CN114340064A - Flexible transparent heater based on ionic liquid gel and preparation method thereof - Google Patents
Flexible transparent heater based on ionic liquid gel and preparation method thereof Download PDFInfo
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- CN114340064A CN114340064A CN202210195351.7A CN202210195351A CN114340064A CN 114340064 A CN114340064 A CN 114340064A CN 202210195351 A CN202210195351 A CN 202210195351A CN 114340064 A CN114340064 A CN 114340064A
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Abstract
The invention provides a flexible transparent heater based on ionic liquid gel and a preparation method thereof, wherein the transparent heater is formed by assembling the ionic liquid gel, an electrode and an alternating current power supply; the flexible transparent heater is prepared by taking the ionic liquid gel as an ionic conductor and utilizing the ionic liquid gel to rapidly generate Joule heat under the action of alternating current. The ionic liquid gel-based flexible transparent heater provided by the invention has excellent and stable force, light, electricity and thermal properties, such as transmittance of more than 90%, pressure resistance of more than 130V, temperature resistance of-100-500 ℃, steady-state temperature of 20-500 ℃ and heating rate of 1-50 ℃/s, and can be uniformly heated in a bending and stretching state, so that the ionic liquid gel-based flexible transparent heater has wide application prospects in the aspects of antifogging and deicing of windows of vehicles, outdoor display screens and the like, and in the aspects of wearable thermal therapy equipment, foldable electronic screens and other flexible electronic devices.
Description
Technical Field
The invention belongs to the technical field of flexible electronics, and particularly relates to a flexible transparent heater based on ionic liquid gel and a preparation method thereof.
Background
The transparent heater is a visual transparent heating device comprising a conductive network, and the heating principle is realized by that current flows through the conductive network to generate joule heat. The first application of a transparent heater was to apply a hard transparent tin oxide conductive coating to the windshield of an aircraft cockpit during world war ii, to address the problem of anti-fogging and de-icing of aircraft flying at high altitudes. Until 1995, rigid transparent conductive oxides (such as indium tin oxide) have been the most widely used conductive material in the field of transparent heaters. At present, a rigid transparent heater is widely applied to the aspects of antifogging and deicing of vehicle windows, outdoor display screens and the like, but cannot meet the requirements of wearable thermotherapy equipment, foldable electronic screens and other new-generation flexible electronic devices. In recent decades, flexible transparent heaters based on novel conductive materials such as carbon nanotubes, graphene, silver nanowires, and conductive polymers have been developed. The flexible transparent heater is mainly prepared by a composite design strategy of a conductive material and a flexible polymer matrix, which inevitably brings about three serious common problems: (1) the increase in the content of the conductive component reduces transparency while improving conductivity; (2) the heater performance is reduced due to the uneven distribution of the conductive components and the local hot spots generated by the joints; (3) poor interfacial adhesion between the conductive component and the polymeric matrix reduces the stability of the heater under cyclic force thermal loads.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the present invention provides a flexible transparent heater based on an ionic liquid gel and a method for preparing the same, which is intended to solve at least one of the three problems.
In order to achieve the purpose, the invention adopts the technical scheme that:
a flexible transparent heater based on ionic liquid gel is assembled by the ionic liquid gel, electrodes and an alternating current power supply; the ionic liquid gel is used as an ionic conductor, the electrodes are arranged at two ends of the ionic conductor, and the electrodes are electrically connected with the alternating current power supply to form a closed loop. The flexible transparent heater has the transmittance of more than 90 percent, the pressure resistance of more than 130V, the temperature resistance of-100-500 ℃, the steady-state temperature of 20-500 ℃ and the heating rate of 1-50 ℃/s, and can be uniformly heated in a bending and stretching state.
In one embodiment, the material of the electrodes may be graphite, a conductive metal, or an alloy thereof.
In one embodiment, the flexible transparent heater is used for anti-fog and de-icing of vehicle windows or outdoor displays.
In one embodiment, the flexible transparent heater is used for a heating component of a wearable thermal therapy device or a foldable electronic screen.
The invention also provides a preparation method of the flexible transparent heater based on the ionic liquid gel, which comprises the following steps:
(1) preparing ionic liquid gel, cutting into a required shape, and attaching electrodes at two ends to form tight adhesion;
(2) and connecting the electrode with an alternating current power supply to form a closed loop.
In one embodiment, the preparation method of the ionic liquid gel comprises the following steps: adding a monomer, a cross-linking agent and an initiator into the ionic liquid, and uniformly mixing to obtain a precursor solution; and injecting the precursor solution into a mold, and carrying out chemical reaction to obtain the ionic liquid gel.
