Electrochromic apparatus having an N-doped conductive polymer as a transparent conductive layer, an ion storage layer, and / or an electrochromic layer

Abstract

To provide electrochromic devices containing an n-doped organic conductive polymer.SOLUTION: The present disclosure presents electrochromic devices incorporating an n-doped organic conductive polymer capable of functioning as a transparent conductor, and / or ion storage material, and / or an electrochromic material in the electrochromic devices.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. application No. 18 / 099,850, filed on 20 January 2023, and to international application PCT / US2022 / 048711, filed on 2 November 2022. The entire contents of the above applications are incorporated herein by reference.

[0002] The present invention relates to an electrochromic device having an n-doped organic conductive polymer that can serve as a transparent conductive layer and / or an ion storage layer and / or an electrochromic layer. [Background technology]

[0003] An electrochromic apparatus (ECD) typically consists of seven layers, including two non-conductive layers as a substrate, one or two transparent conductive (TC) layers, an electrochromic layer as the working electrode (WE), an ion storage layer as the counter electrode (CE), and an electrolyte layer. The electrochromic layer changes color when an external electrical bias is applied. Meanwhile, in the ion storage layer, a reaction opposite to that in the electrochromic layer occurs, balancing the charge generated in the electrochromic layer. Between the electrochromic layer and the ion storage layer is an electrolyte layer that functions as an ion source and ion conduction channel. The electrochromic layer and the ion storage layer are placed on a transparent conductor, which is the current collector for the apparatus. When two transparent conductive layers are selected, the apparatus functions as a transmissive apparatus. When one transparent conductor is used (for example, the other conductive layer is a reflective conductive layer), it typically functions as a reflective apparatus. The most commonly used TC layer in ECDs is indium tin oxide (ITO) for most EC materials due to its low sheet resistance, high light transmittance, and sufficiently large potential window. However, ITO has a small bending radius and bending strain, is mechanically brittle, and has limited applications in roll-to-roll manufacturing and flexible electronics. In addition, indium is a rare earth metal with limited mineral reserves. As the demand for ITO increases, the availability of indium will be severely restricted within 20 years, although its price has been soaring in recent years. Therefore, finding a low-cost ITO substitute that offers high performance is highly desirable, and further reducing costs by simplifying the equipment structure by reducing the number of ECD layers is even more valuable. Furthermore, it is desirable to improve performance and durability by combining permeable ion storage materials that can be treated in solution and exhibit minimal color change with electrochromic materials. [Overview of the project] [Means for solving the problem]

[0004] This disclosure relates to an electrochromic device comprising an n-doped organic conductive polymer.

[0005] In one embodiment, the electrochromic apparatus of the present disclosure includes a first insulating substrate, a first conductive layer disposed on the first insulating substrate, an ion storage layer disposed on the first conductive layer, an electrolyte layer disposed on the ion storage layer, an electrochromic layer disposed on the electrolyte layer, a second conductive layer disposed on the electrochromic layer, and a second insulating substrate disposed on the second conductive layer. In this electrochromic apparatus, the first conductive layer or the second conductive layer or the ion storage layer, or any combination thereof, is defined by formula [ka] This formula contains an n-doped organic conductive polymer. In this formula, X is O, S, or Se, each of m and n is an integer greater than zero, and each of R1 and R2 is independently hydrogen or C1~C 10 Selected from one of the alkyl groups, M + is a cation ri, m - is mM + It is a negative charge that balances it. In some embodiments, X is O, and each of R1 and R2 is hydrogen, and M + is a proton. In some embodiments, the first conductive layer, or the second conductive layer, or the ion storage layer, or any combination of the first conductive layer, the second conductive layer, and the ion storage layer, consists of the n-doped organic conductive polymer of the Disclosure. In some embodiments, both the first conductive layer and the ion storage layer contain the n-doped organic conductive polymer of the Disclosure and are integrated into a single layer.

[0006] Both inorganic and organic electrochromic materials may be used in the electrochromic layer of the electrochromic apparatus disclosed herein. In some embodiments, the electrochromic layer of the electrochromic apparatus disclosed herein includes one or more electrochromically conjugated polymers, including WO3, NiO, IrO2, V2O5, isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or copolymers containing acceptor units including benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. Various types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) may be used in the electrolyte layer of the electrochromic apparatus disclosed herein. In some embodiments, the electrolyte layer in the electrochromic apparatus disclosed herein includes a solid electrolyte or a gel electrolyte. Either inorganic or organic ion storage materials may be used for the ion storage layer in the electrochromic apparatus disclosed herein. In some embodiments, if the ion storage layer does not include the n-doped organic conductive polymer of this disclosure, the ion storage layer in the electrochromic apparatus disclosed herein includes one or more oxides of metal elements in groups 4-12, or mixtures of oxides, or one oxide doped with any other metal oxide. In some embodiments, at least one of the first conductive layer and the second conductive layer is transparent. In some embodiments, both the first conductive layer and the second conductive layer are transparent. In some embodiments, the first conductive layer or the second conductive layer includes a reflective conductive layer.

[0007] In another embodiment, the electrochromic apparatus of the present disclosure comprises a first insulating substrate, a first conductive layer disposed on the first insulating substrate, and a formula [ka] a first electrochromic layer comprising an n-doped organic conductive polymer, an electrolyte layer disposed over the first electrochromic layer, a second electrochromic layer disposed over the electrolyte layer and comprising a p-doped electrochromic material, a second conductive layer disposed over the second electrochromic layer, and a second insulating substrate disposed over the second conductive layer. In this formula, X is O, S or Se, each of m and n is an integer greater than zero, and each of R1 and R2 is independently hydrogen or C1-C 10 selected from one of the alkyls, M + is a cation ri, m - is mM + It is a negative charge that balances it. 。In some embodiments, X is O, each of R1 and R2 is hydrogen, and M + is a proton. In some embodiments, the first electrochromic layer disposed over the first conductive layer consists of the n-doped organic conductive polymer of the present disclosure.

