CN110517898A - The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated - Google Patents
The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated Download PDFInfo
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Abstract
The present invention relates to the preparation methods of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, comprising the following steps: 1) preparation of graphene oxide and aniline mixed liquor；2) CoAl-LDH is prepared using hydro-thermal method；3) polyaniline graphene and CoAl-LDH are mixed to get finely dispersed mixed solution, are then filtered by vacuum, calcine to obtain the graphene@CoAl-LDH combination electrode material of polyaniline-coated.Compared with prior art, the present invention obtain polyaniline-coated graphene@CoAl-LDH combination electrode material preparation method it is simple and feasible, environmentally protective, and cost is controllable, obtained electrode material can be applied to the research of supercapacitor.
Description
Technical field
The invention belongs to materials chemistry energy storage fields, are related to a kind of combination electrode material of morphology controllable, specifically, relate to
And a kind of preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated.
Background technique
Layered bi-metal oxide (LDH) is typical two-dimension nano materials, and LDH has good electro-chemical activity and plate
Layer structure, is expected to obtain Faraday pseudo-capacitance and Electric double-layer capacitor simultaneously.Simultaneously as they have flexible ion exchange energy
Power, the extensive research that electrode material for super capacitor is applied so as to cause people.CoAl-LDH, divalent Co ion and trivalent
Al ion is a kind of most common research type, facilitates faradic redox reaction due to Co2+And Co3+Turn
It changes.Therefore, it is a kind of active material that CoAl-LDH can be used as during fake capacitance, but since inherently poor is led
Electrical property causes the experiment capacity of CoAl-LDH to be often far below theoretical capacity.
It the use of other active materials synthesis LDH composite material is the ideal method for promoting electronics and ion-transfer.In recent years,
The nanostructured carbon materials such as carbon nanotube (CNTs), carbon fiber, graphene are considered as the ideal intercalation material of LDH.However, not
Evitable to be, LDH and carbon material can be superimposed during the experiment by Van der Waals force, reduce capacitive property.Such as
What inhibits the generation of above situation to influence the capacitive property of capacitor into present technical problem urgently to be resolved.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of polyaniline-coateds
The preparation method of graphene@CoAl-LDH combination electrode material, can solve bimetallic oxide electric conductivity in the prior art
The disadvantages of bad, easy to reunite with other carbon materials, while the combination electrode material has good cyclical stability and capacitive character
Energy.
The purpose of the present invention can be achieved through the following technical solutions:
The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, comprising the following steps:
(1) mixed solution of graphene oxide and polyaniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to not
It is ultrasonically treated in proportion；
It is uniform that dispersing agent progress ultrasonic disperse is added in polyaniline；
Graphene oxide dispersion proportionally carries out mixing ultrasonic disperse with dispersing polyaniline agent, then in graphite oxide
Initiator and inorganic acid are added in alkene-aniline mixed liquor；
(2) hydro-thermal method prepares CoAl-LDH
Cobalt salt is stirred according to different proportion with deionized water and mixes, and aluminium salt and deionized water are carried out according to different proportion
It is stirred, cobalt salt is mixed with aluminum salt solution according to different proportion, urea is then added and carries out hydro-thermal reaction, wait be down to
It after room temperature, is washed, vacuum drying obtains CoAl-LDH；
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor is mixed with CoAl-LDH by different proportion, vacuum pumping is carried out
Filter film forming, then natural air drying, finally carries out calcination processing under nitrogen protection and obtains the graphene@CoAl- of polyaniline-coated
LDH combination electrode material.
In the present invention, in step (1), the ultrasonic time of graphene oxide and deionized water is 1-2h, graphene oxide with
The mixing mass ratio of deionized water is 1:2-3:2.
In the present invention, in step (1), aniline be added dispersing agent in carry out mixing ultrasonic disperse it is uniform, dispersing agent be 12
Sodium alkyl benzene sulfonate, aniline are uniformly mixed with dispersing agent according to mass ratio 6:1.
In the present invention, in step (1), graphene oxide dispersion is 1:40-1:1 according to mass ratio with aniline dispersion liquid
It is uniformly mixed, graphene oxide dispersion mixes ultrasound 1-2h with aniline dispersion liquid.
