Ferrocenyl polyacrylate photon gel electrochromic device as well as preparation method and application thereof
By preparing ferrocene-based polyacrylate gel and opal photonic crystal composites through in-situ photopolymerization in electrolyte solution, a sandwich-structured electrochromic device was constructed, solving the problems of reversible structural color change under low voltage and liquid electrolyte leakage, realizing low-voltage driven reversible structural color change and wide application.
Patent Information
- Application Number
- CN202511321308.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-16
- Publication Date
- 2025-11-07
AI Technical Summary
Existing electrochromic devices struggle to achieve reversible structural color changes at low voltages, and the liquid electrolyte poses a risk of leakage, impacting their application scenarios and response time.
Ferrocene-based polyacrylate gel was prepared by in-situ photopolymerization in an electrolyte solution and then combined with an opal photonic crystal to construct a sandwich-structured electrochromic device. The reversible electrochemical transition of ferrocene groups between neutral and oxidized states was used to change the swelling state of the gel network, thereby achieving low-voltage driven structural color change.
It achieves reversible structural color change under low voltage, avoids the risk of leakage of liquid electrolyte, and has broad application prospects.
Smart Images
Figure CN120909033A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of electrochromic devices, more particularly to a ferrocene-based polyacrylate photonic gel electrochromic device and a preparation method and application thereof. BACKGROUND
[0002] Electrochromic devices have broad application prospects in the fields of smart windows, smart displays, flexible electronics, etc. due to their ability to reversibly adjust optical properties under the action of an applied electric field. Traditional electrochromic materials (WO3, polyaniline, etc.) cause electron transitions through electrochemical redox reactions to achieve color change, but their color change range is limited by the difference in light absorption characteristics between the oxidized and reduced states of the materials, and there are problems such as single color change.
[0003] The introduction of structural color enriches the color change of electrochromic devices. Photonic crystals produce structural color through Bragg diffraction of light by periodic structures, have the advantages of bright color and resistance to photo-bleaching, and are an important class of structural color-producing materials. The structural color of photonic crystals can be controlled by changing the micro-nano structure parameters such as lattice spacing and effective refractive index, providing a new idea for the design of electrochromic devices.
[0004] In recent years, the electrochromism of photonic crystal based on structure color is mainly achieved by electrophoresis of colloidal microspheres under electric field. For example, Ge et al. (Yu W, Zhao Y, Ge J. Electrically triggered photonic crystal anti-counterfeiting tags with multi-level response fabricated by regioselective modification of ITO electrode surface [J]. Journal of Colloid and Interface Science, 2024, 659: 603-610.) used supersaturated SiO2 microspheres to precipitate in propylene carbonate to construct a liquid photonic crystal. The distance between the microspheres was changed by the electrostatic interaction between the electrode and the SiO2 microspheres under the external electric field, and the color changed from red to blue within 0-3 V. Fu et al. (Fu Q, Yu W, Bao G, et al. Electrically responsive photonic crystals with bistable states for low-power electrophoretic color displays [J]. Nature Communications, 2022, 13(1): 7007.) added PEG-20000 to improve the viscosity of the system, so that the microsphere array assembled by electric field induction could still maintain the structural color after the pressure was removed, realizing the double stable state characteristics. However, the increase in viscosity is not conducive to the rapid assembly and disassembly of microspheres under electric field, reducing the electric response sensitivity. Further, the introduction of low dielectric constant aniline weakens the shielding effect of the medium on the external electric field, improving the electric response sensitivity and the color change range (Bao G, Yu W, Fu Q, et al. Low-voltage and wide-tuning-range SiO2 / aniline electrically responsive photonic crystal fabricated by solvent assisted charge separation [J]. Journal of Materials Chemistry C, 2023, 11: 3513-3520.). In addition, low-voltage driving significantly reduces energy consumption. At present, the electrochromism of liquid photonic crystal system has the advantages of low driving voltage, wide color change range and low energy consumption through continuous optimization. The color change function is achieved by electrophoresis of charged microspheres in liquid electrolyte under external electric field.Liquid media also face the risk of easy leakage, which also limits their further application.
