CN108470630B - Composite electrode material for intelligent supercapacitor and preparation method and application thereof - Google Patents

Composite electrode material for intelligent supercapacitor and preparation method and application thereof Download PDF

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CN108470630B
CN108470630B CN201810399155.5A CN201810399155A CN108470630B CN 108470630 B CN108470630 B CN 108470630B CN 201810399155 A CN201810399155 A CN 201810399155A CN 108470630 B CN108470630 B CN 108470630B
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孙莹
叶童童
林保平
杨洪
张雪勤
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract

The material is prepared by bonding an alkyl carbazole polymer with a side chain containing a bromine atom group to an acidified hydroxylated carbon nanotube in a covalent bond mode through Williamson ether forming reaction. Through electrochemical and spectroelectrochemical tests, 174.7 W.h.kg can be obtained for the intelligent device prepared by the electrode material‑1And after 5000 cycles, the specific capacity retention is as high as 96%. In addition, the device showed a rapid and reversible color change from dark brown to light gray within the investigated potential window.

Description

Composite electrode material for intelligent supercapacitor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a composite electrode material for an electrochromic supercapacitor, a preparation method of the composite electrode material and the electrochromic supercapacitor prepared from the electrode material.
Background
Because of the comprehensive excellent performances such as high specific capacity, high power density, ultra-long cycle life, high stability, environmental friendliness and the like, the super capacitor has a huge application prospect in many fields such as portable and wearable electronic products, but how to further improve the application efficiency is an important problem to be solved urgently at present. For example, people are urgently required to develop a super capacitor capable of reflecting the working state of the super capacitor intuitively and in real time, so that the electrochromic intelligent super capacitor arouses great interest of people.
Polypyrrole (PPy), Polyaniline (PANI) and Polythiophene (PT) and their derivatives are common conjugated polymers and are also widely used as electrochromic materials. The materials are simple to prepare, rich in color change and quick in response time, but have poor electrochemical stability and conductivity, so that the application of the materials as electrode materials in electrochromic supercapacitors is greatly limited. Accordingly, there is an increasing effort to design composite materials that can improve the conductivity and stability of conjugated polymers.
Carbon nanotubes are considered as promising materials for electrochemical energy storage devices due to their strong mechanical properties, high conductivity and large specific surface area, and they can also be prepared into composite materials with polymers, metal oxides, etc., expanding their application range. However, carbon nanotubes are a nanomaterial that is very prone to agglomeration, have poor compatibility with polymer materials, are prone to separate imaging when mixed, and exhibit large phase separation domains when formed into films. Therefore, it is necessary to combine the polymer material and the carbon nanotube in a suitable manner to improve the miscibility between the two materials and achieve the synergy of the properties.
To solve this problem, we know that carbon nanotube surface modification or functionalization is the key to overcome this obstacle. Kuila et al first starting from poly-3-hexylthiophene (P3HT) using POCl3DMF is taken as an oxidant to change two end groups of poly-3-hexylthiophene into aldehyde groups, then THF is taken as a solvent, lithium aluminum hydride is taken as a reducing agent to obtain the compound with CH2OH as end group of poly 3-hexylthiophene, and finally reacting the multi-wall carbon nano-tube after acidification and acyl chlorination with CH2And (3) performing esterification reaction on the poly-3-hexylthiophene with OH as a terminal group under the condition that triethylamine catalyzes THF to serve as a solvent to obtain a final product P3 CNT. (Kuila, B.K.; Park, K.; Dai, L., Soluble P3HT-Grafted Carbon Nanotubes: Synthesis and Photostructural applications. macromolecules 2010,43(16),6699-6705.) although conventional covalent modification of Carbon Nanotubes has been mainly carried out by three-step methods of acidification, acid chloride and esterification. The complexity of the synthesis process is increased because each reaction time is long and yields are high. Is not beneficial to large-scale industrial production.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a composite electrode material for an intelligent supercapacitor, and a preparation method and application thereof, aiming at overcoming the defects that the synthesis method is complex, the cost is high, the composite effect is poor, the composite cannot be processed by solution and the like in the traditional carbon nanotube covalent modification process.