In the present invention, in step (1), initiator and inorganic acid are sequentially added in graphene oxide-aniline mixed liquor, then
Controlled at 0-2 DEG C, revolving speed is that 100-300r/min stirring 12-14h obtains mixed liquor, is centrifuged, gained filtrate deionization
Water washing to efflux pH until 7.
In the present invention, in step (1), initiator is ammonium sulfate, and inorganic acid is concentrated hydrochloric acid, graphene oxide-aniline mixing
The mass ratio of the monomer of aniline and initiator is 2:1-20:1 in solution；The monomer of aniline and the mass ratio of inorganic acid are 3:5-3:
7。
In the present invention, in step (2), the cobalt salt that can be used includes cobalt nitrate, cobalt acetate or cobalt chloride, can be used
Aluminium salt includes aluminum nitrate, aluminum acetate or aluminium chloride.
In the present invention, in step (2), the mixed proportion of cobalt salt and deionized water is 6mg:1ml-40mg:1ml, cobalt salt with
The mixing time of deionized water is 15-30min.
In the present invention, in step (2), the mixed proportion of aluminium salt and deionized water is 8mg:1ml-30mg:1ml, aluminium salt with
The mixing time of deionized water is 15-30min.
In the present invention, in step (2), the molal weight ratio of cobalt salt and aluminium salt is 7:1-1:1, and the mixing of cobalt salt and aluminium salt is stirred
Mixing the time is 15-30min.
In the present invention, in step (2), the mass ratio of cobalt salt and urea is 1:1-1:8.
In the present invention, in step (2), hydrothermal temperature is 90-120 DEG C, time 12-24h.
In the present invention, in step (3), graphene oxide-aniline mixed liquor and CoAl-LDH mixing ultrasonic disperse sand core
Funnel carries out suction filtration film forming, then natural air drying 48-72h, graphene oxide-aniline mixed liquor and CoAl-LDH mass ratio
For 1:10-10:1, preferably 1:4.
In the present invention, in step (3), calcination temperature is 350-650 DEG C to the hybrid films being prepared under nitrogen protection, is forged
The burning time is 48-72h.
Compared with prior art, the present invention is by conditional filtering, final choice graphene oxide-aniline mixed liquor with
CoAl-LDH mass ratio is 1:10-10:1, is especially 1:4 in mass ratio, can be to avoid occurring in graphene oxide preparation process
Reunite.Graphene oxide is mixed with aniline solution, the graphene oxide of the polyaniline-coated being prepared can be to avoid
The agglomeration of graphene oxide, while the chemical property of electrode material can be improved.The electrode of morphology controllable in order to obtain
The appearance of material is groped by experiment, and selection is proportionally added into dispersing agent dodecyl sodium sulfate, and initiator ammonium sulfate is added
Appearance control is carried out, obtains the electrode material of morphology controllable, and then influence the performance of electrode material.In order to improve traditional electrode
The electric conductivity of material, this patent select while mixing bimetallic oxide-CoAl-LDH, carry out the optimization of electric conductivity, and pass through
Graphene oxide-polyaniline mixed liquor and CoAl-LDH is prepared in hydro-thermal reaction, is then filtered by vacuum, utilizes calcining
It is carbonized, the electric conductivity of the electrode material being had excellent performance, more traditional electrode material is improved, and solves oxygen
The phenomenon that graphite alkene is easy to reunite, and influences electrode material performance, while overcoming single metal oxide poor circulation, list
The low disadvantage of only carbon material energy density, gained combination electrode material not only good cycling stability, charge-discharge performance is excellent, and
Morphology controllable is strong, specific capacitance value with higher, is development and application in the ideal electrode material of supercapacitor.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene@CoAl-LDH mixed film of the polyaniline-coated prepared in embodiment 1；
Fig. 2 is the section electron microscope of the graphene@CoAl-LDH mixed film of the polyaniline-coated prepared in embodiment 2；
Fig. 3 is the X-ray diffraction of the graphene@CoAl-LDH electrode material of the polyaniline-coated prepared in embodiment 2
Figure；
