Electrochromic device structure comprising reference electrode and preparation method

Abstract

The invention discloses an electrochromic device structure containing a reference electrode and a preparation method. The structure comprises at least one reference electrode, and a first conductive substrate layer, an electrochromic layer, an electrolyte layer, an ion storage layer and a second conductive substrate layer which are stacked from bottom to top, the reference electrodes are arranged on the side, close to the electrochromic layer or the ion storage layer, in the electrolyte layer, the reference electrodes make contact with the electrolyte layer, do not participate in the electrochromic reaction and are used for providing potential reference, and when the two reference electrodes are introduced, one reference electrode can serve as a third electrode to form a voltage loop with the first conductive substrate layer, and the other reference electrode can serve as a fourth electrode to form a voltage loop with the second conductive substrate layer. The other electrode and any one of the other three electrodes form a voltage loop; according to the technical scheme, the voltage and current changes of the electrochromic layer and the ion storage layer in the electrochromic device can be monitored, in-situ electrochromic spectrum research is achieved, the potential of the electrochromic layer is accurately controlled based on potential reference, and the electrochemical and spectral repeatability of the device is improved.

Description

Technical Field

[0001] The present application relates to the technical field of electrochromism and electrochemistry, and in particular to a structure and a preparation method of an electrochromic device including a reference electrode. Background Art

[0002] Electrochromic devices refer to a type of device whose apparent color changes under the action of different external electric fields, that is, its spectral state (transmittance or reflectivity) is regulated by the electric field.

[0003] At present, the electrochemical spectra of electrochromic materials reported in the literature are all measured in an electrochemical cell using a three-electrode system. However, the packaging of electrochromic devices basically adopts a simple two-electrode form, and only uses the potential step method to control the coloring and fading of electrochromic devices. Compared with the three-electrode system, the counter electrode of the two-electrode system acts as both a polarization electrode and a reference electrode, which makes the electrode potential measured more susceptible to the influence of polarization current. And as far as conductive polymer electrochromic materials are concerned, a large number of reports show that their conductivity varies greatly under different doping states, which means that in a two-electrode system, with different degrees of redox, the conductive polymer film will continuously change the ohmic polarization in the device, and the partial pressure of the film will change with the change of the external voltage, resulting in a situation where the measurement is inconsistent with the applied voltage, thereby affecting the precise electrochemical control of such devices.

[0004] In the study of using electrochromic devices as spectral control elements, they are required to have reliable optical control, which means that their film potential must be more precise. Summary of the invention

[0005] The purpose of the present application is to solve the problems in the prior art that electrochromic materials cannot be measured in situ and that the existing electrochromic devices cannot be accurately electrochemically controlled due to the influence of polarization, to provide an electrochromic device capable of in situ measurement, to introduce a reference electrode into the electrochromic device to provide an accurate potential reference for the electrochromic layer, to realize in situ electrochromic spectral research and analysis of potential matching during the electrochromic process.

[0006] The technical solution of the present application is: to provide an electrochromic device structure including a reference electrode, comprising at least one reference electrode, and a first conductive substrate layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and a second conductive substrate layer stacked from bottom to top;

[0007] The reference electrode is arranged on a side of the electrolyte layer close to the electrochromic layer, and a partition is arranged between the reference electrode and the electrochromic layer, or the reference electrode is arranged on a side of the electrolyte layer close to the ion storage layer, and a partition is arranged between the reference electrode and the ion storage layer;

[0008] The reference electrode is in contact with the electrolyte layer and is used to provide a potential reference for the electrochromic layer.

[0009] Furthermore, the electrochromic device structure also includes a working electrode connection layer and a counter electrode connection layer;

[0010] There is a lateral displacement between the first conductive substrate layer and the second conductive substrate layer, the electrochromic layer is arranged above the first conductive substrate layer and in an area where the first conductive substrate layer and the second conductive substrate layer overlap each other, and the working electrode connection layer is arranged on an area on the first conductive substrate layer that extends laterally relative to the second conductive substrate layer;

[0011] The ion storage layer is arranged below the second conductive substrate layer and in the overlapping region between the first conductive substrate layer and the second conductive substrate layer, and the counter electrode connection layer is arranged on the second conductive substrate layer and in the region extending laterally relative to the first conductive substrate layer.

[0012] Further, the reference electrode comprises an insulating flexible substrate and an electrode material, the electrode material is coated on the insulating flexible substrate, the material of the reference electrode is selected from Ag or AgCl; the material of the insulating flexible substrate is selected from polyethylene terephthalate, polyimide, polypropylene, polystyrene or polydimethylsiloxane;

[0013] The electrochromic layer uses a conductive polymer electrochromic material, which is a polymer of one material selected from the group including the following materials or a copolymer of multiple materials: aniline, pyrrole, thiophene, 3-hexylthiophene, 3,4-ethylenedioxythiophene, o-phenylenediamine, m-phenylenediamine, o-toluidine, o-anisidine, o-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid and thieno[3,4-B]-1,4-dioxin-2-methanol.

[0014] The technical solution of the present application also provides a method for preparing an electrochromic device including a reference electrode, comprising:

[0015] Step 1, preparing a reference electrode of a predetermined size;

[0016] Step 2, coating the electrochromic layer material on the first conductive substrate layer, removing the electrochromic layer material of a predetermined width on one side edge after curing, and providing a working electrode connection layer at the position where the material is removed;

[0017] Step 3, sticking the reference electrode on the electrochromic layer by means of an insulating double-sided tape, wherein the area of ​​the insulating double-sided tape is larger than the area of ​​the reference electrode on the side close to the electrochromic layer;

[0018] Step 4, coating the ion storage layer material on the second conductive substrate layer, removing the ion storage layer material of a predetermined width on one side edge after curing, and providing a counter electrode connection layer at the position where the material is removed;

[0019] Step 5, laminating the electrochromic layer and the ion storage layer together, and setting an electrolyte layer between the electrochromic layer and the ion storage layer;

[0020] Step 6, sealing the edge of the electrochromic device.

[0021] Furthermore, step 1 includes: coating a reference electrode material on a prepared substrate, performing a thermal annealing treatment, and cutting the substrate into a predetermined size after solidification to obtain a reference electrode.

[0022] Further, step 5 comprises:

[0023] The electrochromic layer is bonded to the ion storage layer through adhesive, a cavity is set in the center area of ​​the adhesive, and liquid electrolyte is injected into the cavity so that the reference electrode is in direct contact with the liquid electrolyte.

[0024] Alternatively, a gel electrolyte is coated on the ion storage layer, and the ion storage layer and the electrochromic layer film are laminated facing each other, so that the reference electrode is in direct contact with the gel electrolyte.