[0005] Therefore, researchers have tried to achieve electrochromism of photonic crystals in non-liquid media. For example, Park et al. (Chang H K, Park J. Flexible All-Solid-State Electrically Tunable Photonic Crystals [J]. Advanced Optical Materials, 2018, 6, 1800792) combined a full solid-state dielectric elastomer with a PS opal photonic crystal, and used the shrinkage of the dielectric elastomer under an electric field to change the lattice spacing, achieving electrochromism. However, the driving voltage required for the deformation of the dielectric elastomer is as high as kV level, and the application scenario is limited. In order to drive color change at low voltage, the strategy of combining electrochemical redox active materials with photonic crystals has been widely studied. For example, Yang et al. (Hsieh C-H, Lin F-T, Lin K-Y A, et al. Assembly of Nanometer-Sized Hollow Sphere Colloidal Crystals for Applications as Tunable Photonic Materials [J]. ACS Applied Nano Materials, 2022, 5, 15855-15864.) combined a conductive polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) with hollow SiO2 opal to prepare a PEDOT:PSS photonic crystal. The lattice spacing was changed by the osmotic swelling of the electrolyte permeating into the PEDOT:PSS with electron injection, and the structural color red shift was achieved at a low voltage of 1 V. In addition, the combination of conductive polymers such as polypyrrole (Xu L, Wang J, Song Y, et al. electrically-tunable-polypyrrole-inverse-opals-with-switchable-stopband-conductivity-and-wettability [J]. Chemistry of Materials, 2008, 20, 3554-3556.) and polyaniline with photonic crystals also achieved low-voltage-driven structural color change. However, the filling of electrolyte solution is still faced with the risk of leakage during the assembly of electrochromic devices. And the diffusion of ions in the electrolyte to the polymer network requires a certain time, resulting in an undesirable response time.
[0006] Therefore, it is still a challenge to prepare a low-voltage driven photonic crystal electrochromic device without additional liquid electrolyte. SUMMARY
[0007] The present application aims to overcome the above-mentioned defects in the prior art, and provides a ferrocenyl polyacrylate photonic gel electrochromic device and a preparation method and application thereof. The gel electrolyte is prepared by in-situ photopolymerization of acrylate derivatives containing ferrocene groups and acrylate crosslinking agents in an electrolyte solution, and is compounded with opal photonic crystals to construct an electrochromic photonic crystal. The gel electrolyte has the characteristics of liquid electrolyte ion transmission and the non-flowing advantage of solid-state system, effectively reducing the risk of electrolyte leakage. In addition, through the reversible electrochemical transformation of the ferrocene groups grafted in the gel network between the neutral state and the oxidized state, the reversible swelling of the gel network is induced, and the lattice spacing is changed, finally realizing the low-voltage driven reversible structural color change. The ferrocenyl polyacrylate photonic gel electrochromic device prepared by the present application has the characteristics of low-voltage reversible color change, and the design of the gel electrolyte avoids the risk of liquid electrolyte flow and leakage, providing a new idea for the design of electrochromic devices based on photonic crystal structural color.
[0008] To achieve the above-mentioned purpose, the technical solutions of the present application are as follows: A ferrocenyl polyacrylate photonic gel electrochromic device, as shown in Figure 1 The electrochromic device is a sandwich structure, specifically comprising a bottom layer, a top layer and an intermediate layer. The bottom layer and the top layer are located on the upper and lower sides of the intermediate layer, respectively. The bottom layer and the top layer are transparent electrode layers. The intermediate layer is a photonic gel layer, which is composed of opal photonic crystals and ferrocenyl polyacrylate gel. The ferrocenyl polyacrylate gel is obtained by in-situ photopolymerization of acrylate derivatives containing ferrocene groups, acrylate crosslinking agents and photoinitiators in an electrolyte solution.
