CN106683898A - Composite electrode material for supercapacitor, preparation method thereof and supercapacitor - Google Patents
Composite electrode material for supercapacitor, preparation method thereof and supercapacitor Download PDFInfo
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- CN106683898A CN106683898A CN201611193487.5A CN201611193487A CN106683898A CN 106683898 A CN106683898 A CN 106683898A CN 201611193487 A CN201611193487 A CN 201611193487A CN 106683898 A CN106683898 A CN 106683898A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a composite electrode material for a supercapacitor, which belongs to the technical field of electrode materials. The composite electrode material includes a hexagonal boron nitride foam, a graphene oxide thin film and polyaniline nanofibers. The graphene oxide thin film is uniformly coated on the surface of the hexagonal boron nitride foam and is connected therewith to form integrated boron nitride-oxide graphene foam. The polyaniline nanofibers are attached to the surface of the boron nitride-oxide graphene foam to form a coaxial one-dimensional array structure. The invention also provides a preparation method of the above-mentioned electrode material and a supercapacitor prepared using the electrode material. The provided composite electrode material for the supercapacitor by the invention has the characteristics of high specific capacity and high stability, and has a wide practical application value and an industrial production prospect.
Description
Technical field
The present invention relates to electrode material field, it particularly relates to a kind of combination electrode material of ultracapacitor and its
Preparation method and by made by above-mentioned electrode material ultracapacitor.
Background technology
Ultracapacitor, a kind of quick charge, energy storage device of electric discharge between ordinary capacitor and secondary cell.
In recent years, ultracapacitor is big with its power density as a kind of new energy storage device, has extended cycle life, in energy storage technology
On play important role.
Affect the performance of ultracapacitor mainly on electrode material therefore a kind of with the high reversible electricity of high conductivity
Pole material becomes the emphasis of research.Although the model of existing various ultracapacitors occurs in relevant report, yet with electricity
Pole Materials are rapid, and new nano composite material can produce more superior capacitive property by synergism, and this is all
The development of ultracapacitor of new generation opens wide prospect.
The research that template-directing method prepares three-dimensional grapheme base electrode material is relatively more, and common method has solid template method
With ice template method.Using the electrode material ratio of solid template method preparation if any nickel foam（Wang J, Chao DL, Liu JL,
et al. Ni3S2@MoS2 core/shell nanorod arrays on Ni foam for high-perfor-mance
electrochemical energy storage[J]. Nano Energy 2014,7(7): 151）, cetyl trimethyl
Ammonium bromide (CTAB)（Yang S, Feng X, Wang L, et al. Graphene-Based Nanosheets with a
Sandwich Structure[J]. Angewand-teChemie, 2010, 122(28)）, polystyrene spheres（PS）（Wang
S Y, Ma L, GanM Y, et al. Free-standing 3D graphene/polyaniline composite
film electrodes for high-performance supercapacitors[J]. Journal of Power
Sources, 2015,299 (12): 347）With polymethyl methacrylate (PMMA) etc., these templates are required for through template
Removal step, and time length, solvent consumption are big, not environmentally.
Ice template method prepares multi-level poroid three-dimensional grapheme framework, layer by layer the synergism between hole be conducive to its
Application in energy storage device.Vinod etc.（Vinod S, Tiwary C S, Autreto1 P A D, et al.Low-
density three-dimensional foam using self-reinforced hybrid two-dimensional
atomic layers[J], Nature Communications, 2014,5:4541）By a certain amount of graphene oxide and six
After square boron nitride difference supersound process, then lyophilization 48h, the graphene oxide-boron nitride material of three-dimensional is finally given, it is this
Material, with more preferable mechanical strength and heat stability, expands it in storage compared with traditional low-density nanofoam materials
Range of application in energy device material, but its preparation method needs to be carried out under conditions of extremely low, such as it is subzero 40 DEG C, and
Cooling time is longer, and preparation cost is higher.
