CN104252970A - Co3O4-graphene @ nickel cobalt double hydroxide composite material with three-dimensional network structure, as well as preparation method and application thereof - Google Patents

Co3O4-graphene @ nickel cobalt double hydroxide composite material with three-dimensional network structure, as well as preparation method and application thereof Download PDF

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CN104252970A
CN104252970A CN201410553841.5A CN201410553841A CN104252970A CN 104252970 A CN104252970 A CN 104252970A CN 201410553841 A CN201410553841 A CN 201410553841A CN 104252970 A CN104252970 A CN 104252970A
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electrode
graphene
composite material
nickel cobalt
net structure
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CN104252970B (en
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麦立强
瞿龙兵
杨超
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Wuhan University of Technology WUT
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a Co3O4-graphene @ nickel cobalt double hydroxide composite material with a three-dimensional network structure, as well as a preparation method thereof. The composite material takes cobaltosic oxide nano brush formed by connecting ultrathin nanosheets as a framework structure; ultrathin graphene films are adhered to surfaces of the ultrathin nanosheets, so as to form cobaltosic oxide-graphene long sheets; a nickel cobalt double hydroxide nanosheet is embedded into the space between every two cobaltosic oxide-graphene long sheets. The composite material has the benefits that the composite electrode material has excellent electronic transmission capacity and ion diffusion capacity, and finally ensures that the composite electrode material has excellent rate capability, the cycling stability is properly improved, the method adopts a simple hydrothermal method, a sintering method is combined wiht an electrolytic deposition method with two optimized steps, and the material prepared is high in purity and good in uniformity.

Description

Three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material and its preparation method and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material and preparation method thereof, this composite material can be used as ultracapacitor active material.
Background technology
Along with the continuous growth of energy demand, exploring the new cleaning fuel material possessing premium properties has become a current challenge.Cobaltosic oxide, cobalt hydroxide and nickel hydroxide are as ultracapacitor fake capacitance material, and they have high theoretical specific capacity, are easy to preparation, advantages of environment protection, become worldwide extensive research gradually.Simultaneously Graphene is as a kind of material with carbon element with high conductivity also through being usually used in and electrode material for super capacitor compound, improves the high rate performance of electrode material with this.
In order to obtain the electrode material for super capacitor possessing excellent properties, many about transition metal oxide (manganese dioxide, ruthenic oxide, cobaltosic oxide, nickel oxide, molybdenum dioxide etc.) compound of/transition metal oxide, the compound of metal oxide/metal hydroxides, the compound studied and report of metal oxide/carbon-based material and metal oxide/conducting polymer, and also achieve certain achievement and solve some ultracapacitors development problems faced.But the electrode material for super capacitor of these compounds still can not reach the requirement as excellent clean energy resource material.Most important is exactly for the research of current composite construction electrode material, obtain the electrode material with superelevation comprehensive electrochemical, (as high specific capacity, good high rate capability, fabulous discharge and recharge invertibity and cyclical stability) is still a very large challenge.With regard to current reported document, also do not have researcher when meeting the high active material load capacity of unit are, the electrode active material obtained still has comprehensive chemical property recited above.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, meet the requirement of Green Chemistry, there is the three-dimensional net structure Co of good electric chemical property 3o 4-Graphene nickel cobalt double-hydroxide composite material and preparation method thereof.
To achieve these goals, technical scheme of the present invention is: three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material, its cobaltosic oxide nano brush be unified into using ultrathin nanometer sheet is as skeleton structure, the surface of ultrathin nanometer sheet is glued with ultra-thin graphene film and forms cobaltosic oxide-Graphene lengthy motion picture, nickel cobalt double hydroxide nano sheet is embedded between described cobaltosic oxide-Graphene two lengthy motion picture, it adopts following method to obtain, and includes following steps:
1) take nickel foam as electrode base sheet, be dipped into ultrasonic preliminary treatment in the dilute sulfuric acid of 0.1mol/L, after taking out, use deionized water supersound washing, then by washed electrode base sheet dry for standby;
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g urea are dissolved in 70ml deionized water for stirring and form settled solution;
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed in reactor and react, take out reactor, naturally cool to room temperature, take out nickel foam, ultrasonic, dry, then sinter in argon gas and air, obtain cobaltosic oxide electrode material;
4) using step 3) in the cobaltosic oxide electrode material that obtains as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of 30 milliliters of Graphenes prepared using Ha Mofa and 3.58 grams of sodium hydrogen phosphates are as electrolyte, deposit, take out work electrode after end, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing;
5) using step 4) in cobaltosic oxide-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, cobalt nitrate and nickel nitrate are as electrolyte, deposit, take out work electrode after end, with deionized water rinsing, dry and obtain three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material.