[0009] Optionally, the ferrocenyl polyacrylate gel includes 15% to 35% of acrylate derivatives containing ferrocene groups, 10% to 20% of acrylate crosslinking agents, 50% to 70% of electrolyte solution and 1% to 10% of photoinitiator by mass fraction.
[0010] Optionally, the protein photonic crystal is constructed by at least one of polystyrene microspheres, polymethyl methacrylate microspheres, poly(styrene-methyl methacrylate) microspheres, poly(styrene-methyl methacrylate-acrylic acid) microspheres, poly(styrene-methyl methacrylate-butyl acrylate) microspheres, silica microspheres, cerium dioxide microspheres, titanium dioxide microspheres, and silica-coated polystyrene microspheres with a particle size of 150-220 nm (preferably 160-210 nm, more preferably 175-190 nm).
[0011] Optionally, the acrylate derivative containing ferrocene group is one of the following structures: wherein n is an integer selected from 0-2, and R is selected from -H or -CH3.
[0012] wherein n is an integer selected from 1-5, and R is selected from -H or -CH3.
[0013] wherein n is an integer selected from 1-4, and R is selected from -H or -CH3.
[0014] wherein n is an integer selected from 1-5, and R is selected from -H or -CH3.
[0015] Optionally, the electrolyte solution has a lithium salt as a solute and a carbonate organic solvent as a solvent.
[0016] Optionally, the lithium salt has a molar concentration of 0.1-2 M.
[0017] Optionally, the carbonate organic solvent includes at least one of vinyl carbonate, propylene carbonate, dimethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate. Preferably, the carbonate organic solvent includes at least one of vinyl carbonate, propylene carbonate, and dimethyl carbonate.
[0018] Optionally, the lithium salt includes one of lithium bis(trifluoromethane)sulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium bis(fluorosulfonyl)imide, and lithium trifluoromethanesulfonate. Preferably, the lithium salt is lithium bis(trifluoromethane)sulfonimide or lithium hexafluorophosphate.
[0019] Optionally, the acrylate crosslinking agent includes at least one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. Preferably, the acrylate crosslinking agent includes at least one of polyethylene glycol diacrylate (200), polyethylene glycol diacrylate (400), polyethylene glycol diacrylate (600), and ethoxylated trimethylolpropane triacrylate (428).
[0020] Optionally, the material of the transparent electrode layer is selected from at least one of indium tin oxide (ITO) conductive glass, fluorine-doped tin oxide (FTO) conductive glass, conductive polymer film and metal mesh transparent electrode.
[0021] The application further discloses a preparation method of the ferrocenyl polyacrylate photonic gel electrochromic device. (1) preparing a protein photonic crystal on the surface of the bottom transparent electrode through a dip-coating method, then fixing a double-sided tape as a spacing layer along the edge of the photonic crystal, and finally covering a top transparent electrode and closely adhering to the double-sided tape to form a sandwich structure; (2) uniformly mixing an acrylate derivative containing a ferrocene group, an acrylate crosslinking agent, an electrolyte solution and a photoinitiator to prepare a precursor solution; (3) pouring the precursor solution into the sandwich structure in step (1), and curing for 5-10 min through ultraviolet light to form a photonic crystal gel layer between the bottom layer and the top layer, so that the ferrocenyl polyacrylate photonic gel electrochromic device is obtained.
[0022] Specifically, the whole process is operated at room temperature, the conditions are mild, the operation steps are simple, and the electrochromic device can be obtained after curing without additional assembly steps. The application has wide applicability.
[0023] Optionally, the dip-coating temperature is 60 ºC, and the cycle number is 1.
[0024] Optionally, the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone (907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone (369), phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (819), benzoin dimethyl ether and benzoin ethyl ether.
[0025] Optionally, the mass fraction of the photoinitiator in the precursor solution is 1%-10%.
[0026] The application further discloses application of the ferrocenyl polyacrylate photonic gel electrochromic device in preparation of a color-changing element.