The technical scheme is as follows: a composite electrode material for an intelligent supercapacitor is prepared by bonding an alkyl carbazole polymer with a side chain containing a bromine atom group to an acidified hydroxylated carbon nanotube in a covalent bond mode through Williamson ether forming reaction.
The preparation method of the composite electrode material for the intelligent supercapacitor comprises the following steps: firstly preparing an alkyl carbazole monomer, then carrying out microwave polymerization on the alkyl carbazole monomer and a polymerization unit to obtain a side chain carbazole polymer, and finally compounding the side chain carbazole polymer and the acidified hydroxylated carbon nanotube to obtain a final compound.
The preparation method of the alkyl carbazole monomer comprises the following steps: weighing 2, 7-dibromocarbazole, dissolving the 2, 7-dibromocarbazole in DMF, adding NaH, adding 1, 8-dibromooctane, reacting for 24h at 60 ℃, extracting with dichloromethane after reaction, and separating and purifying a crude product through a silica gel column to obtain an alkyl carbazole monomer; the molar ratio of the 2, 7-dibromocarbazole to the 1, 8-dibromooctane to the NaH is 1: (2.5-3.0): (1.5-2.0), and the eluent used for separating and purifying the silica gel column is a mixture of petroleum ether and dichloromethane, and the molar ratio of the petroleum ether to the dichloromethane is 12: 1.
The preparation method of the side chain carbazole polymer comprises the following steps: adding an alkyl carbazole monomer and a polymerization unit into a reaction vessel according to the molar ratio of 1:1, then adding a catalyst, adding an organic solvent, introducing inert gas, and placing the whole reactor into a microwave reactor at the temperature of 100 ℃ and 120 ℃ for reaction for 1-4 h.
The preparation method of the compound comprises the following steps: adding the hydroxylated carbon nano tube subjected to acidification treatment into a reactor containing an alkaline solution, carrying out ultrasonic treatment for 4 hours, adding a side chain carbazole polymer and a phase transfer catalyst, continuing the ultrasonic treatment for 1 hour, wherein the molar ratio between the side chain carbazole polymer and the phase transfer catalyst is 0.6-0.1%, then carrying out reaction on the whole reactor at 70 ℃ for 20 hours, adding trichloromethane for extraction after the reaction is finished, dissolving the reacted carbon nano tube in a lower organic layer, and then carrying out precipitation on a lower organic layer in a methanol solution to obtain a final compound.
In the preparation method of the side chain carbazole polymer, the organic solvent is tetrahydrofuran, N, N-dimethylformylAt least one of amine, toluene and chlorobenzene, and the catalyst is Pd2(dba)3、p(o-tol)3Palladium chloride, palladium acetate or bis (dibenzylideneacetone) palladium (0), wherein the molar ratio between the catalyst and the raw material is 10-0.1%, the reaction temperature is 110 ℃, and the reaction time is 1 h; the polymerized unit is at least one of the following compounds:
Figure GDA0002161283270000031
the alkaline solution was 1 g/mL-1The above phase transfer catalyst was methyltrioctylammonium chloride (Aliquat 336).
The acidizing treatment of the hydroxylated carbon nano tube comprises the following steps: proportionally, 3g of carbon nanotubes are concentrated in 132mL of H2SO4And 44mL concentrated HNO3The obtained mixed acid solution is uniformly mixed, ultrasonically dispersed for 45min at room temperature, then placed in a reaction bottle at 70 ℃, stirred and acidified for 2.5h, cooled to room temperature, diluted by adding distilled water until the pH is neutral, centrifuged by a centrifugal tube at 9000r/min, poured on filter paper and placed in a vacuum drying oven, and dried overnight to obtain the hydroxylated carbon nanotube after acidification treatment.
The material is applied to preparing an electrochromic supercapacitor electrode.
An electrode of the electrochromic supercapacitor is made of the material.
