A complementary electrochromic film and electrochromic device

Abstract

The utility model relates to the technical field of electrochromic diaphragm, especially to a complementary electrochromic diaphragm and electrochromic device. The utility model provides an electrochromic diaphragm, which comprises: a cathode conductive layer, an N-type electrochromic composite layer, an electrolyte layer, a P-type electrochromic composite layer and an anode conductive layer arranged in sequence. The P-type electrochromic composite layer comprises a P-type reversible electrochromic layer and a transparent pseudo-capacitive material layer arranged on at least one side of the P-type reversible electrochromic layer facing the electrolyte layer or the anode conductive layer. The transparent pseudo-capacitive material layer is used to provide electric charges to the P-type reversible electrochromic layer under the action of external voltage to maintain the capacitance capacity matching of the P-type reversible electrochromic layer and the N-type reversible electrochromic layer after the contrast ratio of the electrochromic diaphragm decays. The utility model significantly improves the light and dark state contrast ratio recovery ability of the diaphragm after aging, strengthens the charge balance, and avoids the imbalance of single-pole capacity.

Description

Technical Field

[0001] This utility model relates to the field of electrochromic film technology, and in particular to a complementary electrochromic film and electrochromic device. Background Technology

[0002] Electrochromic devices are functional devices that can reversibly change their optical properties (such as transmittance or reflectance) under an applied voltage. Complementary electrochromic devices are often composed of two matching color-changing materials, one of which undergoes oxidation in an electrochemical reaction, while the other undergoes reduction, thereby achieving color change while maintaining overall charge balance.

[0003] Currently, P-type conductive polymer materials are widely used in anodic color-changing layers due to their good processability, fast response, and tunable color properties; while N-type inorganic or organic color-changing materials are used in cathodic color-changing layers. These complementary films can achieve a wide range of transmittance changes under positive and negative bias voltages, exhibiting excellent light modulation performance.

[0004] However, under accelerated aging conditions such as long-term high temperature, high humidity, or strong light (such as xenon lamp irradiation), the contrast of the device usually undergoes irreversible decay, which manifests as a decrease in bright state transmittance and an increase in dark state transmittance, seriously affecting product performance and commercial applications. Utility Model Content

[0005] The purpose of this invention is to provide a complementary electrochromic film to solve the technical problem of irreversible degradation of device contrast after long-term aging due to charge imbalance in the prior art.

[0006] In a first aspect, the present invention provides a complementary electrochromic film, comprising: a cathode conductive layer, an N-type electrochromic composite layer, an electrolyte layer, a P-type electrochromic composite layer and an anode conductive layer stacked sequentially; The N-type electrochromic composite layer includes an N-type reversible electrochromic layer and a transparent pseudocapacitive material layer disposed on at least one side of the N-type reversible electrochromic layer facing the electrolyte layer and the side facing the cathode conductive layer. and / or; The P-type electrochromic composite layer includes a P-type reversible electrochromic layer and a transparent pseudocapacitive material layer disposed on at least one of the sides of the P-type reversible electrochromic layer facing the electrolyte layer and the side facing the anode conductive layer.

[0007] In an optional embodiment, the transparent pseudocapacitive material layer is selected from one or a combination of MXene layers, doped conductive polymer layers, carbon-based material layers, and sub-nanometer oxide layers.

[0008] In an optional embodiment, the P-type reversible electrochromic layer is selected from one or a combination of PEDOT layer, PProDOT layer and PolyTPD layer.

[0009] In an optional embodiment, the N-type reversible electrochromic layer is selected from one or a combination of WO3 layer, NiO layer and N-type polymer layer.

[0010] In an optional embodiment, both the P-type reversible electrochromic layer and the N-type reversible electrochromic layer are initially in a neutral colored state.

[0011] In an optional embodiment, the transparent pseudocapacitive material layer is located between the P-type reversible electrochromic layer and the electrolyte layer.

[0012] In an optional embodiment, the electrochromic film further includes a first base layer disposed on the outer surface of the cathode conductive layer and a second base layer disposed on the outer surface of the anode conductive layer.

