CN112521555A - Antifreeze heat-resistant hydrogel electrolyte for electrochromic device - Google Patents
Antifreeze heat-resistant hydrogel electrolyte for electrochromic device Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1506—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
- G02F1/1508—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
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Abstract
The invention relates to an antifreeze heat-resistant hydrogel electrolyte for an electrochromic device. Deionized water is used as a solvent, carboxylated chitosan and acrylamide are used as main monomers, N-methylene bisacrylamide is used as a cross-linking agent, lithium salt is used as an electrolyte, polyethylene glycol and glycerol are used as additives, 2-hydroxy-2-methyl-1-phenyl-1-acetone is used as a photoinitiator, free radical polymerization is carried out under the irradiation of an ultraviolet lamp, and the hydrogel electrolyte with good freezing resistance and heat resistance is prepared by adjusting the adding amount of the polyethylene glycol and the glycerol. The hydrogel electrolyte is further used for preparing an electrochromic device with a sandwich structure, the device has a wide working temperature range, shows good circulation stability in a temperature range of-40-60 ℃, and is suitable for preparing flexible devices. The novel hydrogel electrolyte provided by the invention has the advantages of simple preparation method, cheap and easily-obtained raw materials, high ionic conductivity, high transparency, high stability, excellent high and low temperature tolerance and wide application prospect.
Description
Technical Field
The invention relates to preparation and application of a novel hydrogel electrolyte, in particular to preparation of an antifreeze heat-resistant carboxylated chitosan modified polyacrylamide hydrogel electrolyte, and belongs to the technical field of electrochromism.
Background
Electrochromic phenomena have received much attention since their discovery in 1969, with potential applications in display and light emission and transmission management. Under the background of the era of advocating energy conservation and emission reduction, the electrochromic intelligent window has wide application prospect in energy-saving buildings. Based on mechanisms such as electrochemical oxidation reduction and ion extraction, scientists design and develop a series of excellent electrochromic materials and show excellent electrochromic properties. In addition, in order to obtain better device performance to meet the practical application requirements, a solid electrolyte is usually introduced to make a sandwich structure device. In the sandwich electrochromic device, the solid electrolyte has more environmental sensitivity due to the diversified components and complex interaction of chemical bonds, physical bonds and the like, so that the cycling stability of the device is reduced. Therefore, the development of a solid electrolyte having excellent properties is important for promoting the practical use of an electrochromic device.
The hydrogel is a functional polymer material with a three-dimensional network structure, which is formed by hydrophilic polymers and takes water as a dispersion medium. The highly crosslinked polymer network provides the hydrogel with excellent mechanical properties and deformability. Since the hydrogel contains a large number of free water molecules, the hydrogel generally has high ionic conductivity and is widely applied to electrochromic devices.
As a photoelectric device operating in indoor and outdoor light radiation environments, an electrochromic device must have strong environmental tolerance to ensure the applicability and stability of the device. Such as seasonal temperature changes, regional air temperature differences, etc. Therefore, the high and low temperature operation performance of the hydrogel electrolyte is an important point that the electrochromic device cannot escape. However, no relevant electrochromic research case is reported at present. Moreover, due to the existence of free water in the hydrogel, the possibility of low-temperature icing and high-temperature gasification dehydration generally exists, and the performance of the device is greatly reduced. Therefore, the development of the antifreezing heat-resistant hydrogel electrolyte has very important significance for promoting the practical application of the electrochromic device.
Disclosure of Invention
Aiming at the influence of the environment on the electrolyte in the electrochromic device, the invention provides a preparation method of an antifreeze heat-resistant hydrogel electrolyte for the electrochromic device.
Another objective of the present invention is to provide a simple method for manufacturing an electrochromic device, which comprises fixing a hollow partition between two electrodes with 3M double-sided adhesive tape, filling with a hydrogel solution, and curing the gel solution inside the device under the irradiation of an ultraviolet lamp; not only can ensure that the electrolyte layer is very thin, but also can prolong the service life of the device.
An antifreeze heat-resistant hydrogel electrolyte for an electrochromic device and a device preparation method comprise the following steps:
(1) preparation of hydrogel electrolyte: under the condition of room temperature, adding lithium salt into deionized water, fully stirring and dissolving to obtain a salt solution, sequentially adding a main monomer, a photoinitiator, a cross-linking agent and an additive, and stirring and dissolving to obtain a hydrogel solution;
(2) preparing an electrode material: depositing Prussian blue and poly-viologen films on the conductive glass by using a constant current deposition method and a constant voltage electrodeposition method, and respectively using the Prussian blue and the poly-viologen films as an anode and a cathode of the electrochromic device;
(3) manufacturing an electrochromic device: and (3) fixing a hollow partition groove between the two electrodes prepared in the step (2) by using a 3M double faced adhesive tape, dripping the hydrogel solution prepared in the step (1), and irradiating under an ultraviolet lamp to solidify the hydrogel to obtain the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreezing heat-resistant hydrogel.