The content of the invention
The first object of the present invention is to provide a kind of ultracapacitor combination electrode material.
To realize above-mentioned technical purpose, the technical solution used in the present invention is as follows：
A kind of ultracapacitor combination electrode material, including hexagonal boron nitride foam, graphene oxide film and polyaniline receive
Rice fiber, the graphene oxide film is evenly coated at hexagonal boron nitride foam surface, is interconnected to form integral type nitridation
Boron-oxygen graphite alkene foamed materialss, the polyaniline nano fiber is attached to boron nitride-graphene oxide foam surface life
Into coaxial one-dimensional array structure.
Hexagonal boron nitride, Graphene and polyaniline have the property that：
Most of performance of boron nitride is more excellent than carbon materials, and for hexagonal boron nitride, its coefficient of friction very low and high temperature is stablized
Property preferable, resistance to heat shocks is preferable, intensity is very high, heat conductivity is higher, the coefficient of expansion is relatively low, corrosion-resistant and can microwave or thoroughly red thoroughly
Outside line.
Graphene has many excellent specific properties such as carrier mobility, electrical conductivity, thermal conductivity, light transmission, the intensity of superelevation.
Polyaniline price is low, and capacitive character is high, and synthesis step is simple, and environmental stability is good, and redox reaction is reversible, is most
Have one of promising conducting polymer, be also a kind of attractive electrode material for being applied to ultracapacitor.
Using the ultracapacitor combination electrode material of above-mentioned technical proposal, Graphene is respectively provided with larger with boron nitride
Specific surface area, the two is combined, and a kind of foam-body material of three-dimensional drape shape of preparation is deposition conducting polymer or transition
The ideal three-dimensional carrier of metal-oxide, it both make use of the high conductivity of Graphene, and using hexagonal boron nitride specific surface area
Greatly, the corrosion resistant feature of good stability, the former advantageously reduces conducting polymer or transition metal oxide in expansion and receives
The change of the volume for contracting and causing, while being conducive to the diffusion of electrolyte ion, the latter is as three dimensional structure template and oxygen
Graphite alkene is combined, and forms the foam-body material of the big three-dimensional drape shape of specific surface area, with reference to the unique capacitance characteristics of PANI,
Design ultracapacitor combination electrode material.
Above-mentioned polyaniline nano fiber diameter is about 30 ~ 50nm, can not only increase the contact area with electrolyte, suppresses
The expansion of volume, contributes to shortening the evolving path of ion, and is conducive to improving the utilization rate of electrode material.
Preferably, the mass percent of the graphene oxide film, hexagonal boron nitride foam and polyaniline nano fiber
For 1：1~10：8~50.
It is highly preferred that the quality percentage of the graphene oxide film, hexagonal boron nitride foam and polyaniline nano fiber
Than for 1：1~5：10~30.
The second object of the present invention is to provide the preparation method of above-mentioned superbattery combination electrode material, the preparation method
Comprise the steps：
Step 1：Hexagonal boron nitride thin film
Boron nitride powder is dissolved in dimethylformamide, supersound process is until be uniformly dispersed, bath temperature is maintained at 20 ~ 30
DEG C, after supersound process, solution is centrifuged, vacuum filter, respectively deionized water, absolute ethanol washing, then
It is dried, hexagonal boron nitride is obtained；
Step 2：Hexagonal boron nitride-graphene oxide binary complex is produced
It is 1 by mass ratio:1~10:1 graphene oxide and hexagonal boron nitride distinguish supersound process 30 ~ 40 in deionized water
Min, is then mixed to form the disperse system solution of 7 ~ 15 mg/ml, by reaction promoter resorcinol, glutaraldehyde and sodium tetraborate five
Hydrate is added in the disperse system solution of graphene oxide-boron nitride, 2 ~ 3h of supersound process, 20 ~ 48h of lyophilization, is obtained
Hexagonal boron nitride-graphene oxide（Cellular）Foams；
Step 3：The preparation of hexagonal boron nitride-graphene oxide-polyaniline
Obtained hexagonal boron nitride-graphene oxide foams in step 2 are added to into the HClO4 solution that concentration is 1mol/L
In, supersound process is subsequently adding ethanol in proper amount up to being uniformly dispersed（Ethanol is 1 with the volume ratio of reaction solution:3~8）To reaction
In solution, add appropriate aniline monomer solution and form it into unified intermixture in -10 DEG C ~ 10 DEG C 30 ~ 40 min of stirring,
The hexagonal boron nitride-graphene oxide foams are 1 with the mass ratio of aniline monomer：4~25；
By oxidant（NH4）During 2S2O8 (APS) is dissolved in HClO4,0 DEG C is cooled to, oxidizing agent solution is obtained, toward intermixture
Quickly add the oxidizing agent solution of above-mentioned cooling, 12 ~ 24h of stirring reaction under the conditions of 0 DEG C obtains green flocky precipitate, so
Afterwards and use HClO4（0.1 mol/L）Solution and washing with alcohol, are dried 12 ~ 24 h and combination electrode material are obtained.
