrolyte with the metabisulfite solution of 0.1mol/L.Reduction potential is 1.0V, and the recovery time is 200s, namely makes the foam nickel electrode that deposits Graphene.
Embodiment 7
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 8 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 1mg/mL, system temperature control is at 40 degree.Taking out the nickel foam drying after about 30 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, in this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, being reference electrode with the saturated calomel electrode, is electrolyte with the metabisulfite solution of 0.1mol/L.Reduction potential is-1.5V that the recovery time is 600s, namely makes the nickel foam that deposits Graphene.
Be dipped into this nickel foam that deposits Graphene in the carbon nano-tube aqueous solutions that mass concentration is 2mg/ml and the taking-up drying, make the foam nickel electrode that deposits Graphene and carbon nano-tube simultaneously thus.
Embodiment 8
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 4mg/mL, system temperature control is at 80 degree.Taking out the nickel foam drying after about 5 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, in this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, being reference electrode with the saturated calomel electrode, is electrolyte with the metabisulfite solution of 0.6mol/L.Reduction potential is-1.0V that the recovery time is 400s, namely makes the nickel foam that deposits Graphene.
Be dipped into this nickel foam that deposits Graphene in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml and the taking-up drying, make the foam nickel electrode that deposits Graphene and carbon nano-tube simultaneously thus.
Embodiment 9
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 10mg/mL, system temperature control is at 60 degree.Taking out the nickel foam drying after about 10 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction with three-electrode method, in this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, being reference electrode with the saturated calomel electrode, is electrolyte with the metabisulfite solution of 1mol/L.Reduction potential is 1.0V, and the recovery time is 200s, namely makes the nickel foam that deposits Graphene.
Be dipped into this nickel foam that deposits Graphene in the carbon nano-tube aqueous solutions that mass concentration is 1.5mg/ml and the taking-up drying, make the foam nickel electrode that deposits Graphene and carbon nano-tube simultaneously thus.
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 1mg/mL, system temperature control is at 40 degree.Taking out the nickel foam drying after about 30 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out cyclic voltammetric electrochemical deposition manganese dioxide and redox graphene with three-electrode method, potential region is-1.5V, sweep speed and be 50mV/s, the circulation number of turns is 2 circles, namely makes the foam nickel electrode that deposits manganese dioxide and Graphene.In this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the manganese acetate solution of 1mol/L, namely make required electrode of super capacitor after the drying.
Embodiment 11
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 4mg/mL, system temperature control is at 80 degree.Taking out the nickel foam drying after about 5 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out cyclic voltammetric electrochemical deposition manganese dioxide and redox graphene with three-electrode method, potential region is 1.4V, sweep speed and be 50mV/s, the circulation number of turns is 1 circle, namely makes the foam nickel electrode that deposits manganese dioxide and Graphene.In this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the manganese acetate solution of 0.1mol/L, namely make required electrode of super capacitor after the drying.
Embodiment 12
Nickel foam is cut into suitable size, use glacial acetic acid, acetone, ethanol and washed with de-ionized water 10 minutes successively.Then cleaned nickel foam is dipped in the graphene oxide solution that concentration is 10mg/mL, system temperature control is at 60 degree.Taking out the nickel foam drying after about 15 minutes gets final product.
The nickel foam that deposits graphene oxide is carried out cyclic voltammetric electrochemical deposition manganese dioxide and redox graphene with three-electrode method, potential region is 1.0V, sweep speed and be 50mV/s, the circulation number of turns is 3 circles, namely makes the foam nickel electrode that deposits manganese dioxide and Graphene.In this process, be work electrode with the nickel foam that deposits graphene oxide, be to electrode with platinum electrode, be reference electrode with the saturated calomel electrode, be electrolyte with the manganese acetate solution of 0.65mol/L, namely make required electrode of super capacitor after the drying.
Be example with embodiment 1 prepared asymmetric ultracapacitor sample, it is carried out loop test under different scanning rates, its test result is referring to Fig. 7, and the test result of embodiment 2,3 obtained samples is similar therewith.As can be seen from Figure 7, this asymmetric ultracapacitor current potential window is 0-1.8V, the cyclic voltammetry curve of sweeping under the speed in difference is approximate rectangle and has reasonable symmetry, sweep at height simultaneously that tangible distortion does not take place figure under the speed (200mV/s), illustrated that this asymmetric ultracapacitor has good electrochemical capacitor characteristic.
Be example with the embodiment 4 prepared foam nickel electrodes that deposit Graphene, it is carried out loop test under different scanning rates, shown the cyclic voltammogram as test result among Fig. 4, embodiment 5,6 test result are similar therewith.As can be seen from Figure 4, difference sweep speed under cyclic voltammetry curve all near rectangle, proved that the foam nickel electrode that deposits Graphene has desirable electric double layer capacitance characteristic.
The electrode sample that is made respectively with embodiment 4 and embodiment 7 is example, and it is carried out current density is the charge-discharge test of 1A/g, and its concrete test result is referring to Fig. 5.Other embodiment are similar therewith as 5,6 and 8,9 test result.As can be seen from Figure 5, the single charging and discharging curve of two kinds of electrodes is subtriangular and has reasonable symmetry, its voltage is linear variation in time, the electrode charge and discharge good reversibility is described, it is obviously long than the foam nickel electrode that deposits Graphene that but the foam nickel electrode that deposits Graphene and carbon nano-tube discharges and recharges the time, illustrated that the foam nickel electrode that deposits Graphene and carbon nano-tube is owing to the introducing of carbon nano-tube has higher electric capacity.