Fig. 4 is the constant current charge-discharge of the graphene@CoAl-LDH electrode material of the polyaniline-coated prepared in embodiment 2
Performance map；
Fig. 5 is the section electron microscope of the graphene@CoAl-LDH mixed film of the polyaniline-coated prepared in embodiment 3.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, comprising the following steps:
(1) mixed solution of graphene oxide and polyaniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to matter
Then amount is ultrasonically treated 1-2h than being that 1:2-3:2 is mixed；
Polyaniline is mixed with dispersing agent neopelex according to mass ratio 6:1, and it is uniform then to carry out ultrasonic disperse；
Graphene oxide dispersion is mixed with dispersing polyaniline agent according to mass ratio 1:40-1:1, then carries out mixing ultrasound
Disperse 1-2h, initiator ammonium sulfate and inorganic acid concentrated hydrochloric acid, the list of aniline are sequentially added in graphene oxide-aniline mixed liquor
The mass ratio of body and initiator is 2:1-20:1；The mass ratio of initiator and inorganic acid is 3:5-3:7, then controlled at 0-
2 DEG C, revolving speed is that 100-300r/min stirring 12-14h obtains mixed liquor, is centrifuged, gained filtrate is washed with deionized to outflow
The pH of liquid is until 7；
(2) hydro-thermal method prepares CoAl-LDH
Cobalt nitrate and deionized water are that 15-30min is mixed in 6mg:1ml-40mg:1ml in proportion；
Aluminum nitrate and deionized water are that 15-30min is mixed in 8mg:1ml-30mg:1ml in proportion；
15-30min is mixed in above-mentioned solution, the molal weight of cobalt nitrate and aluminum nitrate ratio is 7 in mixed solution:
The mass ratio of 1-1:1, subsequent addition urea progress hydro-thermal reaction, cobalt nitrate and urea is 1:1-1:8, the temperature control of hydro-thermal reaction
It is made as 90-120 DEG C, reaction time 12-24h, reaction terminates to be washed, vacuum drying obtains CoAl- wait be cooled to room temperature
LDH；
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor is mixed with CoAl-LDH, mixed mass ratio is 1:
10-10:1 mixing dispersion, carries out suction filtration film forming with sand core funnel, then natural air drying 48-72h, finally under nitrogen protection, control
Temperature processed is 350-650 DEG C, and calcination processing 48-72h obtains the graphene@CoAl-LDH combination electrode material of polyaniline-coated.
More detailed case study on implementation below, by following case study on implementation further illustrate technical solution of the present invention with
And the technical effect that can be obtained.
Embodiment 1
The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, includes the following steps:
(1) mixed solution of graphene oxide and aniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to 1:
2 ratios are mixed, and carry out mixing ultrasonic treatment 1h, then that aniline addition dispersing agent progress ultrasonic disperse is uniform, dispersion
Agent is neopelex, and the mass ratio of aniline and dispersing agent is 6:1.Graphene oxide dispersion is pressed with aniline dispersing agent
Mixing ultrasonic disperse 1h is carried out according to the mass ratio of 1:10.Then sequentially added in aniline graphene oxide dispersion initiator and
Inorganic acid, initiator are ammonium sulfate, and the mass ratio of aniline monomer and initiator in graphene oxide-aniline mixed liquor is 8:1.
Inorganic acid is concentrated hydrochloric acid, and the mass ratio of aniline monomer and inorganic acid in graphene oxide-aniline mixed liquor is 3:5.Then it controls
Temperature processed is 0 DEG C, and revolving speed is that 100 r/min stirring 12h obtains mixed liquor, is centrifuged, gained filtrate is washed with deionized to stream
The pH of liquid is until 7 out.
(2) hydro-thermal method prepares CoAl-LDH
Cobalt nitrate and deionized water according to the mass ratio of 10:1 carry out that ultrasonic 15min, aluminum nitrate and deionization is mixed
Water according to the mass ratio of 12:1 carries out that ultrasonic 15min is mixed, and cobalt nitrate and aluminum nitrate solution are carried out according to 6:1 ratio
Ultrasound 15min is mixed, urea is then added and carries out hydro-thermal reaction, cobalt nitrate is mixed with urea according to mass ratio 1:2, to water
Thermal response is cooled to room temperature, and is washed, and 60 DEG C of vacuum drying obtain CoAl-LDH product.