[0008] Either inorganic or organic p-doped electrochromic materials may be used in the second electrochromic layer of the electrochromic apparatus disclosed herein. In some embodiments, the p-doped electrochromic material in the electrochromic apparatus disclosed herein includes electrochromic conjugated polymers comprising one or more NiO, IrO2, V2O5, isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or copolymers containing acceptor units comprising benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. In some embodiments, the p-doped electrochromic material is a p-doped electrochromic polymer. Various types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) may be used in the electrochromic layer of the electrochromic apparatus disclosed herein. In some embodiments, the electrolyte layer in the electrochromic apparatus disclosed herein includes a solid electrolyte or a gel electrolyte.

[0009] In some embodiments, one of the first conductive layer or the second conductive layer comprises an inorganic conductive material. In some embodiments, the inorganic conductive material comprises indium tin oxide or a metal. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent. In some embodiments, both the first conductive layer and the second conductive layer are transparent. In some embodiments, the first conductive layer or the second conductive layer is reflective and comprises a reflective conductive material.

[0010] Certain features of various embodiments of the present technology are particularly set forth in the appended claims. A better understanding of the features and advantages of the present technology can be obtained by referring to the following detailed description of embodiments for purposes of illustration that utilize the principles of the present disclosure. The accompanying drawings include the following.

Brief Description of the Drawings

[0011] [Figure 1] FIG. 8 is a cross-sectional view of an electrochromic device including a layer of an n-doped organic conductive polymer of the present disclosure that functions as a transparent conductive layer, according to one exemplary embodiment of the present disclosure. [Figure 2(A)] FIG. 11 is a diagram containing the electrical conductivity of an n-PBDF thin film, an exemplary n-doped organic conductive polymer at different thicknesses, according to some exemplary embodiments. [Figure 2(B)] FIG. 14 is a diagram containing the transmittance of an n-PBDF thin film, an exemplary n-doped organic conductive polymer at different thicknesses, according to some exemplary embodiments. [Figure 2(C)] FIG. 17 is a diagram containing the sheet resistance and transmittance at 550 nm of an n-PBDF thin film, an exemplary n-doped organic conductive polymer at different thicknesses, according to some exemplary embodiments. [Figure 3(A)] FIG. 20 shows an exemplary design of a three-electrode electrochromic device including a layer of n-PBDF, an exemplary n-doped organic conductive polymer that functions as the TC layer of the electrochromic device. FIG. 20 is a schematic diagram of a three-electrode electrochromic device according to one exemplary embodiment. [Figure 3(B)] FIG. 23 shows an exemplary design of a three-electrode electrochromic device including a layer of n-PBDF, an exemplary n-doped organic conductive polymer that functions as the TC layer of the electrochromic device. FIG. 23 is a cross-sectional view of the working electrode in FIG. 3(A). [Figure 4(A)]This figure includes cyclic voltammograms of electrochromic polymer (ECP)-B on an ITO / substrate and on an exemplary n-doped organic conductive polymer n-PBDF / substrate, as well as cyclic voltammograms of n-PBDF on a platinum button electrode. [Figure 4(B)] This is a diagram showing the spectroelectrochemical analysis of ECP-B on n-PBDF / substrate. [Figure 5(A)] This figure shows the charge capacitance of n-PBDF, an exemplary n-doped organic conductive polymer. It is a cyclic voltammogram of a 30 nm thick n-BDF thin film on ITO at different rates in 0.2 M tetrabutylammonium-bis-trifluoromethanesulfoneimidate (TBA-TFSI) in propylene carbonate (PC). [Figure 5(B)] This figure shows the charge capacitance of n-PBDF, an exemplary n-doped organic conductive polymer. It also shows the average current density at 0.3V (vs. Ag / AgCl) plotted against scanning speed. [Figure 6] This is a cross-sectional view of an electrochromic device, according to some exemplary embodiments of the present disclosure, which includes a layer of the n-doped organic conductive polymer of the present disclosure that functions as an ion storage layer. [Figure 7(A)] This is a diagram of an exemplary ITO / exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic apparatus, including a layer of n-PBDF functioning as an ion storage layer, according to one exemplary embodiment. This is a diagram of spectroelectrochemical analysis in colored and decolorized states, according to one exemplary embodiment. [Figure 7(B)] This is a diagram of an exemplary ITO / exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic apparatus, including a layer of n-PBDF functioning as an ion storage layer, according to one exemplary embodiment. This is a diagram of switching dynamics derived from stepwise potential fast chronoamperometry (SPFC), according to one exemplary embodiment. [Figure 8]A cross-sectional view of an electrochromic apparatus according to some exemplary embodiments of the present disclosure, including a layer of the n-doped organic conductive polymer of the present disclosure that simultaneously functions as both an ion storage layer and a TC layer for a counter electrode, and another layer of the n-doped organic conductive polymer of the present disclosure that functions as a TC layer for a working electrode. [Figure 9(A)] This is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic apparatus, comprising a layer of n-PBDF that simultaneously functions as both an ion storage layer and a TC layer for the counter electrode, and another layer of n-PBDF that functions as a TC layer for the working electrode, according to one exemplary embodiment. This is a diagram of spectroelectrochemical analysis in colored and decolorized states, according to one exemplary embodiment. [Figure 9(B)] This is a diagram illustrating an exemplary n-doped organic conductive polymer n-PBDF / ECP-B electrochromic apparatus, comprising a layer of n-PBDF that simultaneously functions as both an ion storage layer and a TC layer for the counter electrode, and another layer of n-PBDF that functions as a TC layer for the working electrode. This is a diagram illustrating the switching dynamics derived from an SPFC, according to one exemplary embodiment. [Figure 10(A)] This is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-M electrochromic apparatus, comprising a layer of n-PBDF that simultaneously functions as both an ion storage layer and a TC layer for the counter electrode, and another layer of n-PBDF that functions as a TC layer for the working electrode, according to one exemplary embodiment. This is a diagram of spectroelectrochemical analysis in colored and decolorized states, according to one exemplary embodiment. [Figure 10(B)] This is a diagram illustrating an exemplary n-doped organic conductive polymer n-PBDF / ECP-M electrochromic apparatus, comprising a layer of n-PBDF that simultaneously functions as both an ion storage layer and a TC layer for the counter electrode, and another layer of n-PBDF that functions as a TC layer for the working electrode. This is a diagram illustrating the switching dynamics derived from an SPFC, according to one exemplary embodiment. [Figure 11(A)]This is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic apparatus, comprising a layer of n-PBDF that simultaneously functions as both an ion storage layer and a TC layer for the counter electrode, and another layer of n-PBDF that functions as a TC layer for the working electrode, according to one exemplary embodiment. This is a diagram of spectroelectrochemical analysis in colored and decolorized states, according to one exemplary embodiment. [Figure 11(B)] This is a diagram illustrating an exemplary n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic apparatus, comprising a layer of n-PBDF that simultaneously functions as both an ion storage layer and a TC layer for the counter electrode, and another layer of n-PBDF that functions as a TC layer for the working electrode. This is a diagram illustrating the switching dynamics derived from an SPFC, according to one exemplary embodiment. [Figure 12] This figure shows the absorbance spectroscopic electrochemical analysis of an exemplary n-doped organic conductive polymer n-PBDF in 0.2 M TBA-TFSI in PC, with the applied voltage increased from -0.3 V to 0.9 V. [Figure 13] This is a cross-sectional view of an electrochromic device, according to one exemplary embodiment, which includes a layer of the n-doped organic conductive polymer of the present disclosure, serving as an electrochromic layer for a counter electrode. [Figure 14(A)] This is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / PEDOT:PSS electrochromic apparatus, including a layer of n-PBDF serving as an electrochromic layer for a counter electrode, according to one exemplary embodiment. This is a diagram of spectroelectrochemical analysis in colored and decolorized states, according to one exemplary embodiment. [Figure 14(B)] This is a diagram of an exemplary n-doped organic conductive polymer n-PBDF / PEDOT:PSS electrochromic apparatus, including a layer of n-PBDF functioning as an electrochromic layer for the counter electrode, according to one exemplary embodiment. This is a diagram of switching dynamics derived from SPFC, according to one exemplary embodiment. [Modes for carrying out the invention]