[0025] The technical solution of the present application also provides an application of an electrochromic device in voltage and current measurement and control, wherein the positive electrode and the negative electrode of an external source meter are respectively connected to the working electrode connection layer and the counter electrode connection layer to supply power to the electrochromic device, the working electrode connection layer and the counter electrode connection layer are respectively connected to an ammeter to form a current loop, and the working electrode connection layer and the reference electrode are respectively connected to a voltmeter to form a voltage loop;

[0026] When the electrochromic device is voltage-controlled, the relative potential between the working electrode connection layer and the reference electrode is observed by a voltmeter, and based on the observation result, the relative potential is accurately adjusted to a target value by a source meter;

[0027] When the electrochromic device is subjected to current control, the current between the working electrode connection layer and the counter electrode connection layer is observed by an ammeter, and the current is precisely adjusted by a source meter based on the observation result.

[0028] The technical solution of the present application also provides an application of an electrochromic device in electrochromic spectrum research, wherein the positive electrode and the negative electrode of the source meter are respectively connected to the working electrode connection layer and the counter electrode connection layer to supply power to the electrochromic device, the working electrode connection layer is used as the first electrode, the counter electrode connection layer is used as the second electrode, and the reference electrode close to the electrochromic layer is used as the third electrode. The first electrode and the third electrode are respectively connected to a voltmeter to form a voltage loop, wherein the source meter is used to supply power;

[0029] Taking the potential of the third electrode as a reference, the potential of the first electrode is adjusted to different target potentials through the source meter, the spectral response of the electrochromic layer corresponding to different target potentials is obtained, and the spectral characteristics of the electrochromic layer at different target potentials are recorded to form a database for spectral research.

[0030] The technical solution of the present application also provides an application of an electrochromic device in potential matching analysis, wherein the electrochromic device comprises two reference electrodes, one of which is close to the electrochromic layer and the other is close to the ion storage layer, the working electrode connection layer is used as the first electrode, the counter electrode connection layer is used as the second electrode, the reference electrode close to the electrochromic layer is used as the third electrode, and the reference electrode close to the ion storage layer is used as the fourth electrode;

[0031] When measuring the potential change of the electrochromic layer, the positive electrode and the negative electrode of the first source meter are connected to the first electrode and the third electrode respectively, the electrochromic device is powered, the first electrode and the third electrode are connected to the voltmeter respectively to form a first voltage loop, and the first source meter is used to repeatedly scan within a set potential range to record a first potential change curve between the first electrode and the third electrode;

[0032] When measuring the potential change of the ion storage layer, the positive electrode and the negative electrode of the second source meter are connected to the fourth electrode and the second electrode respectively, the electrochromic device is powered, the fourth electrode and the second electrode are connected to the voltmeter respectively to form a second voltage loop, and the second source meter is used to repeatedly scan within the set potential range to record the second potential change curve between the fourth electrode and the second electrode;

[0033] The potential matching between the electrochromic layer and the ion storage layer is calculated based on the first potential change curve and the second potential change curve, and the materials for making the electrochromic layer and the ion storage layer are selected according to the potential matching between the electrochromic layer and the ion storage layer, specifically including the following steps:

[0034] S301: Select one material from two groups of candidate materials as an electrochromic layer and an ion storage layer, respectively, to manufacture an electrochromic device;

[0035] S302: repeatedly scanning within a set potential range using a first source meter to obtain a first potential change curve of the electrochromic layer, and at the same time, performing potential monitoring using a second source meter to obtain a second potential change curve of the ion storage layer;

[0036] S303: within the set potential range, observe whether the change directions of the first potential change curve and the second potential change curve are opposite. If not, it is determined that the potentials of the electrochromic layer and the ion storage layer do not match. If opposite, the second potential change curve is reversed in the vertical direction, and the two points corresponding to the horizontal coordinates in the first potential change curve and the second potential change curve after the reverse processing are used as a group of comparison points, and the average distance between the comparison points is calculated. When the average distance is greater than a preset threshold, it is determined that the potentials of the electrochromic layer and the ion storage layer do not match. When the average distance is less than or equal to the preset threshold, it is determined that the potentials of the electrochromic layer and the ion storage layer match.

[0037] Recording the materials used for the potential-matched electrochromic layer and the ion storage layer, and the corresponding potential range;

[0038] S304: Update the set potential range, rescan the electrochromic layer and the ion storage layer with mismatched potentials, obtain the updated first potential change curve and the second potential change curve, and determine whether the potentials of the electrochromic layer and the ion storage layer match according to the method in S303. When the potentials of the electrochromic layer and the ion storage layer match, record the currently used material and the corresponding potential range. When the potentials of the electrochromic layer and the ion storage layer match, continue to update the set potential range and determine the potential match until the preset number of iterations is completed.

[0039] The technical solution of the present application also provides a patterned electrochromic device prepared by a method for preparing an electrochromic device including a reference electrode, comprising at least one reference electrode and one or more electrochromic layers distributed according to a predetermined pattern, wherein the reference electrode is a common electrode for the areas where all the electrochromic layers are located, and is used to provide a unified potential reference for the areas where all the electrochromic layers are located.

[0040] The beneficial effects of this application are:

[0041] First, the technical solution in the present application provides a low-cost, easy-to-manufacture device structure and preparation method including a reference electrode. One or more reference electrodes are introduced into the electrochromic device. The reference electrode does not participate in the electrochromic reaction and can provide a stable potential reference for the electrochromic layer. By comparing the potential between the reference electrode and the working electrode, the voltage applied to the working electrode can be accurately controlled, while avoiding measurement errors caused by electrode potential drift. Compared with existing devices, the technical solution in the present application can eliminate the voltage deviation caused by the ohmic polarization of the electropolymer electrochromic material through the reference electrode, improve the accuracy and stability of the electrochemical control, and thus improve the electrochemical repeatability and spectral repeatability of the device.

[0042] Second, the technical solution in the present application can be better applied to the research on electrochromic spectra. Taking the electrochromic device as a universal spectral control element, by controlling the potential difference between the reference electrode and the working electrode, the potential on the working electrode can be more accurately adjusted to the target potential, and the spectral characteristics of the electrochromic layer under different target potentials can be accurately obtained, avoiding the problem of inaccurate spectral characteristic analysis caused by the inability to accurately measure the working electrode potential. The technical solution in the present application can non-destructively monitor the voltage and current changes of the electrochromic layer in the electrochromic device, and realize the in-situ spectral research of the electrochromic device.