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor and CoAl-LDH are filtered by vacuum into according to 1:6 ratio
Film, then natural air drying, finally carries out calcination processing under nitrogen protection, and calcination temperature is 350 DEG C, and calcination time 60h is obtained
The graphene@CoAl-LDH combination electrode material of polyaniline-coated needed for experiment.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned resulting polyaniline packet
The surface of the graphene CoAl-LDH mixed film covered is scanned, and resulting scanning electron microscope is as shown in Figure 1, can be with from Fig. 1
Find out that the surface distribution of mixed film is continuous, illustrates being sufficiently mixed for the two.
Electrochemical property test:
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode,
Working electrode is the Pt net of carrying active substance, with three-electrode system electrochemical workstation and blue electric system test material electricity
Chemical property.The results show that the combination electrode material of preparation is in 2Ag-1Charging and discharging curve under galvanostatic conditions is at symmetric triangular
Shape shows good fake capacitance behavior.It is 2Ag in electric current-1It sweeps in the stable circulation linearity curve under speed, the specific volume quantitative change of material
Change less, after 6000 circulations, specific capacity is still positively retained at 80% or so, protrudes it with good stable circulation
Property.
Embodiment 2
A kind of preparation method of graphene@CoAl-LDH combination electrode material, includes the following steps:
(1) mixed solution of graphene oxide and aniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to 1:
1 ratio is mixed, and carries out mixing ultrasonic treatment 1.5h, then that aniline addition dispersing agent progress ultrasonic disperse is uniform, point
Powder is neopelex, and the mass ratio of aniline and dispersing agent is 6:1.Graphene oxide dispersion and aniline dispersing agent
Mixing ultrasonic disperse 1.5h is carried out according to the mass ratio of 1:8.Then it is added in aniline graphene oxide dispersion and successively causes
Agent and inorganic acid, initiator are ammonium sulfate, and the mass ratio of aniline monomer and initiator in graphene oxide-aniline mixed liquor is
6:1.Inorganic acid is concentrated hydrochloric acid, and the mass ratio of aniline monomer and inorganic acid in graphene oxide-aniline mixed liquor is 2:1.So
Afterwards controlled at 3 DEG C, revolving speed is that 200 r/min stirring 14h obtains mixed liquor, is centrifuged, gained filtrate is washed with deionized
To efflux pH until 7.
(2) hydro-thermal method prepares CoAl-LDH
Cobalt nitrate and deionized water according to the mass ratio of 8:1 carry out that ultrasonic 30min, aluminum nitrate and deionized water is mixed
It according to the mass ratio of 10:1 carries out that ultrasonic 30min is mixed, cobalt nitrate and aluminum nitrate solution is mixed according to 2:1 ratio
Ultrasound 30min is closed, urea is then added and carries out hydro-thermal reaction, cobalt nitrate is mixed with urea according to mass ratio 1:4, to hydro-thermal
Reaction is cooled to room temperature, and is washed, and 60 DEG C of vacuum drying obtain CoAl-LDH product.
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor and CoAl-LDH are filtered by vacuum into according to 1:4 ratio
Film, then natural air drying, finally carries out calcination processing under nitrogen protection, and calcination temperature is 400 DEG C, and calcination time 48h is obtained
The graphene@CoAl-LDH combination electrode material of polyaniline-coated needed for experiment.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned resulting polyaniline packet
The section for the mixed film that the graphene@CoAl-LDH covered is prepared is scanned, resulting scanning electron microscope (SEM) photograph such as Fig. 2 institute
Show.As can be seen from Figure 2 polyaniline-graphite oxide is uniformly distributed with CoAl-LDH flaky material, forms intercalation configuration.Using
X-ray diffraction instrument (XRD) is tested at 2-80 °, as shown in figure 3, CoAl peak value is corresponding with the peak value of standard card.
Electrochemical property test method is with embodiment 1, and under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt
Electrode, reference electrode are Ag/AgCl electrodes, and working electrode is the Pt net of carrying active substance, with three-electrode system in electrochemistry
The chemical property of work station and blue electric system test material.As shown in figure 4, the combination electrode material of preparation is in 2Ag-1Constant current
Under the conditions of charging and discharging curve at symmetrical triangular shape, show good fake capacitance behavior, electric current be 2Ag-1Under specific capacitance
Amount can achieve 2244F/g, and after 6000 circulations, specific capacity is still positively retained at 90% or so, and prominent its has good
Cyclical stability.