[0027] Optionally, the ferrocenyl polyacrylate photonic gel electrochromic device is applied in the fields of intelligent display, flexible electronics and information coding.
[0028] The application has the following beneficial effects: The application uses a ferrocenyl polyacrylate gel as a building material, is combined with a protein photonic crystal, and constructs a photonic crystal gel between two transparent electrodes. When a positive voltage is applied, that is, the positive electrode of an external power source is connected to the transparent electrode close to the photonic crystal, the ferrocenyl groups on the photonic crystal gel network are oxidized into positively charged ferrocenyl ions by losing electrons, in order to maintain electrical neutrality, the negative ions and solvents in the gel migrate to the vicinity of the positive electrode, causing the gel network near the positive electrode to swell, thereby increasing the lattice spacing of the photonic crystal and causing the structural color to red shift. As the positive voltage increases, the number of oxidized ferrocenyl groups in the gel network increases, and the degree of red shift of the structural color also increases. When a reverse voltage is applied, that is, the negative electrode of the external power source is connected to the transparent electrode close to the photonic crystal, the ferrocenyl positive ions on the gel network are reduced into neutral ferrocenyl groups by obtaining electrons, and at the same time, the negative ions and solvents paired with the ferrocenyl positive ions migrate away from the vicinity of the negative electrode, causing the gel network near the negative electrode to shrink, thereby reducing the lattice spacing of the photonic crystal and causing the structural color to blue shift and recover. The photonic crystal gel electrochromic device prepared by the application not only has the characteristics of reversible color change at low driving voltage. In addition, the design of the gel electrolyte does not need to fill liquid electrolyte, avoiding the risk of liquid leakage. The ferrocenyl polyacrylate photonic crystal gel electrochromic device of the application has wide application prospects in the fields of intelligent display, flexible electronics, information coding and the like. At the same time, the preparation process of the application is simple and the conditions are mild. BRIEF DESCRIPTION OF DRAWINGS
[0029] Figure 1 It is a structural schematic diagram of the ferrocenyl polyacrylate photonic gel electrochromic device in embodiment 1.
[0030] Figure 2 It is a preparation flowchart of the ferrocenyl polyacrylate photonic gel electrochromic device in embodiment 1.
[0031] Figure 3 The polystyrene opal photonic crystal template with a particle size of ~177 nm prepared by dip-coating method in Examples 1 and 4-10 (a) and its reflection spectrum in the normal direction (b), the inset is a digital photo of the opal photonic crystal template, showing a light purple structural color, and the maximum reflection peak is located at 409 nm.
[0032] Figure 4 The molecular structure of ferrocene methacrylate and its nuclear magnetic resonance spectrum in Example 1.
[0033] Figure 5 The color changing process digital photos (a) and its corresponding reflection spectrum (b) of the ferrocene-based polyacrylate photonic gel electrochromic device prepared in Example 1 under different positive voltages, with the increase of voltage, the structural color gradually red-shifts from blue-purple to cyan, green, and finally to yellow-green, the scale of the digital photo is 1 cm.
[0034] Figure 6 The color recovery process digital photos (a) and its corresponding reflection spectrum (b) of the ferrocene-based polyacrylate photonic gel electrochromic device prepared in Example 1 under-2.5 V reverse voltage, with the extension of action time, the structural color gradually blue-shifts from yellow-green to green, cyan, and finally recovers to blue-purple, the scale of the digital photo is 1 cm. DETAILED DESCRIPTION
[0035] The application will be further described in conjunction with specific embodiments, but not in any way limit the application.
[0036] The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified.
[0037] Example 1 A preparation method of a ferrocene-based polyacrylate photonic gel electrochromic device, comprising the following steps: (1) Constructing an opal photonic crystal of polystyrene microspheres with a particle size of ~177 nm on the surface of the bottom ITO glass by dip-coating method, the dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided adhesive tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top ITO glass and tightly adhere to the double-sided adhesive tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0038] (2) Ferrocenyl methacrylate, polyethylene glycol diacrylate (600), 1M lithium bis(trifluoromethane)sulfonimide in propylene carbonate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator were mixed in a mass ratio of 15:10:70:5 and ultrasonically dispersed to obtain a precursor solution.