Further limit, the rotating speed of centrifugal separation processes is 1000 ~ 2500r/min in the step 1, and centrifugation time is 10
~60min。
Present invention aim to overcome that the intrinsic template removal process of existing three-dimensional grapheme based composites is complicated, introduce many
The problems such as planting solvent, and boron nitride and Graphene are first formed by three-dimensional drape composite foam material using freezing ice template method,
Then in material surface one-dimensional growth polyaniline nanofiber array, the three-dimensional composite material of three is obtained, is beneficial to it and answers
Application of the condensation material on ultracapacitor, the preparation method is used for super capacitor using hexagonal boron nitride as three-dimensional template first
Device field of material preparation.For the documents such as Vinod, the preparation method can between -40 ~ -20 DEG C, and freeze when
Between greatly reduce, saved cost.
The third object of the present invention is to provide a kind of ultracapacitor, and the electrode of the ultracapacitor is by above-mentioned super capacitor
Device is made with combination electrode material.
The present invention has the advantages that compared to existing technology：
In the combination electrode material, boron nitride/graphene oxide forms the formwork structure of three-dimensional drape, this configuration increases poly-
The polymerization contact area of aniline and polymerization site, are easy to the coaxial polyaniline fiber battle array in this body structure surface one-dimensional growth nanometer
Row.The nanostructured of coaxial heterogeneous can effectively lift the electrochemistry storing up electricity performance of polyaniline, while strengthening the electricity of composite construction
Chemical stability；Polyaniline nano fiber is coated on the surface of boron nitride/graphene oxide three dimensional structure, there is provided extra charge and discharge
Electric electron channel；Therefore, the characteristics of combination electrode material has height ratio capacity and high stability concurrently, can be used as ultracapacitor
Main electrode material, while the combination electrode material also has actual application value in related electrochemical field.Jing chemical properties
Test, the quality specific capacitance of the composite up to 465F/g, test after 1000 circulations, and specific capacity is still tieed up by constant current charge-discharge
Hold more than 90%.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of boron nitride/graphene oxide three-dimensional drape structure；
Fig. 2 is the scanning electron microscope (SEM) photograph of boron nitride-graphene oxide-polyaniline composite；
Fig. 3 is the preparation technology flow chart of boron nitride-graphene oxide-polyaniline composite；
Fig. 4 is polyaniline, three kinds of Different electrodes materials of graphene oxide-polyaniline and boron nitride-graphene oxide-polyaniline
Cyclic voltammetry curve figure；
Fig. 5 is cyclic voltammetry curve contrast of the boron nitride-graphene oxide-polyaniline composite under different scanning rates
Figure；
Fig. 6 is charging and discharging curve contrast of the boron nitride-graphene oxide-polyaniline composite under different constant current densities
Figure；
Fig. 7 is polyaniline, three kinds of Different electrodes materials of graphene oxide-polyaniline and boron nitride-graphene oxide-polyaniline exist
Specific capacitance value curve chart under different electric current densities；
Fig. 8 is polyaniline, the cyclical stability comparison diagram of boron nitride-graphene oxide-polyaniline electrode material.