In the step (1), the lithium salt is one of lithium chloride, lithium bromide or lithium tetrafluoroborate, and the concentration is 1 mol/L.
In the step (1), the main monomers are carboxylated chitosan and acrylamide, and the mass ratio of the carboxylated chitosan to the acrylamide is 1: 1-3.
In the step (1), the cross-linking agent is N, N-methylene bisacrylamide, and accounts for 1-10% of the mass of the acrylamide.
The photoinitiator in the step (1) is 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP), and the addition amount of the photoinitiator is 10-50 mu L.
The additives in the step (1) are polyethylene glycol and glycerol; polyethylene glycol is used as an interpenetrating network chain segment, and the mass fraction of the polyethylene glycol is 0-25% of the mass of the carboxylated chitosan; the glycerol is used as a temperature-resistant solvent, and the volume fraction of the glycerol is 0-60%.
In the electrodeposition process in the step (2), ITO conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode.
The invention has the following advantages:
the method for preparing the hydrogel electrolyte is simple and convenient, the hydrogel has frost resistance and heat resistance, can keep complete morphological characteristics and high ionic conductivity within the range of-40-60 ℃, and a device based on the hydrogel also has excellent electrochromic performance within the range of-40-60 ℃, and has good application prospect in the fields of intelligent electrochromic windows and flexible electronic equipment.
Drawings
Fig. 1 is a structural view of an electrochromic device.
FIG. 2 is a photograph showing the appearance of the hydrogel electrolytes of examples 1, 2 and 3 at-40 ℃; the results show that the hydrogel electrolyte can maintain good transparency and flexibility under low temperature conditions.
FIG. 3 shows the ionic conductivities of the hydrogel electrolytes of examples 1, 2 and 3 at room temperature, -40 ℃ and 60 ℃ respectively; as can be seen from the figure, the hydrogel electrolyte can still have better ionic conductivity no matter under the conditions of high temperature or low temperature.
FIG. 4 is a graph of UV absorption spectra and cycling stability at room temperature for an electrochromic device fabricated with the hydrogel of example 1; it can be seen that at the maximum absorption wavelength of 680nm, the transmittance difference of the electrochromic device can still be maintained at 94.8% of the initial state after 1000 cycles.
FIG. 5 is a graph of the cycling stability of an electrochromic device at-40 ℃ and 60 ℃; the result shows that the hydrogel electrolyte has excellent frost resistance and heat resistance, so that the electrochromic device still maintains good cycle stability under extreme conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to the following embodiments.
Example 1
(1) Preparation of hydrogel electrolyte:
adding 0.4g of carboxylated chitosan and 20 mu L of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into 5mL of lithium bromide aqueous solution, and stirring until the mixture is dissolved; 0.8g of acrylamide and 0.04g of N, N-methylene bisacrylamide are weighed and added into the solution, and the solution is continuously stirred for 2 hours; then 0.06g of polyethylene glycol-1000 is added and stirred until the mixture is completely dissolved; finally, adding glycerol with the volume fraction of 50%, and stirring for 30min to obtain a hydrogel solution;
(2) preparing an electrode:
preparing Prussian blue film by constant current deposition method, weighing 0.329g of K3Fe(CN)60.162g of FeCl3Dissolving 1.491g of KCl and 1mol/L of HCl in 100mL of deionized water to obtain an electrodeposition solution, and depositing for 800s under the constant current of 50 muA; preparing the poly-violet thin film by adopting a constant voltage deposition method, and weighing 0.848g of BVBr20.136g KH2PO41.567g of K2HPO4And 3.683g of K4Fe(CN)6Dissolving in 100mL deionized water, and depositing at-0.75V constant voltage until the total charge reaches 150 mC; in the electrodeposition process, ITO conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode;
(3) preparing an electrochromic device:
fixing a hollow partition groove with a certain size and thickness on the ITO conductive glass deposited with the poly-violet fine film by using a 3M double-sided adhesive, dripping the obtained uniform hydrogel solution into the partition groove, then pasting the ITO conductive glass deposited with the Prussian blue film, irradiating for 2min under an ultraviolet lamp to solidify the hydrogel, and obtaining the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreezing heat-resistant hydrogel.
Example 2
(1) Preparation of hydrogel electrolyte:
adding 0.6g of carboxylated chitosan and 30 mu L of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into 5mL of lithium chloride aqueous solution, and stirring until the mixture is dissolved; weighing 1.2g of acrylamide and 0.05g of N, N-methylene bisacrylamide, adding the acrylamide and the N, N-methylene bisacrylamide into the solution, and continuing stirring for 2 hours; then 0.1g of polyethylene glycol-1000 is added and stirred until the mixture is completely dissolved; finally, adding glycerol with the volume fraction of 50%, and uniformly stirring to obtain a hydrogel solution;
(2) the electrodes and electrochromic devices were prepared in the same manner as in example 1.