[0043] Third, the technical solution in the present application can be applied to the potential matching analysis in the electrochromic process. Reference electrodes are respectively arranged near the electrochromic layer and the ion storage layer. The potential changes of the working electrode and the counter electrode can be accurately measured through different reference electrodes to help analyze the potential matching of the electrochromic layer and the ion storage layer. According to the potential matching of the electrochromic layer and the ion storage layer, more suitable materials for making the electrochromic layer and the ion storage layer can be screened. Compared with existing devices, the technical solution in the present application can realize in-situ measurement of the device and improve the accuracy of the measurement results. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The advantages of the above and / or additional aspects of the present application will become apparent and easily understood in the description of the embodiments in conjunction with the following drawings, in which:

[0045] Figure 1 is a schematic structural diagram of an electrochromic device including a reference electrode according to an embodiment of the present application;

[0046] Figure 2 CV curve diagram and corresponding electrochromic spectrum diagram of the three-electrode electrochromic device prepared in Example 1;

[0047] Figure 3 It is a CV curve diagram and a corresponding electrochromic spectrum diagram of an existing two-electrode electrochromic device;

[0048] Figure 4 CV curve of the three-electrode electrochromic device prepared in Example 2 and electrochromic spectra of the device under different test cycles;

[0049] Figure 5 1 is a test circuit diagram of the three-electrode electrochromic device prepared in Example 1 and a diagram of the voltage change of the entire device during the corresponding CV cycle;

[0050] Figure 6 is a graph showing the potential variation of different ion storage layers of the four-electrode electrochromic device prepared in Example 3;

[0051] Figure 7 It is a structural schematic diagram and a physical picture of the packaged three-electrode device prepared in Example 1;

[0052] Figure 8 This is a physical picture of the packaged four-electrode device prepared in Example 3.

[0053] Among them, 1-first conductive substrate layer, 11-conductive material ITO, 2-electrochromic layer, 3-electrolyte layer, 4-ion storage layer, 5-second conductive substrate layer, 6-reference electrode, 7-working electrode connecting layer, 8-working electrode connecting layer, 9-packaging glue. DETAILED DESCRIPTION

[0054] In order to more clearly understand the above-mentioned purposes, features and advantages of the present application, the present application is further described in detail below in conjunction with the accompanying drawings and specific implementation methods. It should be noted that the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

[0055] In the following description, many specific details are elaborated to facilitate a full understanding of the present application. However, the present application may also be implemented in other ways different from those described herein. Therefore, the protection scope of the present application is not limited to the specific embodiments disclosed below.

[0056] like Figure 1 As shown, this embodiment provides an electrochromic device structure including a reference electrode, including at least one reference electrode 6, and a first conductive substrate layer 1, an electrochromic layer 2, an electrolyte layer 3, an ion storage layer 4 and a second conductive substrate layer 5 stacked from bottom to top.

[0057] The reference electrode 6 is arranged on a side of the electrolyte layer 3 close to the electrochromic layer 2 and is isolated from the electrochromic layer 2 , or the reference electrode 6 is arranged on a side of the electrolyte layer 3 close to the ion storage layer 4 and is isolated from the ion storage layer 4 .

[0058] The reference electrode 6 is in direct contact with the electrolyte layer 3 and is not connected to the electrochromic layer 2 and the ion storage layer 4. The reference electrode 6 does not participate in the electrochromic reaction and is only used to provide an accurate potential reference for the electrochromic layer 2 for subsequent measurement and comparison.

[0059] Specifically, the potential of the working electrode (with the first conductive substrate layer 1 as the working electrode) will change with the change of the external current, while the reference electrode 6 can provide a stable potential that is not affected by the current. As a fixed potential reference, by measuring the potential difference between the working electrode and the reference electrode 6, the potential change of the working electrode can be accurately reflected, thereby judging the electrochemical state of the electrochromic material and further inferring the change of its optical state; by comparing with the stable potential provided by the reference electrode 6, the potential applied to the first conductive substrate layer 1 can be accurately controlled, thereby achieving the adjustment of its spectral response and improving the electrochemical repeatability and spectral repeatability of the electrochromic device.

[0060] The electrochromic device structure also includes a working electrode connection layer 7 and a counter electrode connection layer 8, such as Figure 1 As shown, a lateral displacement is arranged between the first conductive substrate layer 1 and the second conductive substrate layer 5, the electrochromic layer 2 is arranged in an area above the first conductive substrate layer 1 and overlapping with the first conductive substrate layer 1 and the second conductive substrate layer 5, and the working electrode connecting layer 7 is arranged in an area on the first conductive substrate layer 1 that extends laterally relative to the second conductive substrate layer 5; the ion storage layer 4 is arranged below the second conductive substrate layer 5 and overlapping with the first conductive substrate layer 1 and the second conductive substrate layer 5, and the counter electrode connecting layer 8 is arranged in an area on the second conductive substrate layer 5 that extends laterally relative to the first conductive substrate layer 1.

[0061] In this embodiment, the first conductive substrate layer 1 is used as the working electrode, the second conductive substrate layer 5 is used as the counter electrode, the working electrode connecting layer 7 is arranged on the working electrode, and the counter electrode connecting layer 8 is arranged on the counter electrode; when the electrochromic device is tested, the working electrode connecting layer 7 is used as the first electrode, and the counter electrode connecting layer 8 is used as the second electrode, and the working electrode connecting layer 7 and the counter electrode connecting layer 8 are respectively used to connect corresponding external circuits.

[0062] In this embodiment, the first conductive substrate layer 1, the second conductive substrate layer 5 and the reference electrode 6 can constitute three electrodes and two circuits; wherein the two circuits include: a voltage circuit formed by connecting the first conductive substrate layer 1 and the reference electrode 6 to an external circuit respectively, and a current circuit formed by connecting the first conductive substrate layer 1 and the second conductive substrate layer 5 to an external circuit respectively.

[0063] Specifically, the positive electrode and the negative electrode of the external source meter are connected to the working electrode connection layer 7 and the counter electrode connection layer 8 respectively to supply power to the electrochromic device, the working electrode connection layer 7 and the counter electrode connection layer 8 are connected to the ammeter respectively to form a current loop, and the working electrode connection layer 7 and the reference electrode 6 are connected to the voltmeter respectively to form a voltage loop.

[0064] When the electrochromic device is voltage-controlled, the relative potential between the working electrode connection layer 7 and the reference electrode 6 is observed by a voltmeter, and based on the observation result, the relative potential is accurately adjusted to the target value by a source meter.

[0065] When the electrochromic device is subjected to current control, the current between the working electrode connection layer 7 and the counter electrode connection layer 8 is observed by an ammeter. Based on the observation result, the current is accurately adjusted by a source meter. At the same time, the relative potential between the working electrode connection layer 7 and the reference electrode 6 can be monitored by a voltmeter to detect potential changes in time for adjustment.

[0066] In this embodiment, the equipment used to control the three-electrode two-circuit circuit includes but is not limited to an electrochemical workstation, a source meter, a charge-discharge device or a semiconductor test analyzer.

[0067] The reference electrode 6 includes an insulating flexible substrate and an electrode material, which is obtained by coating the electrode material on the insulating flexible substrate and subjecting the coating to a curing process.

[0068] The material of the reference electrode 6 includes but is not limited to Ag / AgCl and lithium alloy; preferably, the reference electrode 6 is prepared by scraping Ag / AgCl slurry onto an insulating flexible substrate.

[0069] The material of the insulating flexible substrate is selected from polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), polystyrene (PS) or polydimethylsiloxane (PDMS); preferably, the insulating flexible substrate is a black substrate, which prevents aging of the reference electrode 6 due to light.

