Integrated electrode flexible quasi-solid intelligent thermal control device and preparation method and application thereof

Abstract

The invention provides an integrated electrode flexible quasi-solid intelligent thermal control device and a preparation method and application thereof. The integrated electrode flexible quasi-solid intelligent thermal control device comprises an infrared transparent substrate, an integrated electrochromic layer, a gel electrolyte layer and a counter electrode. The one-dimensional inorganic nano material and the two-dimensional nano sheet are physically compounded to form the conductive electrochromic layer, and a transparent conductive electrode does not need to be used; based on the conductivity and low infrared emissivity of the one-dimensional nanostructure and the two-dimensional nanosheet of the electrochromic material, the prepared electrochromic device has good infrared emissivity regulation and control performance, including high infrared emissivity regulation and control amplitude, high response speed and long cycle life. The problems that in a conventional electrochromic thermal control device, a transparent conductive electrode is not transparent in infrared, and an inorganic material is poor in flexibility, low in response speed, short in cycle life and poor in conductivity are mainly solved.

Description

Technical Field

[0001] The present invention relates to the field of electrochromic intelligent thermal control technology, and in particular to an integrated electrode flexible quasi-solid-state intelligent thermal control device and a preparation method and application thereof. Background Art

[0002] Electrochromic intelligent control refers to the reversible change of the infrared emissivity of the material under the action of external voltage. It has the advantages of a large infrared control range, active temperature control, and high control accuracy. Dynamic temperature adaptive control materials introduce the concepts of adaptability and intelligent control. They can dynamically adjust their own optical properties to respond to external changes, and can dynamically adjust their own performance according to changes in the external environment, thereby achieving more efficient and flexible infrared adaptive camouflage in a wider range of scenarios. Dynamically controlling the infrared characteristics of objects such as human bodies and military equipment to make them the same as the surrounding environment within a specific spectral range to achieve concealment and protection of the target has attracted widespread attention from scientific researchers. In order to achieve this goal, it is necessary to be able to accurately control the infrared radiation of the object itself. According to the Stefan-Boltzmann law, it can be seen that infrared radiation is proportional to the fourth power of its absolute temperature and its own emissivity. Therefore, adaptive thermal camouflage can be achieved by controlling the changes in temperature and emissivity. Electrochromic intelligent thermal control devices have the advantages of low energy consumption, light weight, easy control, and simple structure. They have good application potential in the fields of adaptive infrared camouflage and intelligent thermal control of spacecraft, and have become a research hotspot in the field of dynamic control of infrared radiation.

[0003] For research in the field of dynamic regulation of infrared radiation, the ability to regulate infrared emissivity is very important in thermal radiation regulation, but there are still problems such as poor flexibility, long response time, small infrared regulation range, and short cycle life. At present, the organic and polymer electrochromic thermal control devices studied can show multi-color performance, but in actual application, compared with inorganic electrochromic materials, the photostability, thermal stability, chemical stability and thermal radiation stability of organic materials are all poor. Inorganic electrochromic intelligent thermal control devices have the advantages of good infrared regulation ability, flexibility and cycle stability, and have good application prospects in spacecraft intelligent thermal control.

[0004] Therefore, it is necessary to design an integrated electrode flexible quasi-solid-state intelligent thermal control device to solve the problems of opacity of infrared transparent electrodes and poor flexibility, poor conductivity, slow ion transport and poor cycle stability of inorganic electrochromic materials. Summary of the invention

[0005] In view of this, the present invention proposes an integrated electrode flexible quasi-solid-state intelligent thermal control device, which aims to solve the shortcomings of infrared opacity of the current infrared transparent conductive layer. The traditional molybdenum trioxide inorganic material has the disadvantages of long response time, poor conductivity and poor flexibility, resulting in the problem that the electrochromic intelligent thermal control device based on molybdenum trioxide has a small infrared regulation range and cannot meet the application requirements of existing infrared adaptive camouflage and spacecraft intelligent thermal control. The organic material has poor photostability, thermal stability, chemical stability and thermal radiation stability.

