CN111320756B - Electroactive polysiloxane, preparation method of film thereof and application of film in color/fluorescence double-indication supercapacitor - Google Patents
Electroactive polysiloxane, preparation method of film thereof and application of film in color/fluorescence double-indication supercapacitor Download PDFInfo
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- -1 polysiloxane Polymers 0.000 title claims abstract description 24
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 19
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003990 capacitor Substances 0.000 claims description 18
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- 238000004132 cross linking Methods 0.000 claims description 17
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- CFXJWYZEPGPKNV-XMHGGMMESA-N (z)-3-anthracen-9-yl-2-(4-nitrophenyl)prop-2-enenitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(\C#N)=C\C1=C(C=CC=C2)C2=CC2=CC=CC=C12 CFXJWYZEPGPKNV-XMHGGMMESA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 3
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
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- YMNKUHIVVMFOFO-UHFFFAOYSA-N anthracene-9-carbaldehyde Chemical compound C1=CC=C2C(C=O)=C(C=CC=C3)C3=CC2=C1 YMNKUHIVVMFOFO-UHFFFAOYSA-N 0.000 claims description 2
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- PXNJGLAVKOXITN-UHFFFAOYSA-N 2-(4-nitrophenyl)acetonitrile Chemical compound [O-][N+](=O)C1=CC=C(CC#N)C=C1 PXNJGLAVKOXITN-UHFFFAOYSA-N 0.000 description 2
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
- 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, 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
- 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
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Abstract
An electroactive polysiloxane, a preparation method of a film thereof and application of the film in a color/fluorescence double-indication supercapacitor belong to the technical field of functional polymer materials. The invention is that the nucleophilic substitution reaction is carried out on the electroactive aniline Tetramer (TA) and the AIE active fluorescent monomer (ZAAT) and the isocyanatopropyl triethoxysilane respectively to generate two functionalized siloxane monomers; and then an electroactive polysiloxane film (PSZT) is formed on the ITO electrode of the three-electrode system. The thin film shows excellent electrochromic/electroluminescent fluorescent color-changing behavior, and by integrating energy storage and electrochromic/electrically-controlled fluorescent functions, an intelligent symmetrical supercapacitor device with a color/fluorescent double indicator is assembled, the energy state of the device can be simultaneously displayed through color change from light green yellow to dark green and through the on/off of a fluorescent switch, and the reliability of single color indication is improved.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to electroactive polysiloxane prepared by taking a novel aniline oligomer as an electroactive unit and a cyanostyrene derivative as an AIE (alpha-amino-ethyl) active fluorescent group through electrochemical hydrolysis crosslinking, a film thereof and application of the film in a color/fluorescence double-indication supercapacitor.
Background
Polyaniline, as a conductive high molecular polymer, can undergo redox reaction at a low driving voltage, accompanied by reversible changes in various colors. Meanwhile, the reversible redox property endows the polyaniline with excellent pseudocapacitance performance, so that the polyaniline can be applied to the fields of electrochromism, supercapacitor energy storage, intelligent display, information encryption, military camouflage and the like. The aniline oligomer is used as a model compound of polyaniline developed in the later stage, not only inherits almost all advantages of polyaniline, but also has strong molecular designability and more excellent dissolution processing performance, and greatly expands the number of high-molecular functional materials of aniline groups. Therefore, the aniline oligomer chain segment is expected to be introduced into the polymer structure to endow the polymer with more excellent electrochemical properties.
The aniline oligomer is connected with a polymer system as an electroactive group and a fluorescent group through molecular design, and the redox state of the aniline oligomer and the fluorescent group are controlled by voltage to generate energy/electron transfer effect, so that the fluorescence can be regulated and controlled reversibly. In terms of solid fluorescence, a molecular structure with aggregation-induced emission properties (AIE) is more beneficial for obtaining smart thin film materials with higher fluorescence contrast. In the invention, the synthesized polysiloxane contains a high-efficiency solid luminescent cyanostyrene derivative as an AIE fluorescent group, and aims to improve the contrast of fluorescence. In addition, the hydrolysis crosslinking reaction is beneficial to forming a micro-porous and through polymer network structure, and ions in the electrolyte are more easily embedded and removed, so that the electrochemical stability, the response speed and the like of the electroactive polymer are improved.
The invention aims to synthesize a novel electroactive polysiloxane containing aniline oligomers and AIE fluorescence activity. The polymer has excellent charge storage property of pseudo capacitance due to the fact that the polymer contains an electroactive aniline tetramer structure. The polymer is loaded on an ITO substrate through electrochemical hydrolysis to prepare a symmetrical super capacitor, and the excellent electrochromic/electric control fluorescence property of the super capacitor enables the charge and discharge process of the super capacitor to be visualized through color change or fluorescence switching. The functions of electrochromic and electric control fluorescence dual indication are integrated in one device and applied to the super capacitor, energy visualization can be realized in two different modes, and reliability of capacitance indication effect is improved. In addition, the reversible switch of the fluorescence of the electrode material is switched in the process of energy storage and release, so that the indicating function of the device can be applied even in a dark environment, and the application scene of the device is expanded.
