CN109786125B - Azophenyl super capacitor - Google Patents
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Abstract
The invention discloses an azobenzene super capacitor, which comprises a working electrode, a reference electrode, a counter electrode and an electrolyte, wherein the working electrode is made of an azobenzene compound Azo-Cn, and the structural formula of the azobenzene compound Azo-Cn is as follows:
. According to the invention, the azobenzene compound Azo-Cn with excellent redox property and hydrophilicity can be used as an electrode material of a super capacitor to prepare a novel super capacitor, so that the electrochemical performance of the super capacitor is greatly improved.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to an azobenzene super capacitor.
Background
In recent years, supercapacitors have been used as a new type of energy storageThe device is of great interest. The lithium ion battery has the characteristics of high power density, large specific capacitance, long cycle life and the like, and forms two types of energy storage materials with complementary advantages with the lithium ion battery. Generally, supercapacitors are classified into electric double layer capacitors and pseudocapacitors. Pseudocapacitors have a higher specific capacitance and energy density due to their faraday reaction, making them more attractive than electric double layer capacitors. MnO2Is one of the most common pseudocapacitor electrode materials because of its very high specific capacitance>1370F/g), environmental friendliness, low cost, etc. But MnO2Low electrical conductivity (10)-5-10-6S·cm-1) Making its magnification not high. In order to further improve the performance of the pseudocapacitor, the development of a pseudocapacitor electrode new material based on rapid reaction, excellent electronic conductivity, long cycle life and high energy density is of great significance to the development of high-performance super capacitors.
Azobenzene is a molecule formed by connecting two benzene rings through nitrogen-nitrogen double bonds, and has good photoisomerization characteristics and redox characteristics, so azobenzene derivatives are often used as redox substrates to prepare modified electrodes for developing electrochemical and biological sensors.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an azobenzene super capacitor, aiming at solving the problem that the electrochemical performance of the prior super capacitor is still low.
The technical scheme of the invention is as follows:
the azobenzene super capacitor comprises a working electrode, a reference electrode, a counter electrode and an electrolyte, wherein the working electrode is made of an azobenzene compound Azo-Cn, and the structural formula of the azobenzene compound Azo-Cn is as follows:
the preparation method of the azobenzene super capacitor comprises the following steps: respectively dissolving equimolar compounds 1 and 2 in hot water at 70 ℃, dropwise adding the aqueous solution of the compounds 2 into the aqueous solution of the compounds 1 under stirring until the system does not generate precipitates, filtering, washing and drying to obtain a crude product, and then recrystallizing the crude product with absolute ethyl alcohol to obtain the azophenyl compound Azo-Cn;
the structural formula of the compound 1 is shown as follows:
the structural formula of the compound 2 is shown as follows:
wherein n is 8,12, 16.
The preparation method of the working electrode of the azobenzene super capacitor comprises the following steps: weighing azophenyl compound Azo-Cn, adding a conductive agent and a bonding agent, mixing into paste, pressing on a carrier, and baking to obtain the working electrode.
The preparation method of the azo-phenyl supercapacitor comprises the following steps:
weighing 1mg of azobenzene compound Azo-Cn, adding 4mg of conductive agent and 1mg of adhesive, mixing into paste, pressing on a carrier, and baking at 100 ℃ for 5h to obtain the working electrode.
The azobenzene super capacitor is characterized in that the adhesive is 60 wt% of polytetrafluoroethylene aqueous solution.
The azobenzene super capacitor is characterized in that the conductive agent is acetylene black.
The azobenzene super capacitor is characterized in that the carrier is a foamed nickel sheet.
The azobenzene super capacitor is characterized in that the size of the foam nickel sheet is 1cm multiplied by 5 cm.
The azobenzene super capacitor is characterized in that the reference electrode is Ag/AgCl, the counter electrode is Pt wire, and the electrolyte is Na2SO4。
Has the advantages that: according to the invention, through a self-assembly means, water-soluble methyl orange molecules containing azobenzene and quaternary ammonium salts with different alkyl chain lengths are subjected to ion self-assembly to obtain an azobenzene compound with hydrophilicity and hydrophobicity capable of being regulated and controlled through tail chain length, the azobenzene compound has excellent redox property and hydrophilicity, and can be used as an electrode material of a super capacitor, so that the electrochemical performance of the super capacitor can be greatly improved.