[0039] (3) The precursor solution was injected into the gap of the "sandwich" structure, and ultraviolet light was used for curing for 5 min to obtain a photonic gel electrochromic device.
[0040] Figure 1 It is a structural schematic diagram of the ferrocenyl polyacrylate photonic gel electrochromic device in this embodiment, and is also applicable to all examples.
[0041] Figure 2 It is a preparation flowchart of the ferrocenyl polyacrylate photonic crystal gel electrochromic device in this embodiment, and is also applicable to all examples.
[0042] Figure 3 It is a polystyrene microsphere opal photonic crystal template with a particle size of ~177 nm prepared by the dip-coating method in this embodiment (a) and its reflection spectrum in the normal direction (b), and the inset is a digital photo of the opal photonic crystal template, which presents a light purple structural color, and the maximum reflection peak is located at 409 nm.
[0043] Figure 4 It is the molecular structure of ferrocenyl methacrylate and its nuclear magnetic resonance spectrum in this embodiment.
[0044] Figure 5 It is a digital photo of the color change process of the ferrocenyl polyacrylate photonic gel electrochromic device prepared in this embodiment under the action of different forward voltages (a) and its corresponding reflection spectrum (b). With the increase of the voltage, the structural color gradually red shifts from blue-violet to cyan, green, and finally to yellow-green. The scale of the digital photo is 1 cm.
[0045] Figure 6 It is a digital photo of the color recovery process of the ferrocenyl polyacrylate photonic gel electrochromic device prepared in this embodiment under the action of a reverse voltage of -2.5 V (a) and its corresponding reflection spectrum (b). With the extension of the action time, the structural color gradually blue shifts from yellow-green to green and cyan, and finally recovers to blue-violet. The scale of the digital photo is 1 cm.
[0046] Example 2 As Figure 2 A ferrocenyl polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) Construct opal photonic crystal of polystyrene microspheres with a particle size of ~ 186 nm on the surface of the bottom layer FTO conductive glass by dip-coating method. The dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top layer ITO glass and tightly adhere to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0047] (2) Mix ferrocene methoxyethyl acrylate, polyethylene glycol diacrylate (600), 1M lithium bis(trifluoromethane) sulfonimide propylene carbonate solution and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator in a mass ratio of 20:10:65:5, and ultrasonic dispersion uniformly as a precursor solution for standby.
[0048] (3) The precursor solution is perfused into the gap of the "sandwich" structure, and ultraviolet light curing for 5 min to obtain a photonic gel electrochromic device.
[0049] Among them, the ferrocene methoxyethyl acrylate (CAS: 1246927-23-0 ) has the following structural formula: .
[0050] Example 3 As Figure 2 , a ferrocene-based polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) Construct opal photonic crystal of polystyrene microspheres with a particle size of ~ 177 nm on the surface of the bottom layer FTO glass by dip-coating method. The dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top layer FTO glass and tightly adhere to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0051] (2) Mix ferrocene methacrylate, polyethylene glycol diacrylate (200), 1.5M lithium hexafluorophosphate propylene carbonate solution and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator in a mass ratio of 15:10:70:5, and ultrasonic dispersion uniformly as a precursor solution for standby.
[0052] (3) The precursor solution is perfused into the gap of the "sandwich" structure, and ultraviolet light curing for 5 min to obtain a photonic gel electrochromic device.
[0053] Example 4 As Figure 2A ferrocenyl polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) Constructing an opal photonic crystal of poly(styrene-methyl methacrylate-butyl acrylate) microspheres with a particle size of ~177 nm on the surface of the bottom ITO glass by dip-coating method. The dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top ITO glass and tightly adhere to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0054] (2) Ferrocene methoxy ethoxy ethyl acrylate, polyethylene glycol diacrylate (600), 0.5 M lithium bis(trifluoromethane) sulfonimide propylene carbonate solution and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (819) photoinitiator are mixed in a mass ratio of 21:14:60:5, and ultrasonic dispersion is used as a precursor solution for standby.