By such scheme, step 2) described in cabaltous nitrate hexahydrate be 0.291g, urea is 0.3g.
By such scheme, step 3) described in reaction temperature be 120 DEG C, the reaction time is 9 hours.
By such scheme, step 3) described in argon gas in sintering temperature be 450 DEG C, sintering time is 5 hours, and in air, sintering temperature is 300 DEG C, and sintering time is 5 hours.
By such scheme, step 4) described in deposition current be 1mAcm -2, sedimentation time is 10 minutes.
By such scheme, step 5) described in the concentration of electrolyte be 0.01-0.05mol/L cobalt nitrate and 0.005-0.025mol/L nickel nitrate, deposition current is 1-5mAcm -2, sedimentation time is 4-20 minute.
Described three-dimensional net structure Co 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, includes following steps:
1) take nickel foam as electrode base sheet, be dipped into ultrasonic preliminary treatment in the dilute sulfuric acid of 0.1mol/L, after taking out, use deionized water supersound washing, then by washed electrode base sheet dry for standby;
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g urea are dissolved in 70ml deionized water for stirring and form settled solution;
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed in reactor and react, take out reactor, naturally cool to room temperature, take out nickel foam, ultrasonic, dry, then sinter in argon gas and air, obtain cobaltosic oxide electrode material;
4) using step 3) in the cobaltosic oxide electrode material that obtains as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of 30 milliliters of Graphenes prepared using Ha Mofa and 3.58 grams of sodium hydrogen phosphates are as electrolyte, deposit, take out work electrode after end, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing;
5) using step 4) in cobaltosic oxide-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, cobalt nitrate and nickel nitrate are as electrolyte, deposit, take out work electrode after end, with deionized water rinsing, dry and obtain three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material.
Described three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material is as the application of electrode of super capacitor active material.
The invention has the beneficial effects as follows: three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material fully remains the advantage of cobaltosic oxide and the high specific capacity of nickel cobalt double-hydroxide, and graphene film, can as the high-speed channel of electrical conductivity in this three-dimensional net structure as mid portion.Simultaneously, this kind of structure is three-dimensional net structure, nickel cobalt double hydroxide nano sheet is embedded between cobaltosic oxide-Graphene two lengthy motion picture, make this kind of combination electrode material have very excellent electric transmission and ion-diffusibility, finally make this kind of combination electrode material have very excellent high rate performance.And because double hydroxide nano sheet is well embedded between cobaltosic oxide-Graphene two lengthy motion picture, last cyclical stability have also been obtained extraordinary raising; What the present invention adopted is simple hydro thermal method, the electro-deposition method that sintering process is optimized in conjunction with two steps, and the material purity prepared is very high, homogeneity is very good.Present invention process is simple, and the electrode material chemical property prepared is very excellent, meets the requirement to electrode material for super capacitor performance on market, is very beneficial for the marketization and promotes.