Disclosure of Invention
The invention aims to provide a cross-linked porous electroactive polysiloxane containing aniline tetramer and AIE active fluorescent group, a film thereof and application of the film in color/fluorescence dual indication in the charge storage of a super capacitor.
The synthesis and structural formula of the electrochemical hydrolysis crosslinked electroactive polysiloxane containing the aniline tetramer and the AIE active fluorescent group are shown as follows:
wherein,
firstly, synthesizing electroactive aniline Tetramer (TA) and AIE active fluorescent monomer (ZAAT), and then respectively carrying out nucleophilic substitution reaction on two functionalized monomers and isocyanatopropyltriethoxysilane to generate two functionalized siloxane monomers (Si-TA and Si-ZAAT); these two monomers were further mixed in a ratio of 3:1, and then spin-coating on transparent conductive glass ITO (indium tin oxide) as a working electrode, taking a Pt wire as a counter electrode and taking Ag/AgCl as a reference electrode to form a three-electrode system. A monomer coated on the ITO surface of the conductive glass is subjected to hydrolytic crosslinking under the drive of voltage by a cyclic voltammetry scanning method in 1M hydrochloric acid electrolyte to generate an electroactive polysiloxane film (PSZT). The test represents the nuclear magnetic hydrogen spectrum of the monomer, the infrared absorption spectrum and the electron microscope morphology of the polymer, and further proves the successful preparation of the cross-linked network porous polymer. The polymer film is tested for electrochromic property, electrically-controlled fluorescence property, color/fluorescence dual-indication property in constant-current charging and discharging and the like through a series of electrochemical property tests (including cyclic voltammetry scanning, spectroelectrochemical method, spectroamperometry, constant-current charging and discharging scanning method, electrochemical alternating-current impedance spectroscopy and the like).
The electroactive polysiloxane (I) is prepared by the following steps:
(1) dissolving N-phenyl-1, 4-p-phenylenediamine (18.4g, 0.1mol) in 150-180 mL of anhydrous ether, dropwise adding the solution into a 1.0M hydrochloric acid solution (1500-2000 mL) and stirring for 3-5 hours; then 28.0g of ferric chloride hexahydrate is dissolved in 100mL of 1.0M hydrochloric acid solution, and gradually dropped into the N-phenyl-1, 4-p-phenylenediamine solution within 30-40 minutes; continuously stirring for 3-5 hours, obtaining a crude product through reduced pressure filtration, washing for 2-4 times by using 1.0M hydrochloric acid and 1-2 times by using 1.0M ammonia water respectively, reducing excessive hydrazine hydrate for 12-20 hours, and finally obtaining a product TA through reduced pressure filtration and vacuum drying;
(2) dissolving 3- (triethoxysilyl) propyl isocyanate (0.4947g, 2mmol) and TA (0.732g, 2mmol) in a DMAc solution, and stirring for 4-5 hours under a nitrogen atmosphere to obtain an aniline tetramer functionalized siloxane precursor Si-TA;
(3) dissolving 9-anthracenal (0.4947g, 2mmol) and p-nitrophenylacetonitrile (0.4947g, 2mmol) in 30-50mL of ethanol solution, heating and refluxing for 1-2 hours, and then adding 200-300 mu L of 2M tetrabutylammonium hydroxide aqueous solution; heating and refluxing the obtained mixture for 12-15 hours, filtering to obtain a yellow solid, washing with ethanol for 2-3 times, and drying in vacuum to obtain a yellow intermediate (Z) -3- (anthracene-9-yl) -2- (4-nitrophenyl) acrylonitrile (ZANT);
ZANT (0.65g, 2.0mmol), Pd/C (0.065g) and N2H4.H2O (0.9mL, 16.0mmol) was added to absolute ethanol (50-70mL) in N2Heating and refluxing for 8-10 hours under the atmosphere, filtering to obtain a green solid, washing with ethanol, and transferring the crude productAdding into dichloromethane, filtering to remove insoluble Pd/C, and removing solvent under reduced pressure; then using petroleum ether and dichloromethane of 5:1-10:1(V: V) as eluent, purifying by column chromatography on a silica gel column, and drying in vacuum to obtain orange yellow solid, namely (Z) -2- (4-aminophenyl) -3- (anthracene-9-yl) acrylonitrile (ZAAT);
(4) 3- (triethoxysilyl) propyl isocyanate (0.7420g, 3mmol) and ZAAT (0.732g, 2mmol) were dissolved in 2mL DMAc solution at 70-90 deg.C and N2Heating and stirring for 8-10 hours under the atmosphere; then adding dichloromethane, concentrating under reduced pressure, and further purifying by column chromatography (petroleum ether/dichloromethane is used as a mobile phase, and V/V is 2: 1-4: 1) to obtain a yellow target product, namely an AIE active siloxane monomer Si-ZAAT;
(5) in N2In the atmosphere, sealing a DMAc solution of 25% of Si-TA and Si-ZAAT (the molar ratio of Si-TA to Si-ZAAT is 3:1), and stirring at room temperature for 1-3 hours; depositing the obtained mixed solution of Si-TA and Si-ZAAT on a hydrophilic ITO substrate by a spin coating method, and drying for 2-5 hours at 30-50 ℃ under vacuum; an ITO substrate modified by the Si-TA and Si-ZAAT mixture is used as a working electrode (PSZT/ITO electrode) to construct a three-electrode battery system, Ag/AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode; in 0.1M HCl solution, scanning from 0-0.8V by using cyclic voltammetry to enable Si-TA and Si-ZAAT to generate a hydrolysis crosslinking reaction, wherein the scanning speed is 10-100mV/s, and thus an electroactive Polysiloxane (PSZT) film is obtained on an ITO substrate.