In one embodiment, the monomer is one or more of acrylics, acrylamides, acrylates; the ionic liquid is one or more of imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid and piperidine ionic liquid.
In one embodiment, in the precursor solution, the mass fraction of the monomer is 10% to 60%, the mass fraction of the cross-linking agent is 0% to 5%, the mass fraction of the initiator is 0.001% to 1%, and the balance is the ionic liquid.
In one embodiment, the cut shape of the ionic liquid gel can be a cuboid, a cylinder, or the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention develops a novel ionic flexible transparent heater based on the technical route of generating Joule heat by ionic conduction under the action of ionic liquid gel and alternating current, and provides a brand new material selection and heating principle for the traditional electronic flexible transparent heater.
(2) The ionic flexible transparent heater provided by the invention simultaneously solves the three technical difficulties of transparency-conductivity conflict, uneven heating, poor interface bonding and the like of the traditional electronic flexible transparent heater.
(3) The ionic liquid gel-based flexible transparent heater provided by the invention has excellent and stable force, light, electricity and thermal properties, such as transmittance of more than 98%, pressure resistance of 130V-180V, temperature resistance of-100-500 ℃, steady temperature of 20-500 ℃ and heating rate of 1-50 ℃/s, and can be uniformly heated in bending and stretching states.
Drawings
Fig. 1 is a heating principle of a conventional electronic type flexible transparent heater.
Fig. 2 is a heating principle of the ionic flexible transparent heater of the present invention.
Fig. 3 is a schematic diagram of the heating performance of an ionic liquid gel-based flexible transparent heater.
Fig. 4 is a schematic view of uniform heating of an ionic liquid gel-based flexible transparent heater in a deformed state.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The current transparent heaters all adopt a technical route of generating joule heat by electronic conduction under the action of direct current, as shown in fig. 1. Under the direct current power supply or constant current, the heater heats the object by using the heat energy generated by the Joule effect of the current flowing through the conductive polymer composite material, the electronic conductor components are generally indium tin oxide, nano silver wires, carbon nano tubes or graphene, when the current passes through the electronic conductors, the current does work to consume the electric energy and generate heat, and at the moment, the current carrier is the electron and makes directional motion in the electric field. However, these electronic conductors have disadvantages in transparency, heating performance and heating stability.
Under the action of alternating current, the ionic conduction can also generate Joule heat, and can be considered as a brand new alternative technical route. The ionic liquid gel is a novel ionic conductive material which takes ionic liquid as a dispersion medium and has a three-dimensional cross-linked network structure, and has the advantages of high stretchability of a polymer network, high transparency, high ionic conductivity, high thermochemical stability, fire resistance, non-volatility and the like of the ionic liquid. The polymer network in the ionic liquid gel and the ionic liquid have good compatibility on the molecular scale, and the three defects of the traditional electronic transparent heater are hopefully solved.
Therefore, based on the heating principle that joule heat is generated by ionic conduction under the action of ionic liquid gel and alternating current, the invention hopes to develop a brand-new ionic flexible transparent heater.
Referring to fig. 2, the flexible transparent heater of the present invention is assembled by an ionic liquid gel, electrodes and an ac power supply, wherein the ionic liquid gel is used as an ionic conductor, the electrodes are disposed at two ends of the ionic conductor, and the electrodes are electrically connected with the ac power supply to form a closed loop.
The ionic liquid gel is an ionic conductor formed by swelling a three-dimensional polymer network by a large amount of ionic liquid, wherein the content of the ionic liquid consisting of anions and cations is more than 70 percent, when sinusoidal alternating voltage is applied to the ionic liquid gel-based transparent heater, current carriers are ions, and the anions and the cations move back and forth in the gel network, collide and rub to generate heat to heat an object due to the periodic change of the alternating voltage.
The ionic flexible transparent heater has excellent and stable force, light, electricity and thermal properties. Testing the light transmittance of the heater in the visible wavelength range (400-; the voltage resistance value of the ionic flexible transparent heater under different frequencies is more than 100V, wherein the alternating current power supply is provided by a waveform generator and a high-voltage amplifier, and the current value is measured by a high-precision digital multimeter. Testing the temperature application range of the ionic liquid gel by using a thermogravimetric analyzer and a differential scanning calorimetry to obtain the temperature resistance of the ionic flexible transparent heater of-100-500 ℃; testing the heating performance of the ionic flexible transparent heater, which increases with the heating time, under different voltages by using an infrared measurement imager to obtain the ionic flexible transparent heater with the steady-state temperature of 20-500 ℃; and the heating rate of the ionic flexible transparent heater is 1-50 ℃/s by calculating the temperature of the heater increased in unit time; it was also observed that the ionic flexible transparent heater could be uniformly heated in both the bent and stretched states. Therefore, the ionic flexible transparent heater has wide application prospect in the aspects of antifogging and deicing of vehicle windows, outdoor display screens and the like and in the aspects of flexible electronic devices such as wearable thermotherapy equipment and foldable electronic screens.