Has the advantages that: the invention firstly adopts Williamson ether forming reaction to modify the multi-walled carbon nano-tube in one step, compared with the traditional covalent modification method of acidification, acyl chlorination and esterification, the one-step compounding method is simple, the waste of products caused by multiple reactions is avoided, and the compounding efficiency is improved. The method has certain guiding significance for the subsequent covalent modification of the carbon nano tube or the graphene and the like. In the composite electrode, the carbon nanotubes serve as conductive carriers of electrons, so that the rapid and efficient electron transmission between the carbon nanotubes and the polymer is promoted, and a larger specific capacitance is provided. In addition, the application of proper amount of carbon nanotube improves the mechanical property of polymerThis can reduce mechanical changes in the polymer material during charging and discharging, and thus can greatly improve the stability of the material. More importantly, the p/n all-doped composite material is formed, so that the composite material can work under a voltage window as wide as 4.8V, and higher energy density is obtained. Meanwhile, the symmetrical electrochromic supercapacitor device assembled by the electrode material shows obvious and reversible color transition between dark brown (discharge state) and light gray (charged state), and has high optical contrast at the wavelength of 465 nm. In conclusion, the composite electrode material has high energy density and high cycle stability, and can show reversible color change in the charge and discharge process, so that the composite electrode material can be used as an electrode material of a new-generation intelligent supercapacitor. Through electrochemical and spectroelectrochemical tests, 174.7 W.h.kg can be obtained for the intelligent device prepared by the electrode material-1And after 5000 cycles, the specific capacity retention is as high as 96%. In addition, the device showed a rapid and reversible color change from dark brown to light gray within the investigated potential window.
Drawings
FIG. 1 is a transmission electron microscope image of a multi-walled carbon nanotube-polymer composite; in the figure, (a) is a field emission scanning electron microscope image of the composite electrode material, (b) is a field emission scanning electron microscope image of the composite electrode material, and (a) and (b) are different in shooting position;
FIG. 2 is a transmission electron microscope image of a multi-walled carbon nanotube-polymer composite; in the figure, (c) is a transmission electron microscope image of the composite electrode material, (d) is a transmission electron microscope image of the composite electrode material, and (c) (d) shooting positions are different;
FIG. 3 is a comparison graph of cyclic voltammetry curves of a multi-walled carbon nanotube-polymer composite at different scan rates;
FIG. 4 is a graph comparing the charge and discharge curves of a multi-walled carbon nanotube-polymer composite at different constant current densities;
FIG. 5 is a graph of specific capacitance values of a multi-walled carbon nanotube-polymer composite at different current densities;
FIG. 6 is a graph of specific capacitance retention of a multi-walled carbon nanotube-polymer composite after 5000 cycles;
FIG. 7 is an absorption spectrum of a multi-walled carbon nanotube-polymer composite in bleached and colored states (digital photographs of the bleached and colored states are presented in inset form);
FIG. 8 is a graph of the transition time of a multi-walled carbon nanotube-polymer composite film from a bleached state to a colored state (or from a colored state to a bleached state);
FIG. 9 is a comparison graph of cyclic voltammograms of a symmetric electrochromic supercapacitor at different scan rates;
FIG. 10 is a comparative plot of charge and discharge curves for a symmetric electrochromic supercapacitor at different constant current densities;
FIG. 11 is a graph of specific capacitance values of symmetric electrochromic supercapacitors at different current densities;
FIG. 12 is a graph of specific capacitance retention for a symmetric electrochromic supercapacitor after 5000 cycles;
FIG. 13 is an absorption spectrum of a symmetric electrochromic supercapacitor in the wavelength range of 300-800nm in the bleached and colored state (digital photographs of the bleached and colored states are presented in inset form);
fig. 14 is a graph of cycle performance measurements for a symmetric electrochromic supercapacitor over 1500 s.
Detailed Description
In describing embodiments of the invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. It is to be understood that each specific element includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction times, etc.) but with some experimental error and deviation. The solvents used in the examples below were all purchased from famous reagents companies, all reagents and raw materials were used without special treatment unless otherwise indicated.
In order that those skilled in the art can better understand the present invention, the following technical solutions are further described with reference to the accompanying drawings and examples.
Figure 1 shows a field emission scanning electron micrograph of the MWCNT-PBDTC composite electrode material showing a surface morphology with significantly larger nanotube diameters due to the presence of polymer on the nanotube surface, which is significantly different from the clean and smooth surface of the unmodified MWCNTs described in other studies.
Figure 2 shows a transmission electron micrograph of the MWCNT-PBDTC composite electrode material from which we observed that the polymer modified carbon nanotubes were less entangled and well dispersed in the solvent (chloroform) used to prepare the TEM samples.