[0070] The first conductive substrate layer 1 includes a transparent substrate and a conductive material (ITO) on the transparent substrate. Similarly, the second conductive substrate layer 5 includes a transparent substrate and a conductive material on the transparent substrate. The conductive material of the first conductive substrate layer 1 is a transparent conductive material or a reflective conductive material, and the conductive material of the second conductive substrate layer 5 is a transparent conductive material.

[0071] The electrochromic layer 2 and the working electrode connection layer 7 are both arranged on one side of the conductive material on the first conductive substrate layer 1 , and the ion storage layer 4 and the counter electrode connection layer 8 are both arranged on one side of the conductive material on the second conductive substrate layer 5 .

[0072] The transparent substrate is made of glass or PET (polyethylene terephthalate, a commonly used polymer plastic); the transparent conductive material is made of one or a combination of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), and silver nanowires; the reflective conductive material is made of silver, gold, and aluminum.

[0073] The electrochromic layer 2 material is selected from conductive polymer electrochromic material and inorganic oxide electrochromic material; wherein the conductive polymer electrochromic material is a polymer of one material selected from the group including the following materials or a copolymer of multiple materials: aniline, pyrrole, thiophene, 3-hexylthiophene, 3,4-ethylenedioxythiophene, o-phenylenediamine, m-phenylenediamine, o-toluidine, o-anisidine, o-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid and thieno[3,4-B]-1,4-dioxin-2-methanol; the inorganic oxide electrochromic material includes but is not limited to tungsten oxide, vanadium oxide, titanium oxide, nickel oxide, molybdenum oxide, and Prussian blue.

[0074] In this embodiment, the steps of packaging the reference electrode 6 into the electrochromic device are as follows:

[0075] S101: sticking the reference electrode 6 onto the electrochromic layer 2 film by means of an insulating double-sided tape, wherein the area of ​​the insulating double-sided tape is larger than the area of ​​the reference electrode 6 on the side close to the electrochromic layer 2 film (i.e., the insulating double-sided tape is disposed between the reference electrode 6 and the electrochromic layer 2 to isolate the reference electrode 6 and the electrochromic layer 2);

[0076] S102: connecting the electrochromic layer 2 film to which the reference electrode 6 is attached to the ion storage layer 4 film through acrylic foam (VHB) glue, wherein a cavity is left in the center area of ​​the VHB glue;

[0077] S103: injecting electrolyte into the cavity using a needle, so that the side of the reference electrode 6 away from the electrochromic layer 2 film is in direct contact with the electrolyte (i.e., the effective material surface of the reference electrode 6 is exposed to the electrolyte);

[0078] S104: Use ultraviolet curing (UV) glue or epoxy glue to seal the device.

[0079] In this embodiment, a liquid electrolyte can be selected to make the electrolyte layer 3, such as the electrolyte in the above S103, or a gel electrolyte can be selected, such as a gel electrolyte. When the gel electrolyte is used, the content of the above S103 is replaced by: spin coating or scraping the gel electrolyte on the ion storage layer 4 film, and laminating it with the electrochromic layer 2 film after the reference electrode 6 is pasted, so that the side of the reference electrode 6 away from the electrochromic layer 2 film is in direct contact with the gel electrolyte.

[0080] Preferably, when testing the electrochromic layer 2 , the reference electrode 6 is pasted on the side close to the working electrode to reduce the distance between the reference electrode 6 and the working electrode, thereby reducing the resistance caused by the electrolyte layer 3 .

[0081] In this embodiment, the reference electrode 6 may also be adhered to the ion storage layer film by means of insulating double-sided tape, and the remaining operations are similar to the operations of S101 to S104 above, which will not be described in detail here.

[0082] The electrochromic device in this embodiment may be a partitioned or patterned device, that is, the electrochromic device may include one or more independent working electrodes; in a partitioned or patterned device, different regions containing independent working electrodes may share the same reference electrode 6.

[0083] In this embodiment, if the electrochromic device introduces two reference electrodes 6, one of the reference electrodes 6 can be set on the side of the electrolyte layer 3 close to the electrochromic layer 2, and the other reference electrode 6 can be set on the side of the electrolyte layer 3 close to the ion storage layer 4, and the first conductive substrate layer 1, the second conductive substrate layer 5 and the two reference electrodes 6 together constitute a four-electrode device; during use, the reference electrode close to the electrochromic layer 2 can be used as the third electrode, and the reference electrode close to the ion storage layer 4 can be used as the fourth electrode, wherein the first conductive substrate layer 1 and the third electrode are respectively connected to an external circuit to form a voltage circuit, the first conductive substrate layer 1 and the second conductive substrate layer 5 are respectively connected to an external circuit to form a current circuit, and the fourth electrode can be matched with any one of the first conductive substrate layer 1, the second conductive substrate layer 5 or the third electrode to form a voltage circuit when connected to an external circuit.

[0084] When two reference electrodes 6 are introduced, another reference electrode 6 can be pasted on the ion storage layer 4 using the same method based on the above S101 to S104. The steps of encapsulating the two reference electrodes 6 into the electrochromic device are as follows:

[0085] S201: sticking the first reference electrode onto the electrochromic layer 2 film by means of insulating double-sided tape, so that the area of ​​the insulating double-sided tape is larger than the area of ​​the first reference electrode close to the electrochromic layer 2 film, and sticking the second reference electrode onto the ion storage layer 4 film by means of insulating double-sided tape, so that the area of ​​the insulating double-sided tape is larger than the area of ​​the second reference electrode close to the ion storage layer 4 film;

[0086] S202: connecting the electrochromic layer 2 film to which the first reference electrode is attached to the ion storage layer 4 film to which the second reference electrode is attached through VHB glue, wherein a cavity is left in the center area of ​​the VHB glue;

[0087] S203: injecting electrolyte into the cavity using a needle, so that the side of the first reference electrode away from the electrochromic layer 2 film is in direct contact with the electrolyte, and the side of the second reference electrode away from the ion storage layer 4 film is in direct contact with the electrolyte;

[0088] S204: Use ultraviolet curing (UV) glue or epoxy glue to seal the device.

[0089] This embodiment provides a method for preparing an electrochromic device including a reference electrode, comprising:

[0090] Step 1, preparing a reference electrode 6 of a predetermined size;

[0091] In this embodiment, the reference electrode 6 can be prepared by a wet method. Specifically, a reference electrode material is coated on a prepared substrate, subjected to thermal annealing, and cut into a predetermined size after solidification to obtain the reference electrode 6.