The structure of each reaction monomer related by the invention is as follows:
structural formula of TA:
the structural formula of Si-TA:
ZANT structural formula:
ZAAT structural formula:
structural formula of Si-ZAAT:
the invention also relates to the application of the electroactive Polysiloxane (PSZT) in a color/fluorescence double-indication super capacitor, and the related test method comprises the following steps:
two identical PSZT/ITO prepared in the above steps are used as electrodes which are respectively used as a positive electrode and a negative electrode of a super capacitor, and PVA/HCl is used as a gel electrolyte (the preparation method of the PVA/HCl gel electrolyte comprises the steps of taking 6g of concentrated hydrochloric acid with mass fraction of 37%, dissolving 6g of PVA in 10g of deionized water, heating at 85 ℃ for 3 hours, and cooling to room temperature). And (3) respectively attaching copper adhesive tapes to the ITO glass surfaces of the positive electrode and the negative electrode to reduce contact resistance, uniformly coating the PSZT surfaces of the positive electrode and the negative electrode with a liquid transfer gun, pasting and fixing the positive electrode and the negative electrode in a face-to-face manner (the PSZT surface is opposite to the PSZT surface) for 1-2 hours, and forming a symmetrical supercapacitor after fixing. In the electrochemical measurement, the PSZT/ITO electrode of the anode is used as a working electrode, and the PSZT/ITO electrode of the cathode is used as a counter electrode.
The mass specific capacitance of the device is calculated by using a constant current charging and discharging method, and the formula is as follows:
wherein Δ t is the discharge time(s); i is a discharge current (A); m is the total mass (g) of the substances Si-TA and Si-ZAAT in the electrode; Δ U is a voltage variation range (V).
The ultraviolet transmittance in the constant current charging and discharging process is tested on line: the constant current charge and discharge test is adopted to be used together with an ultraviolet-visible spectrophotometer, the charge and discharge voltage is 0-0.8V, and the relation between the transmittance change and the voltage of the device at 700nm is tested under the current density of 1A/g. And finally, applying voltages of 0, 0.4, 0.8, -0.4 and-0.8V to the prepared device respectively, and recording the color change of two electrodes of the device. And simultaneously, under the excitation of a 5w ultraviolet lamp, the fluorescence intensity changes of the recording electrode at 0, 0.8 and 0.8V.
Drawings
FIG. 1: nuclear magnetic hydrogen spectra of intermediates and functionalized siloxane monomers involved in the synthesis of the polymers of the present invention.
FIG. 2: cyclic voltammogram (a) of the synthetic polymer of the invention; the infrared spectrums (b) of the mixture before electrochemical hydrolysis and the polymer after hydrolytic crosslinking, and the electron microscope topography (c) before and after electrochemical hydrolytic crosslinking.
FIG. 3: the Si-TA and Si-ZAAT mixture synthesized by the invention has different solvent ratios DMAc-H2Fluorescence Spectroscopy in O solution (internal graph: DMAc-H2Fluorescence change pattern in O mixed solution) (a); a sol-gel transition diagram and a fluorescence picture thereof under ultraviolet light (b); fluorescence spectra (c) of the gel and sol states (mixture of Si-TA and Si-ZAAT) of the polymer PSZT.
FIG. 4: the transmittance spectrogram of the synthesized polymer PSZT/ITO electrode under different potentials (0-0.8V) and the color photograph (a) of the PSZT film under different voltages are shown; the transmittance of the PSZT film at alternating voltages of 0V and 0.8V is changed, and the transition time chart of the colored state and the bleached state is shown in (b).
FIG. 5: the polymer PSZT synthesized by the invention has a fluorescence spectrum (a) under different voltages of 0.0-0.8V; fluorescence spectrum of PSZT/ITO electrode under alternating voltage of 0V and 0.8V and switching time of fluorescence switch (b).
FIG. 6: the PSZT/ITO single electrode prepared by the invention has cyclic voltammetry curves (a) under different scanning rates; EIS diagram of PSZT/ITO in three-electrode solution system (b); PSZT/ITO electrode with current density of 0.25-10A g-1Constant current charge-discharge curve (c) in 0.1M HCl solution; PSZT/ITOThe electrodes are at different current densities of 0.25-10A g-1The specific capacitance curve (d) of (a).