The electrode sample that makes respectively with embodiment 8 and embodiment 10 is example, and it is carried out sweep speed is the loop test of 50mV/s, and its concrete test result is referring to Fig. 6.Other embodiment as 7,9 and embodiment 11,12 test result similar therewith.As can be seen from Figure 6, the potential window that deposits the foam nickel electrode of Graphene and manganese dioxide is 0～0.8V, the potential window that deposits the foam nickel electrode of Graphene and carbon nano-tube is-0.8～0.2V, the cyclic voltammogram area difference of two kinds of electrodes is not very big simultaneously, therefore can mate preferably, realize with the foam nickel electrode that deposits Graphene and manganese dioxide serving as that positive pole and the foam nickel electrode that deposits Graphene and carbon nano-tube are the preparation of the asymmetric ultracapacitor of negative pole.
Those skilled in the art will readily understand; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method based on the asymmetric electrode of super capacitor of nickel foam is characterized in that, this method comprises the following steps:
(a) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(b) be persursor material with the nickel foam that deposits graphene oxide, make the both positive and negative polarity of asymmetric ultracapacitor respectively, its process is specially:
(b1) adopt three-electrode method that described persursor material is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way; The foam nickel electrode that then this is deposited Graphene is dipped in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml～2mg/ml and takes out dry, make the nickel foam that deposits carbon nano-tube and Graphene simultaneously thus, and with its negative pole as asymmetric ultracapacitor;
(b2) adopt three-electrode method that described persursor material is carried out the cyclic voltammetric electrochemical deposition, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration is that the manganese acetate aqueous solution of 0.1mol/L～1mol/L is as electrolyte, make the nickel foam that deposits manganese dioxide and Graphene simultaneously in this way, and with its positive pole as asymmetric ultracapacitor.
2. the preparation method based on the electrode of super capacitor of nickel foam is characterized in that, this method comprises the following steps:
(i) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(ii) adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration is that the sulfate solution of 0.1mol/L～1mol/L is as electrolyte, make the nickel foam that deposits Graphene in this way, and with its electrode as ultracapacitor.
3. the preparation method based on the electrode of super capacitor of nickel foam is characterized in that, this method comprises the following steps:
(A) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(B) adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the constant voltage electrochemical reduction, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration be the sulfate solution of 0.1mol/L～1mol/L as electrolyte, make the nickel foam that deposits Graphene in this way;
(C) nickel foam that this is deposited Graphene is dipped in the carbon nano-tube aqueous solutions that mass concentration is 0.2mg/ml～2mg/ml and takes out dry, make the nickel foam that deposits Graphene and carbon nano-tube simultaneously thus, and with its electrode as ultracapacitor.
4. the preparation method based on the electrode of super capacitor of nickel foam is characterized in that, this method comprises the following steps:
(I) nickel foam is cleaned, then it is dipped in the graphite oxide aqueous solution that mass concentration is 1mg/ml～10mg/ml, obtain to deposit the nickel foam of graphene oxide thus;
(II) adopt three-electrode method that the nickel foam that deposits graphene oxide is carried out the cyclic voltammetric electrochemical deposition, wherein with the deposition graphene oxide nickel foam as work electrode, platinum electrode is as auxiliary electrode, saturated calomel electrode is as reference electrode, molar concentration is that the manganese acetate aqueous solution of 0.1mol/L～1mol/L is as electrolyte, make the nickel foam that deposits Graphene and manganese dioxide simultaneously in this way, and with its electrode as ultracapacitor.
5. as any described method of claim 1-4, it is characterized in that for the operation of above-mentioned cleaning nickel foam, its detailed process is for to clean nickel foam successively with glacial acetic acid, acetone, ethanol and deionized water, scavenging period is 5～30 minutes.
6. as any described method of claim 1-5, it is characterized in that for above-mentioned nickel foam is dipped into the operation of graphite oxide aqueous solution, its system temperature is controlled as 40 ℃～80 ℃ scope.
7. as any described method of claim 1-3, it is characterized in that, carry out the operation of constant voltage electrochemical reduction for above-mentioned employing three-electrode method, reduction potential is set to-1.5V～+ 1.0V, the recovery time was set to 200 seconds～800 seconds.
8. as claim 1 or 4 described methods, it is characterized in that, carry out the operation of cyclic voltammetric electrochemical deposition for above-mentioned employing three-electrode method, potential region is set to-1.5V～+ 1.4V, to sweep speed and be 50mV/s, the circulation number of turns is 1～3 circle.
9. asymmetric ultracapacitor, it is characterized in that, the negative pole of this ultracapacitor is made of the nickel foam that deposits carbon nano-tube and Graphene simultaneously, positive pole is made of the nickel foam that deposits manganese dioxide and Graphene simultaneously, give superimposed by solid electrolyte between two electrodes and separate with barrier film, described electrolyte is made of the mixed liquor of polyacrylic acid potassium and potassium chloride, and described barrier film is selected from polypropylene screen, glass fibre or kraft capacitor paper etc.
10. asymmetric ultracapacitor product as claimed in claim 9 is characterized in that, under the test condition of electrochemistry constant current charge-discharge, the ratio electric capacity of this asymmetric ultracapacitor is 37.2F/g～69.4F/g, and energy density is 18.2-31.8wh/kg.
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