[0092] Step 2, coating the electrochromic layer material on the first conductive substrate layer 1, and performing a thermal annealing treatment, after curing, removing the electrochromic material of a predetermined width on one side edge to form the electrochromic layer 2, and pasting a conductive glue at the position where the material is removed to form a working electrode connection layer 7;

[0093] In this embodiment, the electrochromic layer material is coated on one side of the first conductive substrate layer 1 where the conductive material (ITO) is provided, and an area of ​​a specific width on one edge of the ITO surface is used as the first predetermined position. After the electrochromic layer material at the first predetermined position is removed, a conductive adhesive is used to adhere the exposed ITO surface to form a working electrode connection layer 7; wherein the conductive adhesive can be copper foil conductive adhesive.

[0094] Step 3, sticking the reference electrode 6 on the electrochromic layer 2 by means of an insulating double-sided tape, wherein the area of ​​the insulating double-sided tape is larger than the area of ​​the reference electrode 6 on the side close to the electrochromic layer 2;

[0095] In this embodiment, the insulating double-sided tape is used for bonding and isolation, and the reference electrode 6 is not connected to the electrochromic layer 2 and does not participate in the electrochromic reaction.

[0096] Step 4, coating the ion storage layer material on the second conductive base layer 5, and performing a thermal annealing treatment, after curing, removing the ion storage layer material of a predetermined width on one side edge to form the ion storage layer 4, and pasting a conductive glue at the position where the material is removed to form the electrode connection layer 8;

[0097] In this embodiment, the ion storage layer material is coated on one side of the second conductive substrate layer 5 where the conductive material (ITO) is provided, and an area of ​​a specific width on one edge of the ITO surface is used as the second predetermined position. After removing the ion storage layer material at the second predetermined position, a conductive adhesive is used to adhere the exposed ITO surface to form an electrode connection layer 8.

[0098] Step 5, laminating the electrochromic layer 2 and the ion storage layer 4 together, and providing an electrolyte layer 3 between the electrochromic layer 2 and the ion storage layer 4, to form an electrochromic device, specifically comprising:

[0099] The electrochromic layer 2 to which the reference electrode 6 is attached is bonded to the ion storage layer 4 by means of an adhesive, a cavity is provided in the center area of ​​the adhesive, a liquid electrolyte is injected into the cavity to form an electrolyte layer 3, and the reference electrode 6 is in direct contact with the liquid electrolyte. Alternatively, a gel electrolyte is coated on the ion storage layer 4 to form an electrolyte layer 3, and the ion storage layer 4 coated with the gel electrolyte is bonded to the film of the electrochromic layer 2 to which the reference electrode 6 is attached facing each other, and the reference electrode 6 is in direct contact with the gel electrolyte.

[0100] Step 6: Use packaging glue 9 to seal the edge of the electrochromic device.

[0101] In this embodiment, the reference electrode 6 may also be adhered to the ion storage layer film by means of insulating double-sided tape, and the remaining operations are similar to those of the above steps 1 to 6, which will not be described again.

[0102] In this embodiment, when preparing the electrochromic device by the method of steps 1 to 6 above, multiple reference electrodes 6 can also be introduced. For example, when two reference electrodes 6 are introduced, the two reference electrodes 6 can be respectively adhered to the electrochromic layer 2 and the ion storage layer by insulating double-sided tape, which will not be repeated here.

[0103] In this embodiment, the electrochromic device including the reference electrode 6 can be applied to voltage and current measurement and control. Specifically, the positive electrode and the negative electrode of the external source meter (i.e., the power supply for power supply) can be connected to the working electrode connection layer 7 and the counter electrode connection layer 8 respectively to supply power to the electrochromic device, and the working electrode connection layer 7 and the counter electrode connection layer 8 are respectively connected to the ammeter to form a current loop, and the working electrode connection layer 7 and the reference electrode 6 are respectively connected to the voltmeter to form a voltage loop;

[0104] When the electrochromic device is voltage-controlled, the relative potential between the working electrode connection layer 7 and the reference electrode 6 is observed by a voltmeter, and based on the observation result, the relative potential is accurately adjusted to the target value by a source meter; when the electrochromic device is current-controlled, the current between the working electrode connection layer 7 and the counter electrode connection layer 8 is observed by an ammeter, and based on the observation result, the current size is accurately adjusted by a source meter.

[0105] The electrochromic device including the reference electrode can also be applied to the research of electrochromic spectrum. Specifically, the positive electrode and the negative electrode of the source meter can be connected to the working electrode connection layer 7 and the counter electrode connection layer 8 respectively to supply power to the electrochromic device. The working electrode connection layer 7 is used as the first electrode, the counter electrode connection layer 8 is used as the second electrode, and the reference electrode 6 close to the electrochromic layer 2 is used as the third electrode. The first electrode and the third electrode are respectively connected to a voltmeter to form a voltage loop.

[0106] With the potential of the third electrode as a reference, the potential of the first electrode is adjusted to different target potentials through the source meter, the spectral response of the electrochromic layer 2 corresponding to the different target potentials is obtained, and the spectral characteristics of the electrochromic layer 2 at different target potentials are recorded to form a database for spectral research, so as to facilitate subsequent spectral research.

[0107] The electrochromic device including the reference electrode can also be used for analyzing potential matching. Specifically, the reference electrode close to the electrochromic layer 2 can be used as the third electrode, and the reference electrode close to the ion storage layer 4 can be used as the fourth electrode.

[0108] When measuring the potential change of the electrochromic layer 2, the positive and negative electrodes of the first source meter are connected to the first electrode and the third electrode respectively to power the electrochromic device, and the first electrode and the third electrode are connected to the voltmeter respectively to form a first voltage loop. The first source meter is used to repeatedly scan within the set potential range (such as from -1V to +1V, and then back to -1V), and the first potential change curve between the first electrode and the third electrode is recorded.

[0109] When measuring the potential change of the ion storage layer 4, the positive and negative electrodes of the second source meter are connected to the fourth electrode and the second electrode respectively to power the electrochromic device, and the fourth electrode and the second electrode are connected to the voltmeter respectively to form a second voltage loop. The second source meter is used to repeatedly scan within the set potential range to record the second potential change curve between the fourth electrode and the second electrode.

[0110] Based on the first potential change curve and the second potential change curve, the potential matching of the electrochromic layer and the ion storage layer can be analyzed, and the materials for making the electrochromic layer and the ion storage layer can be selected according to the potential matching of the electrochromic layer and the ion storage layer, which specifically includes the following steps:

[0111] S301: Select one material from each of the two groups of candidate materials as the electrochromic layer and the ion storage layer, and use the methods in steps 1 to 6 to manufacture an electrochromic device;

[0112] S302: Connecting the electrochromic device to an external first source meter and a second source meter according to the above method, using the first source meter to repeatedly scan within a set potential range to obtain a first potential change curve of the electrochromic layer, and at the same time, using the second source meter to monitor the potential to obtain a second potential change curve of the ion storage layer;

[0113] In the above-mentioned process of potential monitoring using the second source meter, the source meter can be used as a high-impedance voltmeter and continuously measure the potential of the ion storage layer. In actual operation, a current of 10nA is continuously applied to the output end of the second source meter (the current here is much smaller than the device current and therefore will not affect the actual operation of the device). The receiving end of the second source meter continuously monitors the potential changes of the ion storage layer and obtains the corresponding potential change curve.