[0012] The following description provides certain specific details to give a full understanding of the various embodiments of this disclosure. However, those skilled in the art will understand that this disclosure may be implemented without these details. Furthermore, while various embodiments of this disclosure are disclosed herein, many adjustments and modifications can be made within the scope of this disclosure by the general knowledge common to those skilled in the art. Such modifications include substituting with known equivalents for any aspect of this disclosure to achieve substantially the same results in substantially the same way.

[0013] Unless otherwise required by context, throughout this specification and the claims, the word “comprise” and its variations, such as “comprises” and “comprising,” shall be interpreted in an unrestricted, inclusive sense, i.e., “including, but not limited to.” Throughout this specification, enumerations of numerical ranges of values ​​are intended to serve as abbreviations for each individual value within the range, including the value defining the range, and each individual value is incorporated herein as individually listed. In addition, the singular forms “a,” “an,” and “the” shall include multiple references unless the context expressly indicates otherwise.

[0014] Throughout this specification, any reference to “one embodiment” or “a particular embodiment” means that any specific feature, structure, or characteristic described in relation to that embodiment is included in at least one embodiment of this disclosure. Therefore, occurrences of the phrase “in one embodiment” or “in a particular embodiment” in various places throughout this specification do not necessarily all refer to the same embodiment, although in some instances they may refer to the same embodiment. Furthermore, in one or more embodiments, specific features, structures, or characteristics may be combined in any preferred manner.

[0015] The various embodiments described herein are based on the formula [ka] The subject is an electrochromic device containing an n-doped organic conductive polymer. In this formula, X is O, S, or Se, each of m and n is an integer greater than zero, and each of R1 and R2 is independently hydrogen or C1~C 10 Selected from one of the alkyl groups, M + is a cation ri, m - is mM + It is a negative charge that balances it. In some embodiments, X is O, and each of R1 and R2 is hydrogen, and M + n is a proton, and the n-doped organic conductive polymers according to these embodiments are called n-PBDFs. Layers containing the n-doped organic conductive polymers of this disclosure can function as transparent conductive (TC) layers, and / or ion storage layers, and / or electrochromic layers. Throughout this specification, three specific electrochromic polymers are used for exemplary purposes. It should be understood that this disclosure is not limited to these examples. ECP-Magenta (ECP-M) is an exemplary magenta-colored ECP. ECP-Blue (ECP-B) is an exemplary blue-colored ECP. ECP-Black (ECP-BK) is an exemplary black-colored ECP. The structures of exemplary ECP-M, ECP-B, and ECP-BK are shown below, respectively, where n is an integer greater than zero.