FIG. 7: the cyclic voltammetry curve (a) of the super capacitor device prepared by the invention under different scanning rates; GCD curves (b) for ultracapacitor devices at various current densities; the GCD curve of the super capacitor device in the voltage range of 0-0.8V and the current density of 1A/g corresponds to the curve (c) of the change of the film transmittance at the wavelength of 700 nm; and (d) a picture of color indication and fluorescence indication of the supercapacitor device during charging and discharging.
FIG. 1 shows the nuclear magnetic hydrogen spectra of the intermediate of the polymer and the functionalized siloxane monomer. Wherein, nuclear magnetic hydrogen spectrum (a) of TA:1h NMR (400MHz in DMSO) < delta > 7.68(s,1H),7.44(s,1H),7.15 (s,1H), 7.14-7.09 (m,2H), 6.98-6.92 (m,2H),6.87(ddd, J ═ 8.9,3.5,2.4Hz,6H), 6.81-6.74 (m,4H), 6.69-6.61 (m,1H), 6.54-6.48 (m,2H),4.61(s, 2H). Nuclear magnetic hydrogen spectrum (b) of Si-TA:1h NMR (400MHz, DMSO) δ 8.10(s,1H),7.77(s,1H),7.59(d, J ═ 14.0Hz,2H),7.25 to 7.12(m,4H),7.03(dd, J ═ 25.1,9.1Hz,4H),6.92(d, J ═ 14.4 Hz,8H),6.75 to 6.63(m,1H),6.03(t, J ═ 5.5Hz,1H),3.77(q, J ═ 7.0Hz,6H),3.05 (d, J ═ 6.1Hz,2H),1.57 to 1.43(m,2H),1.17(t, J ═ 7.0Hz,9H),0.64 to 0.51(m, 2H). Nuclear magnetic hydrogen spectrum (c) of ZAAT:1h NMR (400MHz, DMSO) δ 8.70(s,1H),8.52(s, 1H), 8.21-8.13 (m,2H), 8.09-8.01 (m,2H),7.64(d, J ═ 8.3Hz,2H),7.58(dd, J ═ 6.6,2.6Hz,4H),6.73(d, J ═ 8.3Hz,2H),5.71(s, 2H). Nuclear magnetic hydrogen spectrum (d) of Si-ZAAT:1H NMR(400MHz,DMSO)δ8.78(d,J＝3.4Hz,2H),8.74(s,1H),8.19(dd,J＝5.8, 4.0Hz,2H),8.11–8.05(m,2H),7.86(d,J＝8.8Hz,2H),7.61(ddd,J＝12.7,6.9, 3.4Hz,6H),6.31(t,J＝5.7Hz,1H),3.78(q,J＝7.0Hz,6H),3.10(dd,J＝12.9,6.7 Hz,2H),1.57–1.46(m,2H),1.17(t,J＝7.0Hz,9H),0.63–0.55(m,2H)。
FIG. 2a shows the CV curve of electrochemical hydrolytic crosslinking of siloxane monomers Si-TA and Si-ZAAT attached to an ITO substrate in a 0.1M hydrochloric acid solution. Ions in the electrolyte are continuously inserted/extracted into/from the polymer film under the drive of voltage, and hydrolysis crosslinking reaction is generated. In a 100-turn CV cycle curve, the peak current is obvious at 0.53V/0.38VAn increase indicates that the hydrolysis reaction proceeded smoothly. After 100CV cycles, the peak current gradually stabilized, confirming that the hydrolytic crosslinking reaction was complete. As shown in fig. 2b, FTIR infrared spectroscopy also confirmed the electrochemical hydrolytic crosslinking reaction between the two functionalized siloxane monomers. The spectrum showed 3329cm-1Is N-H telescopic vibration, 2926cm-1And 2883cm-1Alkyl C-H stretching vibration. Furthermore, at 1311cm-1Is C-N telescopic vibration, 1228cm-1Is the out-of-plane vibration of Si-C. The mixture of Si-TA and Si-ZAAT was 1077cm before crosslinking-1The characteristic tensile vibration of Si-O-C is shown. PSZT after crosslinking reaction was 1155cm-12900cm for significant Si-O-Si characteristic tensile vibration-1The C-H stretching vibration of the alkyl group nearby is obviously reduced, which indicates that the hydrolysis crosslinking reaction occurs. In addition, as shown in fig. 2c, SEM also shows the difference in morphology of the polymer before and after scanning through CV. The mixture film was uniform, flat and dense before hydrolysis. However, the polysiloxane film after the hydrolysis reaction becomes a loose porous network interpenetrating structure due to the aggregation and release of small molecules during the hydrolytic crosslinking reaction.