Drawings
FIG. 1 is an electrochemical reaction equation of Azo-phenyl complex Azo-Cn in the present invention.
FIG. 2 shows the reaction scheme for the synthesis of Azo-phenyl complex Azo-Cn in example 1.
FIG. 3 shows the Azo-phenyl complex Azo-Cn of example 1 at 100 mV. multidot.s-1CV diagram of (a).
FIG. 4 shows the Azo-phenyl complex Azo-Cn of example 1 at 100 mV. multidot.s-1Comparative graph of specific capacitance of (c).
FIG. 5 is a graph of CV for the Azo-phenyl complex Azo-C8 of example 1 at various scan rates.
FIG. 6 is a graph showing the change of the specific capacitance of the Azo-phenyl complex Azo-C8 with the scanning rate in example 1.
FIG. 7 is a constant current charge and discharge curve of Azo-phenyl complex Azo-C8 at different current densities in example 1.
FIG. 8 is a graph showing the dependence of the specific capacitance of the Azo-phenyl complex Azo-C8 on the current density in example 1.
FIG. 9 shows that the current density in example 1 is 50 A.g-1The dependence of the specific capacity retention of the Azo-phenyl complex Azo-C8 on the cycle number is shown.
Detailed Description
The invention provides an azobenzene super capacitor, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an azobenzene super capacitor, which comprises a working electrode, a reference electrode, a counter electrode and an electrolyte, wherein the working electrode is made of an azobenzene compound Azo-Cn, and the structural formula of the azobenzene compound Azo-Cn is as follows:
the azophenyl compound provided by the invention has excellent redox characteristics and hydrophilicity, and can greatly improve the electrochemical performance of a super capacitor when being used as a super capacitor electrode material, and the electrochemical reaction equation of the azophenyl compound is shown in figure 1.
Specifically, the preparation method of the azobenzene compound Azo-Cn comprises the following steps: respectively dissolving equimolar compounds 1 and 2 in hot water at 70 ℃, dropwise adding the aqueous solution of the compounds 2 into the aqueous solution of the compounds 1 under stirring until the system does not generate precipitates, filtering, washing and drying to obtain a crude product, and then recrystallizing the crude product with absolute ethyl alcohol to obtain the azophenyl compound Azo-Cn;
the structural formula of the compound 1 is shown as follows:
the structural formula of the compound 2 is shown as follows:
wherein n is 8,12, 16.
According to the invention, through a self-assembly means, water-soluble methyl orange molecules (namely compound 1) containing azophenyl and quaternary ammonium salts (namely compound 2) with different alkyl chain lengths are subjected to ionic self-assembly to obtain the azophenyl compound with hydrophily and hydrophobicity which can be regulated and controlled through tail chain length.
Specifically, the preparation method of the working electrode comprises the following steps: weighing azophenyl compound Azo-Cn, adding a conductive agent and a bonding agent, mixing into paste, pressing on a carrier, and baking to obtain the working electrode.
The present invention will be described in detail below with reference to examples.
Examples
1. Reagent
Methyl orange (analytical pure) was purchased from majon chemical reagent factory, Tianjin; cetyl trimethylammonium bromide (analytically pure) was purchased from majol chemical industries, Tianjin; dodecyl trimethyl ammonium bromide (99% purity) was purchased from Shanghai Michelin Biochemical technology, Inc.; octyl trimethyl ammonium chloride (99% pure) was purchased from Shanghai Michelin Biochemical technology, Inc.; foamed nickel and polytetrafluoroethylene emulsions, purchased from the Taiyuan Ministry of sales of source batteries for facing force; all experimental waters were Millipore ultrapure water. Common chemicals and drugs were used analytically pure (A.R.) after standard purification procedures.
2. Synthesis of Azo-Cn Azo-phenyl Complex (n ═ 8,12,16)
Taking the composite Azo-C8 as an example, the preparation process is as follows: equimolar methyl orange (1.00g, 3.06mmol) and octyl trimethyl ammonium bromide (0.64g, 3.06mmol) were dissolved in 100mL and 30mL of hot water at 70 ℃ respectively, and then an aqueous solution of octyl trimethyl ammonium chloride was added dropwise to the aqueous solution of methyl orange with stirring until no further precipitation of the system occurred. Filtering, washing the precipitate with hot water for several times, vacuum drying at 60 deg.C for 12h to obtain yellow powder, and recrystallizing the crude product with 10 times of anhydrous ethanol to obtain Azo-phenyl complex Azo-C8. The Azo-C12 and Azo-C16 compound are prepared by the same method. The reaction formula for the synthesis of azophenyl complex Azo-Cn (n ═ 8,12,16) is shown in fig. 2.