[0114] S303: within the set potential range, observe whether the change directions of the first potential change curve and the second potential change curve are opposite. If not, it is determined that the potentials of the electrochromic layer and the ion storage layer do not match. If opposite, the second potential change curve is vertically reversed (i.e., the second potential change curve is vertically reversed with the horizontal line of the middle value of the potential range as a reference, so that the change direction of the second potential change curve is the same as that of the first potential change curve), and the two points corresponding to the horizontal coordinates in the first potential change curve and the second potential change curve after the reverse processing are used as a group of comparison points, and the average distance between the comparison points is calculated. When the average distance is greater than a preset threshold, it is determined that the potentials of the electrochromic layer and the ion storage layer do not match. When the average distance is less than or equal to the preset threshold, it is determined that the potentials of the electrochromic layer and the ion storage layer match.

[0115] Recording the materials used for the potential-matched electrochromic layer and the ion storage layer, and the corresponding potential range;

[0116] S304: Update the set potential range, rescan the electrochromic layer and the ion storage layer with mismatched potentials, obtain the updated first potential change curve and the second potential change curve, and determine whether the potentials of the electrochromic layer and the ion storage layer match according to the method in S303. When the potentials of the electrochromic layer and the ion storage layer match, record the currently used material and the corresponding potential range. When the potentials of the electrochromic layer and the ion storage layer match, continue to update the set potential range and determine the potential match until the preset number of iterations is completed.

[0117] It should be noted that, under ideal conditions, for an electrochromic device without polarization, the number of electrons gained and lost at the two poles of the electrochromic layer and the ion storage layer is equal, and when the applied voltage changes or the applied voltage is reversed, there is no charge accumulation on the two electrode materials, so the two potential change curves change in opposite directions, that is, when the control voltage curve is the first potential change curve, if the material of the other pole can also be non-polarized or fail within this potential range, its second potential change curve changes in the opposite direction to the first potential change curve, and the closer the degree of change, the higher the degree of matching. There may be instantaneous maximum values ​​in the curve, and such maximum values ​​are ignored during calculation; therefore, more suitable materials for making the electrochromic layer and the ion storage layer can be screened out based on the potential matching between the electrochromic layer and the ion storage layer. In addition, in theory, the peaks of the first potential change curve and the second potential change curve that change in opposite directions do not correspond to each other, but the peak of the second potential change curve appears after a period of time after the peak of the first potential change curve appears. When judging whether the change directions of the first potential change curve and the second potential change curve are opposite, the situation where the peak of the second potential change curve appears after a period of time after the peak of the first potential change curve appears can be regarded as opposite (in theory, the two curves are generally opposite but not very similar, or opposite and highly similar), such as Figure 6 The black line (corresponding to the first potential change curve) and the red line (corresponding to the second potential change curve) in the middle.

[0118] In the above S301 to S304, the distance between the two points corresponding to the horizontal coordinates is used to judge the matching of the electrochromic layer and the ion storage layer. Here, the Pearson correlation coefficient or variance can also be used as a reference for judgment. In addition, the above method can also guide us to quickly screen out suitable electrochromic materials-ion storage layer material pairs by using different materials, or changing the film thickness of the same material, that is, when the device is working, the voltages of the two layers are within the reasonable voltage threshold of the material; especially when the ion storage layer material is also an electrochromic material, its potential range in the actual device can be effectively controlled to prevent over-oxidation or over-reduction from causing the material life to decay rapidly.

[0119] In this embodiment, the electrochromic device can be connected to an external circuit, and current and voltage can be applied to the electrochromic device through the external circuit, such as a Keithley 2400 source meter. The voltage and current of different electrodes can be measured using existing measuring instruments, such as an electrochemical station. The source meter includes two functions: a power supply and a voltage (current) meter. That is, when the source meter is used as a voltage source, it can output a voltage between the positive and negative electrodes, and at the same time, it can return the current of the circuit between the positive and negative electrodes. Similarly, when the source meter is used as a current source, it can output a current between the two poles and measure the voltage of the circuit between the two poles at the same time.

[0120] In this embodiment, the electrochromic device can be a patterned electrochromic device prepared by the method of steps 1 to 6 above, and the patterned electrochromic device includes at least one reference electrode 6 and one or more electrochromic layers 2 distributed according to a predetermined pattern, wherein the reference electrode 6 can serve as a common electrode for the area where all the electrochromic layers 2 are located, and is used to provide a unified potential reference for the area where all the electrochromic layers 2 are located.

[0121] Example 1:

[0122] Using Ag / AgCl material as the reference electrode, a three-electrode polyaniline electrochromic device was prepared. The specific operation is as follows:

[0123] S401: Apply the Ag / AgCl slurry on the PET substrate, place it on a hot plate at 120° C. for annealing for 30 minutes, and after it is completely cured, cut the PET into small strips of 0.5 cm×3 cm as the Ag / AgCl reference electrode;

[0124] S402: Spin-coat the chemically polymerized PANI:PSS on the ITO glass substrate, place it on a hot plate at 130° C. for annealing for 10 minutes, wipe off the electrochromic material with a width of 0.5 cm at the edge of the film, and use copper foil conductive tape to stick the exposed ITO glass;

[0125] S403: Paste the Ag / AgCl reference electrode on the PANI:PSS film through an insulating double-sided tape so that its short side is perpendicular to the copper foil conductive tape;

[0126] S404: sticking a VHB adhesive with a 1.2×1.7 cm through hole in the center onto another clean ITO glass substrate, and sticking a copper foil conductive tape onto the position of the ITO glass substrate where the VHB adhesive is not set;

[0127] S405: Paste the PANI:PSS film on the other side of the VHB glue so that the through hole in the center of the VHB glue forms a cavity in the device, and inject formic acid into the cavity of the device using a syringe as electrolyte layer 3;

[0128] S406: Use UV glue to seal the four edges of the device to obtain a No. 1 three-electrode polyaniline electrochromic device.

[0129] Figure 7 This is a physical picture of the No. 1 three-electrode polyaniline electrochromic device prepared in Example 1. The No. 1 three-electrode polyaniline electrochromic device was tested as follows:

[0130] The three-electrode polyaniline electrochromic device No. 1 was tested using Chenhua 604D electrochemical workstation, and the results are as follows: Figure 2The CV curve (scan rate is 100mv / s) shown in (a) of FIG. 1 is also shown. At the same time, the transmittance test bench constructed by the avatens spectrometer and the deuterium tungsten lamp is used to test the No. 1 three-electrode polyaniline electrochromic device, and the results are as follows: Figure 2 Electrochromic spectrum shown in (b).