As shown in FIG. 3a, the AIE activity of the Si-TA and Si-ZAAT mixtures was analyzed in detail. When the molar ratio is 3: siloxane monomer of 1 (Si-ZAAT: Si-TA) does not fluoresce in readily soluble DMAc. The significant AIE effect was demonstrated when the mixture fluoresced strongly in an insoluble pure water solvent. For example, when the proportion of water in the mixed solvent is increased from 0 to 40%, the fluorescence intensity is weak. When the proportion of water in the mixed solution was increased from 50% to 95%, the fluorescence emission intensity at a wavelength of 524nm sharply increased. This is because the intramolecular rotation of the aggregated state is restricted, inhibiting the excited state energy dissipated by the free rotation of the olefinic double bond in solution, and thus promoting radiative transition of fluorescence. As shown in fig. 3b, we investigated the gel properties of the polymer due to the "water-locking" function of the chemically hydrolyzed cross-linked network structure. The mixture of Si-TA and Si-ZAAT has good solubility in THF solution and no fluorescence in sol state. A few drops of 1.0M HCl solution were added dropwise to the mixture solution, left to stand for 12 hours to gradually solidify and become a gel, and fluorescence rapidly increased under ultraviolet irradiation. The chemically polymerized PSZT gel has the property of gel-induced fluorescence enhancement. FIG. 3c shows fluorescence spectra of PSZT in gel and sol state (mixture of Si-TA and Si-ZAAT). The PSZT gel state is very fluorescent, and the central emission wavelength is 503 nm. The PSZT gel state is similar to the solid state of Si-TA and Si-ZAAT mixture, the free rotation of benzene ring and naphthalene ring is greatly inhibited through the fixed net structure, and the fluorescence luminous efficiency of the gel state is enhanced.
As shown in fig. 4, the electrochromic behavior of PSZT was tested by using an electrochemical workstation in combination with UV-vis spectroscopy. As shown in fig. 4a, as the applied voltage is gradually increased from 0V to 0.8V, the transmittance in most visible regions is decreased accordingly. The color of the thin film electrode changed from light yellow green (at 0V) to green (at 0.4V) and finally to dark green (at 0.8V) due to the gradual formation of the strongly absorbing oxidation state structure of the aniline oligomer. The stability of the PSZT film during electrochromic at alternating voltages of 0V and 0.8V was investigated in view of the corrosive effect of the acidic electrolyte on the ITO substrate. The range of transmission change was relatively stable over the first 100 cycles, indicating that the hydrolytically crosslinked polymer was relatively stable and also exhibited good corrosion protection properties against ITO substrates. This also enhances the stability of the electroactive PSZT film to some extent. As can be seen from the enlarged EC curve in FIG. 4b, an optical contrast value of about 35.6% is found at 700nm between its colored and bleached states. According to the change of the transmittance and the charge consumption, the Coloring Efficiency (CE) of the PSZT film in the oxidation stage is calculated to be 56.5cm2and/C. The switching time of the coloration/bleaching process, calculated from the maximum transmission change at 700nm, was 11.1s/11.6 s.
As shown in fig. 5a, the electrically controlled fluorescence of PSZT was studied in detail because the electrically active TA group in polysiloxane affects the luminescence of AIE group. Therefore, the rule of fluorescence quenching of the PSZT/ITO electrode under different applied voltages of 0.0V-0.8V is tested by a spectroelectrochemical method. The fluorescence of the PSZT film at 503nm decreased with increasing applied voltage, and the fluorescence quenching degree was 85% at 0.8V. When the applied voltage drops to 0V, the fluorescence reversibly returns to the original intensity. This EFC behavior is attributed to the interaction between the TA and AIE groups. Energy transfer between the quinoid structure of TA oxidized at high voltage and the excited state of AIE suppresses the path of radiation transition, resulting in fluorescence quenching phenomenon. According to FIG. 5b, the switch time for the fluorescence on/off state is calculated to be about 8.9s/9.7s for the enlarged EFC curves of 0V and 0.8V. The experimental results demonstrate its high fluorescence quenching rate, good cycling stability, moderate switching response time and low starting voltage in EFC behavior.
As shown in FIG. 6a, cyclic voltammograms of PSZT at different scan rates of 10-100mV/s were investigated. Only one pair of redox peaks reversible at 0.53V/0.38V was observed in the CV curve, indicating a transition between reduced and oxidized states in the oligoaniline segment. The peak current increases significantly with increasing scan rate, demonstrating a surface-limited redox reaction and a fast charge transfer process. Furthermore, the PSZT/ITO electrodes were also examined by EIS measurements. As shown in FIG. 6b, R is in the Nyquist plotfThe value of 43 Ω indicates a low internal resistance of PSZT, mainly due to the loose porous network microstructure formed during the electrochemically assisted hydrolytic crosslinking. The linear diffusion resistance deviates slightly from 45 deg., resulting in a diffusion process equivalent to spherical diffusion due to its rough electrode surface. As shown in FIG. 6c, to evaluate the pseudocapacitance performance of the PSZT/ITO electrode, the pseudo-capacitance performance was measured at 0.25-10A g in 0.1M HCl solution-1The GCD measurements were performed at different current densities. The charging and discharging time of the PSZT/ITO electrode is significantly shortened when the current density is increased. Furthermore, at 0.25A g-1176F g can be obtained at a current density of-1Has reached the standard of polyaniline type capacitor materials. Furthermore, the specific capacitance versus current density relationship is shown in FIG. 6d, where the capacitance slowly decreases with increasing current density and is at 10A g-1The highest 73% is maintained at high current densities. The inhibition of the volume effect by the highly crosslinked reticular skeleton of the PSZT film greatly improves the charge-discharge rate and the stability. In addition, the abundance of pores in the PSZT film facilitates passage between the electrode and electrolyte interface due to more contact sitesFast ion migration.