Alternatively, in the present invention, the material of the electrode is graphite, a conductive metal such as silver, copper, gold, platinum, aluminum, tungsten, nickel, or iron, or an alloy thereof.
The ionic liquid gel is prepared by the following method:
(1) adding a monomer, a cross-linking agent and an initiator into the ionic liquid, and uniformly mixing to obtain a precursor solution. Wherein, the monomer can be one or more of acrylic acid, acrylamide, acrylate and the like; the ionic liquid can be one or more of imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid, piperidine ionic liquid and the like; in the precursor solution, the mass fraction of the monomer is 10-60%, the mass fraction of the cross-linking agent is 0-5%, and the mass fraction of the initiator is 0.001-1%.
(2) And injecting the precursor solution into a mold, and carrying out chemical reaction to obtain the ionic liquid gel.
After the ionic liquid gel is obtained, the ionic liquid gel is cut into a specific shape, such as a rectangular parallelepiped or a cylinder, and the size and shape of the ionic liquid gel can be adjusted arbitrarily according to needs. Then, electrodes are attached to the two ends of the conductive film to form tight adhesion; and finally, connecting the electrode with an alternating current power supply to form a closed loop, thus obtaining the flexible transparent heater. In order to verify the effect of the technical scheme, the following embodiments are provided:
example 1
A flexible transparent heater based on ionic liquid gel is prepared by the following steps:
(1) adding a monomer (hydroxyethyl acrylate) with the mass fraction of 20% and an initiator (2-hydroxy-2-methyl propiophenone) with the mass fraction of 0.02% into an ionic liquid (1-ethyl-3-methylimidazol ethyl sulfate) and uniformly mixing to obtain a precursor solution;
(2) injecting the precursor solution into a glass mold clamped with a silica gel gasket with the thickness of 2mm, and placing the glass mold under the irradiation of an ultraviolet lamp for free radical polymerization reaction for 4 hours to obtain ionic liquid gel;
(3) cutting the ionic liquid gel into a rectangular size of 40mm multiplied by 30mm, respectively covering aluminum sheet electrodes with the size of 40mm multiplied by 10mm at two ends, assembling into an electrode/gel/electrode structure, and heating the gel with the area of 40mm multiplied by 10 mm;
(4) connecting the electrodes at two ends with an alternating current power supply to form a closed loop, and obtaining the ionic liquid gel-based flexible transparent heater.
The prepared flexible transparent heater was tested to have a transmittance of 98% or more, a pressure resistance of 180V (10)4Hz) and a temperature resistance of-50 to 250 ℃, and the flexible transparent heater has different heating properties at different voltages. It can be seen from figure 3 that the higher the applied voltage, the faster the heater rate, the shorter the time required to reach the steady state temperature, and the higher its steady state temperature, at 104The steady state temperature of the heater at Hz and 150V can be as high as 180 ℃ with a heating rate of 3.6 ℃/s. In addition, the flexible transparent heater maintains uniform heating performance in bent and stretched states.
Example 2
A flexible transparent heater based on ionic liquid gel is prepared by the following steps:
(1) adding a monomer (acrylic acid) with the mass fraction of 30%, a cross-linking agent (N, N' -methylene bisacrylamide) with the mass fraction of 1% and an initiator (ammonium persulfate) with the mass fraction of 0.001% into an ionic liquid (1-butyl-3-methylimidazole triflate) and uniformly mixing to obtain a precursor solution;
(2) injecting the precursor solution into a glass mold clamped with a silica gel gasket with the thickness of 2mm, and placing the glass mold in a thermostat for heating and reacting for 4 hours to obtain ionic liquid gel;
(3) cutting the ionic liquid gel into a rectangular size of 40mm multiplied by 30mm, respectively covering copper metal thin sheet electrodes with the size of 40mm multiplied by 10mm at two ends to assemble an electrode/gel/electrode structure, wherein the heatable gel area is 40mm multiplied by 10 mm;
(4) connecting the electrodes at two ends with an alternating current power supply to form a closed loop, and obtaining the ionic liquid gel-based flexible transparent heater.