[0016] [ka]

[0017] Conventional electrochemical discharged cells (ECDs) consist of seven layers, including two non-conductive layers as a substrate, one or two transparent conductive (TC) layers (one for the working electrode and one for the counter electrode) disposed on the substrate, an electrochromic layer as the working electrode (WE), an ion storage layer as the counter electrode (CE), and an electrolyte layer inserted between the WE and CE. In this disclosure, a layer comprising the n-doped organic conductive polymer of this disclosure can serve as a TC layer, or / and an ion storage layer, or / and an electrochromic layer. In some embodiments, the n-doped organic conductive polymer of this disclosure can replace conventional ITO to make a highly transparent conductor, and a layer comprising the n-doped organic conductive polymer of this disclosure can function as at least one TC layer in an ECD. In some embodiments, a layer comprising the n-doped organic conductive polymer of this disclosure can function as an ion storage layer in an ECD. In some embodiments, a layer comprising the n-doped organic conductive polymer of this disclosure can function separately as both a TC layer for the counter electrode and an ion storage layer. In some embodiments, a layer comprising the n-doped organic conductive polymer of the Disclosure can function simultaneously as both a TC layer for the counter electrode and an ion storage layer (e.g., integrated as a single layer), resulting in a reduction in layers and a simplification of the structure of the electrochromic device. In some embodiments, a layer comprising the n-doped organic conductive polymer of the Disclosure can function separately as an ion storage layer for the counter electrode and a TC layer for the working electrode. In some embodiments, a layer comprising the n-doped organic conductive polymer of the Disclosure can function simultaneously as both a TC layer for the counter electrode and an ion storage layer (e.g., integrated as a single layer), and as a TC layer for the working electrode, resulting in a reduction in layers and a simplification of the structure of the electrochromic device. In some embodiments, a layer comprising the n-doped organic conductive polymer of the Disclosure can function separately as both a TC layer for the counter electrode and an ion storage layer, and as a TC layer for the working electrode.In some embodiments, a layer comprising the n-doped organic conductive polymer of the Disclosure can undergo redox reactions to exhibit electrochromic properties and function as an electrochromic layer (replacing a conventional ion storage layer as a counter electrode) and can be combined with an electrochromic layer comprising a p-doped electrochromic material as a working electrode. In some embodiments, the ECD of the Disclosure comprises a layer comprising the n-doped organic conductive polymer of the Disclosure. A layer comprising the n-doped organic conductive polymer of the Disclosure that functions as a TC layer and / or ion storage layer may also contain an electrolyte salt (e.g., Li) in addition to the n-doped organic conductive polymer of the Disclosure. + Salt, Na + Salt, TBA + The layer may also contain other components that do not significantly affect the optical properties and electrical conductivity of the layer, such as (tetrabutylammonium) or several stabilizers for modifying mechanical properties (e.g., PEG (polyethylene glycol), polystyrene). The layer comprising the n-doped organic conductive polymer of the present disclosure, which functions as an electrochromic layer, may also contain an electrolyte salt (e.g., Li) in addition to the n-doped organic conductive polymer of the present disclosure. + Salt, Na + Salt, TBA + The material may also contain other components that do not significantly affect the optical properties and electrical conductivity of the layer, such as (tetrabutylammonium) or several stabilizers for modifying mechanical properties (e.g., PEG (polyethylene glycol), polystyrene), or several other n-doped electrochromic materials such as WO3, viologen, or n-doped electrochromic polymers. A p-doped electrochromic material means that the material undergoes an electrochromic process when oxidized. An n-doped electrochromic material means that the material undergoes an electrochromic process when reduced.

[0018] In this disclosure, the n-doped organic conductive polymer exhibits low sheet resistance, high light transmittance, and a large potential window compared to most EC materials, thereby making the n-doped organic conductive polymer an organic transparent conductor for ECDs. In addition, the n-doped organic conductive polymer is mechanically flexible and can be easily applied to roll-to-roll manufacturing and flexible ECDs, competing with conventional transparent conductor ITO. In the ECD disclosed herein, if the layer containing the n-doped organic conductive polymer functions simultaneously as both an ion storage layer and a TC layer for the counter electrode, the structure of the ECD can be simplified, and thus it can be manufactured at a lower cost and with improved throughput. Therefore, the technology of this disclosure can provide high-performance ECDs at a lower cost.

[0019] In one embodiment, the electrochromic apparatus of the present disclosure includes a layer comprising the n-doped organic conductive polymer of the present disclosure, which remains transparent and does not undergo redox reactions within the potential window of the apparatus to which it is applied. There are three main different types of configurations of the electrochromic apparatus of the present disclosure. Exemplary configurations of each type are shown and discussed below.

[0020] A first type of electrochromic device of the present disclosure has at least one TC layer comprising the n-doped organic conductive polymer of the present disclosure. As shown in Figure 1, such exemplary configurations may have a first insulating substrate 102, a first conductive layer 104 disposed on the first insulating substrate 102 and comprising the n-doped organic conductive polymer of the present disclosure, an ion storage layer 106 disposed on the first conductive layer 104, an electrolyte layer 108 disposed on the ion storage layer 106, an electrochromic layer 110 disposed on the electrolyte layer 108, a second conductive layer 112 disposed on the electrochromic layer 110, a second insulating substrate 114 disposed on the second conductive layer 112, and circuit wiring 116 for operating the electrochromic device 100. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent (when the conductive layer is transparent, it is called a TC layer). In some embodiments, both the first and second conductive layers are transparent (in the case of these ECDs of the present disclosure, there are two TC layers). In some embodiments, the first or second conductive layer includes a reflective conductive layer, such as a metal layer, to form a reflective ECD. In some embodiments, the first conductive layer 104 may include a transparent conductor (e.g., ITO) that does not contain the n-doped organic conductive polymer of the present disclosure, and the second conductive layer 112 includes the n-doped organic conductive polymer of the present disclosure. In some embodiments, both the first conductive layer 104 and the second conductive layer 112 contain the n-doped organic conductive polymer of the present disclosure. In some embodiments, at least one of the first conductive layer 104 and the second conductive layer 112 consists of the n-doped organic conductive polymer of the present disclosure.