As shown in FIG. 7, a symmetrical supercapacitor device is assembled by two prefabricated PSZT/ITO electrodes and HCl-polyvinyl alcohol gel electrolyte. As shown in FIG. 7a, the CV curve shows that the peak redox current increases as the scan rate increases from 20mV/s to 200mV/s, which is related to the reversible redox process of the aniline segment. The CV curve measured on the device has a smaller capacitor area and reduced shape symmetry compared to the CV curve of a single PSZT/ITO electrode in solution due to the increased impedance between the gel electrolyte and the PSZT/ITO electrode. As shown in fig. 7b, as the current density increases, the charge and discharge time is correspondingly shortened. The specific capacitance of the supercapacitor is calculated from the discharge part of the galvanostatic experiment. At 0.25A g-1The maximum specific capacitance of the device is 82F g-1With current density from 0.25A g-1Increased to 1A g-1The specific capacitance is reduced to 56F g-1; when the current density increased to 10A g-1The specific capacitance of the device drops to 37F g-1. The reduction in specific capacitance of the device is due to the volume effect of the conductive polymer film during charging and discharging. To visualize its energy storage by color studies, the supercapacitor was tested for periodic transmittance change at 700nm corresponding to GCD using an electrochemical workstation in combination with UV-vis spectroscopy. As shown in fig. 7c, the transmittance fluctuates regularly from 70% to 36% over five charge-discharge cycles. The transmittance of 70% corresponds to its discharge complete state (0V), and the transmittance of 36% corresponds to its charge complete state (0.8V). To visually investigate the color tunable indication function in the supercapacitor, its actual performance was tested by applying a constant voltage, as shown in fig. 7 d. When a voltage of 400s of 0V is applied, both PSZT/ITO electrodes of the device show a pale greenish yellow color. When 0.4V and 0.8V were applied to the device in sequence, the PSZT/ITO electrode of the anode changed to green and dark green cathodes, respectively, with the PSZT/ITO electrode of the cathode still being the initial light yellow-green color. In addition, when a negative voltage (-0.4V and-0.8V) is applied to the device, a corresponding color change occurs in the cathode PSZT/ITO electrode, while the anode PSZT/ITO electrode remains yellowish green. Of super-capacitor devicesFluorescence indicates behavior, and significant fluorescence of both poles of the supercapacitor was observed by applying 0V to both PSZT/ITO electrodes. When the voltage is increased to 0.8V, the fluorescence of the anode PSZT/ITO electrode is almost completely quenched, and the fluorescence of the cathode PSZT/ITO electrode is still obvious. When a negative voltage (-0.8V) was applied to the device, the cathode PSZT/ITO electrode fluorescence quenched, while the anode PSZT/ITO electrode showed strong fluorescence. In addition, the color/fluorescence dual indication function can effectively improve the visualization accuracy of the supercapacitor. Therefore, the super capacitor with the color/fluorescence double indication function can show potential application in intelligent energy storage devices.
The data prove that the novel bifunctional polysiloxane containing the electroactive aniline oligomer and the AIE active fluorescent group is designed and synthesized, and the polymer film prepared by the electrochemical hydrolysis crosslinking method has the electrochromic/electrically-controlled fluorescent property. And proves that the double responses of the electrochromic and the electrically-controlled fluorescence can indicate the electric quantity of the assembled super capacitor. The energy state of the intelligent symmetrical super capacitor based on the porous network penetrated polysiloxane film can be indicated by the adjustable color from light yellow green to dark green, and can be displayed by the fluorescence on/off state of the electrode, so that the reliability of electric quantity visualization is improved. Therefore, the intelligent super capacitor with the color/fluorescence double indication function has wide and attractive application prospect in the intelligent energy storage display system.
Detailed Description
Example 1: preparation of electroactive Polysiloxane (PSZT) thin films
(1) N-phenyl-1, 4-p-phenylenediamine (18.4g, 0.1mol) was dissolved in 150mL of anhydrous ether, and the solution was added dropwise to a 1.0M hydrochloric acid solution (1500mL) and stirred for 3 hours; then 28.0g of ferric chloride hexahydrate is dissolved in 100mL of 1.0M hydrochloric acid solution, and the obtained solution is gradually dropped into the above stirred solution within 30 minutes; stirring for 3 hours, filtering under reduced pressure to obtain a crude product, washing with hydrochloric acid (1M) for 3 times, washing with 1.0M ammonia water for 2 times, reducing excessive hydrazine hydrate for 12 hours, filtering under reduced pressure, and drying under vacuum to obtain a product TA (12.5 g);
(2) 3- (triethoxysilyl) propyl isocyanate (0.4947g, 2mmol) and TA (0.732g, 2mmol) were charged in a three-necked round bottom flask and dissolved in DMAc solution and stirred under nitrogen atmosphere for 4 hours to give the aniline tetramer functionalized siloxane precursor Si-TA (1.02 g); the above steps (1) to (2) are processes for preparing the siloxane monomer of the electroactive aniline tetramer.