Accompanying drawing explanation
Fig. 1 is the three-dimensional net structure Co of embodiment 1 3o 4the synthesis mechanism figure of-Graphene nickel cobalt double-hydroxide composite material;
Fig. 2 is the three-dimensional net structure Co of embodiment 1 3o 4the x-ray diffraction pattern of-Graphene nickel cobalt double-hydroxide composite material;
Fig. 3 is step 3 in embodiment 1) cobaltosic oxide that obtains and step 4) the Fourier infrared spectrum figure of cobaltosic oxide-Graphene electrodes material that obtains;
Fig. 4 is step 4 in embodiment 1) the X-radial energy spectrogram of cobaltosic oxide-Graphene that obtains;
Fig. 5 is cobaltosic oxide-Graphene and three-dimensional net structure Co 3o 4the SEM figure of-Graphene nickel cobalt double-hydroxide composite material, wherein Fig. 5 a and Fig. 5 b is step 4 in embodiment 1 respectively) cobaltosic oxide-Graphene of obtaining and step 5) the three-dimensional net structure Co that obtains 3o 4the SEM figure of-Graphene nickel cobalt double-hydroxide composite material;
Fig. 6 is cobaltosic oxide Graphene and three-dimensional net structure Co 3o 4the TEM figure of-Graphene nickel cobalt double-hydroxide composite material, wherein Fig. 6 a and Fig. 6 b is step 4 in embodiment 1 respectively) the cobaltosic oxide Graphene that obtains and step 5) the three-dimensional net structure Co that obtains 3o 4the TEM figure of-Graphene nickel cobalt double-hydroxide composite material;
Fig. 7 is the three-dimensional net structure Co of embodiment 1 3o 4the high rate performance figure of-Graphene nickel cobalt double-hydroxide composite material;
Fig. 8 is step 3 in embodiment 1) cobaltosic oxide of nanometer brush pattern that obtains, step 4) in cobaltosic oxide-Graphene of obtaining and step 5) in the three-dimensional net structure Co that obtains 3o 4the cycle performance figure of-Graphene nickel cobalt double-hydroxide composite material.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
The concrete steps that Ha Mofa prepares Graphene are:
A) 1g graphite is mixed with the 23ml concentrated sulfuric acid in 250ml conical flask, at room temperature stir 24 hours;
B) under 40 DEG C of water bath condition, in conical flask, 100mg NaNO is added 3, and stir 5 minutes, make NaNO 3abundant dissolving;
C) in conical flask, 500mg KMnO is slowly added 4(controlling reaction temperature below 45 DEG C), stirs 30 minutes;
D) in conical flask, add 3ml distilled water, wait for and again add 3ml distilled water after 5 minutes, wait for and add 40ml distilled water after 5 minutes, stir 15 minutes;
E) stop water-bath, in conical flask, add 140ml distilled water and 10ml 30%H 2o 2, at room temperature stir 5 minutes, with cessation reaction;
F) use centrifuge, 10000 revs/min, 3 minutes, with 5%HCl solution washing twice, be then washed with distilled water to neutrality;
G) obtained sediment is dispersed in 100ml distilled water, and ultrasonic 60 minutes of 90Hz, time ultrasonic, water level is parallel with liquid level, please washs at once after ultrasonic;
H) by g) step gained solution, 5000 revs/min, 5 minutes centrifugal, and to get after supernatant liquor 5000 revs/min again, 5 minutes centrifugal twice, gained clear liquid was graphene solution.
Three-dimensional net structure Co 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, it comprises the steps:
1) nickel foam is as electrode base sheet, first ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) preliminary treatment 20 minutes are dipped into, take out rear deionized water to wash 2 times under ultrasonic (60Hz), each 20 minutes at every turn, then by washed nickel foam substrate dry for standby;
2) deionized water for stirring 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of urea being dissolved in 70 milliliters forms settled solution in 1 hour;
3) by step 2) in the settled solution that obtains and step 1) in the size handled well be that the nickel foam of 20mm*60mm*0.4mm proceeds in reactor, react 9 hours under the condition of 120 DEG C, take out reactor, naturally cool to room temperature, take out nickel foam, under 40Hz ultrasonic 5 minutes in deionized water, dry at 70 DEG C, then in argon gas, sinter 5 hours at 450 DEG C respectively, in air, at 300 DEG C, sintering obtains cobaltosic oxide electrode material for 5 hours;
4) using step 3) in the length that the obtains cobaltosic oxide in nickel foam as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of the Graphene that 30 milliliters of Ha Mofa prepare and 3.58 grams of sodium hydrogen phosphates are as electrolyte, and cathodic deposition current value is 1mAcm -2, sedimentation time is 10 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, within 10 minutes, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing
5) using step 4) in the length cobaltosic oxide in nickel foam-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 0.05 mole of often liter of cobalt nitrate and 0.025 mole of often liter of nickel nitrate are as electrolyte, and cathodic deposition current value is 5mAcm -2, sedimentation time is 4 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, with deionized water rinsing 10 minutes, 70 DEG C of oven dry obtained three-dimensional net structure cobaltosic oxide-Graphene nickel cobalt double-hydroxide combination electrode material.
As shown in Figure 1, synthesis mechanism of the present invention is: first by the hydro thermal method of Optimal improvements, by controlling the concentration of reactant, reaction temperature and reaction time prepare the long cobaltosic oxide in nickel foam with nanometer brush pattern, then the electro-deposition method by optimizing makes graphene film be deposited on the surface of cobaltosic oxide, is combined into nucleus growth and primary reconstruction mechanism obtains the final Co with three-dimensional net structure finally by electrochemical deposition method 3o 4-Graphene nickel cobalt double-hydroxide composite material.