Embodiment 3
A kind of preparation method of graphene@CoAl-LDH combination electrode material, includes the following steps:
(1) mixed solution of graphene oxide and aniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to 1:
4 ratios are mixed, and carry out mixing ultrasonic treatment 2h, then that aniline addition dispersing agent progress ultrasonic disperse is uniform, dispersion
Agent is neopelex, and the mass ratio of aniline and dispersing agent is 2:1.Graphene oxide dispersion is pressed with aniline dispersing agent
Mixing ultrasonic disperse 2h is carried out according to the mass ratio of 1:6.Then be added in aniline graphene oxide dispersion successively initiator and
Inorganic acid, initiator are ammonium sulfate, and the mass ratio of aniline monomer and initiator in graphene oxide-aniline mixed liquor is 4:1.
Inorganic acid is concentrated hydrochloric acid, and the mass ratio of aniline monomer and inorganic acid in graphene oxide-aniline mixed liquor is 1:2.Then it controls
Temperature processed is 3 DEG C, and revolving speed is that 300 r/min stirring 14h obtains mixed liquor, is centrifuged, gained filtrate is washed with deionized to stream
The pH of liquid is until 7 out.
(2) hydro-thermal method prepares CoAl-LDH
Cobalt nitrate and deionized water according to the mass ratio of 6:1 carry out that ultrasonic 20min, aluminum nitrate and deionized water is mixed
It according to the mass ratio of 8:1 carries out that ultrasonic 20min is mixed, cobalt nitrate and aluminum nitrate solution is mixed according to 2:1 ratio
Ultrasonic 20min is then added urea and carries out hydro-thermal reaction, and cobalt nitrate is mixed with urea according to mass ratio 1:1, anti-to hydro-thermal
It should be cooled to room temperature, be washed, 60 DEG C of vacuum drying obtain CoAl-LDH product.
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor and CoAl-LDH are filtered by vacuum into according to 1:5 ratio
Film, then natural air drying, finally carries out calcination processing under nitrogen protection, and calcination temperature is 380 DEG C, and calcination time 72h is obtained
The graphene@CoAl-LDH combination electrode material of polyaniline-coated needed for experiment.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to above-mentioned resulting polyaniline packet
The section of the graphene@CoAl-LDH mixed film covered is scanned, and resulting scanning electron microscope (SEM) photograph is as shown in Figure 5.It can from Fig. 5
To find out the clearly demarcated intercalation configuration of structure, it was demonstrated that the abundant reaction of the two, but if material proportion is improper, influence electrochemistry
The test of performance.
Electrochemical property test:
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode,
Working electrode is the Pt net of carrying active substance, with three-electrode system electrochemical workstation and blue electric system test material electricity
Chemical property.The combination electrode material of preparation is in 2Ag-1Charging and discharging curve under galvanostatic conditions is shown at symmetrical triangular shape
Good fake capacitance behavior, after 6000 circulations, specific capacity is still positively retained at 70% or so, due to combination electrode material
Load is excessive, influences the test of chemical property.
Embodiment 4
The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, includes the following steps:
(1) mixed solution of graphene oxide and aniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to 3:
2 ratios are mixed, and carry out mixing ultrasonic treatment 1h, then that aniline addition dispersing agent progress ultrasonic disperse is uniform, dispersion
Agent is neopelex, and the mass ratio of aniline and dispersing agent is 6:1.Graphene oxide dispersion is pressed with aniline dispersing agent
Mixing ultrasonic disperse 1h is carried out according to the mass ratio of 1:40.Then sequentially added in aniline graphene oxide dispersion initiator and
Inorganic acid, initiator are ammonium sulfate, and the mass ratio of aniline monomer and initiator in graphene oxide-aniline mixed liquor is 2:1.
Inorganic acid is concentrated hydrochloric acid, and the mass ratio of aniline monomer and inorganic acid in graphene oxide-aniline mixed liquor is 3:7.Then it controls
Temperature processed is 2 DEG C, and revolving speed is that 300 r/min stirring 14h obtains mixed liquor, is centrifuged, gained filtrate is washed with deionized to stream
The pH of liquid is until 7 out.