[0021] The n-doped organic conductive polymers of this disclosure can function as high-performance transparent conductors. To demonstrate this, n-PBDF is used as an exemplary n-doped organic conductive polymer, and its optical transmittance, electrical conductivity, and sheet resistance at various thicknesses are investigated. Figure 2(A) shows the conductivity of thin films with thicknesses ranging from 16 nm to 94 nm. The conductivity of the thin films increases with increasing thickness. Around a thickness of 94 nm, it reaches 6100 S / cm. The optical transmittance of the n-PBDF thin film is shown in Figure 2(B). As shown in Figure 2(B), the n-PBDF thin film exhibits high transmittance in the visible region (e.g., 400–700 nm). The high conductivity of the thin film and its high transmittance in the visible region indicate that the n-doped organic conductive polymers of this disclosure are suitable for use as transparent conductors. This is further evident in Figure 2(C), where sheet resistance and optical transmittance are plotted with thickness. At the 550nm wavelength, where the human eye is most sensitive, the optimized n-PBDF thin film exhibits a low sheet resistance of 45Ω / sq and high transmittance (T 550 It exhibits a conductivity of >80%, making it competitive with conventional transparent conductor ITO. Therefore, the n-doped organic conductive polymer of this disclosure is established as a high-performance transparent conductor.

[0022] To simplify the demonstration of the n-doped organic conductive polymer of this disclosure as a TC layer in an ECD, a three-electrode electrochromic apparatus 300 is employed. As shown in the schematic diagram in Figure 3(A), the ECD 300 disclosed herein includes a counter electrode (e.g., Pt) CE, a reference electrode (e.g., Ag / AgCl) RE, and a working electrode WE. As shown in the cross-sectional view of the working electrode WE in Figure 3(B), the working electrode WE includes a piece of glass or PET as a substrate, a layer of the n-doped organic conductive polymer of this disclosure as a transparent conductor, and a layer of an electrochromic material (e.g., ECP-B) as an electrochromic layer. In one embodiment, T 550 (Transmittance at wavelength 550nm) > 85% and R sA layer of exemplary n-doped organic conductive polymer n-PBDF with a sheet resistance < 80 Ω / sq is first coated onto a bare glass substrate, followed by the coating of an electrochromic layer, e.g., ECP-B. This glass slide is then immersed in a liquid electrolyte to prepare a three-electrode electrochromic apparatus. In one embodiment, upon application of a positive potential up to 0.7 V (vs. Ag / AgCl), ECP-B is gradually oxidized and becomes permeable. This process is captured in spectroelectrochemical analysis measurements of ECP-B in the n-PBDF / substrate structure, as shown in Figure 4(B). As the applied voltage increases, the transmittance of ECP-B in the visible region (e.g., 400-700 nm) increases. When the same measurement is performed using ITO as the transparent electrode, a very similar electrochromic response is recorded. Figure 4(A) shows the CV measurement results for ECP-B on ITO / substrate, ECP-B on n-PBDF / substrate, and n-PBDF itself obtained on a platinum button working electrode. The ECP-B electrochromic layer shows that ECP-B has the same oxidation initiation point at around -0.2V (vs. Ag / AgCl) on both the ITO transparent conductor and the n-PBDF transparent conductor, which is about 0.8V lower than the oxidation initiation point of n-PBDF (0.58V for Ag / AgCl). Therefore, when the voltage applied to n-PBDF is lower than 0.58V, n-PBDF does not undergo a redox reaction. Overall, these results demonstrate that the n-doped organic conductive polymer of this disclosure can be used as a TC layer in electrochromic devices without adversely affecting the optical and electrical properties of the electrochromic device, and can be comparable to inorganic TC (e.g., ITO).

[0023] In addition to permeability, the n-doped organic conductive polymers of this disclosure exhibit high charge density. n-PBDF, an exemplary n-doped organic conductive polymer, is used for demonstration. As shown in Figure 5(A), the volume specific capacity (C) of the n-PBDF thin film was determined by recording cyclic voltammograms at different scanning speeds in a 0.2 M TBA-TFSI(PC) electrolyte. *The following measurements were taken. According to the cyclic voltammogram, a non-zero current plateau in the range of -0.2V to +0.4V represents bilayer capacitance. As shown in Figure 5(B), the capacitive behavior is also confirmed by the linear increase in current density with increasing scanning speed. Both high optical transmittance and large charge capacitance ensure that the n-doped organic conductive polymer of this disclosure is suitable for use as an ion storage material in ECDs.

[0024] A second type of electrochromic device of the present disclosure has a layer comprising the n-doped organic conductive polymer of the present disclosure as an ion storage layer. An exemplary ECD scheme having a layer comprising the n-doped organic conductive polymer of the present disclosure functioning as an ion storage layer is shown in Figure 6. The ECD includes a first insulating substrate 602, a first conductive layer 604 disposed on the first insulating substrate 602, an ion storage layer 606 disposed on the first conductive layer 604 and comprising the n-doped organic conductive polymer of the present disclosure, an electrolyte layer 608 disposed on the ion storage layer 606 comprising the n-doped organic conductive polymer of the present disclosure, an electrochromic layer 610 disposed on the electrolyte layer 608, a second conductive layer 612 disposed on the electrochromic layer 610, a second insulating substrate 614 disposed on the second conductive layer 612, and circuit wiring 616 for operating the electrochromic device 600. The n-doped organic conductive polymer layer of this disclosure functions as an ion storage layer and can act in conjunction with either an inorganic or organic electrochromic material in the electrochromic layer 610 (working electrode). In some embodiments, the ion storage layer 606 consists of the n-doped organic conductive polymer of this disclosure. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent. In some embodiments, both the first conductive layer and the second conductive layer are transparent. In some embodiments, the first conductive layer or the second conductive layer includes a reflective conductive layer, such as a metal layer, to form a reflective ECD.