[0006] In one aspect, the present invention provides an integrated electrode flexible quasi-solid-state intelligent thermal control device, comprising:

[0007] An infrared transparent substrate, an integrated electrochromic layer, a gel electrolyte layer and a counter electrode, wherein the infrared transparent substrate, the integrated electrochromic layer, the gel electrolyte layer and the counter electrode are sequentially connected to form an electrode flexible quasi-solid-state intelligent thermal control device;

[0008] The infrared transparent substrate, the integrated electrochromic layer, the gel electrolyte layer and the counter electrode form an integrated structure.

[0009] Furthermore, the integrated electrochromic layer is specifically:

[0010] Inorganic integrated electrochromic layer or organic integrated electrochromic layer;

[0011] Wherein, the inorganic integrated electrochromic layer or the organic integrated electrochromic layer is a one-dimensional and two-dimensional composite material structure;

[0012] The inorganic integrated electrochromic layer is made of molybdenum oxide, tungsten oxide or a new carbon material;

[0013] The material of the organic integrated electrochromic layer is polyaniline, polythiophene, polypyrrole or Prussian blue;

[0014] The thickness of the integrated electrochromic layer is 5 to 10 μm; the sheet resistance of the integrated electrochromic layer is 5 to 50 Ω / square.

[0015] The one-dimensional and two-dimensional composite material is a composite material of molybdenum oxide and MXene;

[0016] Further, the gel electrolyte layer material is a gel electrolyte and an electrolyte solution;

[0017] The electrolyte is an aqueous solution of zinc sulfate;

[0018] The gel electrolyte includes one of a polymer gel electrolyte, a polymer-ceramic gel electrolyte, a mixed solvent gel electrolyte and a polymer-liquid electrolyte;

[0019] The thickness of the gel electrolyte is 50-300 μm.

[0020] Further, the counter electrode comprises one of an activated carbon electrode, a polyaniline electrode, a MXene electrode, a nickel oxide electrode, a Prussian blue electrode and a Zn electrode;

[0021] The thickness of the counter electrode is 1 to 500 μm.

[0022] Further, the infrared transparent substrate comprises at least one of polyethylene (PE), polydimethylsiloxane (PDMS), polycarbonate, polyimide, thermoplastic polyurethane (PU) and a few-layer graphene layer, and the infrared transparent substrate is a flexible film substrate;

[0023] The infrared transparent substrate has a thickness of 1 to 500 μm.

[0024] On the other hand, the present invention proposes a method for preparing an integrated electrode flexible quasi-solid-state intelligent thermal control device, which is characterized by comprising:

[0025] (1) hot pressing and vacuum filtering the integrated electrochromic layer on the infrared transparent substrate to obtain the infrared transparent substrate@integrated electrochromic layer;

[0026] (2) curing the gel electrolyte with ultraviolet light to obtain a gel electrolyte layer;

[0027] (3) placing the gel electrolyte layer and the counter electrode in sequence below the infrared transparent substrate@integrated electrochromic layer, sealing the obtained infrared transparent substrate@integrated electrochromic layer, the gel electrolyte layer, and the counter electrode, and then pressing them together to obtain a variable emissivity integrated electrode flexible quasi-solid-state electrochromic device.

[0028] Furthermore, the gel electrolyte is prepared from raw materials of a gel electrolyte and an electrolyte, wherein the electrolyte is an aqueous solution of zinc sulfate.

[0029] Furthermore, the integrated electrode flexible quasi-solid-state intelligent thermal control device is applied in the fields of infrared camouflage and thermal control.