[0013] In an optional embodiment, the first substrate layer and / or the second substrate layer is one or a combination of glass, PET layer and PEN layer.

[0014] In an optional embodiment, the cathode conductive layer and / or the anode conductive layer is one or a combination of an ITO layer and a metal mesh layer.

[0015] Secondly, this utility model provides a complementary electrochromic device, comprising two outer glass layers and an electrochromic film as described in any of the foregoing embodiments, fixed between the two outer glass layers.

[0016] Compared with the prior art, the complementary electrochromic film and electrochromic device provided by this utility model have the following technical advantages: The complementary electrochromic film provided by this utility model includes: a cathode conductive layer, an N-type electrochromic composite layer, an electrolyte layer, a P-type electrochromic composite layer, and an anode conductive layer stacked sequentially; the N-type electrochromic composite layer includes an N-type reversible electrochromic layer and a transparent pseudocapacitive material layer disposed on at least one of the N-type reversible electrochromic layer facing the electrolyte layer and the side facing the cathode conductive layer; and / or; the P-type electrochromic composite layer includes a P-type reversible electrochromic layer and a transparent pseudocapacitive material layer disposed on at least one of the P-type reversible electrochromic layer facing the electrolyte layer and the side facing the anode conductive layer.

[0017] A transparent pseudocapacitive material layer is introduced on at least one side of the P-type reversible electrochromic layer, facing the electrolyte layer and the side facing the anode conductive layer. The transparent pseudocapacitive material layer can provide charge to the P-type reversible electrochromic layer under the action of an external voltage after the contrast of the electrochromic film decays, so as to maintain the capacitance matching between the P-type reversible electrochromic layer and the N-type reversible electrochromic layer. Since the transparent pseudocapacitive material layer can quickly release charge when the voltage is applied, it compensates for the problem of insufficient charge supply in the P-type reversible electrochromic layer after high-temperature aging, so that the N-type reversible electrochromic layer can be fully oxidized, thereby achieving capacitance matching and color restoration. The charge balance calibration achieved by the transparent pseudocapacitive material layer not only significantly improves the contrast recovery capability of the bright and dark states after film aging, but also strengthens the charge balance and avoids unipolar capacitance imbalance. Since the material is transparent and has no additional optical interference, it is compatible with existing film structures and supports batch integration, improving the long-term stability and reliability of the film. The principle and effect of introducing a transparent pseudocapacitive material layer on at least one side of the N-type reversible electrochromic layer facing the electrolyte layer and the side facing the cathode conductive layer are the same as described above, and will not be repeated here.

[0018] The complementary electrochromic device provided by this utility model includes the aforementioned electrochromic film. Therefore, the technical advantages and effects achieved by it include those achieved by the aforementioned electrochromic film, which will not be elaborated here.

[0019] Other features and advantages of this invention will be described in detail in the following detailed description section. Attached Figure Description

[0020] To more clearly illustrate the specific embodiments of this utility model or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this utility model. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0021] Figure 1 A schematic diagram of the electrochromic film structure provided in an embodiment of this utility model; Figure 2 A flowchart illustrating the recovery process of the complementary electrochromic device provided in this embodiment of the present invention; Figure 3 The time-transmittance curves of the xenon lamps in the control group and the experimental group obtained in the first embodiment of this utility model before storage are shown. Figure 4 Time-transmittance curves of xenon lamps in the control group and experimental group after 7 days of storage, provided as an embodiment of this utility model. Figure 5 The time-transmittance curves of the control group and the experimental group devices before high-temperature storage are obtained in Implementation Case 2 provided for the present utility model embodiment; Figure 6 Absorption spectra of the comparative group before and after high-temperature storage, obtained in Implementation Case 2 of this utility model; Figure 7 Absorption spectra of the experimental group before and after high-temperature storage, provided as an embodiment of this utility model in Example 2; Figure 8 The time-transmittance curves of the control group and the experimental group devices after 5 days of high-temperature storage are provided in the second embodiment of this utility model. Figure 9 The time-transmittance curves of the xenon lamps in the control group and the experimental group obtained in Implementation Case 3 of this utility model before storage; Figure 10 The time-transmittance curves of the xenon lamps in the control group and experimental group obtained in Implementation Case 3 of this utility model after 5 days of storage.