[0131] Figure 3 (a) is the CV curve of the existing two-electrode device. Figure 3 (b) is the spectrum of the existing two-electrode device Figure 3 After comparison, it can be clearly found that in the No. 1 three-electrode polyaniline electrochromic device with Ag / AgCl reference electrode, the voltage range of electrochromism is significantly reduced, and the electrochemical repeatability is significantly improved. Figure 3 The peak value of the cyclic voltammetry curve (CV curve) of the two-electrode device changes continuously in each cycle. Figure 2 The CV curves of the No. 1 three-electrode polyaniline electrochromic device are basically the same. The spectral repeatability and stability of the No. 1 three-electrode polyaniline electrochromic device are improved, especially the improvement of long wavelengths (750nm, 850nm) is more obvious.

[0132] like Figure 5 As shown in (a), when a three-electrode polyaniline electrochromic device No. 1 was subjected to cyclic voltammetry scanning, a Keithley 2400 source meter was used to monitor the voltage change between the positive electrode (i.e., electrochromic layer 2 / working electrode) and the counter electrode. It was found that during the process of applying a voltage of -0.2v to +0.8v to the working layer, the voltage between the positive and negative electrodes (the positive electrode was the working electrode, and the negative electrode was the counter electrode) changed from -2v to +1.6v, as shown in Fig. Figure 5 As shown in (b), this change is caused by the strong polarization effect generated in the device. It can be seen that the CV curve obtained by CV scanning using a two-electrode device has poor repeatability and is quite different from the actual situation.

[0133] Example 2: Based on Example 1, an ion storage layer is added, and the ion storage layer uses Pedot:PSS material. A second three-electrode polyaniline electrochromic device is prepared according to the methods in steps 1 to 6.

[0134] Figure 4 (a) shows the cyclic voltammetry curve of the second three-electrode polyaniline electrochromic device after 100 cycles of testing. Figure 4 (b) shows the spectral repeatability of the electrochromic spectrum of the No. 2 three-electrode polyaniline electrochromic device within 100 cycles of testing. Figure 4 (c) shows the spectral repeatability of the electrochromic spectrum of the second three-electrode polyaniline electrochromic device in the first three cycles of the test. Figure 4As can be seen from (c) in the figure, the No. 2 three-electrode polyaniline electrochromic device with a reference electrode has good electrochemical repeatability and spectral repeatability.

[0135] Example 3: Two identical Ag / AgCl reference electrodes are introduced, namely the first reference electrode and the second reference electrode, and three four-electrode polyaniline electrochromic devices are prepared according to the method in steps 1 to 6, such as Figure 8 As shown, the first four-electrode polyaniline electrochromic device uses Pedot:PSS material as the ion storage layer, the second four-electrode polyaniline electrochromic device uses TiO2 material as the ion storage layer, and the third four-electrode polyaniline electrochromic device does not have an ion storage layer;

[0136] like Figure 6 In (a), cyclic voltammetry scans were performed using the first reference electrodes of the three four-electrode polyaniline electrochromic devices, and a source meter was used to monitor the voltage change between the second reference electrode and the ion storage layer (counter electrode).

[0137] from Figure 6 It can be seen from (b) that in the process of voltage control of the device, the voltages distributed when using different ion storage layers are quite different. When Pedot:PSS material is selected as the ion storage layer, the device exhibits good ion conductivity and electrochemical stability, and it can respond quickly to voltage changes, and the voltage response curve is relatively smooth; when TiO2 material is selected as the ion storage layer, it can be clearly seen that the device responds slowly to voltage changes, and the voltage response curve is not smooth. When TiO2 is used as the ion storage layer, the charge storage and transmission capabilities are relatively weak, affecting the overall performance of the device; when there is no ion storage layer, the voltage response curve shows a relatively unstable voltage fluctuation, and the performance of the device is greatly affected.

[0138] By setting a reference electrode, the voltage division data in the actual device can be obtained more accurately. These accurate data are helpful in understanding the role of each functional layer in the operation of the device. By analyzing these data, we can better screen and optimize more matching materials for each layer.

[0139] The steps in this application can be adjusted in order, combined, and deleted according to actual needs.

[0140] The units in the device of the present application can be combined, divided and deleted according to actual needs.

[0141] Although the present application is disclosed in detail with reference to the accompanying drawings, it should be understood that these descriptions are merely exemplary and are not intended to limit the application of the present application. The scope of protection of the present application is defined by the appended claims and may include various modifications, alterations and equivalents made to the invention without departing from the scope and spirit of the present application.

Claims

1. An electrochromic device structure comprising a reference electrode, comprising at least one reference electrode (6), and a first conductive substrate layer (1), an electrochromic layer (2), an electrolyte layer (3), an ion storage layer (4) and a second conductive substrate layer (5) stacked from bottom to top; The reference electrode (6) is arranged on a side of the electrolyte layer (3) close to the electrochromic layer (2), and a separation is provided between the reference electrode (6) and the electrochromic layer (2); or, the reference electrode (6) is arranged on a side of the electrolyte layer (3) close to the ion storage layer (4), and a separation is provided between the reference electrode (6) and the ion storage layer (4); The reference electrode (6) is in contact with the electrolyte layer (3) and is used to provide a potential reference for the electrochromic layer (2).

2. The electrochromic device structure comprising a reference electrode as claimed in claim 1, wherein: The electrochromic device structure further comprises a working electrode connection layer (7) and a counter electrode connection layer (8); The first conductive substrate layer (1) and the second conductive substrate layer (5) are laterally displaced from each other, the electrochromic layer (2) is arranged above the first conductive substrate layer (1) and in an area where the first conductive substrate layer (1) and the second conductive substrate layer (5) overlap each other, and the working electrode connection layer (7) is arranged on an area on the first conductive substrate layer (1) that extends laterally relative to the second conductive substrate layer (5); The ion storage layer (4) is arranged below the second conductive substrate layer (5) and in an area where the first conductive substrate layer (1) and the second conductive substrate layer (5) overlap each other, and the counter electrode connection layer (8) is arranged on an area of ​​the second conductive substrate layer (5) that extends laterally relative to the first conductive substrate layer (1).

3. The electrochromic device structure comprising a reference electrode as claimed in claim 1, wherein: The reference electrode (6) comprises an insulating flexible substrate and an electrode material, wherein the electrode material is coated on the insulating flexible substrate, and the material of the reference electrode (6) is selected from Ag or AgCl; the material of the insulating flexible substrate is selected from polyethylene terephthalate, polyimide, polypropylene, polystyrene or polydimethylsiloxane; The electrochromic layer (2) is made of a conductive polymer electrochromic material, which is a polymer of a material selected from the group consisting of the following materials or a copolymer of multiple materials: aniline, pyrrole, thiophene, 3-hexylthiophene, 3,4-ethylenedioxythiophene, o-phenylenediamine, m-phenylenediamine, o-toluidine, o-anisidine, o-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid and thieno[3,4-B]-1,4-dioxin-2-methanol.