[0030] Compared with the prior art, the beneficial effect of the present invention lies in that an integrated electrode flexible quasi-solid-state intelligent thermal control device of the present invention adopts one-dimensional and two-dimensional composite materials as an integrated electrochromic layer. Due to the good flexibility of the one-dimensional nanomaterial and the high conductivity of the two-dimensional nanomaterial, the prepared electrochromic device has good infrared emissivity regulation performance, including a high infrared emissivity regulation range, faster response speed and good cycle stability, has better flexibility, and is more conducive to the transmission of ions. Compared with the existing infrared electrochromic devices, the response speed and cycle life are significantly improved, the cycle stability is good, and a higher infrared emissivity regulation range is achieved in the two atmospheric windows of thermal infrared (3-5μm and 8-14μm). BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present invention. Moreover, the same reference symbols are used throughout the accompanying drawings to represent the same components. In the accompanying drawings:

[0032] Figure 1 A structural diagram of an integrated electrode flexible quasi-solid-state intelligent thermal control device provided by an embodiment of the present invention;

[0033] Figure 2 A flowchart of a method for preparing an integrated electrode flexible quasi-solid-state intelligent thermal control device provided by an embodiment of the present invention;

[0034] Figure 3 This is an X-ray diffraction diagram of the one-dimensional nanomaterial in the integrated electrochromic layer of Example 1 of the present invention;

[0035] Figure 4 This is a surface morphology image of a one-dimensional nanomaterial in an integrated electrochromic layer in Example 1 of the present invention;

[0036] Figure 5 This is an X-ray diffraction diagram of the two-dimensional nanomaterial in the integrated electrochromic layer of Example 1 of the present invention;

[0037] Figure 6 This is a cross-sectional view of the two-dimensional nanomaterial in the integrated electrochromic layer of Example 1 of the present invention;

[0038] Figure 7 This is an X-ray diffraction diagram of the integrated electrochromic layer of Example 1 of the present invention;

[0039] Figure 8 This is a surface morphology image of the integrated electrochromic layer of Example 1 of the present invention;

[0040] Fig. 9This is a cross-sectional view of the integrated electrochromic layer of Example 1 of the present invention;

[0041] Fig.10 This is an infrared emissivity diagram of the variable emissivity integrated electrode flexible quasi-solid-state electrochromic device according to Example 1 of the present invention;

[0042] Fig.11 Schematic diagram of dynamic control of the variable emissivity integrated electrode flexible quasi-solid-state electrochromic device in this experimental example 1

[0043] Fig.12 This is a response time diagram of the variable emissivity integrated electrode flexible quasi-solid-state electrochromic device according to Example 1 of the present invention;

[0044] Fig.13 This is a cycle diagram of the variable emissivity integrated electrode flexible quasi-solid-state electrochromic device according to Example 1 of the present invention;

[0045] In the figure: 100 - infrared transparent substrate; 200 - integrated electrochromic layer; 300 - gel electrolyte layer; 400 - pairs of electrodes. DETAILED DESCRIPTION

[0046] The exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to be able to fully convey the scope of the present invention to those skilled in the art. It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the implementation regulations.

[0047] Reference Figure 1 As shown, in some embodiments of the present application, an integrated electrode flexible quasi-solid-state intelligent thermal control device includes:

[0048] An infrared transparent substrate 100, an integrated electrochromic layer 200, a gel electrolyte layer 300 and a counter electrode 400, wherein the infrared transparent substrate 100, the integrated electrochromic layer 200, the gel electrolyte layer 300 and the counter electrode 400 are connected in sequence to form an electrode flexible quasi-solid-state intelligent thermal control device; the infrared transparent substrate 100, the integrated electrochromic layer 200, the gel electrolyte layer 300 and the counter electrode 400 are an integrated structure.