[0055] (3) The precursor solution is perfused into the gap of the "sandwich" structure, and ultraviolet curing is performed for 5 min to obtain a photonic gel electrochromic device.
[0056] Wherein, ferrocene methoxy ethoxy ethyl acrylate (CAS: 1253184-27-8 ) structural formula: .
[0057] Example 5 As Figure 2 A ferrocenyl polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) Constructing an opal photonic crystal of polystyrene microspheres with a particle size of ~177 nm on the surface of the bottom ITO glass by dip-coating method. The dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top ITO glass and tightly adhere to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0058] (2) (Ferrocene methoxy butyl) methyl methacrylate, ethoxylated trimethylolpropane triacrylate (428), 1.2 M lithium tetrafluoroborate propylene carbonate solution and 2-methyl-1-(4-methylthio phenyl)-2-morpholine-1-propanone (907) photoinitiator are mixed in a mass ratio of 27:18:50:5, and ultrasonic dispersion is used as a precursor solution for standby.
[0059] (3) The precursor solution is injected into the gap of the "sandwich" structure, and ultraviolet light is cured for 5 min to obtain a photonic gel electrochromic device.
[0060] wherein the ferrocene methoxybutyl methacrylate (CAS: 1891036-05-7 ) has the following structural formula: .
[0061] Example 6 As Figure 2 , a ferrocene-based polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) A protein photonic crystal of poly(styrene-methyl methacrylate-butyl acrylate) microspheres with a particle size of ~177 nm is constructed on the surface of the bottom ITO glass by dip-coating. The dip-coating temperature is 60 °C, and the cycle number is 1. Then a double-sided tape is fixed along the edge of the photonic crystal as a spacer layer, and finally a top ITO glass is covered and tightly attached to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0062] (2) Ferrocene carbonyl ethoxy acrylate, polyethylene glycol diacrylate (600), 0.8M lithium bisfluorosulfonylimide ethylene carbonate solution and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator are mixed in a mass ratio of 15:20:60:5 and uniformly ultrasonically dispersed as a precursor solution for standby.
[0063] (3) The precursor solution is injected into the gap of the "sandwich" structure, and ultraviolet light is cured for 5 min to obtain a photonic gel electrochromic device.
[0064] wherein the ferrocene carbonyl ethoxy acrylate (CAS: 1188524-25-5 ) has the following structural formula: .
[0065] Example 7 As Figure 2 , a preparation method of a ferrocene-based polyacrylate photonic gel electrochromic device, comprising the following steps: (1) A protein photonic crystal of silica microspheres with a particle size of ~177 nm is constructed on the surface of the bottom metal mesh transparent electrode by dip-coating. The dip-coating temperature is 60 °C, and the cycle number is 1. Then a double-sided tape is fixed along the edge of the photonic crystal as a spacer layer, and finally a top ITO glass is covered and tightly attached to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0066] (2) Ferrocenyl tetraethoxy acrylate, polyethylene glycol diacrylate (200), 0.6 M lithium bis(trifluoromethanesulfonyl)imide in dimethyl carbonate and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (369) photoinitiator were mixed in a mass ratio of 25:10:60:5 and ultrasonically dispersed uniformly as a precursor solution for standby.
[0067] (3) The precursor solution was perfused into the gap of the "sandwich" structure, and ultraviolet light was cured for 5 min to obtain a photonic gel electrochromic device.
[0068] wherein the ferrocenyl tetraethoxy acrylate (CAS: 2504214-32-6 ) has the following structural formula: .
[0069] Example 8 As Figure 2 , a ferrocenyl polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) A protein photonic crystal with polystyrene microspheres with a particle size of ~177 nm was constructed on the surface of the bottom FTO glass by dip-coating. The dip-coating temperature was 60 °C, and the cycle number was 1. Then a double-sided tape was fixed along the edge of the photonic crystal as a spacer layer, and finally a top ITO glass was covered and tightly attached to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure was used to fill the photopolymerization precursor solution.