[0022] Icons: 1-Anode conductive layer; 2-Cathode conductive layer; 3-P-type reversible electrochromic layer; 4-Transparent pseudocapacitive material layer; 5-Electrolyte layer; 6-N-type reversible electrochromic layer. Detailed Implementation

[0023] The technical solution of this utility model will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of this utility model, not all embodiments. Based on the embodiments of this utility model, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this utility model.

[0024] In the description of this utility model, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating the orientation or positional relationship, are based on the orientation or positional relationship shown in the accompanying drawings and are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this utility model. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0025] In the description of this utility model, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0026] Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by this utility model.

[0027] The present invention will be further described in detail below through specific embodiments and in conjunction with the accompanying drawings.

[0028] The specific structure is as follows: Figure 1 As shown.

[0029] This embodiment provides a complementary electrochromic film, comprising: a cathode conductive layer 2, an N-type electrochromic composite layer, an electrolyte layer 5, a P-type electrochromic composite layer, and an anode conductive layer 1, sequentially stacked; the N-type electrochromic composite layer includes an N-type reversible electrochromic layer 6 and a transparent pseudocapacitive material layer disposed on at least one side of the N-type reversible electrochromic layer 6 facing the electrolyte layer 5 and the side facing the cathode conductive layer 2; and / or; the P-type electrochromic composite layer includes a P-type reversible electrochromic layer 3. A transparent pseudocapacitive material layer 4 is disposed on at least one side of the P-type reversible electrochromic layer 3 facing the electrolyte layer 5 and the side facing the anode conductive layer 1. The initial charge capacities of the P-type reversible electrochromic layer 3 and the N-type reversible electrochromic layer 6 may be the same or different. The transparent pseudocapacitive material layer 4 is used to provide charge to the P-type reversible electrochromic layer 3 under the action of an external voltage after the contrast of the electrochromic film decays, so as to maintain the capacitance matching between the P-type reversible electrochromic layer 3 and the N-type reversible electrochromic layer 6. Here, capacitance matching means that the capacitance is the same or approximately the same.

[0030] In this embodiment, a transparent pseudocapacitive material layer 4 is introduced on at least one side of the P-type reversible electrochromic layer 3 facing the electrolyte layer 5 and the side facing the anode conductive layer 1. The transparent pseudocapacitive material layer 4 can provide charge to the P-type reversible electrochromic layer 3 under the action of an external voltage after the contrast of the electrochromic film decays, so as to maintain the capacitance matching between the P-type reversible electrochromic layer 3 and the N-type reversible electrochromic layer 6. Since the transparent pseudocapacitive material layer 4 can quickly release charge when the voltage is applied, it compensates for the problem of insufficient charge supply of the P-type reversible electrochromic layer 3 after high-temperature aging, so that the N-type reversible electrochromic layer 6 can be fully oxidized, thereby achieving capacitance matching and color restoration. The charge balance calibration is achieved through the transparent pseudocapacitive material layer 4, which not only significantly improves the contrast recovery capability of the bright and dark states after the film ages, but also strengthens the charge balance and avoids unipolar capacitance imbalance. Since the material is transparent and has no additional optical interference, it is compatible with existing film structures and supports batch integration, improving the long-term stability and reliability of the film.

[0031] The principle and effect of introducing a transparent pseudocapacitive material layer on at least one side of the N-type reversible electrochromic layer facing the electrolyte layer and the side facing the cathode conductive layer are the same as described above, and will not be repeated here.

[0032] In this embodiment, the cathode conductive layer 2 serves as the cathode-side conductive carrier of the membrane. Its core function is to efficiently transmit electrons and uniformly distribute the electric field. On the one hand, it needs to stably receive electrons input from the external circuit and uniformly transfer the electrons to the adjacent N-type reversible electrochromic layer 6 to provide a sufficient electron source for the electrochromic reaction of the N-type layer. On the other hand, it needs to have excellent conductivity and chemical stability to avoid oxidation or corrosion during long-term electrochemical cycling, while ensuring the overall light transmittance of the membrane and not affecting the visual presentation of the electrochromic effect.