Specific embodiment
In order that those skilled in the art may be better understood the present invention, with reference to the accompanying drawings and examples to this
Bright technical scheme is further illustrated.
A kind of ultracapacitor combination electrode material, including hexagonal boron nitride（h-BN）Foam, graphene oxide（GO）
Thin film and polyaniline（PANI）Nanofiber, the graphene oxide film is evenly coated at boron nitride foam surface, mutually interconnects
Connect to form integral type boron nitride-graphene oxide foamed materialss, the polyaniline nano fiber is attached to boron nitride-graphite oxide
Alkene foam surface generates coaxial one-dimensional array structure.
In the combination electrode material, the quality of graphene oxide film, Three-dimensional boron nitride foam and polyaniline nano fiber
Percentage ratio is 1:1~10:8 ~ 50, preferably 1:1~5:10~30.
Polyaniline nano fiber is the array structure of coaxial one-dimensional growth, and it not only causes to increase itself and electrolyte
Contact area, suppresses the expansion of volume, contributes to shortening the evolving path of ion, and is conducive to improving the utilization of electrode material
Rate.
Fig. 1 shows scanning electron microscope (SEM) photograph of the hexagonal boron nitride/graphene oxide electrode material in 500nm and 200nm, Fig. 2
The scanning electron microscope (SEM) photograph of hexagonal boron nitride/graphene oxide/polyaniline electrode material in the application in 500nm and 200nm is shown,
Wherein 500nm may be considered the top view of electrode material surface, and 200nm is profile, therefrom can be seen, the application's answers
Composite electrode material compares hexagonal boron nitride/graphene oxide and has the three-dimensional stereo effect for becoming apparent from, and this accordingly causes electrode
Material has larger specific surface area, is conducive to shortening the evolving path of ion, it is determined that it is in super capacitor material
Using value, this also demonstrates the reasonability of aforementioned theory analysis.
For the preparation of above-mentioned ultracapacitor combination electrode material, it is main include progressively generating as shown in Figure 3 h-BN,
The process of h-BN/GO, h-BN/GO/PANI.Embodiment 1 ~ 3 gives the embodiment for preparing the application combination electrode material.
Embodiment 1：
（1）, hexagonal boron nitride（h-BN）Produce：First boron nitride powder is added to into dimethylformamide（DMF）In, then super
Supersound process 4h in acoustic generator, while keeping bath temperature constant（25℃）.After supersound process, solution is carried out centrifugation point
From (1500 r/min), the min of centrifugation time 15, the supernatant after separation is carefully poured out and is carried out vacuum filter, spends respectively
Ionized water, ethanol purge, are then dried, and hexagonal boron nitride is obtained.
（2）, hexagonal boron nitride-graphene oxide（h-BN/GO）Binary complex is produced：By the oxidation stone of phase homogenous quantities
Black alkene and hexagonal boron nitride distinguish the min of supersound process 30 in deionized water, then mix to form 7.6 mg/ml's
Disperse system solution.Resorcinol（Concentration is made into for 0.19 mg/ml）, glutaraldehyde（Concentration is made into for 0.152 μ l/ml）, four
Sodium borate pentahydrate is added in the disperse system solution of graphene oxide-boron nitride, supersound process 2h, then in vertical freezing
Lyophilizing 24h in drying machine, finally obtains the cellular foam of graphene oxide-boron nitride.
（3）, hexagonal boron nitride-graphene oxide-polyaniline（h-BN/GO/PANI）Produce：By the nitridation of above-mentioned preparation
Boron-oxygen graphite alkene foams（45 mg）In being added to the HClO4 solution of the mol/L of 75 ml 1, supersound process is until dispersion
Uniformly, 15 ml ethanol are subsequently adding in reaction solution, the aniline monomer of appropriate volume is added（Being made into concentration is
0.05mol/L）And stir 30 min at 0 DEG C and form it into unified intermixture.