From the above morphological analysis chart, in the composite electrode material of the present application, the composition between the polymer and the carbon nanotube is good, and the polymer and the carbon nanotube can be uniformly dispersed in a general organic solvent, which correspondingly results in the supercapacitor material having good conductivity, and the existence of the carbon nanotube improves the mechanical stability of the polymer, determines the application value of the polymer in the supercapacitor material, and proves the rationality of the theoretical analysis.
The preparation of the composite electrode material for the super capacitor mainly comprises the process of gradually generating alkyl carbazole monomers, side chain bromine-containing carbazole polymers and compounds. Example 1 gives an example of the preparation of a composite electrode material of the present application.
Example 1
Preparation of alkyl carbazole monomer: 2, 7-Dibromocarbazole (1g, 3mmol) was dissolved in 7.5mL of DMF, and NaH (0.5g) was added and stirred at room temperature for 30 min. 1, 8-dibromooctane (4.11g, 15mmol) was added dropwise to the above solution, and 2.5mL of DMF was added to wash the wall of the flask, followed by reaction at room temperature for 24 hours. After the reaction was completed, the mixture was extracted with 100mL of deionized water to remove NaH, and then the filtrate was rotary evaporated to 5mL, and then 100mg of silica gel powder was added and rotary evaporated again to powder. And (3) separating and purifying the crude product by a silica gel column (eluent is petroleum ether and dichloromethane with the molar ratio of 12:1, and 100mL of petroleum ether is added to wash out excessive 1, 8-dibromooctane) to obtain a colorless oily liquid compound, and sealing a preservative film (perforated) and drying in vacuum after spin-drying by a rotary evaporator to obtain the 2, 7-dibromo-9- (8-bromooctyl) carbazole.
Design and synthesis of side chain bromocarbazole-containing Polymer (PBDTC): 2, 7-dibromo-9- (8-bromooctyl) carbazole (0.1mmol) and 4, 8-bis [5- (2-ethylhexyl) thiophen-2-yl]-2, 6-bis (trimethylstannyl) benzo [1,2-b:4,5-b']Adding dithiophene (BDT75) (0.1mmol) into a 25mL microwave reaction bottle, adding toluene (4mL) and DMF (0.4mL), then blowing nitrogen into the bottle to deoxidize the solution, and adding Pd after blowing nitrogen2(dba)3(4mg) and p (o-tol)3(10mg), adding magnetons, repeatedly blowing nitrogen into the bottle to deoxidize the solution, covering the bottle with a cover, reacting in a microwave reaction kettle for 1h at 110 ℃, cooling to room temperature, and dropwise adding the solution into a methanol solution stirred by the magnetons for precipitation. Filtering, collecting precipitate, washing the obtained solid substance with acetone and n-hexane as solvents respectively by using a Soxhlet extractor, dissolving the solid substance in chloroform again, and repeatedly dropwise adding the solid substance into a methanol solution stirred by magnetons for precipitation. The precipitate was collected by filtration and placed in a vacuum drying oven to obtain the final polymer.
Preparation of hydroxylated carbon nanotubes: 3g of carbon nanotubes were concentrated in 98 wt.% of H2SO4(132mL) with 68 wt.% concentrated HNO3(44mL) is evenly mixed in the mixed acid solution, ultrasonic dispersion is carried out for 45min at room temperature, and then the mixture is placed in a reaction bottle for stirring and acidification treatment for 2.5h at 70 ℃. After cooling to room temperature, adding a large amount of distilled water to dilute until the pH is neutral, centrifuging the solution at 9000r/min by using a centrifuge tube several times, pouring the solution onto filter paper, putting the filter paper into a vacuum drying oven, and drying the filter paper overnight to obtain the hydroxylated carbon nanotube (MWCNT) after acidification treatment.