[0033] In this embodiment, the N-type reversible electrochromic layer 6 is the core functional layer of the film that enables cathode-side electrochromism. Its main function is to achieve reversible optical state changes based on ion insertion or extraction: under external voltage drive, this layer receives electrons from the cathode conductive layer 2 and inserts cations from the electrolyte layer 5. Through the synergistic effect of ions and electrons, the electronic energy level of the material in the layer changes, thereby achieving reversible adjustment of light transmittance.

[0034] In this embodiment, the electrolyte layer 5 plays a dual crucial role as both an ion transport channel and an electrochemical isolation barrier within the membrane: First, it must possess high ionic conductivity to provide a smooth channel for cation migration between the N-type reversible electrochromic layer 6 and the P-type reversible electrochromic layer 3, ensuring that the electrochromic reactions of the two layers proceed synchronously; Second, it must possess excellent electronic insulation to prevent direct electron conduction between the cathode conductive layer 2 and the anode conductive layer 1 (avoiding short circuits), while simultaneously isolating the two electrochromic materials from direct contact to prevent material failure caused by chemical reactions.

[0035] In this embodiment, the anode conductive layer 1 and the cathode conductive layer 2 form a symmetrical conductive structure. The core function is to collect electrons and uniformly bear voltage. During the electrochromic process, the anode conductive layer 1 will conduct electrons generated by the P-type reversible electrochromic layer 3 to the external circuit to form a complete current loop. At the same time, it needs to work together with the cathode conductive layer 2 to form a uniform electric field inside the film to ensure that ions in the electrolyte layer 5 migrate uniformly and avoid uneven color change caused by excessively high local ion concentration.

[0036] In this embodiment, the P-type reversible electrochromic layer 3 is the core layer of electrochromic coating on the anode side of the membrane, and it complements the N-type reversible electrochromic layer 6. Its function is to adjust the transmittance through a reversible redox reaction: under the action of an external voltage, this layer loses electrons (is oxidized) and releases cations to the electrolyte layer 5. Through the synergy of electron transfer and ion migration, the transmittance changes reversibly.

[0037] In this embodiment, the transparent pseudocapacitive material layer 4 functions to first convert the reduced substances in the N-type reversible electrochromic layer 6 back to their pre-reduction state, thereby achieving material equivalence with the P-type reversible electrochromic layer 3. For example, assuming the initial state is: the N layer is 100% N material, and the P layer is 100% P material; after a spontaneous reduction reaction: the N layer has 70% N material remaining, and 30% converted to P material, while the P layer remains 100% P material. Thus, the reacting substances in the N and P layers are unbalanced. Therefore, when a reverse voltage is applied, only 70% of the P material in the P layer will be converted, leaving 30% P material. This results in reduced transmittance in the bright state. The transparent pseudocapacitive material layer 4 functions to convert the P material in the N layer back to N material, restoring the N layer to 100% material again, thus achieving material balance between the N and P layers.

[0038] In this embodiment, the electrolyte layer 5 contains an ion-conducting medium that supports charge transfer between the two electrodes.

[0039] In this embodiment, under natural conditions, high temperature, or xenon lamp storage, the N-type reversible electrochromic layer 6 is prone to spontaneous reduction, gradually fading even without bias voltage. Since light is still lost through scattering and additional absorption as it passes through the film, the bright-state transmittance of the device decreases. At this time, due to the spontaneous reduction of the N-type reversible electrochromic layer, the amount of material available to react with the P-type reversible electrochromic layer 3 decreases. Even with a reverse voltage applied, the remaining reactants in the N-type reversible electrochromic layer cannot consume the charge provided by the P-type reversible electrochromic layer 3, resulting in insufficient consumption of the material in the P-type reversible electrochromic layer 3, leading to increased dark-state transmittance and decreased contrast. By introducing a transparent pseudocapacitive material layer 4, charge can be rapidly released when voltage is applied, compensating for the insufficient charge supply of the P-type reversible electrochromic layer 3 after high-temperature aging, allowing the N-type reversible electrochromic layer 6 to complete sufficient oxidation, thereby achieving capacitance matching and color restoration.

