Electrochromic device with n-doped conductive polymer as transparent conductive layer, ion storage layer and / or electrochromic layer

Abstract

Disclosed are electrochromic devices comprising an n-doped organic conductive polymer that can be used in a transparent conductor, and / or an ion storage material, and / or an electrochromic material in an electrochromic device.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of international application No. PCT / US2022 / 048711 filed on November 2, 2022. The entire contents of the above application are incorporated herein by reference in their entirety. Technical Field

[0002] The present invention relates to an electrochromic device comprising an n-doped organic conductive polymer, wherein the n-doped organic conductive polymer can be used for a transparent conductive layer or / and an ion storage layer or / and an electrochromic layer. Background Art

[0003] Electrochromic devices (ECD) are usually composed of seven layers, including two non-conductive layers as substrates, one or two transparent conductive (TC) layers, an electrochromic layer as a working electrode (WE), an ion storage layer as a counter electrode (CE), and an electrolyte layer. When an external electrical bias is applied, the electrochromic layer undergoes a color change. At the same time, the ion storage layer undergoes a reaction opposite to that in the electrochromic layer to balance the charge generated at the electrochromic layer. Between the electrochromic layer and the ion storage layer is an electrolyte layer, which serves as an ion source and an ion conduction channel. The electrochromic layer and the ion storage layer are arranged on a transparent conductor, which is the current collector of the device. When two transparent conductor layers are selected, the device is used as a transmissive device. When only one layer of transparent conductor is used (for example, the other conductive layer is a reflective conductive layer), it is usually used as a reflective device. The most commonly used TC layer in ECDs is indium tin oxide (ITO) because it has low sheet resistance, high optical transparency and a voltage window large enough for most EC materials. However, ITO is mechanically fragile, has a small bending radius and strain, which limits the application of ITO in roll-to-roll manufacturing and flexible electronic devices. In addition, indium is a rare earth mineral with scarce mineral reserves. With the increase in demand for ITO, the availability of indium will be highly limited within two decades, and prices have been proven to soar in recent years. Therefore, it is highly desirable to find an ITO alternative that can provide high performance and low cost, and it is expected that the number of layers of ECDs can be reduced to simplify the device structure, thereby further reducing costs. Further, it is also expected that solution-processable, minimally discolored transmissive ion storage materials are paired with electrochromic materials to improve performance and durability. Summary of the invention

[0004] The present invention relates to electrochromic devices comprising n-doped organic conducting polymers.

[0005] In one aspect, the disclosed electrochromic device 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 the electrochromic device, the first conductive layer or the second conductive layer or the ion storage layer or any combination thereof includes a layer having a chemical formula n-doped organic conductive polymer. In the chemical formula, X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently selected from hydrogen or C1-C 10 One of the alkyl groups; M + In some embodiments, X is O, 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 is composed of the disclosed n-doped organic conductive polymer. In some embodiments, the first conductive layer and the ion storage layer both include the disclosed n-doped organic conductive polymer and are integrated into a single layer.

[0006] Both inorganic and organic electrochromic materials can be used in the electrochromic layer in the electrochromic device disclosed herein. In some embodiments, the electrochromic layer in the electrochromic device disclosed herein includes WO3, NiO, IrO2, V2O5, isoindigo, polydecylviologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers including 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 receptor units, wherein the receptor units include benzothiadiazole, benzotriazole, or dione pyrrolopyrrole. Different types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) can be used in the electrolyte layer in the electrochromic device disclosed herein. In some embodiments, the electrolyte layer in the electrochromic device disclosed herein includes a solid electrolyte or a gel electrolyte. Both inorganic and organic ion storage materials can be used in the ion storage layer in the electrochromic device disclosed herein. In some embodiments, when the ion storage layer does not include the disclosed n-doped organic conductive polymer, the ion storage layer in the electrochromic device disclosed herein includes one or more oxides of metal elements of Groups 4-12, or a mixture of these oxides, or one of these oxides 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 aspect, the disclosed electrochromic device includes: a first insulating substrate; a first conductive layer disposed on the first insulating substrate; a first electrochromic layer disposed on the first conductive layer and including a n-doped organic conductive polymer; an electrolyte layer disposed on the first electrochromic layer; a second electrochromic layer disposed on the electrolyte layer and including a p-doped electrochromic material; a second conductive layer disposed on the second electrochromic layer; and a second insulating substrate disposed on the second conductive layer. In the chemical formula, X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently selected from hydrogen or C1-C 10 One of the alkyl groups; M + In some embodiments, X is O, each of R1 and R2 is hydrogen, and M + In some embodiments, the first electrochromic layer disposed on the first conductive layer is composed of the disclosed n-doped organic conductive polymer.