By oxidant（NH4）2S2O8 (APS) is dissolved in the HCLO4 of 5 ml, is cooled to 0 DEG C, obtains oxidizing agent solution,.
Quickly add the oxidizing agent solution of above-mentioned cooling toward intermixture, make mixed liquor that 16 h are stirred under condition of ice bath, obtain green
Floccule is precipitated, and then filters and use HClO4（0.1 mol/L）Solution and washing with alcohol, it is dry with blast drier at 50 DEG C
Dry 20 h.
Embodiment 2：
（1）, hexagonal boron nitride（h-BN）Produce：First boron nitride powder is added to into dimethylformamide（DMF）In, then super
Supersound process 4h in acoustic generator, while keeping bath temperature constant（25℃）.After supersound process, solution is carried out centrifugation point
From (1000 r/min), the min of centrifugation time 25, the supernatant after separation is carefully poured out and is carried out vacuum filter, spends respectively
Ionized water, ethanol purge, are then dried, and hexagonal boron nitride is obtained.
（2）, hexagonal boron nitride-graphene oxide（h-BN/GO）Binary complex is produced：It is 1 by mass ratio:3 oxygen
Graphite alkene and hexagonal boron nitride distinguish the min of supersound process 30 in deionized water, then mix to form 10 mg/ml
Disperse system solution.Resorcinol（Concentration is made into for 0.19 mg/ml）, glutaraldehyde（Concentration is made into for 0.152 μ l/ml）,
Sodium tetraborate pentahydrate is added in the disperse system solution of graphene oxide-boron nitride, supersound process 2.5h, then vertical
The h of lyophilizing 36 in freezer dryer, finally obtains the cellular foam of graphene oxide-boron nitride.
（3）, hexagonal boron nitride-graphene oxide-polyaniline（h-BN/GO/PANI）Produce：By the nitridation of above-mentioned preparation
Boron-oxygen graphite alkene foams（60mg）In being added to the HClO4 solution of the mol/L of 80ml 1, supersound process is until dispersion is equal
It is even, 25 ml ethanol are subsequently adding in reaction solution, add the aniline monomer of appropriate volume（Concentration is made into for 0.05mol/
L）And stir 30 min at 0 DEG C and form it into unified intermixture.
By oxidant（NH4）2S2O8 (APS) is dissolved in the HClO4 of 5 ml, is cooled to 0 DEG C, obtains oxidizing agent solution.
Quickly add the oxidizing agent solution of above-mentioned cooling toward intermixture, make mixed liquor that 20 h are stirred under condition of ice bath, obtain green
Floccule is precipitated, and then filters and use HClO4（0.1 mol/L）And washing with alcohol, it is dried 20 with blast drier at 50 DEG C
h。
Embodiment 3：
（1）, hexagonal boron nitride（h-BN）Produce：First boron nitride powder is added to into dimethylformamide（DMF）In, then super
Supersound process 4h in acoustic generator, while keeping bath temperature constant（20℃）.After supersound process, solution is carried out centrifugation point
From (2000 r/min), the min of centrifugation time 30, the supernatant after separation is carefully poured out and is carried out vacuum filter, spends respectively
Ionized water, ethanol purge, are then dried, and hexagonal boron nitride is obtained.
（2）, hexagonal boron nitride-graphene oxide（h-BN/GO）Binary complex is produced：It is 1 by mass ratio:8 oxygen
Graphite alkene and hexagonal boron nitride distinguish the min of supersound process 30 in deionized water, then mix to form 10 mg/ml
Disperse system solution.Resorcinol（Concentration is made into for 0.19 mg/ml）, glutaraldehyde（Concentration is made into for 0.152 μ l/ml）,
Sodium tetraborate pentahydrate is added in the disperse system solution of graphene oxide-boron nitride, supersound process 2.5h, then vertical
The h of lyophilizing 36 in freezer dryer, finally obtains the cellular foam of graphene oxide-boron nitride.