[0040] In the optional technical solution of this embodiment, the transparent pseudocapacitive material layer 4 is selected from one or a combination of MXene layer, doped conductive polymer layer, carbon-based material layer and sub-nanometer oxide layer. It possesses high specific capacitance, good chemical stability and optical transparency.

[0041] In this embodiment, the transparent pseudocapacitor material can be prepared by solution deposition, spraying, electrochemical polymerization, or other methods.

[0042] In the optional technical solutions of this embodiment, the P-type reversible electrochromic layer 3 is selected from one or a combination of PEDOT layer, PProDOT layer and PolyTPD layer.

[0043] In this embodiment, the P-type reversible electrochromic layer 3 is made of P-type conductive polymer materials, such as PEDOT, PProDOT, PolyTPD (poly[N,N'-bis(4-butylphenyl)-N,N'-bisphenylbenzidine]), which have good electrochemical reversibility and structural stability. Its initial state is a neutral colored state with high initial contrast.

[0044] In the optional technical solution of this embodiment, the N-type reversible electrochromic layer 6 is selected from one or a combination of WO3 layer, NiO layer and N-type polymer layer.

[0045] In this embodiment, the N-type reversible electrochromic layer 6 is made of N-type reversible electrochromic material, such as WO3, N-type polymer, etc., which has high stability and its initial state is also a neutral colored state, with high initial light-blocking properties.

[0046] In the optional technical solution of this embodiment, the transparent pseudocapacitive material layer 4 is located between the P-type reversible electrochromic layer 3 and the electrolyte layer 5.

[0047] However, this embodiment is not limited to this. The transparent pseudocapacitive material layer 4 can also be located between the P-type reversible electrochromic layer 3 and the anode conductive layer 1. The transparent pseudocapacitive material layer 4 can also be located between the P-type reversible electrochromic layer 3 and the electrolyte layer 5, as well as between the P-type reversible electrochromic layer 3 and the anode conductive layer 1.

[0048] In the optional technical solution of this embodiment, the electrochromic film further includes a first base layer disposed on the outer surface of the cathode conductive layer 2 and a second base layer disposed on the outer surface of the anode conductive layer 1.

[0049] In the optional technical solutions of this embodiment, the first substrate layer and / or the second substrate layer is one or a combination of glass, PET layer and PEN layer.

[0050] In this embodiment, the first substrate layer may be made of glass, PET, or PEN; the second substrate layer may be made of glass, PET, or PEN; or both the first and second substrate layers may be made of glass, PET, or PEN. Glass has high strength and rigidity, while PET and PEN have good flexibility and impact resistance.

[0051] In the optional technical solutions of this embodiment, the cathode conductive layer 2 and / or the anode conductive layer 1 are one or a combination of an ITO layer and a metal mesh layer.

[0052] In this embodiment, the cathode conductive layer 2 can be made of ITO or a metal mesh; the anode conductive layer 1 can be made of ITO or a metal mesh; or both the cathode conductive layer 2 and the anode conductive layer 1 can be made of ITO or a metal mesh. ITO and metal mesh have good conductivity and light transmittance.

[0053] This embodiment provides a complementary electrochromic device, including the aforementioned electrochromic film. Therefore, the technical advantages and effects achieved by the complementary electrochromic device include those achieved by the aforementioned electrochromic film, which will not be elaborated here.

[0054] Specifically, the complementary electrochromic device also includes two outer glass layers, with the electrochromic film fixed between the two outer glass layers.

[0055] The working mechanism is as follows: When a positive voltage is applied, the P-type reversible electrochromic layer 3 undergoes an oxidation reaction and fades, while the N-type reversible electrochromic layer 6 undergoes a reduction reaction and fades, causing the device to enter the bright state; when a negative voltage is applied, the P-type reversible electrochromic layer 3 undergoes a reduction reaction and becomes colored, while the N-type reversible electrochromic layer 6 undergoes an oxidation reaction and becomes colored, causing the device to enter the dark state. For example... Figure 2As shown, the recovery steps of the complementary electrochromic device of this application are as follows: S1, reduction reaction of the N-type reversible electrochromic layer 6; S2, the dark state transmittance of the device increases or the bright state transmittance decreases; S3, a reverse voltage is applied to the device; S4, the N-type reversible electrochromic layer 6 is oxidized, and the device performance is restored.