[0070] (2) (Ferrocenylmethyl) methacrylate, ethoxylated trimethylolpropane triacrylate (428), 1.2 M lithium bis(trifluoromethanesulfonyl)imide in propylene carbonate solution and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator were mixed in a mass ratio of 20:10:65:5 and ultrasonically dispersed uniformly as a precursor solution for standby.
[0071] (3) The precursor solution was perfused into the gap of the "sandwich" structure, and ultraviolet light was cured for 5 min to obtain a photonic gel electrochromic device.
[0072] wherein the (ferrocenylmethyl) methacrylate (CAS: 31566-61-7 ) has the following structural formula: .
[0073] Example 9 As Figure 2 , a ferrocenyl polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) Construct opal photonic crystal of polystyrene microspheres with a particle size of ~177 nm on the surface of the bottom layer of metal mesh transparent electrode by dip-coating method. The dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top layer of ITO glass and tightly adhere to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0074] (2) Mix ferrocenyl carbonyl butoxy acrylate, polyethylene glycol diacrylate (600), 1.2M lithium bis(trifluoromethane)sulfonimide propylene carbonate solution and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator in a mass ratio of 20:10:60:10, and ultrasonic dispersion uniformly as a precursor solution for standby.
[0075] (3) The precursor solution is perfused into the gap of the "sandwich" structure, and ultraviolet light curing for 5 min to obtain a photonic gel electrochromic device.
[0076] Wherein, ferrocenyl carbonyl butoxy acrylate (CAS: 1248355-76-1 ) has the following structural formula: .
[0077] Example 10 As Figure 2 , a ferrocene-based polyacrylate photonic gel electrochromic device and a preparation method thereof, comprising the following steps: (1) Construct opal photonic crystal of poly(styrene-methyl methacrylate-acrylic acid) microspheres with a particle size of ~177 nm on the surface of the bottom layer of FTO glass by dip-coating method. The dip-coating temperature is 60 °C, and the cycle number is 1. Then fix the double-sided tape as a spacer layer along the edge of the photonic crystal in parallel, and finally cover the top layer of conductive polymer film and tightly adhere to the double-sided tape to form a "sandwich" structure for standby. The gap of the "sandwich" structure is used to fill the photopolymerization precursor solution.
[0078] (2) Mix ferrocene methacrylate, polyethylene glycol diacrylate (200), 0.8M lithium bis(trifluoromethane)sulfonimide propylene carbonate solution and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) photoinitiator in a mass ratio of 15:10:70:5, and ultrasonic dispersion uniformly as a precursor solution for standby.
[0079] (3) The precursor solution is perfused into the gap of the "sandwich" structure, and ultraviolet light curing for 5 min to obtain a photonic gel electrochromic device.
[0080] Examples 2-10 have the same effect as Example 1.
[0081] The above embodiments only express several implementation manners of the present application, which are described in a more specific and detailed manner, but cannot be understood as a limitation on the patent application scope. It should be noted that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.
Claims
1. A ferrocenyl polyacrylate photonic gel electrochromic device, characterized in that, The electrochromic device is a sandwich structure, specifically comprising a bottom layer, a top layer and an intermediate layer; the bottom layer and the top layer are respectively located on the upper and lower sides of the intermediate layer; The bottom layer and the top layer are respectively transparent electrode layers; The intermediate layer is a photonic gel layer, which is composed of a protein photonic crystal and a ferrocene-based polyacrylate gel; The ferrocene-based polyacrylate gel is obtained by in-situ photopolymerization of an acrylate derivative containing a ferrocene group, an acrylate crosslinking agent and a photoinitiator in an electrolyte solution.