With product three-dimensional net structure Co of the present invention 3o 4-Graphene nickel cobalt double-hydroxide composite material is example, and its composition is by x-ray diffractometer, and Fourier infrared spectrum analyzer and X-gamma ray spectrometer are determined.The thing that X-ray diffracting spectrum (XRD) shows composite material is as shown in Figure 2 cobaltosic oxide and double-hydroxide mutually, as shown in Figure 3 Fourier infrared spectrum analyzer and as having equally distributed Graphene in Fig. 4 X-gamma ray spectrometer composite surface material.
As the ESEM of Fig. 5 a and the transmission electron microscope as Fig. 6 a further demonstrate the surface that graphene film is deposited on cobaltosic oxide uniformly, double hydroxide nano sheet is embedded between cobaltosic oxide-Graphene two lengthy motion picture.If Fig. 5 b is the three-dimensional net structure Co obtained 3o 4the scanning electron microscope (SEM) photograph of-Graphene nickel cobalt double-hydroxide composite material.If Fig. 6 b is the three-dimensional net structure Co obtained 3o 4the scanning electron microscope (SEM) photograph of-Graphene nickel cobalt double-hydroxide composite material.
The three-dimensional net structure Co that the present invention prepares 3o 4-Graphene nickel cobalt double-hydroxide composite electrode adopts three-electrode system to carry out the test of ultracapacitor chemical property, with the combination electrode material prepared for work electrode, platinum electrode is as to electrode, silver/silver chloride electrode as reference electrode, at the electro-chemical test of occasion China electrochemical workstation enterprising line correlation.As the three-dimensional net structure Co of Fig. 7 3o 4-Graphene Ni xco 2x(OH) 6Xthe electrochemistry high rate performance test of electrode material shows under the current density of 1A/g, capacity reaches 2550F/g, when current density is 20A/g, capacity still reaches 2116F/g, cycle performance test simultaneously as Fig. 8 shows under the current density of 20A/g, and the capacity after circulation 5000 circle still reaches 92.7% of first lap.
Embodiment 2:
Three-dimensional net structure Co 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, wherein, the preparation method of Graphene is with reference to embodiment 1.It comprises the steps:
1) nickel foam is as electrode base sheet, first ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) preliminary treatment 20 minutes are dipped into, take out rear deionized water to wash 2 times under ultrasonic (60Hz), each 20 minutes at every turn, then by washed nickel foam substrate dry for standby;
2) deionized water for stirring 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of urea being dissolved in 70 milliliters forms settled solution in 1 hour;
3) by step 2) in the settled solution that obtains and step 1) in the size handled well be that the nickel foam of 20mm*60mm*0.4mm proceeds in reactor, react 9 hours under the condition of 120 DEG C, take out reactor, naturally cool to room temperature, take out nickel foam, under 40Hz ultrasonic 5 minutes in deionized water, dry at 70 DEG C, then in argon gas, sinter 5 hours at 450 DEG C respectively, in air, at 300 DEG C, sintering obtains cobaltosic oxide electrode material for 5 hours;
4) using step 3) in the length that the obtains cobaltosic oxide in nickel foam as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of the Graphene that 30 milliliters of Ha Mofa prepare and 3.58 grams of sodium hydrogen phosphates are as electrolyte, and cathodic deposition current value is 1mAcm -2, sedimentation time is 10 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, within 10 minutes, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing
5) using step 4) in the length cobaltosic oxide in nickel foam-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 0.05 mole of often liter of cobalt nitrate and 0.025 mole of often liter of nickel nitrate are as electrolyte, and cathodic deposition current value is 5mAcm -2, sedimentation time is 20 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, with deionized water rinsing 10 minutes, 70 DEG C of oven dry obtained three-dimensional net structure cobaltosic oxide-Graphene nickel cobalt double-hydroxide combination electrode material.
With the Co obtained in this example 3o 4-Graphene nickel cobalt double-hydroxide composite material is example, and under the current density of 1A/g, specific capacity is 1100F/g, and under the current density of 20A/g, specific capacity is 530F/g.