[0049] Specifically, the integrated electrochromic layer 200 is specifically: an inorganic integrated electrochromic layer 200 or an organic integrated electrochromic layer 200; wherein, the inorganic integrated electrochromic layer 200 or the organic integrated electrochromic layer 200 are both one-dimensional and two-dimensional composite material structures; the inorganic integrated electrochromic layer 200 is made of molybdenum oxide, tungsten oxide or a new carbon material; the organic integrated electrochromic layer 200 is made of polyaniline, polythiophene, polypyrrole or Prussian blue; the thickness of the integrated electrochromic layer 200 is 5 to 10 μm; the one-dimensional and two-dimensional composite material is a composite material of molybdenum oxide and MXene, and the sheet resistance of the integrated electrochromic layer 200 is 5 to 50 Ω / square.

[0050] It can be understood that the integrated electrochromic layer 200 adopts one-dimensional and two-dimensional composite materials such as a composite material of molybdenum oxide and MXene, which has the characteristics of both inorganic or organic materials and can effectively control the color and transmittance; the infrared transparent substrate 100 selects at least one of a variety of materials such as a flexible film substrate such as polyethylene, giving the device flexibility and infrared transparency; the various material choices of the inorganic integrated electrochromic layer 200 and the various material choices of the organic integrated electrochromic layer 200 enrich its performance; the gel electrolyte layer 300 is prepared from gel electrolyte and zinc sulfate aqueous solution electrolyte raw materials to provide a stable ion transmission environment. These characteristics work together to give the device good flexibility, intelligent thermal control function and stable working performance, and can be widely used in smart windows, wearable devices and other fields.

[0051] Specifically, the materials of the gel electrolyte layer 300 are gel electrolyte and electrolyte; wherein the electrolyte is an aqueous solution of zinc sulfate. The gel electrolyte includes one of a polymer gel electrolyte, a polymer-ceramic gel electrolyte, a mixed solvent gel electrolyte and a polymer-liquid electrolyte; the thickness of the gel electrolyte is 50 to 300 μm. The counter electrode 400 includes one of an activated carbon electrode, a polyaniline electrode, a MXene electrode, a nickel oxide electrode, a Prussian blue electrode and a Zn electrode; the thickness of the counter electrode 400 is 1 to 500 μm. The infrared transparent substrate 100 includes at least one of polyethylene (PE), polydimethylsiloxane (PDMS), polycarbonate, polyimide, thermoplastic polyurethane (PU) and a few-layer graphene layer, and the infrared transparent substrate 100 is a flexible film substrate; the thickness of the infrared transparent substrate 100 is 1 to 500 μm.

[0052] It can be understood that the infrared transparent substrate 100 has a thickness of 1-500μm, which not only ensures a certain mechanical strength but also has good flexibility and can adapt to a variety of application scenarios; the integrated electrochromic layer 200 has a thickness of 5-10μm and a sheet resistance of 5-50Ω / square, which can efficiently realize color and transmittance changes and accurately control thermal radiation; the gel electrolyte has a thickness of 50-300μm and is available in a variety of types, which can provide a stable ion transmission channel to ensure stable operation of the device; the counter electrode 400 has a variety of types available and a thickness of 1-500μm, which can effectively match different electrochromic reactions and improve the overall performance of the device, making the thermal control device perform well in intelligent temperature regulation, energy saving and other aspects, and has broad application prospects.