Synthesis of Complex MWCNT-PBDTC: 1 g/mL of the solution was put into a 25mL reaction flask-1Adding 10mg of acidized hydroxylated carbon nanotube into 10mL of NaOH solution, performing ultrasonic oscillation for 4h to obtain a suspension, converting phenolic hydroxyl into phenolic sodium salt, adding 100mg of PBDTC and 0.5mL of phase transfer catalyst methyl trioctyl ammonium chloride (Aliquat 336) into the obtained suspension, performing ultrasonic dispersion for 30mim, and performing reflux heating and stirring at 70 ℃ for 20 h; after the reaction, the mixture was allowed to stand for cooling, and 20mL of chloroform was added to dissolve the precipitate (the reacted carbon nanotubes were dissolved in the lower chloroform layer, and the unreacted carbon nanotubes were dispersed in the upper aqueous phase and removed as residueThen) the solution is dried to 5mL by a rotary evaporator, and then the solution is dripped into a methanol solution stirred by magnetons for precipitation, and the precipitate is collected by filtration and put into a vacuum drying box to obtain the final compound MWCNT-PBDTC.
MWCNT-PBDTC was dissolved in chloroform to give 10 mg. multidot.mL-1And carefully spin-coating the solution on an ITO substrate to form a uniform film. The mass of the film active material was found to be 0.1mg cm-2. The spin-coated MWCNT-PBDTC/ITO was then used as the working electrode and coated at 0.5M LiClO4The measurement was carried out in a three electrode configuration in the/PC solution.
Two sheets of MWCNT-PBDTC composite membranes were combined with LiClO4And assembling the-PC-PMMA gel electrolyte to obtain the MWCNT-PBDTC electrochromic symmetric supercapacitor. And the electrochemical and spectroelectrochemical performances of the device are respectively tested.
The obtained intelligent device has both electric double layer and pseudo capacitance properties, and the output energy density of the device is as high as 174.7 W.h.kg-1The voltage range is up to 4.8V. Meanwhile, the cycling stability of the super capacitor is also tested, and the result shows that the specific capacitance is still kept above 96% of the initial value after 5000 continuous charging/discharging cycles. In addition to this, the device exhibits a clear and reversible color transition between dark brown (discharged state) and light gray (charged state), with a high optical contrast at a wavelength of 465 nm.
Performance experiments: in the following experimental tests, the composite MWCNT-PBDTC was selected from example 1.
Tests 1-5 all employed 0.5M LiClO in a three-electrode configuration4the/PC is electrolyte, a foil electrode is used as a counter electrode,
Ag/Ag+(containing 10mM AgNO)3/ACN solution) electrode was the reference electrode. The test was carried out using an electrochemical workstation (CHI 620E).
Test 1: selecting a potential window of-2.8-2.0V, and respectively testing the composite electrode material at different scanning rates of 10 mV · s, 20 mV · s, 50 mV · s and 100mV · s-1Cyclic voltammogram under conditions. The test results are shown in fig. 3.
According to cyclic voltammetry curves at different scanning rates, the curve shape is not greatly changed at different scanning rates, and the composite material is proved to have good rate capability.
And (3) testing 2: constant current charge and discharge test, setting high voltage at 2.0V, low voltage at-2.8V, and constant current density at 0.5, 0.6, 1.5, 1.8 and 2.5 mA-cm-2The charge and discharge were continuously measured for 1 cycle, and the measurement results are shown in FIG. 4. The area specific capacitance and the mass specific capacitance at different current densities were calculated separately and the test results are shown in fig. 5. This gave a linear output of 0.5mA cm-2The maximum mass specific capacitance 175F g can be obtained-1。
And (3) testing: the cycle stability of the composite material is tested, the test result is shown in fig. 6, and the MWCNT-PBDTC composite material is cycled for 5000 times according to the experimental data, the specific capacitance retention rate is more than 95.1%, and the composite material has good cycle stability.
The reason for good performance is as follows (1) the carbon nanotube is used as a conductive carrier of electrons, which promotes fast and efficient electron transmission between the carbon nanotube and the polymer, and can accelerate the diffusion rate between the carbon nanotube and the electrolyte, thereby obtaining a composite membrane structure with high rate performance. (2) The application of a proper amount of carbon nanotubes improves the mechanical properties of the polymer, which can reduce the mechanical deformation of the polymer material caused by volume change during the charge and discharge processes, thereby greatly improving the stability of the material.