(2) hydro-thermal method prepares CoAl-LDH
Cobalt acetate and deionized water according to the mass ratio of 6:1 carry out that ultrasonic 15min, aluminum acetate and deionized water is mixed
It according to the mass ratio of 8:1 carries out that ultrasonic 15min is mixed, cobalt acetate and Burow's Solution is mixed according to 7:1 ratio
Ultrasonic 15min is then added urea and carries out hydro-thermal reaction, and cobalt acetate is mixed with urea according to mass ratio 1:1, and hydro-thermal is controlled
The temperature of reaction is 90 DEG C, and reaction for 24 hours, is cooled to room temperature to hydro-thermal reaction, is washed, 60 DEG C of vacuum drying obtain CoAl-
LDH product.
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor and CoAl-LDH are filtered by vacuum into according to 1:10 ratio
Film, then natural air drying 48h, finally carries out calcination processing under nitrogen protection, and calcination temperature is 500 DEG C, and calcination time is
48h obtains the graphene@CoAl-LDH combination electrode material for testing required polyaniline-coated.
Electrochemical property test:
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode,
Working electrode is the Pt net of carrying active substance, with three-electrode system electrochemical workstation and blue electric system test material electricity
Chemical property.The combination electrode material of preparation is in 2Ag-1Charging and discharging curve under galvanostatic conditions is shown at symmetrical triangular shape
Good fake capacitance behavior, after 6000 circulations, specific capacity is still positively retained at 80% or so.
Embodiment 5
The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, includes the following steps:
(1) mixed solution of graphene oxide and aniline is prepared
Graphene oxide is prepared using the Hummer method of improvement, by the graphene oxide prepared and deionized water according to 1:
1 ratio is mixed, and carries out mixing ultrasonic treatment 1h, then that aniline addition dispersing agent progress ultrasonic disperse is uniform, dispersion
Agent is neopelex, and the mass ratio of aniline and dispersing agent is 6:1.Graphene oxide dispersion is pressed with aniline dispersing agent
Mixing ultrasonic disperse 1h is carried out according to the mass ratio of 1:1.Then sequentially added in aniline graphene oxide dispersion initiator and
Inorganic acid, initiator are ammonium sulfate, and the mass ratio of aniline monomer and initiator in graphene oxide-aniline mixed liquor is 20:
1.Inorganic acid is concentrated hydrochloric acid, and the mass ratio of aniline monomer and inorganic acid in graphene oxide-aniline mixed liquor is 3:7.Then
Controlled at 0 DEG C, revolving speed is that 200 r/min stir 12h and obtain mixed liquor, is centrifuged, gained filtrate be washed with deionized to
The pH of efflux is until 7.
(2) hydro-thermal method prepares CoAl-LDH
Cobalt chloride and deionized water according to the mass ratio of 40:1 carry out that ultrasonic 30min, aluminium chloride and deionization is mixed
Water according to the mass ratio of 30:1 carries out that ultrasonic 30min is mixed, and cobalt chloride and liquor alumini chloridi are carried out according to 1:1 ratio
Ultrasound 30min is mixed, urea is then added and carries out hydro-thermal reaction, cobalt nitrate is mixed with urea according to mass ratio 1:8, to water
Thermal response is cooled to room temperature, and is washed, and 60 DEG C of vacuum drying obtain CoAl-LDH product.
(3) preparation of the graphene@CoAl-LDH combination electrode material of polyaniline-coated
The graphene oxide of above-mentioned preparation-aniline mixed liquor and CoAl-LDH are filtered by vacuum into according to 10:1 ratio
Film, then natural air drying, finally carries out calcination processing under nitrogen protection, and calcination temperature is 650 DEG C, and calcination time 60h is obtained
The graphene@CoAl-LDH combination electrode material of polyaniline-coated needed for experiment.
Electrochemical property test:
Under 1mol/LKOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode,
Working electrode is the Pt net of carrying active substance, with three-electrode system electrochemical workstation and blue electric system test material electricity
Chemical property.The combination electrode material of preparation is in 2Ag-1Charging and discharging curve under galvanostatic conditions is shown at symmetrical triangular shape
Good fake capacitance behavior, after 6000 circulations, specific capacity is still positively retained at 70% or so.