[0053] Specifically, the infrared transparent substrate 100 is preferably a PE flexible substrate, and the transmittance of the PE flexible substrate in the wavelength range of 0.4 to 25 μm is preferably >0.5, and more preferably >0.8; the thickness of the PE flexible substrate is preferably 0.1 to 100 μm, more preferably 20 to 60 μm, and further preferably 40 to 50 μm. The thickness of the integrated electrochromic layer 200 is preferably 5 to 50 μm, more preferably 5 to 20 μm, and further preferably 5 to 10 μm; the sheet resistance of the integrated electrochromic layer 200 is preferably 5 to 500 Ω / square, more preferably 5 to 100 Ω / square, and further preferably 5 to 50 Ω / square. The gel electrolyte layer 300 is preferably prepared by curing an aqueous solution of an electrolyte; the gel electrolyte preferably includes one of a polymer gel electrolyte, a polymer-ceramic mixed gel electrolyte, a mixed solvent gel electrolyte, and a polymer-liquid electrolyte; the polymer-liquid gel electrolyte is preferably polyacrylamide-zinc sulfate (PAM-ZnSO4). The gel electrolyte is preferably a gel electrolyte solution; acrylamide, zinc sulfate heptahydrate and a photoinitiator are dissolved in deionized water to obtain a gel electrolyte precursor solution. The photoinitiator is selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone. The present invention adopts a zinc salt electrolyte, which can better simplify the structure of the integrated electrode flexible quasi-solid-state intelligent thermal control device. The thickness of the gel electrolyte layer 300 is preferably 5 to 300 μm, more preferably 50 to 250 μm, and further preferably 100 to 200 μm; the electrolyte concentration is preferably 0.2 to 1 mol / L, and more preferably 0.5 to 1 mol / L. The counter electrode 400 is preferably one of an activated carbon electrode, a MXene electrode, a polyaniline electrode, a nickel oxide electrode, a Prussian blue electrode and a zinc electrode; the thickness of the counter electrode 400 is preferably 1 to 100 μm, and more preferably 50 to 100 μm. The size of the integrated electrode flexible quasi-solid-state intelligent thermal control device is preferably 2cm×2cm to 3cm×3cm, and more preferably 2.5cm×2.5cm.

[0054] Reference Figure 2 As shown, in some embodiments of the present application, a method for preparing an integrated electrode flexible quasi-solid-state intelligent thermal control device includes:

[0055] S100, hot pressing and vacuum filtering the integrated electrochromic layer 200 on the infrared transparent substrate 100 to obtain the infrared transparent substrate@integrated electrochromic layer;

[0056] S200, UV-curing the gel electrolyte to obtain a gel electrolyte layer 300;

[0057] S300, placing the gel electrolyte layer 300 and the counter electrode 400 in sequence under the infrared transparent substrate 100@integrated electrochromic layer 200, sealing the obtained infrared transparent substrate 100@integrated electrochromic layer 200, the gel electrolyte layer 300, and the counter electrode 400, and then pressing them together to obtain a variable emissivity integrated electrode flexible quasi-solid-state electrochromic device.

[0058] Specifically, an integrated electrode flexible quasi-solid-state intelligent thermal control device is used in the fields of infrared camouflage and thermal control.

[0059] Specifically, the raw material of the integrated electrochromic layer 200 is preferably a mixed solution of molybdenum oxide and MXene; the method for preparing molybdenum oxide nanowires is preferably: mixing a molybdenum source with hydrogen peroxide in an ice-water bath and then performing a hydrothermal reaction to obtain molybdenum oxide nanowires. The molybdenum source preferably includes one of molybdenum powder, molybdenum pentachloride, ammonium molybdate and sodium molybdate; the mass ratio of the molybdenum source to hydrogen peroxide is preferably (0.5-2) g: (10-20) mL, and more preferably (0.5-1) g: (10-12.5) mL.

[0060] Specifically, in the present invention, the temperature of the hydrothermal reaction is preferably 150-180°C, more preferably 165-180°C; the holding time is preferably 12-36h, more preferably 18-24h; after the hydrothermal reaction, the reaction product is preferably cooled, washed and dried in sequence; the final cooling temperature is preferably room temperature; the washing reagent is preferably water and anhydrous ethanol; the number of washings is preferably 3 times or more, more preferably 3 times. The two-dimensional material in the integrated electrochromic layer 200 is preferably MXene, and is preferably prepared using a MXene precursor solution; the preparation method of the MXene precursor solution is preferably: a carbide precursor, hydrochloric acid and lithium fluoride are subjected to an acid etching reaction under oil bath conditions.