(3) 9-Anthranilic aldehyde (0.4947g, 2mmol) and p-nitrophenylacetonitrile (0.4947g, 2mmol) were dissolved in 30mL of ethanol, the mixture was heated to reflux for 2 hours, then 200uL of 2M aqueous tetrabutylammonium hydroxide was added; the mixture was refluxed for 12 hours again, filtered to give a yellow solid, washed 3 times with ethanol, and dried under vacuum to give the yellow intermediate (Z) -3- (anthracen-9-yl) -2- (4-nitrophenyl) acrylonitrile (ZANT); ZANT (0.65g, 2.0mmol), Pd/C (0.065g) and N2H4.H2O (0.9mL, 16.0mmol) was added to absolute ethanol (50mL) in N2Heating and refluxing for 8 hours under an atmosphere, filtering to obtain a green solid, washing with ethanol, transferring the crude product into dichloromethane, removing insoluble Pd/C by filtration, removing the solvent under reduced pressure, purifying the crude product by column chromatography on a silica gel column using 5:1(V: V) petroleum ether and dichloromethane as eluent, and drying under vacuum to obtain an orange-yellow solid which is named as (Z) -2- (4-aminophenyl) -3- (anthracen-9-yl) acrylonitrile (ZAAT) (0.94 g);
(4) 3- (Triethoxysilyl) propyl isocyanate (0.7420g, 3mmol) and ZAAT (0.732g, 2mmol) were placed in a three-necked round-bottomed flask and dissolved in 2mL of DMAc at 80 ℃ in N2Heating and stirring for 8 hours under the atmosphere; the mixed solution was added to dichloromethane and concentrated under reduced pressure, and further purified by column chromatography (petroleum ether/dichloromethane as mobile phase, V/V ═ 2:1) to give Si-ZAAT (1.14g) as a target yellow product; the above steps (3) to (4) are processes for preparing AIE-reactive siloxane monomers.
(5) In N2Sealing a DMAc mixed solution of 25 mass percent of Si-TA and Si-ZAAT (the molar ratio of Si-TA to Si-ZAAT is 3:1) in an atmosphere, and stirring for 3 hours at room temperature; then the obtained mixed solution of Si-TA and Si-ZAAT is passed throughDepositing on a hydrophilic ITO substrate by a spin-coating method, and drying for 3 hours in a vacuum drying oven at 40 ℃; constructing a traditional three-electrode battery system by taking the ITO substrate modified by the mixture as a working electrode, taking Ag/AgCl as a reference electrode and taking a platinum wire as a counter electrode; and (2) in 0.1M HCl solution, performing hydrolytic crosslinking from 0-0.8V scanning by using cyclic voltammetry at a scanning speed of 100mV/s, thereby obtaining the electroactive Polysiloxane (PSZT) film on the ITO substrate.
Claims (4)
1. A preparation method of an electroactive polysiloxane film comprises the following steps:
(1) dissolving 0.1mol of N-phenyl-1, 4-p-phenylenediamine in 150-180 mL of anhydrous ether, dropwise adding the solution into 1500-2000 mL of 1.0M hydrochloric acid solution, and stirring for 3-5 hours; then 28.0g of ferric chloride hexahydrate is dissolved in 100mL of 1.0M hydrochloric acid solution, and gradually dropped into the N-phenyl-1, 4-p-phenylenediamine solution within 30-40 minutes; continuously stirring for 3-5 hours, obtaining a crude product through reduced pressure filtration, washing for 2-4 times by using 1.0M hydrochloric acid and 1-2 times by using 1.0M ammonia water respectively, reducing excessive hydrazine hydrate for 12-20 hours, and finally obtaining a product TA through reduced pressure filtration and vacuum drying;
(2) dissolving 2mmol of 3- (triethoxysilyl) propyl isocyanate and 2mmol of TA in a DMAc solution, and stirring for 4-5 hours under a nitrogen atmosphere to obtain a siloxane precursor Si-TA functionalized by an aniline tetramer;
(3) dissolving 2mmol of 9-anthracenal (0.4947 g) and 2mmol of p-nitroacetonitrile in 30-50mL of ethanol solution, heating and refluxing for 1-2 hours, and then adding 200-300 mu L of 2M tetrabutylammonium hydroxide aqueous solution; heating and refluxing the obtained mixture for 12-15 hours, filtering to obtain a yellow solid, washing with ethanol for 2-3 times, and drying in vacuum to obtain a yellow intermediate (Z) -3- (anthracene-9-yl) -2- (4-nitrophenyl) acrylonitrile ZANT;
2.0mmol of ZANT, 0.065g of Pd/C and 16.0mmol of N2H4.H2Adding O into 50-70mL of absolute ethanol, and adding into N2Heating and refluxing for 8-10 hours under the atmosphere, filtering to obtain a green solid, washing with ethanol, and transferring the crude product to dichloromethaneIn the alkane, insoluble Pd/C is removed by filtration, and the solvent is removed under reduced pressure; then, mixing the raw materials in a volume ratio of 5-10: 1, taking petroleum ether and dichloromethane as an eluent, purifying by column chromatography on a silica gel column, and drying in vacuum to obtain an orange yellow solid, namely (Z) -2- (4-aminophenyl) -3- (anthracene-9-yl) acrylonitrile ZAAT;