In conclusion a kind of preparation side of the graphene@CoAl-LDH combination electrode material of polyaniline-coated of the invention
The charge-discharge performance, XRD and scanning electron microscope performance map of each embodiment, chemical property prepared by embodiment 2 is comprehensively compared in method
Preferably, graphene@CoAl-LDH combination electrode specific capacity with 2244F/g in 2A/g constant current charge-discharge, in circulation 6000
After secondary, nearly 90% specific capacity there remains, protrude it with good cyclical stability, make full use of polyaniline-coated
Carbon material and transition metal oxide synergistic effect, prepare chemical property well and can be applied to answering for supercapacitor
Composite electrode material.
Composite material of the present invention makes full use of polyaniline to adjust to inhibit the poly- of graphene oxide and double layered transition metal material
Collection, the electric conductivity that graphene oxide itself has is high, the high excellent characteristics of specific surface area and CoAl bimetallic oxide specific capacity
High feature overcomes the shortcomings of that traditional material pile ghost image rings capacitive property.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in guarantors of the invention
Within the scope of shield.
Claims (10)
1. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated, which is characterized in that this method packet
It includes:
Prepare the mixed solution of graphene oxide and polyaniline:
Graphene oxide is prepared using the Hummer method of improvement, graphene oxide is uniformly mixed to obtain graphite oxide with deionized water
Alkene dispersion liquid,
Aniline is added dispersing agent and is uniformly dispersed to obtain aniline dispersion liquid,
Graphite oxide is mixed with aniline dispersion liquid, initiator and inorganic acid is added, obtains graphene oxide-aniline mixed liquor；
Prepare CoAl-LDH:
Cobalt salt and deionized water are stirred to obtain cobalt salt solution,
Aluminium salt and deionized water are stirred to obtain aluminum salt solution,
Cobalt salt solution is mixed with aluminum salt solution, urea is then added and carries out hydro-thermal reaction, is cooled to room temperature after the completion, carries out water
It washes, vacuum drying obtains CoAl-LDH；
The preparation of the graphene@CoAl-LDH combination electrode material of aniline cladding
The graphene oxide of above-mentioned preparation-aniline mixed liquor is mixed according to different proportion with CoAl-LDH and is filtered by vacuum into
Film, then natural air drying, the graphene@CoAl-LDH that finally progress calcination processing obtains polyaniline-coated under nitrogen protection are answered
Composite electrode material.
2. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, the mass ratio of the graphene oxide and deionized water is 1:2-3:2.
3. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, the dispersing agent is neopelex, and proportionally mass ratio 6:1 is mixed aniline with dispersing agent
It is even.
4. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, the graphene oxide dispersion is uniformly mixed with dispersing polyaniline liquid according to mass ratio 1:40-1:1.
5. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, sequentially adds initiator and inorganic acid in the mixed solution of graphene oxide dispersion and dispersing polyaniline liquid,
Controlled at 0-2 DEG C, revolving speed is that 100-300r/min stirring 12-14h obtains mixed liquor, is centrifuged, gained filtrate deionization
Water washing to efflux pH until 7.
6. the preparation side of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1 or 5
Method, which is characterized in that the initiator is ammonium sulfate, and the inorganic acid is concentrated hydrochloric acid, in mixed solution the monomer of aniline with draw
The mass ratio for sending out agent is 2:1-20:1；The monomer of aniline and the mass ratio of inorganic acid are 3:5-3:7.
7. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, the cobalt salt is cobalt nitrate, cobalt acetate or cobalt chloride, and the aluminium salt is aluminum nitrate, aluminum acetate or aluminium chloride, cobalt salt
It is 6mg:1ml-40mg:1ml with the mixed proportion of deionized water, the mixed proportion of aluminium salt and deionized water is 8mg:1ml-
The molar ratio of 30mg:1ml, cobalt salt and aluminium salt is 7:1-1:1, and the mass ratio of cobalt salt and urea is 1:1-1:8.
8. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, the temperature of hydro-thermal reaction is 90-120 DEG C, time 12-24h.
9. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, graphene oxide-aniline mixed liquor carries out suction filtration film forming with CoAl-LDH mixing ultrasonic disperse with sand core funnel, so
The mass ratio of natural air drying 48-72h afterwards, graphene oxide-aniline mixed liquor and CoAl-LDH be 1:10-10:1, preferably 1:
4。
10. the preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated according to claim 1,
It is characterized in that, the temperature of calcination processing is 350-650 DEG C, time 48-72h.
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