[0061] Specifically, in the present invention, the carbide precursor is preferably Ti3AlC2; the mass volume ratio of the carbide precursor to hydrochloric acid is preferably (1-3) g:(10-30) mL, more preferably (1-2) g:(15-25) mL; the concentration of hydrochloric acid is preferably 3-12 mol / L, more preferably 9 mol / L; the mass ratio of the carbide precursor to lithium fluoride is preferably 1-3:1-3, more preferably 2-3:2-3. In the present invention, the temperature of the oil bath is preferably 35-45°C, more preferably 38-42°C, and the holding time is preferably 36-60h, more preferably 42-48h; after the acid etching reaction, it is preferably centrifuged and washed until the pH value of the supernatant is 7, and ultrasonic and centrifuged to obtain the supernatant, which is the MXene precursor solution; the ultrasonic temperature is preferably 20-40°C, more preferably 25°C, and the ultrasonic time is preferably 40-90min, more preferably 60-70min; the centrifugal speed is preferably 3000-4000rpm, more preferably 3500rpm, and the centrifugal time is preferably 5-10min, more preferably 5min; the number of centrifugation is preferably 5-10 times, more preferably 5 times.

[0062] Specifically, in the present invention, the infrared transparent substrate 100 is preferably subjected to oxygen plasma treatment or ozone treatment before use. The present invention introduces oxygen-containing functional groups on the surface of the infrared transparent substrate 100 through ozone treatment, which can improve the wettability of the surface of the infrared transparent substrate 100, make the hot pressing effect better, and obtain a more compact integrated electrochromic layer. In the present invention, the mass fraction of the two-dimensional nanosheets in the integrated electrochromic layer 200 is preferably 5% to 30%, more preferably 5% to 20%, and further preferably 15%. The mass of the one-dimensional molybdenum oxide nanowire is preferably 8 to 20 mg, more preferably 8 to 15 mg, and further preferably 10 mg; the concentration of the two-dimensional MXene nanosheet precursor solution is preferably 1 to 3 mg / ml, and more preferably 2 mg / ml. The present invention filters the raw material solution of the integrated electrochromic layer 200, dries it and removes the film in sequence to obtain the integrated electrochromic layer 200. In the present invention, filtration is preferably vacuum filtration; filtration is preferably: determine the mass of molybdenum oxide nanowires, measure MXene solution according to a certain mass ratio, and filter after ultrasonic mixing to obtain an integrated electrochromic layer 200. The measuring device is preferably a pipette; the measuring capacity is preferably 1 to 5 ml, and more preferably 2 to 4 ml. The mixing method of one-dimensional nanowires and two-dimensional nanosheets is preferably ultrasonic mixing; the ultrasonic temperature is preferably 20 to 30°C, and more preferably 25°C; the ultrasonic time is preferably 20 to 40 min, and more preferably 30 min. In the present invention, the gel electrolyte solution is cured to obtain a gel electrolyte layer 300. The curing method is preferably ultraviolet curing and high temperature curing, and more preferably ultraviolet curing.

[0063] Example 1

[0064] like Figure 3 to Figure 9 As shown, the integrated electrode flexible quasi-solid-state intelligent thermal control device provided in this embodiment comprises, from top to bottom, an infrared transparent substrate 100, an integrated electrochromic layer 200, a gel electrolyte layer 300 and a counter electrode 400.

[0065] The infrared transparent substrate 100 is a polyethylene film treated with ozone;

[0066] Molybdenum oxide nanowires and MXene solution were prepared by hydrothermal method and etching method respectively;

[0067] 0.5 g of molybdenum powder was added to 10 ml of hydrogen peroxide solution, reacted at 180 ° C for 24 h, cooled to room temperature, washed with distilled water and anhydrous ethanol for 3 times, and vacuum dried at 60 ° C to obtain MoO3 nanowire material;

[0068] Use 1.6g of LiF, 20ml of 9mol / L HCl and 1g of Ti3AlC2 as raw materials, react in an oil bath at 35℃ for 48h, centrifuge and wash until the pH of the supernatant is 7, ultrasonicate the obtained solution at 25℃ for 1h, and then centrifuge 5 times to obtain the supernatant, which is the MXene solution;

[0069] 10 mg of molybdenum oxide nanowires were ultrasonically dispersed in deionized water, and a MXene solution with a mass fraction of 15% was added and ultrasonically mixed for 30 minutes. After vacuum filtration, the solution was naturally dried at room temperature and peeled off to obtain the integrated electrochromic layer 200.