And (4) testing: the composites were tested for uv-visible absorption spectra in different states (digital photographs of bleached state and color smart window are presented in the inset). As can be seen, the film appeared dark brown in its discharged state, corresponding to an absorption around 445-485nm in the neutral state, mainly due to the π - π absorption on the polymer backbone structure*A conjugation effect. When the potential is changed, the film becomes light gray, pi-pi*The electron transport ability decreased such that the absorption peak at 445-485nm disappeared and a new absorption peak at about 630-730nm appeared. The new absorption peak is generated by the electrochemical doping state generating polarons (radical cations) on the polymer backbone. The results of the tests are shown in figure 7,
and (5) testing: the switching time of the electrode thin film from the bleached state to the colored state (or from the colored state to the bleached state) was tested, and the MWCNT-PBDTC film had a fast switching speed of 5.1/3.3s during bleaching/coloring, respectively. The results of the tests are shown in figure 8,
in conclusion, the MWCNT-PBDTC composite electrode material has larger specific capacitance and excellent cycling stability, and can reversibly show color change in the charging and discharging processes so as to show a charged state, which indicates that the material is very suitable for an electrode material of an electrochromic supercapacitor.
To further evaluate the actual supercapacitor application of the prepared electrodes, symmetrical supercapacitor devices were prepared based on the respective two electrodes and their performance was tested.
Tests 6-10 all utilized LiClO in the device configuration4PC-PMMA gel electrolyte, tested using an electrochemical workstation (CHI 620E).
And 6, testing: selecting a potential window of-2.8-2.0V, and respectively testing the device at different scanning speeds of 10 mV · s, 20 mV · s, 50 mV · s and 100mV · s-1Cyclic voltammogram under conditions. The test results are shown in fig. 9.
According to cyclic voltammetry curves at different scanning rates, the curve shape is not greatly changed at different scanning rates, and the fact that a symmetrical device formed by the composite electrode material for the capacitor has good rate performance is proved.
And 7, testing: constant current charge and discharge test, setting high voltage at 2.0V, low voltage at-2.8V, and constant current density at 0.2, 0.3, 0.7, 1.5 and 2.0 mA-cm-2The charge and discharge were continuously measured for 1 cycle, and the measurement results are shown in fig. 10. The area specific capacitance and the mass specific capacitance at different current densities were calculated, respectively, and the test results are shown in FIG. 11, from which it was possible to obtain a capacitance value of 0.2mA · cm-2The maximum mass specific capacitance of 54.6 Fg can be obtained-1。
And (4) testing 8: the cycle stability of the composite material is tested, the test result is shown in fig. 12, and the MWCNT-PBDTC composite material is cycled for 5000 times according to the experimental data, the specific capacitance retention rate is more than 96%, and the composite material has good cycle stability.
The reason that the cycling stability of the device is better than that of the single electrode tested in the three-electrode system may be due to the two following points (1) the larger volume of electrolyte solution used in the three-electrode configuration test compared to the electrodes used in the device. When the electrode material is immersed in a large volume of electrolyte, irreversible dissolution of the active material in the electrolyte is more likely to occur due to rapid mass transfer. (2) The three-electrode configuration test is an open system, with the electrode material exposed to oxygen dissolved in the electrolyte in air. Instead, the device is relatively sealed, which avoids the effects of air.
And (3) testing: the composites were tested for uv-visible absorption spectra in different states (digital photographs of bleached state and color smart window are presented in the inset). As can be seen, the device appears brownish yellow when not charged, and changes to light gray when charged. The results of the tests are shown in figure 13,
test 10: the stability of the intelligent device to different electrochromic switch potentials was tested. The test results are shown in fig. 14, and it is obvious that the transmittance modulation of the intelligent device is almost unchanged after 1500s, indicating that the device has quite good electrochemical stability.
In conclusion, the electrochromic supercapacitor prepared from the electrode material for the supercapacitor has high energy density and excellent cycling stability, which is very beneficial to practical application.
The composite electrode material for the supercapacitor, the preparation method thereof and the electrochromic supercapacitor provided by the invention are described in detail above. The description of the specific embodiments is only intended to facilitate an understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and such improvements and modifications are also within the scope of the present invention as defined in the appended claims.