[0025] To demonstrate the performance of the n-doped organic conductive polymer-containing layer of the present disclosure as an ion storage layer (counter electrode) for an electrochromic device, the following ECD embodiment uses n-PBDF, an exemplary n-doped organic conductive polymer, as the working electrode in the electrochromic layer, with ECP-B used as the exemplary ECP. 0.2 M in 1:1 PEGDA:PC crosslinked in situ is used as the electrolyte layer 608. The n-PBDF thin film of the present disclosure is used as the ion storage layer 606 for the counter electrode. Figure 7(A) illustrates the transmittance spectrum of the electrochromic device of the present disclosure. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switched between the colored and decolorized states. Figure 7(B) shows the switching dynamics derived from stepwise potential fast chronoamperometry (SPFC), which shows that the electrochromic device achieved a fast switching from 5% to 55% at 612 nm. These results demonstrate that the n-doped organic conductive polymers of this disclosure perform well as ion storage materials for electrochromic devices.

[0026] A third type of electrochromic apparatus of the present disclosure has a layer comprising the n-doped organic conductive polymer of the present disclosure, which functions as both a TC layer and an ion storage layer. One exemplary configuration of an electrochromic apparatus 800 is shown in Figure 8. The ECD 800 comprises a first insulating substrate 802, a layer 804 disposed on the first insulating substrate 802 and comprising the n-doped organic conductive polymer of the present disclosure, an electrolyte layer 806 disposed on the layer 804 comprising the n-doped organic conductive polymer of the present disclosure, an electrochromic layer 808 disposed on the electrolyte layer 806, a TC layer 810 disposed on the electrochromic layer 808, and a second insulating substrate 812 disposed on the conductive layer 810. The conductive layer 810 may comprise the n-doped organic conductive polymer of the present disclosure, or may consist of the n-doped organic conductive polymer of the present disclosure, or may be a TC layer without the n-doped organic conductive polymer of the present disclosure, such as ITO, or may be a reflective conductive layer, such as a metal. The electrochromic apparatus 800 further includes circuit wiring 814 for operating the electrochromic apparatus 800. In this exemplary apparatus 800, a single layer 804 comprising the n-doped organic conductive polymer of the Disclosure functions simultaneously as both a TC layer for the counter electrode and an ion storage layer, thus simplifying the structure of the apparatus at a lower cost and with higher throughput. In some embodiments, due to deformation resulting from other components in each layer, the layer 804 comprising the n-doped organic conductive polymer of the Disclosure may be divided into two separate layers, one of which comprising the n-doped organic conductive polymer of the Disclosure functions as a TC layer and the other layer comprising the n-doped organic conductive polymer of the Disclosure functions as an ion storage layer. The TC layer 810 may also comprise the n-doped organic conductive polymer of the Disclosure, or consist of the n-doped organic conductive polymer of the Disclosure, or may be a TC layer without the n-doped organic conductive polymer of the Disclosure, such as ITO.In some embodiments, layer 804 containing the n-doped organic conductive polymer of the Disclosure may be divided into two separate layers, one layer containing the n-doped organic conductive polymer of the Disclosure as an ion storage layer and one TC layer, for example ITO, that does not contain the n-doped organic conductive polymer of the Disclosure, and TC layer 810 may also contain the n-doped organic conductive polymer of the Disclosure, or may consist of the n-doped organic conductive polymer of the Disclosure. In some embodiments, the electrochromic device of the Disclosure has a layer consisting of the n-doped organic conductive polymer of the Disclosure that functions as both a TC layer and an ion storage layer.

[0027] In one embodiment, n-PBDF, an exemplary n-doped organic conductive polymer, is assembled into an electrochromic apparatus using ECP-B as the electrochromic layer 808 (working electrode), 0.2 M TBATFSI in 1:1 PEGDA:PC crosslinked in situ as the electrolyte layer 806, a thin n-PBDF film as the transparent conductive layer 810 for the working electrode 808, and an n-PBDF layer 804. The n-PBDF layer 804 functions simultaneously as both a transparent conductor for the counter electrode and an ion storage layer. The optical performance of the electrochromic apparatus is shown in Figures 9(A) and 9(B). Figure 9(A) illustrates the transmittance spectrum of the electrochromic apparatus. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic apparatus successfully switched between the colored and decolorized states. Figure 9(B) shows the switching dynamics derived from SPFCs, indicating that the electrochromic device achieves high-speed switching from 18% to 70% at 612 nm. This result demonstrates that the n-doped organic conductive polymer of this disclosure performs excellently as a transparent conductor and ion storage material for counter electrodes.

[0028] The above structural configuration can also be applied to other types of ECPs. For example, ECP-B in the electrochromic layer 808 may be replaced with ECP-M or ECP-BK. The optical performance of an electrochromic device having the ECP-M electrochromic layer 808 is shown in Figures 10(A) and 10(B). Figure 10(A) is a diagram illustrating the transmittance spectrum of the electrochromic device. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switched between the colored and decolorized states. Figure 10(B) shows the switching dynamics derived from the SPFC, which shows that the electrochromic device achieved a high-speed switching from 22% to 78% at 550 nm. This result demonstrates that the n-doped organic conductive polymer of this disclosure performs well as a transparent conductor and ion storage material together with the ECP-M electrochromic layer 808.

[0029] The optical performance of the electrochromic apparatus having the ECP-BK electrochromic layer 808 is shown in Figures 11(A) and 11(B). Figure 11(A) is a diagram illustrating the transmittance spectrum of the electrochromic apparatus. The transmittance spectrum shows a large change during the coloring process, indicating that the electrochromic apparatus successfully switched between the colored and decolorized states. Figure 11(B) shows the switching dynamics derived from the SPFC, which indicates that the electrochromic apparatus achieved a high-speed switching from 7% to 40% at 550 nm. This result demonstrates that the n-doped organic conductive polymer of this disclosure also performs well with the ECP-BK electrochromic layer 808 as a transparent conductor and / or ion storage material.