3. Preparation of Azo-Cn (n-8, 12,16) working electrode
The preparation method of the working electrode comprises the following steps: preparing 0.02 mg/muL of azobenzene compound Azo-Cn (n is 8,12,16) trichloromethane solution, transferring 50 muL of the solution (namely containing 1mg of the compound) to drop into 4mg of acetylene carbon black, performing ultrasonic dispersion for 1 minute, naturally drying, adding 1mg of glue (60 wt% of polytetrafluoroethylene aqueous solution is diluted into 0.02 mg/muL, then transferring 50 muL of the solution), mixing into paste, pressing on a foam nickel sheet (cut into 1cm multiplied by 5cm), and baking at 100 ℃ for 5 hours to obtain the working electrode.
4. Electrochemical testing
Performing cyclic voltammetry and constant-current charge and discharge tests by using a CHI 660E electrochemical workstation, wherein the specific test conditions are as follows: using a three-electrode system, 100mM Na2SO4As electrolyte, anode material of nickel foam sheet of Azo-Cn (n ═ 8,12,16) was used as working electrode, Ag/AgCl (saturated KCl) and Pt wire were used as reference and counter electrode, respectively.
5. Test results
In order to investigate the electrochemical performance of Azo-phenyl supercapacitors constructed by Azo-Cn (n-8, 12,16), Cyclic Voltammetry (CV) and constant current charge and discharge tests were performed on the Azo-Cn supercapacitors. FIG. 3 shows the results of the measurement of Azo-Cn (n-8, 12,16) at 100 mV. multidot.s-1It can be seen from the CV diagram that there is a pair of redox peaks between 0.0 and 0.8V in each of the three CV curves, which are derived from the contribution of the azophenyl group. It was also found from the figure that the curve area of Azo-C8 increased significantly over that of Azo-C12 and Azo-C16 at the same scan rate. The specific capacitance is calculated from the integrated area of fig. 3, the calculation formula:
the calculation results are shown in fig. 4. As can be seen from the view in figure 4,
at the same scan rate of 100 mV. s-1The specific capacitances of Azo-C12 and Azo-C16 were 79.1 Fg-1And 82.2 Fg-1The specific capacitance of Azo-C8 was 165.9 Fg-1. The specific capacitance of Azo-C8 was increased by about one-fold compared to the other two complexes, which may result from the favorable hydrophilic-hydrophobic water balance of Azo-C8 for electron transport and electrolyte ion diffusion in the positive electrode material. Further investigation of the CV plots of Azo-C8 at various scan rates, as shown in FIG. 5, shows that as the scan rate was varied from 10, 20, 50, 100, 200mV · s-1Increasing the area of the curve progressively. The specific capacitance was calculated from the integrated area of fig. 5, and the calculation result is shown in fig. 6. It is seen from fig. 6 that the specific capacitance of Azo-C8 decreases with increasing scan rate. At 200mV · s-1When the specific capacitance is 120.8 Fg-1The specific capacity retention ratio was 54.6%.
Constant-current charge and discharge tests are used for further researching charge and discharge curves of the Azo-C8 under different current densities, and as shown in FIG. 7, the curves show good symmetry and platform characteristics, and show excellent pseudocapacitance performance. Using formulas
Specific capacitance values of Azo-C8 at different current densities were calculated from the discharge curve of fig. 7, as shown in fig. 8. The current densities obtained were 5.0, 10.0, 25.0, 35.0, 50.0 A.g-1The specific capacitances are 204.5, 167.2, 113.6, 86.9 and 64.5 F.g-1. The above results indicate that Azo-C8 has superior pseudocapacitance performance. In addition to the rapid charge and discharge, cycle life is another key parameter we have studied. At 50.0A · g-1After carrying out the Azo-C8 cycle life test, the results of 2000 rapid charge and discharge are shown in FIG. 9, and the specific capacitance value is only attenuated by 16.7% after 2000 cycles, which indicates that the service life is better.