(4) dissolving 3mmol of 3- (triethoxysilyl) propyl isocyanate and 2mmol of ZAAT in 2mL of DMAc solution, and carrying out N reaction at 70-90 DEG C2Heating and stirring for 8-10 hours under the atmosphere; and then adding dichloromethane, concentrating under reduced pressure, and further purifying by column chromatography, wherein petroleum ether and dichloromethane are used as mobile phases, and the volume ratio is 2-4: 1, obtaining a yellow target product, namely an AIE active siloxane monomer Si-ZAAT;
(5) in N2Sealing a DMAc solution of 25% of Si-TA and Si-ZAAT in total mass fraction in an atmosphere, wherein the molar ratio of Si-TA to Si-ZAAT is 3:1, stirring for 1-3 hours at room temperature; depositing the obtained mixed solution of Si-TA and Si-ZAAT on a hydrophilic ITO substrate by a spin coating method, and drying for 2-5 hours at 30-50 ℃ under vacuum; constructing a three-electrode battery system by taking the ITO substrate modified by the Si-TA and Si-ZAAT mixture as a working electrode, taking Ag/AgCl as a reference electrode and taking a platinum wire as a counter electrode; scanning from 0-0.8V in 0.1M HCl solution by using cyclic voltammetry to enable Si-TA and Si-ZAAT to generate a hydrolysis crosslinking reaction, wherein the scanning speed is 10-100mV/s, so that an electroactive polysiloxane film is obtained on an ITO substrate;
wherein each reaction monomer has the following structure,
structural formula of TA:
the structural formula of Si-TA:
ZANT structural formula:
ZAAT structural formula:
structural formula of Si-ZAAT:
the structural formula of the prepared electroactive polysiloxane is shown as follows:
wherein,
2. use of the electroactive polysiloxane film prepared by the process of claim 1 in a supercapacitor with dual color/fluorescence indication.
3. Use of an electroactive silicone film as claimed in claim 2 in a colour/fluorescence double indicating supercapacitor wherein: two identical PSZT/ITO are used as electrodes which are respectively used as a positive electrode and a negative electrode of a super capacitor, and PVA/HCl is used as a gel electrolyte; and respectively sticking copper adhesive tapes on the ITO glass surfaces of the positive electrode and the negative electrode to reduce contact resistance, uniformly coating the PSZT surfaces of the positive electrode, the negative electrode and the electrode with gel electrolyte by using a liquid transfer gun, sticking and fixing the PSZT surfaces of the positive electrode and the negative electrode and the PSZT surface face to face for 1-2 hours, and forming a symmetrical super capacitor after fixing.
4. Use of an electroactive silicone film as claimed in claim 3 in a colour/fluorescence double indicating supercapacitor wherein: 6g of concentrated hydrochloric acid with the mass fraction of 37 percent and 6g of PVA are dissolved in 10g of deionized water, heated for 3 hours at 85 ℃, and cooled to room temperature to obtain the PVA/HCl gel electrolyte.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503839A (en) * | 2018-03-23 | 2018-09-07 | 吉林大学 | Multifunctional mesh shaped polymer and the application of film, preparation method and the film in terms of electrochromism or automatically controlled fluorescence |
| CN109762347A (en) * | 2019-01-24 | 2019-05-17 | 吉林大学 | It is a kind of by the multi-functional netted hybrid film material of covalent bonding and its in the application of electrochemical field |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503839A (en) * | 2018-03-23 | 2018-09-07 | 吉林大学 | Multifunctional mesh shaped polymer and the application of film, preparation method and the film in terms of electrochromism or automatically controlled fluorescence |
| CN109762347A (en) * | 2019-01-24 | 2019-05-17 | 吉林大学 | It is a kind of by the multi-functional netted hybrid film material of covalent bonding and its in the application of electrochemical field |
Non-Patent Citations (4)
| Title |
|---|
| Effect of connecting links on self-assembly and mechanofluorochromism of cyanostyrylanthracene derivatives with aggregation-induced emission;Pengchong Xue，Jipeng Ding etl.;《Dyes and Pigments》;20170527;第12-20页 * |
| Pengchong Xue，Jipeng Ding etl..Effect of connecting links on self-assembly and mechanofluorochromism of cyanostyrylanthracene derivatives with aggregation-induced emission.《Dyes and Pigments》.2017, * |
| 周明娟，晁单明.新型电控荧光聚合物的合成与性能研究.《大学化学》.2018, * |
| 新型电控荧光聚合物的合成与性能研究;周明娟，晁单明;《大学化学》;20181029;第47-52页 * |
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