[0008] Both inorganic and organic p-doped electrochromic materials can be used in the second electrochromic layer in the electrochromic device disclosed herein. In some embodiments, the p-doped electrochromic material in the electrochromic device disclosed herein includes NiO, IrO2, V2O5, isoindigo, polydecyl viologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers including 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 receptor units. One or more of the receptor units include benzothiadiazole, benzotriazole, or pyrrolopyrrole dione. In some embodiments, the p-doped electrochromic material is a p-doped electrochromic polymer. Different types of electrolyte materials (such as liquid electrolytes, gel electrolytes, or solid electrolytes) can be used in the electrochromic layer in the electrochromic device disclosed herein. In some embodiments, the electrolyte layer in the electrochromic devices 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. BRIEF DESCRIPTION OF THE DRAWINGS

[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 will be obtained by reference to the following detailed description, which sets forth illustrative embodiments and in which the principles of the invention are utilized. The accompanying drawings include:

[0011] Figure 1 A cross-sectional view of an electrochromic device according to an example embodiment of the present invention is depicted, the electrochromic device including a layer of the disclosed n-doped organic conductive polymer used as a transparent conductive layer.

[0012] 2(A)-(C) are graphs of conductivity (FIG. 2(A)), transmittance (FIG. 2(B)), and sheet resistance and transmittance at 550 nm (FIG. 2(C)) of example n-doped organic conductive polymer n-PBDF films of different thicknesses according to some example embodiments.

[0013] Figures 3(A)-(B) depict an example design of a 3-electrode electrochromic device including a layer of an example n-doped organic conductive polymer n-PBDF serving as a TC layer of the electrochromic device. Figure 3(A) is a schematic diagram of a 3-electrode electrochromic device according to an example embodiment. Figure 3(B) is a cross-sectional view of the working electrode in Figure 3(A).

[0014] Figures 4(A)-(B) are cyclic voltammograms of electrochromic polymer (ECP)-B contained on ITO / substrate and on an example n-doped organic conductive polymer n-PBDF / substrate and cyclic voltammograms of n-PBDF on a platinum button electrode (Figure 4(A)) and spectro-electrochemistry of ECP-B on n-PBDF / substrate (Figure 4(B)).

[0015] Figures 5(A)-(B) are graphs illustrating the charge capacity of an example n-doped organic conductive polymer n-PBDF. Figure 5(A) is a cyclic voltammogram of a 30 nm thick n-BDF film formed at different rates on ITO in 0.2 M tetrabutylammonium bistrifluoromethanesulfonimide (TBA-TFSI) in propylene carbonate (PC). Figure 5(B) illustrates the average current density at 0.3 V (vs. Ag / AgCl) plotted against scan rate.

[0016] Figure 6 is a cross-sectional view of an electrochromic device according to some example embodiments of the present invention, the electrochromic device including a layer of the disclosed n-doped organic conductive polymer used as an ion storage layer.

[0017] Figures 7(A)-(B) are diagrams of an example ITO / example n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device according to an example embodiment, the electrochromic device including a layer of n-PBDF used as an ion storage layer. Figure 7(A) is a spectroelectrochemistry in the colored and faded states according to an example embodiment, and Figure 7(B) describes the conversion kinetics from step potential fast chronoamperometry (SPFC) according to an example embodiment.