In conclusion, the invention selects a novel azobenzene compound Azo-C8 as the positive electrode material of the super capacitor for the first time. The invention develops a novel azobenzene super capacitor by utilizing the excellent redox property and hydrophilicity of Azo-C8. Through electrochemical characterization such as cyclic voltammetry, constant-current charging and discharging and the like, the super capacitor is found to have the current density of 5.0 A.g-1When the specific capacitance reaches 204.5 F.g-1(ii) a At 50.0A · g-1After carrying out cycle life test of the Azo-C8, the specific capacitance value is attenuated by 16.7% after 2000 cycles, which shows that the Azo-C8 is a good super capacitor anode material, and research results also provide beneficial reference for developing novel super capacitor electrode materials.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. An Azo-phenyl supercapacitor comprises a working electrode, a reference electrode, a counter electrode and an electrolyte, and is characterized in that the working electrode is made of an Azo-phenyl compound Azo-Cn, and the structural formula of the Azo-phenyl compound Azo-Cn is as follows:
2. the Azo-phenyl supercapacitor according to claim 1, wherein the preparation method of the Azo-phenyl composite Azo-Cn comprises the steps of: respectively dissolving equimolar compounds 1 and 2 in hot water at 70 ℃, dropwise adding the aqueous solution of the compounds 2 into the aqueous solution of the compounds 1 under stirring until the system does not generate precipitates, filtering, washing and drying to obtain a crude product, and then recrystallizing the crude product with absolute ethyl alcohol to obtain the azophenyl compound Azo-Cn;
the structural formula of the compound 1 is shown as follows:
the structural formula of the compound 2 is shown as follows:
wherein n is 8,12, 16.
3. The azo-phenyl supercapacitor according to claim 1, wherein the method for preparing the working electrode comprises the steps of: weighing azophenyl compound Azo-Cn, adding a conductive agent and a bonding agent, mixing into paste, pressing on a carrier, and baking to obtain the working electrode.
4. The azo-phenyl supercapacitor according to claim 3, wherein the method for preparing the working electrode specifically comprises the steps of:
weighing 1mg of azobenzene compound Azo-Cn, adding 4mg of conductive agent and 1mg of adhesive, mixing into paste, pressing on a carrier, and baking at 100 ℃ for 5h to obtain the working electrode.
5. The azo-phenyl supercapacitor according to any one of claims 3 to 4, wherein the binder is a 60 wt% aqueous solution of polytetrafluoroethylene.
6. The azo-phenyl supercapacitor according to any one of claims 3 to 4, wherein the conductive agent is acetylene black.
7. The azophenyl supercapacitor according to any one of claims 3 to 4, wherein the support is a foamed nickel sheet.
8. The azophenyl supercapacitor according to claim 7, wherein the foamed nickel plate has dimensions of 1cm x 5 cm.
9. The azophenyl supercapacitor according to claim 1, wherein the reference electrode is Ag/AgCl, the counter electrode is Pt wire, and the electrolyte is Na2SO4。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104307491A (en) * | 2014-10-24 | 2015-01-28 | 武汉理工大学 | Modified graphene for efficiently adsorbing methyl orange dye and preparation method of modified graphene |
| CN105838350A (en) * | 2016-04-16 | 2016-08-10 | 吉林大学 | Electrochromic composite material and prepared electrochromic device |
| CN107658143A (en) * | 2017-09-26 | 2018-02-02 | 东莞理工学院 | A kind of ferrocenyl ultracapacitor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307491A (en) * | 2014-10-24 | 2015-01-28 | 武汉理工大学 | Modified graphene for efficiently adsorbing methyl orange dye and preparation method of modified graphene |
| CN105838350A (en) * | 2016-04-16 | 2016-08-10 | 吉林大学 | Electrochromic composite material and prepared electrochromic device |
| CN107658143A (en) * | 2017-09-26 | 2018-02-02 | 东莞理工学院 | A kind of ferrocenyl ultracapacitor |
Non-Patent Citations (2)
| Title |
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| "甲基橙离子选择电极的研制";刘成梁 等;《化学传感器》;19950331;第15卷(第1期);79-80页 * |
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