[0056] This application provides the following implementation examples: Implementation Case 1: 1. Device Fabrication: Step 1, take an ITO glass substrate and deposit a polyaniline electrochromic layer on the anode side; Step 2, based on Step 1, spin-coat a carbon nanotube solution as a buffer layer for the anode electrochromic material (i.e., transparent pseudocapacitive material layer 4), while the control group does not spin-coat a carbon nanotube solution on the anode side; Step 3, take an ITO glass substrate and deposit WO3 material on the cathode side as a cathode electrochromic layer; Step 4, drop an ultraviolet-curable electrolyte (such as a hydroxypropyl acrylate system electrolyte, mixed with LiClO4 salt and 2,2-diethoxyacetophenone as a photoinitiator) onto the P-type side, attach the cathode to the electrolyte surface, and cure it with ultraviolet light, thereby assembling an electrochromic device based on pseudocapacitive calibration material. 2. Performance Testing: Electrochromic testing was performed on the fabricated devices. The results showed that the transmittance of the devices in the visible light band was measured using a Linshang Technology LS116 transmittance meter, covering the visible light band of 380-760nm. The transmittance of the control group devices was 0.12-23.38%, and that of the devices with the buffer layer was 0.11-21.14%. The experimental data are as follows: Figure 3 As shown. 3. Lifetime Test: After 7 days of storage in an environment simulating sunlight by irradiating the devices with a xenon lamp (90℃), the transmittance range of the control group devices was 0.23-9.57%, while the transmittance range of the devices with the buffer layer was 0.10-19.29%. The experimental data are shown below. Figure 4 As shown, the attenuation rate is far superior to that of the control group, indicating that the device proposed in this study has better resistance to transmittance attenuation.

[0057] Implementation Case 2: 1. Device Fabrication: Step 1, take an ITO / PET flexible substrate and deposit a polypyrrole-based electrochromic material on the anode side; Step 2, based on Step 1, spin-coat an Mxene layer as a buffer layer for the anode electrochromic material (i.e., transparent pseudocapacitive material layer 4), while the control group does not spin-coat a carbon nanotube solution on the anode side; Step 3, take an ITO / PET flexible substrate and spin-coat a MoO3 material on the cathode side as an ion storage layer; Step 4, drop an ultraviolet-curable electrolyte (such as a hydroxypropyl acrylate system electrolyte, mixed with LiClO4 salt and 2,2-diethoxyacetophenone as a photoinitiator) onto the P-type electrode side, attach the cathode to the electrolyte surface, and pre-cur it using low-energy ultraviolet light, thereby assembling an electrochromic device based on pseudocapacitive calibration material. 2. Performance Testing: Electrochromic testing was performed on the fabricated device. The results showed that the transmittance of the device in the visible light band was tested using a Linshang Technology LS116 transmittance meter, covering the visible light band of 380-760nm. Figure 5 As shown, the control group devices ranged from 0.09% to 23.65%, while the experimental group devices ranged from 0.10% to 23.44%. 3. Lifetime Test: After 5 days of storage in a 110℃ oven, the absorption spectrum and transmittance of the devices were tested. In the colored state, the absorption spectrum of the devices was measured using a UV-VIS-NIR spectrometer, covering the visible light wavelength range of 380-760nm. Figure 6 and Figure 7 As shown, the spectral attenuation of the control group devices was severe, while the absorption spectrum of the experimental group devices was almost identical to the initial value. Transmittance tests were performed on both groups of devices, as shown... Figure 8 As shown, the transmittance of the control group devices ranged from 0.16 to 16.26%, while that of the experimental group devices ranged from 0.09 to 21.15%. The attenuation rate was much lower than that of the control group, indicating that the devices prepared in this proposal have better storage stability.