Claims (3)

1. Preparation of composite electrode material for intelligent supercapacitorThe preparation method is characterized by comprising the following steps: preparation of alkyl carbazole monomer: dissolving 3mmol of 2, 7-dibromocarbazole in 7.5mL of DMF, adding 0.5g of NaH, and stirring at room temperature for 30 min; then, 15mmol of 1, 8-dibromooctane is dripped into the solution, 2.5mL of DMF is added to wash the wall of the flask, and the reaction is carried out for 24 hours at room temperature; after the reaction is finished, extracting the mixture by using 100mL of deionized water to remove NaH, then carrying out rotary evaporation on the filtrate until the volume is 5mL, adding 100mg of silica gel powder, and carrying out rotary evaporation again until the powder is obtained; separating and purifying the crude product by a silica gel column to obtain a colorless oily liquid compound, wherein an eluent for separation and purification is petroleum ether and dichloromethane with a molar ratio of 12:1, and adding 100mL of petroleum ether to flush excessive 1, 8-dibromooctane; after spin-drying by a rotary evaporator, sealing and puncturing the preservative film, and performing vacuum drying to obtain 2, 7-dibromo-9- (8-bromooctyl) carbazole; design and synthesis of side chain bromocarbazole-containing polymer PBDTC: 0.1mmol of 2, 7-dibromo-9- (8-bromooctyl) carbazole and 0.1mmol of 4, 8-bis [5- (2-ethylhexyl) thiophen-2-yl]-2, 6-bis (trimethylstannyl) benzo [1,2-b:4,5-b']Adding dithiophene into a 25mL microwave reaction bottle, adding 4mL toluene and 0.4mL DMF, then blowing nitrogen into the bottle to perform deoxidation treatment, and adding 4mg Pd after nitrogen blowing2(dba)3And 10mg p (o-tol)3Adding magnetons, repeatedly blowing nitrogen into a bottle to deoxidize the solution, covering the bottle with a cover, reacting in a microwave reaction kettle at 110 ℃ for 1h, cooling to room temperature, and dropwise adding the solution into a methanol solution stirred by the magnetons for precipitation; filtering, collecting precipitate, washing the obtained solid substance with acetone and n-hexane as solvents respectively by using a Soxhlet extractor, dissolving the solid substance in chloroform again, and repeatedly dropwise adding the solid substance into a methanol solution stirred by magnetons for precipitation; filtering, collecting the precipitate, and putting the precipitate into a vacuum drying oven to obtain a final polymer; preparation of hydroxylated carbon nanotubes: 3g of carbon nanotubes in 132mL of 98 wt.% concentrated H2SO4And 44mL of 68 wt.% concentrated HNO3Uniformly mixing the mixed acid solution, performing ultrasonic dispersion for 45min at room temperature, and then placing the mixture in a reaction bottle for stirring and acidizing for 2.5h at 70 ℃; cooling to room temperature, diluting with distilled water until pH is neutral, centrifuging at 9000r/min for several times, pouring onto filter paper, vacuum drying in oven, and drying overnight to obtain hydroxylated carbon treated by acidificationNanotube MWCNT; synthesis of Complex MWCNT-PBDTC: 1 g/mL of the solution was put into a 25mL reaction flask-1Adding 10mg of acidized hydroxylated carbon nanotube into 10mL of NaOH solution, performing ultrasonic oscillation for 4h to obtain a suspension, converting phenolic hydroxyl into phenolic sodium salt, adding 100mg of PBDTC and 0.5mL of phase transfer catalyst methyl trioctyl ammonium chloride Aliquat 336 into the obtained suspension, performing ultrasonic dispersion for 30 mm, and performing reflux heating and stirring for 20h at 70 ℃; after the reaction, standing and cooling, adding 20mL of chloroform to dissolve the precipitate, and dissolving the reacted carbon nano tube in the lower layer of chloroform; and dispersing the unreacted carbon nano tubes in the upper water phase, removing filter residues, performing rotary drying to 5mL by using a rotary evaporator, dropwise adding the mixture into a methanol solution stirred by magnetons for precipitation, filtering, collecting precipitates, and putting the precipitates into a vacuum drying oven to obtain the final compound MWCNT-PBDTC.
2. Use of the material prepared according to claim 1 for the preparation of electrodes for supercapacitors of the electrochromic type.
3. An electrochromic supercapacitor, characterized in that its electrodes are made of the material obtained according to claim 1.
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