（3）, hexagonal boron nitride-graphene oxide-polyaniline（h-BN/GO/PANI）Produce：By the nitridation of above-mentioned preparation
Boron-oxygen graphite alkene foams（50mg）In being added to the HClO4 solution of the mol/L of 150ml 1, supersound process is until dispersion is equal
It is even, 30 ml ethanol are subsequently adding in reaction solution, add the aniline monomer of appropriate volume（Concentration is made into for 0.05mol/
L）And stir 30 min at 0 DEG C and form it into unified intermixture.
By oxidant（NH4）2S2O8 (APS) is dissolved in the HClO4 of 5 ml, is cooled to 0 DEG C, obtains oxidizing agent solution.
Quickly add the oxidizing agent solution of above-mentioned cooling toward intermixture, make mixed liquor that 20 h are stirred under condition of ice bath, obtain green
Floccule is precipitated, and then filters and use HClO4（0.1 mol/L）Solution and washing with alcohol, it is dry with blast drier at 50 DEG C
Dry 20 h.
Embodiment 4 and embodiment 5 are the comparative examples of pure polyaniline and graphene oxide-polyaniline.
Embodiment 4：
In taking the HClO4 solution of the mol/L of 75ml 1, supersound process is subsequently adding 15 ml ethanol to reaction up to being uniformly dispersed
In solution, the aniline monomer of appropriate volume is added（Concentration is made into for 0.05mol/L）And stir 30 min at 0 DEG C and make its shape
Into unified intermixture.
By oxidant（NH4）2S2O8 (APS) is dissolved in the HClO4 of 5 ml, is cooled to 0 DEG C, obtains oxidizing agent solution.
Quickly add the oxidizing agent solution of above-mentioned cooling toward intermixture, make mixed liquor that 16 h are stirred under condition of ice bath, obtain green
Floccule is precipitated, and then filters and use HClO4（0.1 mol/L）Solution and washing with alcohol, it is dry with blast drier at 50 DEG C
Dry 20 h.
Embodiment 5：
By graphene oxide（45mg）In being added to the HClO4 solution of the mol/L of 75ml 1, supersound process until be uniformly dispersed,
15ml ethanol is subsequently adding in reaction solution, the aniline monomer of appropriate volume is added（Concentration is made into for 0.05mol/L）And
30 min are stirred at 0 DEG C form it into unified intermixture.
By oxidant（NH4）2S2O8 (APS) is dissolved in the HClO4 of 5 ml, is cooled to 0 DEG C, obtains oxidizing agent solution.
Quickly add the oxidizing agent solution of above-mentioned cooling toward intermixture, make mixed liquor that 16 h are stirred under condition of ice bath, then filter
And use HClO4（0.1 mol/L）Solution and washing with alcohol, 20h is dried at 50 DEG C with blast drier.
Performance comparison is tested：In following comparative's experiment, polyaniline is selected from embodiment 4, and graphene oxide-polyaniline is selected from real
Example 5 is applied, boron nitride-graphene oxide-polyaniline is selected from embodiment 1.
Test 1：Electrolyte is mixed into 1 mol/L sulfuric acid solutions, potential window is -0.2 ~ 0.8 V, and sweep speed is 20
MV/s, 1 circulation of charge-discharge test lower polyaniline, graphene oxide-polyaniline and boron nitride-graphene oxide-polyaniline three
The cyclic voltammetry curve of Different electrodes material is planted, as shown in Figure 4.
In cyclic voltammetry curve theory, the area that it is surrounded is bigger, and corresponding chemical property is better, can be seen by Fig. 4
Go out, the chemical property of the boron nitride-graphene oxide-polyaniline composite prepared according to the application preparation method is substantially excellent
In pure polyaniline and graphene oxide-polyaniline.