[0070] By characterizing the physical properties of the integrated electrochromic layer 200, the integrated electrochromic layer 200 is successfully synthesized;

[0071] Figure 5-6 XRD and SEM of MXene nanosheets. Figure 5-6 It can be seen that the present invention successfully prepared MXene, and the MXene nanosheets have good electrical conductivity;

[0072] The electrochromic layer of this embodiment was tested by SEM, and the results are as follows: Figure 7-Figure 8 As shown. Figure 7-Figure 8 It can be seen that the molybdenum oxide nanowires are successfully interspersed among the MXene nanosheets.

[0073] acrylamide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and zinc sulfate heptahydrate are added into deionized water and stirred until completely dissolved, and solidified by ultraviolet light to obtain a gel electrolyte layer 300;

[0074] The gel electrolyte layer 300 and the counter electrode 400 are sequentially stacked under the electrochromic layer of the infrared transparent substrate@integrated electrochromic layer, and are pressed into one by a roller press to obtain an integrated electrode flexible quasi-solid-state intelligent thermal control device.

[0075] Figure 10-11 The infrared emissivity curve and dynamic control schematic diagram of the electrochromic device prepared in this embodiment. Figure 10-11 It can be seen that when a smaller positive pressure is applied, Zn2+ is embedded in the electrochromic layer and the infrared emissivity gradually increases. When a larger positive pressure is applied, Zn2+ escapes from the electrochromic layer and the infrared emissivity gradually decreases, thereby achieving the regulation of infrared emissivity.

[0076] Figure 12-13 The response time and cycle life of the electrochromic device prepared in this embodiment are shown in FIG. Figure 12-13 It can be seen that the electrochromic device of the present invention has a faster response time and a better cycle life, with the coloring and fading times being 7.6s and 8.5s respectively, and a capacity retention rate of 90.25% after 2000 cycles.

[0077] Example 2

[0078] The preparation method of the present invention is the same as that of Example 1, with the only difference being that the mass fraction of MXene is 10%, and the integrated electrochromic layer 200 is prepared by the same method. The surface morphology of the integrated electrochromic layer 200 obtained in this example is still a nanowire and nanosheet intercalation structure, which is basically the same as that of Example 1;

[0079] The infrared emissivity performance of the integrated electrode flexible quasi-solid-state intelligent thermal control device of this embodiment was tested with reference to Example 1. The results showed that the regulation range of the integrated electrode flexible quasi-solid-state intelligent thermal control device of this embodiment in the two atmospheric windows of 3-5μm and 8-14μm was significantly reduced, and the regulation ranges were 0.1 and 0.2 respectively.

[0080] It can be seen from the above embodiments that the electrochromic device provided by the present invention has better flexibility and is more conducive to the transmission of ions. Compared with the existing infrared electrochromic devices, the response speed and cycle life are significantly improved, the cycle stability is good, and a higher infrared emissivity control range is achieved in the two atmospheric windows of thermal infrared (3-5μm and 7.5-14μm).

[0081] It should be noted that:

[0082] In the description provided herein, a large number of specific details are described. However, it is understood that the embodiments of the present application can be practiced without these specific details. In some instances, well-known structures and technologies are not shown in detail so as not to obscure the understanding of this description.