2. The ferrocenyl polyacrylate photogel electrochromic device according to claim 1, characterized in that, The ferrocene-based polyacrylate gel includes 15% to 35% of the acrylate derivative containing a ferrocene group, 10% to 20% of the acrylate crosslinking agent, 50% to 70% of the electrolyte solution and 1% to 10% of the photoinitiator by mass fraction.
3. The ferrocenyl polyacrylate photogel electrochromic device according to claim 1, characterized in that, The protein photonic crystal is constructed from at least one of polystyrene microspheres with a particle size of 150nm to 220nm, polymethyl methacrylate microspheres, poly(styrene-methyl methacrylate) microspheres, poly(styrene-methyl methacrylate-acrylic acid) microspheres, poly(styrene-methyl methacrylate-butyl acrylate) microspheres, silica microspheres, cerium dioxide microspheres, titanium dioxide microspheres and silica-coated polystyrene microspheres.
4. The ferrocenyl polyacrylate photogel electrochromic device according to claim 1, wherein The acrylate derivative containing a ferrocene group is one of the following structures: wherein n is selected from any integer between 0 and 2, and R is selected from -H or -CH3; wherein n is selected from any integer between 1 and 5, and R is selected from -H or -CH3; wherein n is selected from any integer between 1 and 4, and R is selected from -H or -CH3; wherein n is selected from any integer between 1 and 5, and R is selected from -H or -CH3.
5. The ferrocenyl polyacrylate photogel electrochromic device according to claim 1, wherein The electrolyte solution has lithium salt as solute and carbonic acid ester organic solvent as solvent; The molar concentration of the lithium salt is 0.1M to 2M; The carbonic acid ester organic solvent includes at least one of vinyl carbonate, propylene carbonate, dimethyl carbonate, dimethyl carbonate and methyl ethyl carbonate; The lithium salt includes one of lithium bis(trifluoromethane)sulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium bis(fluorosulfonyl)imide and lithium trifluoromethanesulfonate.
6. The ferrocenyl polyacrylate photogel electrochromic device according to claim 1, wherein The acrylate crosslinking agent includes at least one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate and pentaerythritol tetraacrylate.
7. The ferrocenyl polyacrylate photogel electrochromic device according to claim 1, wherein The material of the transparent electrode layer is selected from at least one of indium tin oxide conductive glass, fluorine-doped tin oxide conductive glass, conductive polymer film and metal mesh transparent electrode.
8. A process for the preparation of a ferrocenyl polyacrylate photonic gel electrochromic device according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: (1) preparing a protein photonic crystal on the surface of the bottom layer transparent electrode by dip coating method, then fixing double-sided adhesive tape as a spacer along the edge of the photonic crystal, and finally covering the top layer transparent electrode and tightly adhering to the double-sided adhesive tape to form a sandwich structure; (2) uniformly mixing the acrylate derivative containing a ferrocene group, the acrylate crosslinking agent, the electrolyte solution and the photoinitiator to prepare a precursor solution; (3) pouring the precursor solution into the sandwich structure in step (1), and curing for 5min to 10min by ultraviolet light to form a photonic crystal gel layer between the bottom layer and the top layer, thereby obtaining the ferrocene-based polyacrylate photonic gel electrochromic device.
9. The production method according to claim 8, characterized by, The photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, benzoin dimethyl ether and benzoin ethyl ether; The mass fraction of the photoinitiator in the precursor liquid is 1% to 10%.
10. Use of a ferrocenyl polyacrylate photogel electrochromic device according to any one of claims 1 to 7 for the preparation of a color-changing element, characterized in that, The electrochromic device transforms from a first colored state to a second colored state, specifically comprising: When a positive voltage is applied, the ferrocene group is oxidized into a ferrocenium cation, and charge balance causes anions to migrate into the photonic gel, triggering swelling effect and increasing lattice spacing, resulting in red shift of structural color; When a reverse voltage is applied, the ferrocenium cation is reduced to neutral ferrocene, and charge balance causes anions to migrate out of the photonic gel, eliminating the swelling effect and reducing the lattice spacing, resulting in blue shift of structural color.