Test 2：In three-electrode system, boron nitride-graphene oxide-polyaniline composite will be prepared and make carbon paper electricity
Pole, using the copper piece clip fixed carbon scraps of paper as working electrode, platinum electrode be to electrode saturated calomel electrode be reference electrode, adopt
Electrochemical workstation (CHI604b) is circulated volt-ampere test, and with 1 mol/L sulfuric acid solutions electrolyte, potential window are mixed into
For -0.2 ~ 0.8 V, selection sweep speed is 5mV/s, and 1 circulation of charge-discharge test tests its cyclic voltammetry curve, according to upper
It is the circulation volt under the conditions of 10 mV/s, 20 mV/s, 50 mV/s, 100 mV/s to state same method and test sweep speed respectively again
Peace curve, test result is as shown in Figure 5.
Test 3：Constant current charge-discharge test is carried out using electrochemical workstation, high potential 0.8V, electronegative potential 0V is set, it is permanent
Electric current density is respectively 1A/g, 2A/g, 5A/g, 10A/g and 20A/g, and as a result 1 circulation of continuous charge-discharge test is shown in Fig. 6,
Calculated quality specific capacitance is up to 465F/g under 1A/g electric current densities.
Test 4：Three kinds of polyaniline, graphene oxide-polyaniline and boron nitride-graphene oxide-polyaniline are tested respectively
Specific capacitance value of the Different electrodes material under different electric current densities, as shown in Figure 7, it can be seen that boron nitride-graphene oxide-poly-
The specific capacitance of aniline is up to 465F/g, and graphene oxide-polyaniline specific capacitance is up to 350 F/g, and polyaniline specific capacitance is most
A height of 330 F/g.
Test 5：Test polyaniline, the stable circulation of two kinds of Different electrodes materials of boron nitride-graphene oxide-polyaniline
Property, as shown in figure 8, learn that boron nitride-graphene oxide-polyaniline combination electrode material is circulated 1000 times according to experimental data,
Specific capacitance conservation rate is more than 90%, and the conservation rate of pure polyaniline only has 58.4%, therefore boron nitride-graphene oxide-polyphenyl
Amine combination electrode material cyclical stability compared with polyaniline material is obviously improved.
This is because h-BN/GO three-dimensional drapes structure can promote electrolyte ion to be diffused into PANI Nanowires from electrolyte
Dimension array surface, effectively shortens the passage of ion diffusion, so as to obtain the structure of composite membrane of high rate capability.On the other hand,
Synergism between PANI and graphene oxide overcomes respective shortcoming, and h-BN/GO supports that template can make to gather as one
Aniline nano-fiber array stands the mechanical deformation caused due to the change of volume, and this can prevent electrode material in discharge and recharge
During volume expansion with shrink, thus improve tri compound material h-BN/GO/PANI electrochemical stability.
As fully visible, this three-dimensional composite material containing hexagonal boron nitride formation of foam, has very as electrode material
Specific capacitance value well and superior stable circulation performance, are highly suitable to be applied for the electrode material of ultracapacitor.
Ultracapacitor combination electrode material for providing the present invention above and preparation method thereof and ultracapacitor enter
Go and be discussed in detail.The explanation of specific embodiment is only intended to help and understands the method for the present invention and its core concept.Should refer to
Go out, for those skilled in the art, under the premise without departing from the principles of the invention, can also be to the present invention
Some improvement and modification are carried out, these are improved and modification is also fallen in the protection domain of the claims in the present invention.
Claims (6)
1. a kind of ultracapacitor combination electrode material, it is characterised in that：It is thin including hexagonal boron nitride foam, graphene oxide
Film and polyaniline nano fiber, the graphene oxide film is evenly coated at hexagonal boron nitride foam surface, is connected with each other shape
Integrated boron nitride-graphene oxide foamed materialss, the polyaniline nano fiber is attached to boron nitride-graphene oxide bubble
Foam material surface generates coaxial one-dimensional array structure.