Embodiment 3:
Three-dimensional net structure Co 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, wherein, the preparation method of Graphene is with reference to embodiment 1, and it comprises the steps:
1) nickel foam is as electrode base sheet, first ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) preliminary treatment 20 minutes are dipped into, take out rear deionized water to wash 2 times under ultrasonic (60Hz), each 20 minutes at every turn, then by washed nickel foam substrate dry for standby;
2) deionized water for stirring 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of urea being dissolved in 70 milliliters forms settled solution in 1 hour;
3) by step 2) in the settled solution that obtains and step 1) in the size handled well be that the nickel foam of 20mm*60mm*0.4mm proceeds in reactor, react 9 hours under the condition of 120 DEG C, take out reactor, naturally cool to room temperature, take out nickel foam, under 40Hz ultrasonic 5 minutes in deionized water, dry at 70 DEG C, then in argon gas, sinter 5 hours at 450 DEG C respectively, in air, at 300 DEG C, sintering obtains cobaltosic oxide electrode material for 5 hours;
4) using step 3) in the length that the obtains cobaltosic oxide in nickel foam as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of the Graphene that 30 milliliters of Ha Mofa prepare and 3.58 grams of sodium hydrogen phosphates are as electrolyte, and cathodic deposition current value is 1mAcm -2, sedimentation time is 10 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, within 10 minutes, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing.
5) using step 4) in the length cobaltosic oxide in nickel foam-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 0.01 mole of often liter of cobalt nitrate and 0.005 mole of often liter of nickel nitrate are as electrolyte, and cathodic deposition current value is 1mAcm -2, sedimentation time is 20 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, with deionized water rinsing 10 minutes, 70 DEG C of oven dry obtained cobaltosic oxide-Graphene nickel cobalt double-hydroxide combination electrode material.
The preparation method of Graphene is with reference to embodiment 1.
With the Co obtained in this example 3o 4-Graphene nickel cobalt double-hydroxide composite material is example, and under the current density of 1A/g, specific capacity is 1553F/g, and under the current density of 20A/g, specific capacity is 1126F/g.
Comparative example 4:
Three-dimensional net structure Co 3o 4the preparation method of nickel cobalt double-hydroxide composite material, it comprises the steps:
1) nickel foam is as electrode base sheet, first ultrasonic in the dilute sulfuric acid of 0.1mol/L (60Hz) preliminary treatment 20 minutes are dipped into, take out rear deionized water to wash 2 times under ultrasonic (60Hz), each 20 minutes at every turn, then by washed nickel foam substrate dry for standby;
2) deionized water for stirring 0.291 gram of cabaltous nitrate hexahydrate and 0.3 gram of urea being dissolved in 70 milliliters forms settled solution in 1 hour;
3) by step 2) in the settled solution that obtains and step 1) in the size handled well be that the nickel foam of 20mm*60mm*0.4mm proceeds in reactor, react 9 hours under the condition of 120 DEG C, take out reactor, naturally cool to room temperature, take out nickel foam, under 40Hz ultrasonic 5 minutes in deionized water, dry at 70 DEG C, then in argon gas, sinter 5 hours at 450 DEG C respectively, in air, at 300 DEG C, sintering obtains cobaltosic oxide electrode material for 5 hours;
4) using step 3) in the length that the obtains cobaltosic oxide electrode material in nickel foam as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 0.05 mole of often liter of cobalt nitrate and 0.025 mole of often liter of nickel nitrate are as electrolyte, and cathodic deposition current value is 5mAcm -2, sedimentation time is 4 minutes, then starts electrochemical workstation.After electrochemical workstation quits work, take out work electrode, with deionized water rinsing 10 minutes, 70 DEG C of oven dry obtained three-dimensional net structure cobaltosic oxide nickel cobalt double-hydroxide combination electrode material.
With the three-dimensional net structure Co obtained in this example 3o 4nickel cobalt double-hydroxide composite material is example, and under the current density of 1A/g, specific capacity is 1947F/g, and under the current density of 20A/g, specific capacity is 1201F/g.
Embodiment 4 is do not add the three-dimensional net structure Co that Graphene obtains 3o 4nickel cobalt double-hydroxide composite material.Can draw from chemical property, add the specific capacity of the combination electrode material that Graphene prepares and high rate performance and improve many than the combination electrode material not adding Graphene and prepare.