[0058] Implementation Case 3: 1. Device Fabrication: Step 1, take an ITO substrate and deposit a polythiophene-based P-type electrochromic layer on the anode side; Step 2, based on Step 1, spin-coat a doped conductive polymer PEDOT as a buffer layer for the anode electrochromic material (i.e., transparent pseudocapacitive material layer 4), while the control group does not spin-coat PEDOT on the anode side; Step 3, take an ITO substrate and deposit WO3 material on the cathode side as a cathode electrochromic material; Step 4, drop an ultraviolet-curable electrolyte (such as a hydroxypropyl acrylate system electrolyte, mixed with LiClO4 salt and 2,2-diethoxyacetophenone as a photoinitiator) onto the anode side, attach the cathode to the electrolyte surface, and cure it using ultraviolet light, thereby assembling an electrochromic device based on pseudocapacitive calibration material. 2. Performance Testing: Electrochromic testing was performed on the fabricated devices. The results showed that the transmittance of the devices in the visible light band was measured using a Linshang Technology LS116 transmittance meter, covering the visible light band of 380-760nm. The transmittance of the control group devices was 0.38-21.01%, and that of the devices with buffer layers was 0.39-20.37%. The experimental data are as follows: Figure 9 As shown. 3. Lifetime Test: After 5 days of storage under conditions simulating sunlight by irradiating the device with a xenon lamp (90℃), the data is as follows. Figure 10 As shown, the transmittance of the comparative group devices ranged from 0.74% to 6.53%, while the transmittance of the devices with buffer layers ranged from 0.46% to 18.53%. The attenuation rate was far superior to that of the comparative group devices, proving that the devices prepared in this proposal have better stability.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this utility model, and are not intended to limit it. Although the utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this utility model.

Claims

1. A complementary electrochromic film, characterized in that, include: A cathode conductive layer (2), an N-type electrochromic composite layer, an electrolyte layer (5), a P-type electrochromic composite layer, and an anode conductive layer (1) are stacked sequentially. The N-type electrochromic composite layer includes an N-type reversible electrochromic layer (6) and a transparent pseudocapacitive material layer (4) disposed on at least one side of the N-type reversible electrochromic layer (6) facing the electrolyte layer (5) and the side facing the cathode conductive layer (2). and / or; The P-type electrochromic composite layer includes a P-type reversible electrochromic layer (3) and a transparent pseudocapacitive material layer (4) disposed on at least one side of the P-type reversible electrochromic layer (3) facing the electrolyte layer (5) and the side facing the anode conductive layer (1).

2. The complementary electrochromic film according to claim 1, characterized in that, The transparent pseudocapacitive material layer (4) is selected from one or a combination of MXene layer, doped conductive polymer layer, carbon-based material layer and sub-nano oxide layer.

3. The complementary electrochromic film according to claim 1, characterized in that, The P-type reversible electrochromic layer (3) is selected from one or a combination of PEDOT layer, PProDOT layer and PolyTPD layer.

4. The complementary electrochromic film according to claim 1, characterized in that, The N-type reversible electrochromic layer (6) is selected from one or a combination of WO3 layer, NiO layer and N-type polymer layer.

5. The complementary electrochromic film according to claim 1, characterized in that, The initial state of both the P-type reversible electrochromic layer (3) and the N-type reversible electrochromic layer (6) is a neutral colored state.

6. The complementary electrochromic film according to claim 1, characterized in that, The transparent pseudocapacitive material layer (4) is located between the P-type reversible electrochromic layer (3) and the electrolyte layer (5).

7. The complementary electrochromic film according to any one of claims 1-6, characterized in that, The electrochromic film also includes a first base layer disposed on the outer surface of the cathode conductive layer (2) and a second base layer disposed on the outer surface of the anode conductive layer (1).

8. The complementary electrochromic film according to claim 7, characterized in that, The first substrate layer and / or the second substrate layer are one or a combination of glass, PET layer and PEN layer.

9. The complementary electrochromic film according to claim 7, characterized in that, The cathode conductive layer (2) and / or the anode conductive layer (1) are one or a combination of an ITO layer and a metal mesh layer.

10. A complementary electrochromic device, characterized in that, It includes two outer glass layers and an electrochromic film as described in any one of claims 1-9, fixed between the two outer glass layers.

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