The prepared flexible transparent heater was tested and had a transmittance of 97% or more and a pressure resistance of 150V (10)3Hz), -temperature resistance of 50-400 ℃, high steady state temperature of 150 ℃ and heating rate of 5 ℃/s (10℃/s)3Hz and 100V), and the heater shown in fig. 4 can uniformly heat the performance in a bent and 300% stretched state, and the like.
In further embodiments, the monomer is not limited to hydroxyethyl acrylate and acrylic acid, and may be one or a combination of at least two of acrylic acids, acrylamides, acrylates, and the like. The ionic liquid can also be one or the combination of at least two of imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid, piperidine ionic liquid and the like. The electrode material may be graphite, silver, copper, gold, platinum, aluminum, tungsten, nickel, iron, alloys, and the like.
The flexible transparent heater obtained by the invention has excellent and stable force, optical, electric and thermal properties, and one feasible application is antifogging and deicing of outdoor glass or similar components, wherein the outdoor glass or similar components can be windows of vehicles such as automobiles and trains, and can also be outer screens of display components such as display screens. By arranging the flexible transparent heater of the invention on the interlayer or the outer surface of the component, the antifogging and deicing can be realized by slight heating, obviously, the flexible transparent heater can be assisted by a fan and other mechanisms.
Another possible use is the heating of flexible devices, such as wearable thermo-therapeutic devices, foldable electronic screens, etc., which can provide the wearer with a long-term comfortable wearing experience and information acquisition by using the flexible transparent heater of the invention as the heating element of such devices.
The applicant states that the present invention is illustrated by the above examples of the ionic liquid gel-based flexible transparent heater and the method for preparing the same, but the present invention is not limited to the above detailed method, i.e. it does not mean that the present invention must be implemented by the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A flexible transparent heater based on ionic liquid gel is characterized by being formed by assembling the ionic liquid gel, electrodes and an alternating current power supply; the ionic liquid gel is used as an ionic conductor, the electrodes are arranged at two ends of the ionic conductor, and the electrodes are electrically connected with the alternating current power supply to form a closed loop.
2. The flexible transparent heating based on ionic liquid gel according to claim 1, characterized in that the material of the electrodes is graphite, conductive metal or alloys thereof.
3. The flexible transparent heater based on ionic liquid gel according to claim 1, characterized in that the flexible transparent heater has a transmittance of 90% or more, a pressure resistance of 130V or more, a temperature resistance of-100 ℃ to 500 ℃, a steady-state temperature of 20 ℃ to 500 ℃, a heating rate of 1 ℃/s to 50 ℃/s, and maintains uniform heating in a bent and stretched state.
4. The flexible transparent ionic liquid gel-based heater of claim 1, wherein the flexible transparent heater is used for anti-fog and de-icing of vehicle windows or outdoor displays.
5. The flexible transparent ionic liquid gel-based heater of claim 1, wherein the flexible transparent heater is used for a heating component of a wearable thermal therapy device or a foldable electronic screen.
6. The method for preparing the flexible transparent heater based on the ionic liquid gel as claimed in claim 1, which comprises the following steps:
(1) preparing ionic liquid gel, cutting into a required shape, and attaching electrodes at two ends to form tight adhesion;
(2) and connecting the electrode with an alternating current power supply to form a closed loop.
7. The preparation method of claim 6, wherein the ionic liquid gel is prepared by the following steps: adding a monomer, a cross-linking agent and an initiator into the ionic liquid, and uniformly mixing to obtain a precursor solution; and injecting the precursor solution into a mold, and carrying out chemical reaction to obtain the ionic liquid gel.
8. The preparation method according to claim 7, wherein the monomer is one or more of acrylic acid, acrylamide, and acrylate; the ionic liquid is one or more of imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid and piperidine ionic liquid.
9. The preparation method according to claim 7 or 8, characterized in that in the precursor solution, the mass fraction of the monomer is 10-60%, the mass fraction of the crosslinking agent is 0-5%, the mass fraction of the initiator is 0.001-1%, and the balance is the ionic liquid.
10. The preparation method according to claim 6, wherein the ionic liquid gel is cut into a rectangular parallelepiped or cylindrical shape.
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| CN115652633A (en) * | 2022-09-07 | 2023-01-31 | 南京工业大学 | Ion type breathable intelligent textile fabric and preparation method and application thereof |
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| CN111542138A (en) * | 2020-05-08 | 2020-08-14 | 香港中文大学（深圳） | Electroheating method and application of ion conductor |
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| CN111542138A (en) * | 2020-05-08 | 2020-08-14 | 香港中文大学（深圳） | Electroheating method and application of ion conductor |
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| CN115652633A (en) * | 2022-09-07 | 2023-01-31 | 南京工业大学 | Ion type breathable intelligent textile fabric and preparation method and application thereof |
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