Claims (13)

1. three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material, its cobaltosic oxide nano brush be unified into using ultrathin nanometer sheet is as skeleton structure, the surface of ultrathin nanometer sheet is glued with ultra-thin graphene film and forms cobaltosic oxide-Graphene lengthy motion picture, nickel cobalt double hydroxide nano sheet is embedded between described cobaltosic oxide-Graphene two lengthy motion picture, it adopts following method to obtain, and includes following steps:
1) take nickel foam as electrode base sheet, be dipped into ultrasonic preliminary treatment in the dilute sulfuric acid of 0.1mol/L, after taking out, use deionized water supersound washing, then by washed electrode base sheet dry for standby;
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g urea are dissolved in 70ml deionized water for stirring and form settled solution;
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed in reactor and react, take out reactor, naturally cool to room temperature, take out nickel foam, ultrasonic, dry, then sinter in argon gas and air, obtain cobaltosic oxide electrode material;
4) using step 3) in the cobaltosic oxide electrode material that obtains as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of 30 milliliters of Graphenes prepared using Ha Mofa and 3.58 grams of sodium hydrogen phosphates are as electrolyte, deposit, take out work electrode after end, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing;
5) using step 4) in cobaltosic oxide-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, cobalt nitrate and nickel nitrate are as electrolyte, deposit, take out work electrode after end, with deionized water rinsing, dry and obtain three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material.
2. three-dimensional net structure Co according to claim 1 3o 4-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 2) described in cabaltous nitrate hexahydrate be 0.291g, urea is 0.3g.
3. three-dimensional net structure Co according to claim 1 3o 4-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 3) described in reaction temperature be 120 DEG C, the reaction time is 9 hours.
4. three-dimensional net structure Co according to claim 1 3o 4-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 3) described in argon gas in sintering temperature be 450 DEG C, sintering time is 5 hours, and in air, sintering temperature is 300 DEG C, and sintering time is 5 hours.
5. three-dimensional net structure Co according to claim 1 3o 4-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 4) described in deposition current be 1mAcm -2, sedimentation time is 10 minutes.
6. three-dimensional net structure Co according to claim 1 3o 4-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 5) described in the concentration of electrolyte be 0.01-0.05mol/L cobalt nitrate and 0.005-0.025mol/L nickel nitrate, deposition current is 1-5mAcm -2, sedimentation time is 4-20 minute.
7. three-dimensional net structure Co described in claim 1 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, includes following steps:
1) take nickel foam as electrode base sheet, be dipped into ultrasonic preliminary treatment in the dilute sulfuric acid of 0.1mol/L, after taking out, use deionized water supersound washing, then by washed electrode base sheet dry for standby;
2) 0.2-1.0g cabaltous nitrate hexahydrate and 0.2-1.0g urea are dissolved in 70ml deionized water for stirring and form settled solution;
3) by step 2) settled solution that obtains and step 1) in the nickel foam handled well proceed in reactor and react, take out reactor, naturally cool to room temperature, take out nickel foam, ultrasonic, dry, then sinter in argon gas and air, obtain cobaltosic oxide electrode material;
4) using step 3) in the cobaltosic oxide electrode material that obtains as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, 100 ml solns of 30 milliliters of Graphenes prepared using Ha Mofa and 3.58 grams of sodium hydrogen phosphates are as electrolyte, deposit, take out work electrode after end, obtain cobaltosic oxide-Graphene electrodes material with deionized water rinsing;
5) using step 4) in cobaltosic oxide-Graphene electrodes material of obtaining as work electrode, platinum electrode is as to electrode, saturated calomel electrode is as reference electrode, cobalt nitrate and nickel nitrate are as electrolyte, deposit, take out work electrode after end, with deionized water rinsing, dry and obtain three-dimensional net structure Co 3o 4-Graphene nickel cobalt double-hydroxide composite material.
8. three-dimensional net structure Co according to claim 7 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 2) described in cabaltous nitrate hexahydrate be 0.291g, urea is 0.3g.
9. three-dimensional net structure Co according to claim 7 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 3) described in reaction temperature be 120 DEG C, the reaction time is 9 hours.
10. three-dimensional net structure Co according to claim 7 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 3) described in argon gas in sintering temperature be 450 DEG C, sintering time is 5 hours, and in air, sintering temperature is 300 DEG C, and sintering time is 5 hours.
11. three-dimensional net structure Co according to claim 7 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 4) described in deposition current be 1mAcm -2, sedimentation time is 10 minutes.
12. three-dimensional net structure Co according to claim 7 3o 4the preparation method of-Graphene nickel cobalt double-hydroxide composite material, is characterized in that, step 5) described in the concentration of electrolyte be 0.01-0.05mol/L cobalt nitrate and 0.005-0.025mol/L nickel nitrate, deposition current is 1-5mAcm -2, sedimentation time is 4-20 minute.
13. three-dimensional net structure Co according to claim 1 3o 4-Graphene nickel cobalt double-hydroxide composite material is as the application of electrode of super capacitor active material.
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