2. ultracapacitor combination electrode material according to claim 1, it is characterised in that：The graphene oxide is thin
The mass percent of film, hexagonal boron nitride foam and polyaniline nano fiber is 1：1~10：8~50.
3. ultracapacitor combination electrode material according to claim 2, it is characterised in that：The graphene oxide is thin
The mass percent of film, hexagonal boron nitride foam and polyaniline nano fiber is 1：1~5：10~30.
4. a kind of preparation method of ultracapacitor combination electrode material, it is characterised in that：Comprise the following steps：
Step 1：Hexagonal boron nitride thin film
Boron nitride powder is dissolved in dimethylformamide, supersound process is until be uniformly dispersed, bath temperature is maintained at 20 ~ 30
DEG C, after supersound process, solution is centrifuged, vacuum filter, respectively deionized water, absolute ethanol washing, then
It is dried, hexagonal boron nitride is obtained；
Step 2：Hexagonal boron nitride-graphene oxide binary complex is produced
It is 1 by mass ratio:1~10:1 graphene oxide and hexagonal boron nitride distinguish supersound process 30 ~ 40 in deionized water
Min, is then mixed to form the disperse system solution of 7 ~ 15 mg/ml, and resorcinol, glutaraldehyde and sodium tetraborate pentahydrate are added
In being added to the disperse system solution of graphene oxide-boron nitride, 2 ~ 3h of supersound process, 20 ~ 48h of lyophilization are obtained six sides nitridation
Boron-oxygen graphite alkene foams；
Step 3：The preparation of hexagonal boron nitride-graphene oxide-polyaniline
Obtained hexagonal boron nitride-graphene oxide foams in step 2 are added to into the HClO4 solution that concentration is 1mol/L
In, supersound process is subsequently adding ethanol in proper amount in reaction solution up to being uniformly dispersed, and adds appropriate aniline monomer solution simultaneously
30 ~ 40 min are stirred at -10 DEG C ~ 10 DEG C form it into unified intermixture, the hexagonal boron nitride-graphene oxide foams
It is 1 with the mass ratio of aniline monomer：4~25；
By oxidant（NH4）During 2S2O8 (APS) is dissolved in HClO4,0 DEG C is cooled to, oxidizing agent solution is obtained, toward intermixture
Quickly add the oxidizing agent solution of above-mentioned cooling, 12 ~ 24h of stirring reaction under the conditions of 0 DEG C obtains green flocky precipitate, so
Filter afterwards and successively with HClO4 solution and washing with alcohol, be dried 12 ~ 24 h and combination electrode material is obtained.
5. ultracapacitor combination electrode material according to claim 4, it is characterised in that：It is centrifuged in the step 1
The rotating speed of separation process is 1000 ~ 2500r/min, and centrifugation time is 10 ~ 60min.
6. a kind of ultracapacitor, it is characterised in that：The electrode of the ultracapacitor is by described in any one of claims 1 to 3
Ultracapacitor made with combination electrode material.
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| WO2018236847A1 (en) * | 2017-06-19 | 2018-12-27 | Rogers Corporation | Boron nitride foam, methods of manufacture thereof, and articles containing the boron nitride foam |
| CN115172065A (en) * | 2022-06-16 | 2022-10-11 | 宁德师范学院 | Three-dimensional capacitance electrode material with graphene surface grafted with polyaniline/titanium dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018236847A1 (en) * | 2017-06-19 | 2018-12-27 | Rogers Corporation | Boron nitride foam, methods of manufacture thereof, and articles containing the boron nitride foam |
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| CN115172065A (en) * | 2022-06-16 | 2022-10-11 | 宁德师范学院 | Three-dimensional capacitance electrode material with graphene surface grafted with polyaniline/titanium dioxide |
| CN115172065B (en) * | 2022-06-16 | 2023-04-25 | 宁德师范学院 | Three-dimensional capacitance electrode material with polyaniline/titanium dioxide grafted on graphene surface |
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