Example 3
(1) Preparation of hydrogel electrolyte:
adding 0.6g of carboxylated chitosan and 20 mu L of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into 5mL of lithium tetrafluoroborate aqueous solution, and stirring until the mixture is dissolved; weighing 1.2g of acrylamide and 0.05g of N, N-methylene bisacrylamide, adding the acrylamide and the N, N-methylene bisacrylamide into the solution, and continuing stirring for 2 hours; then 0.12g of polyethylene glycol-1000 is added and stirred until the mixture is completely dissolved; finally, adding glycerol with the volume fraction of 50%, and stirring for 30 min;
(2) the electrodes and electrochromic devices were prepared in the same manner as in example 1.
The above-described embodiments are intended to enable those skilled in the art to understand the disclosure of the present invention and to implement the same, and therefore should not be construed as limiting the scope of the present invention, but rather should be construed as covering equivalent variations or modifications within the spirit of the present invention.
Claims (8)
1. An electrochromic device based on carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel is characterized by comprising two layers of ITO electrodes deposited with electrochromic materials and a layer of transparent antifreeze heat-resistant hydrogel electrolyte.
2. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 1, which is characterized by comprising the following steps:
(1) preparation of hydrogel electrolyte: under the condition of room temperature, adding lithium salt into deionized water, fully stirring and dissolving to obtain a lithium salt solution, sequentially adding a main monomer, a photoinitiator, a cross-linking agent and an additive, and stirring and dissolving to obtain a hydrogel solution;
(2) preparing an electrode material: depositing Prussian blue and poly-viologen films on the conductive glass by using a constant current deposition method and a constant voltage electrodeposition method, and respectively using the Prussian blue and the poly-viologen films as an anode and a cathode of the electrochromic device;
(3) manufacturing an electrochromic device: and (3) fixing a hollow partition groove between the two electrodes prepared in the step (2) by using a 3M double faced adhesive tape, dripping the hydrogel solution prepared in the step (1), and irradiating under an ultraviolet lamp to solidify the hydrogel to obtain the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreezing heat-resistant hydrogel.
3. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 2, wherein the lithium salt in the step (1) is one of lithium chloride, lithium bromide or lithium tetrafluoroborate, and the concentration is 1 mol/L.
4. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 2, wherein the main monomers in the step (1) are carboxylated chitosan and acrylamide, and the mass ratio of the carboxylated chitosan to the acrylamide is 1: 1-3.
5. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 2, wherein the crosslinking agent in the step (1) is N, N-methylene bisacrylamide, which accounts for 1-10% of the mass of acrylamide.
6. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 2, wherein the photoinitiator in the step (1) is 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP), and the addition amount is 10-50 μ L.
7. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 2, wherein the additives in the step (1) are polyethylene glycol and glycerol; polyethylene glycol is used as an interpenetrating network chain segment, and the mass fraction of the polyethylene glycol is 0-25% of the mass of the carboxylated chitosan; the glycerol is used as a temperature-resistant solvent, and the volume fraction of the glycerol is 0-60%.
8. The preparation method of the electrochromic device based on the carboxylated chitosan modified polyacrylamide antifreeze heat-resistant hydrogel as claimed in claim 2, wherein in the electrodeposition process in the step (2), ITO (indium tin oxide) conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114109221A (en) * | 2021-11-15 | 2022-03-01 | 中国石油大学(北京) | Energy-saving and power generation integrated intelligent window and preparation thereof |
| CN114109221B (en) * | 2021-11-15 | 2023-02-17 | 中国石油大学(北京) | Energy-saving and power generation integrated intelligent window and preparation thereof |
| CN114430084A (en) * | 2021-12-13 | 2022-05-03 | 中国科学院深圳先进技术研究院 | Flexible zinc-air battery gel electrolyte and preparation method and application thereof |
| CN114859613A (en) * | 2022-01-25 | 2022-08-05 | 吉林大学 | Liquid electrolyte and preparation method thereof, electrochromic device and preparation method thereof |
| WO2023219255A1 (en) * | 2022-05-11 | 2023-11-16 | 전남대학교산학협력단 | Extremotolerant glycerogel, method for manufacturing same, and applied product containing same |
| CN115554447A (en) * | 2022-09-21 | 2023-01-03 | 京东方科技集团股份有限公司 | Smell release film device |
| CN115554447B (en) * | 2022-09-21 | 2024-04-16 | 京东方科技集团股份有限公司 | Odor release film device |
| CN115536578A (en) * | 2022-09-23 | 2022-12-30 | 浙江大学 | Aromatic ester substituted viologen black electrochromic compound and preparation method and application thereof |
| CN115536578B (en) * | 2022-09-23 | 2024-03-29 | 浙江大学 | Aromatic ester substituted viologen black electrochromic compound and preparation method and application thereof |
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