[0030] Both inorganic and organic electrochromic materials may be used in the electrochromic layer of the electrochromic apparatus disclosed herein. In some embodiments, the electrochromic layer of the electrochromic apparatus disclosed herein includes one or more electrochromically conjugated polymers, including WO3, NiO, IrO2, V2O5, isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or copolymers containing acceptor units including benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. Various types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) may be used in the electrolyte layer of the electrochromic apparatus disclosed herein. In some embodiments, the electrolyte layer in the electrochromic apparatus disclosed herein includes a solid electrolyte or a gel electrolyte.

[0031] Both inorganic and organic ion storage materials may be used for the ion storage layer in the electrochromic apparatus disclosed herein. In some embodiments, if the ion storage layer does not contain the n-doped organic conductive polymer of this disclosure, the ion storage layer in the electrochromic apparatus disclosed herein comprises one or more oxides of metal elements in groups 4-12, or mixtures of oxides, or one oxide doped with any other metal oxide. Substrates 102 and 114 may be any insulating substrate, such as glass or plastic. Substrates 102 and 114 may be flexible to adapt to roll-to-roll manufacturing processes.

[0032] In another embodiment, the disclosure also relates to the use of the n-doped organic conductive polymer of the disclosure as an electrochromic layer. Exemplary organic conductive polymer PBDF and exemplary n-doped organic conductive polymer n-PBDF are redox pairs. Therefore, they can function as electrochromic materials depending on the potential. Spectroelectrochemical characterization of exemplary n-doped organic conductive polymer n-PBDF is performed in 0.2 M TBA-TFSI in PC. As shown in Figure 12, n-PBDF can undergo a redox reaction and exhibits color with maximum absorbance around 850 nm, with absorbance increasing with increasing applied voltage. Figure 13 illustrates the configuration of an electrochromic apparatus 1300 using the n-doped organic conductive polymer of the disclosure as an electrochromic material for a counter electrode, according to one exemplary embodiment. The electrochromic apparatus 1300 includes a first insulating substrate 1302, a first conductive layer 1304 disposed on the first insulating substrate 1302, a first electrochromic layer 1306 disposed on the first conductive layer 1304 and containing the n-doped organic conductive polymer of the Disclosure, an electrolyte layer 1308 disposed on the first electrochromic layer 1306 and containing the n-doped organic conductive polymer of the Disclosure, a second electrochromic layer 1310 disposed on the electrolyte layer 1308 and containing a p-doped electrochromic material, a second conductive layer 1312 disposed on the second electrochromic layer 1310 and containing a p-doped electrochromic material, and a second insulating substrate 1314 disposed on the second conductive layer 1312. In some embodiments, one of the first or second conductive layers 1304 and 1312 may contain an organic or inorganic conductive material (e.g., ITO). In some embodiments, one of the first conductive layer and the second conductive layer includes a reflective conductive material, such as a metal, to form a reflective ECD. In some embodiments, at least one of the first conductive layer or the second conductive layer is transparent. In some embodiments, both the first conductive layer and the second conductive layer are transparent.In some embodiments, the first conductive layer 1304 and the second conductive layer 1312 do not contain the n-doped organic conductive polymer of the Disclosure, because the n-doped organic conductive polymer of the Disclosure may develop color under the applied potential window for the dual polymer ECD as shown herein. The n-doped organic conductive polymer of the Disclosure in the first electrochromic layer 1306 functions as an n-doped ECP. The electrochromic device 1300 further includes circuit wiring 1316 for operating the electrochromic device 1300. In some embodiments, the first electrochromic layer 1306 consists of the n-doped organic conductive polymer of the Disclosure.

[0033] Either inorganic or organic p-doped electrochromic material may be used in the second electrochromic layer 1310. In some embodiments, the p-doped electrochromic material in the second electrochromic layer 1310 includes one or more electrochromic conjugated polymers comprising NiO, IrO2, V2O5, isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or copolymers containing acceptor units comprising benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. In some embodiments, the p-doped electrochromic material is a p-doped electrochromic polymer. Various types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) may be used for the electrolyte layer 1308 in the electrochromic apparatus disclosed herein. In some embodiments, the electrolyte layer 1308 in the electrochromic apparatus disclosed herein comprises a solid electrolyte or a gel electrolyte.

[0034] To demonstrate the performance of the n-doped organic conductive polymer of this disclosure as an EC layer, a dual polymer electrochromic apparatus is fabricated by combining n-PBDF, an exemplary n-doped organic conductive polymer, with PEDOT:PSS, an exemplary p-doped polymer. In one embodiment, n-PBDF is assembled into an electrochromic apparatus using PEDOT:PSS as a p-doped ECP, 0.2 M TBATFSI in 1:1 in situ crosslinked PEGDA:PC as an electrolyte, and n-PBDF as an n-doped ECP. A schematic diagram is shown in Figure 13. As seen in Figure 14(A), spectroelectrochemical measurements were recorded in 0.2V increments between -0.5V and 1.5V (only a few voltages are shown as an example). At one electrode, n-PBDF loses electrons during oxidation and returns to a neutral state, and the absorbance peak around 850 nm rises accordingly. At the other electrode, PEDOT:PSS is reduced, returning to a neutral state, and consequently, the absorbance peak around 700 nm increases. The electrochromic apparatus exhibits high-speed switching dynamics and a high optical contrast of 50%. As shown in Figure 14(B), at an applied voltage of -0.5 V, it reaches a decolorized state within 0.2 seconds, and at an applied voltage of 1.5 V, it becomes colored within 3 seconds. This apparatus is 1900 cm². 2 It exhibits a high coloring efficiency of / C, which is the highest record among known electrochromic devices.