4. A method for preparing an electrochromic device comprising a reference electrode, comprising: Step 1, preparing a reference electrode (6) of a predetermined size; Step 2, coating the electrochromic layer material on the first conductive substrate layer (1), removing the electrochromic layer material of a predetermined width on one side edge after curing, and arranging a working electrode connection layer (7) at the position where the material is removed; Step 3, sticking the reference electrode (6) onto the electrochromic layer (2) by means of an insulating double-sided adhesive tape, wherein the area of ​​the insulating double-sided adhesive tape is larger than the area of ​​the reference electrode (6) on the side close to the electrochromic layer (2); Step 4, coating the ion storage layer material on the second conductive substrate (5), removing the ion storage layer material of a predetermined width on one side edge after curing, and providing a counter electrode connection layer (8) at the position where the material is removed; Step 5, laminating the electrochromic layer (2) and the ion storage layer (4) together, and arranging an electrolyte layer (3) between the electrochromic layer (2) and the ion storage layer (4); Step 6, sealing the edge of the electrochromic device.

5. The method for preparing an electrochromic device comprising a reference electrode according to claim 4, wherein: The step 1 comprises: coating a reference electrode material on a prepared substrate, performing a thermal annealing treatment, and cutting the substrate into a predetermined size after solidification to obtain a reference electrode (6).

6. The method for preparing an electrochromic device comprising a reference electrode according to claim 4, wherein: The step 5 comprises: The electrochromic layer (2) is bonded to the ion storage layer (4) by means of adhesive, a cavity is provided in the center area of ​​the adhesive, a liquid electrolyte is injected into the cavity, and a reference electrode (6) is directly in contact with the liquid electrolyte. Alternatively, a gel electrolyte is coated on the ion storage layer (4), and the ion storage layer (4) and the electrochromic layer (2) film are laminated facing each other, so that the reference electrode (6) is in direct contact with the gel electrolyte.

7. An application of the electrochromic device according to any one of claims 1 to 3 in voltage and current measurement and control, wherein: The positive electrode and the negative electrode of the external source meter are respectively connected to the working electrode connection layer (7) and the counter electrode connection layer (8) to supply power to the electrochromic device, the working electrode connection layer (7) and the counter electrode connection layer (8) are respectively connected to an ammeter to form a current loop, and the working electrode connection layer (7) and the reference electrode (6) are respectively connected to a voltmeter to form a voltage loop; When the electrochromic device is subjected to voltage control, the relative potential between the working electrode connection layer (7) and the reference electrode (6) is observed by a voltmeter, and based on the observation result, the relative potential is accurately adjusted to a target value by a source meter; When the electrochromic device is subjected to current control, the current between the working electrode connection layer (7) and the counter electrode connection layer (8) is observed by an ammeter, and the current magnitude is accurately adjusted by a source meter based on the observation result.

8. An application of the electrochromic device according to any one of claims 1 to 3 in electrochromic spectrum research, wherein: The positive electrode and the negative electrode of the source meter are connected to the working electrode connection layer (7) and the counter electrode connection layer (8) respectively to supply power to the electrochromic device, the working electrode connection layer (7) is used as the first electrode, the counter electrode connection layer (8) is used as the second electrode, the reference electrode (6) close to the electrochromic layer (2) is used as the third electrode, and the first electrode and the third electrode are connected to the voltmeter respectively to form a voltage loop, wherein the source meter is used to supply power; With the potential of the third electrode as a reference, the potential of the first electrode is adjusted to different target potentials through a source meter, the spectral response of the electrochromic layer (2) corresponding to the different target potentials is obtained, and the spectral characteristics of the electrochromic layer (2) at the different target potentials are recorded to form a database for spectral research.

9. An application of the electrochromic device according to any one of claims 1 to 3 in potential matching analysis, wherein: The electrochromic device comprises two reference electrodes (6), one of which is close to the electrochromic layer (2) and the other is close to the ion storage layer (4); the working electrode connection layer (7) is used as the first electrode, the counter electrode connection layer (8) is used as the second electrode, the reference electrode close to the electrochromic layer (2) is used as the third electrode, and the reference electrode close to the ion storage layer (4) is used as the fourth electrode; When measuring the potential change of the electrochromic layer (2), the positive electrode and the negative electrode of the first source meter are connected to the first electrode and the third electrode respectively, the electrochromic device is powered, the first electrode and the third electrode are connected to the voltmeter respectively to form a first voltage loop, and the first source meter is used to repeatedly scan within a set potential range to record a first potential change curve between the first electrode and the third electrode; When measuring the potential change of the ion storage layer (4), the positive electrode and the negative electrode of the second source meter are connected to the fourth electrode and the second electrode respectively, the electrochromic device is powered, the fourth electrode and the second electrode are connected to the voltmeter respectively to form a second voltage loop, and the second source meter is used to repeatedly scan within a set potential range to record a second potential change curve between the fourth electrode and the second electrode; The potential matching between the electrochromic layer and the ion storage layer is calculated based on the first potential change curve and the second potential change curve, and the materials for making the electrochromic layer and the ion storage layer are selected according to the potential matching between the electrochromic layer and the ion storage layer, specifically including the following steps: S301: Select one material from two groups of candidate materials as an electrochromic layer and an ion storage layer, respectively, to manufacture an electrochromic device; S302: repeatedly scanning within a set potential range using a first source meter to obtain a first potential change curve of the electrochromic layer, and at the same time, performing potential monitoring using a second source meter to obtain a second potential change curve of the ion storage layer; S303: within the set potential range, observe whether the change directions of the first potential change curve and the second potential change curve are opposite. If not, it is determined that the potentials of the electrochromic layer and the ion storage layer do not match. If opposite, the second potential change curve is reversed in the vertical direction, and the two points corresponding to the horizontal coordinates in the first potential change curve and the second potential change curve after the reverse processing are used as a group of comparison points, and the average distance between the comparison points is calculated. When the average distance is greater than a preset threshold, it is determined that the potentials of the electrochromic layer and the ion storage layer do not match. When the average distance is less than or equal to the preset threshold, it is determined that the potentials of the electrochromic layer and the ion storage layer match. Recording the materials used for the potential-matched electrochromic layer and the ion storage layer, and the corresponding potential range; S304: Update the set potential range, rescan the electrochromic layer and the ion storage layer with mismatched potentials, obtain the updated first potential change curve and the second potential change curve, and determine whether the potentials of the electrochromic layer and the ion storage layer match according to the method in S403. When the potentials of the electrochromic layer and the ion storage layer match, record the currently used material and the corresponding potential range. When the potentials of the electrochromic layer and the ion storage layer match, continue to update the set potential range and determine the potential match until the preset number of iterations is completed.

10. A patterned electrochromic device prepared by the method according to any one of claims 4 to 6, comprising at least one reference electrode (6), and one or more electrochromic layers (2) distributed in a predetermined pattern, wherein: The reference electrode (6) is a common electrode for the regions where all the electrochromic layers (2) are located, and is used to provide a unified potential reference for the regions where all the electrochromic layers (2) are located.

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