[0083] Furthermore, those skilled in the art will appreciate that although some embodiments described herein include certain features included in other embodiments but not other features, the combination of features from different embodiments is meant to be within the scope of the present application and to form different embodiments.

[0084] The above is only a preferred specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. An integrated electrode flexible quasi-solid-state intelligent thermal control device, characterized in that: include: An infrared transparent substrate, an integrated electrochromic layer, a gel electrolyte layer and a counter electrode, wherein the infrared transparent substrate, the integrated electrochromic layer, the gel electrolyte layer and the counter electrode are sequentially connected to form an integrated electrode flexible quasi-solid-state intelligent thermal control device; The infrared transparent substrate, the integrated electrochromic layer, the gel electrolyte layer and the counter electrode form an integrated structure.

2. The integrated electrode flexible quasi-solid-state intelligent thermal control device according to claim 1, characterized in that: The integrated electrochromic layer is specifically: Inorganic integrated electrochromic layer or organic integrated electrochromic layer; Wherein, the inorganic integrated electrochromic layer or the organic integrated electrochromic layer is a one-dimensional and two-dimensional composite material structure; The inorganic integrated electrochromic layer is made of molybdenum oxide, tungsten oxide or a new carbon material; The material of the organic integrated electrochromic layer is polyaniline, polythiophene, polypyrrole or Prussian blue; The thickness of the integrated electrochromic layer is 5 to 10 μm; the sheet resistance of the integrated electrochromic layer is 5 to 50 Ω / square. The one-dimensional and two-dimensional composite material is a composite material of molybdenum oxide and MXene; 3. The integrated electrode flexible quasi-solid-state intelligent thermal control device according to claim 2, characterized in that: The gel electrolyte layer material is a gel electrolyte and an electrolyte solution; The electrolyte is an aqueous solution of zinc sulfate; The gel electrolyte includes one of a polymer gel electrolyte, a polymer-ceramic gel electrolyte, a mixed solvent gel electrolyte and a polymer-liquid electrolyte; The thickness of the gel electrolyte is 50-300 μm.

4. The integrated electrode flexible quasi-solid-state intelligent thermal control device according to claim 3, characterized in that: The counter electrode comprises one of an activated carbon electrode, a polyaniline electrode, a MXene electrode, a nickel oxide electrode, a Prussian blue electrode and a Zn electrode; The thickness of the counter electrode is 1 to 500 μm.

5. The integrated electrode flexible quasi-solid-state intelligent thermal control device according to claim 4, characterized in that: The infrared transparent substrate comprises at least one of polyethylene (PE), polydimethylsiloxane (PDMS), polycarbonate, polyimide, thermoplastic polyurethane (PU) and a few-layer graphene layer, and the infrared transparent substrate is a flexible film substrate; The infrared transparent substrate has a thickness of 1 to 500 μm.

6. A method for preparing an integrated electrode flexible quasi-solid-state intelligent thermal control device, characterized in that: include: (1) hot pressing and vacuum filtering the integrated electrochromic layer on the infrared transparent substrate to obtain the infrared transparent substrate@integrated electrochromic layer; (2) curing the gel electrolyte with ultraviolet light to obtain a gel electrolyte layer; (3) placing the gel electrolyte layer and the counter electrode in sequence below the infrared transparent substrate@integrated electrochromic layer, sealing the obtained infrared transparent substrate@integrated electrochromic layer, the gel electrolyte layer, and the counter electrode, and then pressing them together to obtain a variable emissivity integrated electrode flexible quasi-solid-state electrochromic device.

7. The method for preparing an integrated electrode flexible quasi-solid-state intelligent thermal control device according to claim 6, characterized in that: The gel electrolyte is prepared from raw materials of a gel electrolyte and an electrolyte, wherein the electrolyte is an aqueous solution of zinc sulfate.

8. The integrated electrode flexible quasi-solid-state intelligent thermal control device according to any one of claims 1 to 5 is applied in the fields of infrared camouflage and thermal control.

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