[0035] The descriptions in this disclosure above are provided for illustrative and illustrative purposes only. This disclosure is not intended to be exhaustive or to be limited to any strictly disclosed form. The breadth and scope of this disclosure should not be limited by any of the exemplary embodiments described above. Many modifications and variations will be apparent to those skilled in the art. These modifications and variations include any relevant combination of the features of this disclosure. The embodiments have been selected and described to best illustrate the principles and practical applications of this disclosure, so that those skilled in the art can understand this disclosure in terms of various embodiments and various modifications suitable for specific intended uses. The scope of this disclosure is intended to be defined by the following claims and their equivalents. [Explanation of symbols]

[0036] 100 Electrochromic apparatus 102 First insulating substrate 104 First conductive layer 106 Ion storage layer 108 Electrolyte layer 110 Electrochromic layer 112 Second conductive layer 114 Second insulating substrate 116 Circuit wiring CE counter electrode RE reference electrode WE working electrode 600 Electrochromic apparatus 602 First insulating substrate 604 First conductive layer 606 Ion storage layer 608 Electrolyte layer 610 Electrochromic layer 612 Second conductive layer 614 Second insulating substrate 616 Circuit wiring 800 Electrochromic apparatus 802 First insulating substrate 804 layer containing n-doped organic conductive polymer 806 Electrolyte layer 808 Electrochromic layer 810 Conductive layer 812 Second insulating substrate 814 Circuit wiring 1300 Electrochromic apparatus 1302 First insulating substrate 1304 First conductive layer 1306 First electrochromic layer 1308 Electrolyte layer 1310 Second electrochromic layer 1312 Second conductive layer 1314 Second insulating substrate 1316 Circuit wiring

Claims

1. First insulating substrate, A first conductive layer disposed on a first insulating substrate, An ion storage layer is placed on the first conductive layer. An electrolyte layer placed on top of the ion storage layer, An electrochromic layer placed on top of the electrolyte layer, A second conductive layer placed on top of the electrochromic layer, and A second insulating substrate placed on a second conductive layer. Includes, The first conductive layer, the second conductive layer, or the ion storage layer, or any combination of the first conductive layer, the second conductive layer, and the ion storage layer, is defined by the formula 【Chemistry 1】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, M ＋ The polymer contains an n-doped organic conductive polymer (where is a cation and m- is a negative charge that balances mM+), Electrochromic device.

2. X is O, R １ and R ２ Each of them is hydrogen, M ＋ The electrochromic apparatus according to claim 1, wherein is a proton.

3. The electrochromic apparatus according to claim 1, wherein the first conductive layer, the second conductive layer, or the ion storage layer, or any combination of the first conductive layer, the second conductive layer, and the ion storage layer, is made of the n-doped organic conductive polymer.

4. The electrochromic apparatus according to claim 1, wherein both the first conductive layer and the ion storage layer contain the n-doped organic conductive polymer and are integrated into a single layer.

5. The electrochromic layer is WO ３ , NiO, IrO ２ , V ２ O ５ , isoin digo, poly (decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly (3,4-ethylenedioxythiophene) and its derivatives, poly (propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, electrochromic conjugated polymers containing these, and copolymers thereof, or one or more of copolymers containing acceptor units containing benzothiadiazole, benzotriazole or diketopyrrolopyrrole, The electrochromic device according to claim 1.

6. The electrochromic apparatus according to claim 1, wherein the electrolyte layer comprises a solid electrolyte or a gel electrolyte.

7. The electrochromic apparatus according to claim 1, wherein, if the ion storage layer does not contain the n-doped organic conductive polymer, the ion storage layer contains one or more oxides of metal elements in groups 4 to 12, a mixture of oxides, or an oxide doped with any other metal oxide.

8. The electrochromic apparatus according to claim 1, wherein at least one of the first conductive layer or the second conductive layer is transparent.

9. The electrochromic apparatus according to claim 1, wherein both the first conductive layer and the second conductive layer are transparent.

10. The electrochromic apparatus according to claim 1, wherein the first conductive layer or the second conductive layer includes a reflective conductive layer.

11. First insulating substrate, A first conductive layer disposed on a first insulating substrate, It is placed on the first conductive layer, and the formula 【Chemistry 2】 (In the formula, X is O, S, or Se, and each of m and n is an integer greater than zero, R １ and R ２ Each of them independently contains hydrogen or C １ ~C １０ Selected from one of the alkyl groups, M ＋ A first electrochromic layer contains an n-doped organic conductive polymer (where is a cation and m- is a negative charge that balances mM+), An electrolyte layer placed on top of the first electrochromic layer, A second electrochromic layer containing p-doped electrochromic material is placed on top of the electrolyte layer. A second conductive layer disposed on the second electrochromic layer, and A second insulating substrate placed on a second conductive layer. Electrochromic apparatus, including

12. X is O, R １ and R ２ Each of them is hydrogen, M ＋ The electrochromic apparatus according to claim 11, wherein is a proton.

13. The electrochromic apparatus according to claim 11, wherein the first electrochromic layer disposed on the first conductive layer is made of the n-doped organic conductive polymer.

14. The p-doped electrochromic material is NiO, IrO ２ , V ２ O ５ The electrochromic apparatus according to claim 11, comprising an electrochromic conjugated polymer including isoindigo, poly(decyl viologen) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, or one or more copolymers containing acceptor units including benzothiadiazole, benzotriazole, or diketopyrrolopyrrole.

15. The electrochromic apparatus according to claim 11, wherein the p-doped electrochromic material is a p-doped electrochromic polymer.

16. The electrochromic apparatus according to claim 11, wherein the electrolyte layer comprises a solid electrolyte or a gel electrolyte.

17. The electrochromic apparatus according to claim 11, wherein one of the first conductive layer or the second conductive layer includes an inorganic conductive material.

18. The electrochromic apparatus according to claim 17, wherein the inorganic conductive material comprises indium tin oxide or a metal.

19. The electrochromic apparatus according to claim 11, wherein at least one of the first conductive layer or the second conductive layer is transparent.

20. The electrochromic apparatus according to claim 11, wherein the first conductive layer or the second conductive layer includes a reflective conductive layer.

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