[0018] Figure 8 is a cross-sectional view of an electrochromic device according to some example embodiments of the present invention, which includes a layer of the disclosed n-doped organic conductive polymer serving as both an ion storage layer and a TC layer for a counter electrode and another layer of the disclosed n-doped organic conductive polymer serving as a TC layer for a working electrode.

[0019] Figures 9(A)-(B) are diagrams of an example n-doped organic conductive polymer n-PBDF / ECP-B electrochromic device according to an example embodiment, the electrochromic device includes a layer of n-PBDF used as both an ion storage layer and a TC layer for a counter electrode and another layer of n-PBDF used as a TC layer for a working electrode. Figure 9(A) is the spectroelectrochemistry in the colored and faded states according to an example embodiment, and Figure 9(B) describes the conversion kinetics from the SPFC according to an example embodiment.

[0020] Figures 10(A)-(B) are diagrams of an example n-doped organic conductive polymer n-PBDF / ECP-M electrochromic device according to an example embodiment, the electrochromic device including a layer of n-PBDF used as both an ion storage layer and a TC layer for a counter electrode and another layer of n-PBDF used as a TC layer for a working electrode. Figure 10(A) is the spectroelectrochemistry in the colored and faded states according to an example embodiment, and Figure 10(B) describes the conversion kinetics from the SPFC according to an example embodiment.

[0021] Figures 11(A)-(B) are diagrams of an example n-doped organic conductive polymer n-PBDF / ECP-BK electrochromic device according to an example embodiment, the electrochromic device includes a layer of n-PBDF used as both an ion storage layer and a TC layer for a counter electrode and another layer of n-PBDF used as a TC layer for a working electrode. Figure 11(A) is the spectroelectrochemistry in the colored and faded states according to an example embodiment, and Figure 11(B) describes the conversion kinetics from the SPFC according to an example embodiment.

[0022] Fig.12 is the absorption spectroelectrochemistry of an example n-doped organic conducting polymer n-PBDF in 0.2 M TBA-TFSI in PC with the applied voltage increasing from -0.3 V to 0.9 V.

[0023] Fig.13 is a cross-sectional view of an electrochromic device including a layer of the disclosed n-doped organic conductive polymer used as an electrochromic layer for a counter electrode according to an example embodiment.

[0024] Figures 14(A)-(B) contain images of an example n-doped organic conductive polymer n-PBDF / PEDOT:PSS electrochromic device according to an example embodiment, the electrochromic device including a layer of n-PBDF used as an electrochromic layer for a counter electrode. Figure 14(A) is the spectroelectrochemistry in the colored and faded states according to an example embodiment, and Figure 14(B) describes the conversion kinetics from the SPFC according to an example embodiment. DETAILED DESCRIPTION

[0025] In the following description, certain specific details are set forth in order to provide a thorough understanding of various embodiments of the present invention. However, it will be appreciated by those skilled in the art that the present invention can be implemented without these details. Moreover, although various embodiments of the present invention are disclosed herein, many adaptations and modifications may be made within the scope of the present invention according to the common knowledge of those skilled in the art. These modifications include replacing any aspect of the present invention with known equivalents in order to achieve the same results in substantially the same manner.

[0026] Unless the context requires otherwise, in this specification and claims, the word "comprise" and variations thereof (e.g., "comprising" and "containing") are to be interpreted in an open, inclusive sense, i.e., "including, but not limited to." References to numerical ranges of values ​​are intended to be used as shorthand notation to refer individually to each separate value falling within the range, including the values ​​defining the range, and each separate value is incorporated into the specification as if individually recited. In addition, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0027] Reference in this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in conjunction with the embodiment is included in at least one embodiment of the present invention. Thus, the phrases "in one embodiment" or "in an embodiment" appearing in various places in this specification do not necessarily all refer to the same embodiment, but may do so in some cases. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0028] Various embodiments described herein relate to an electrochromic device comprising a device having the formula n-doped organic conductive polymer. In the chemical formula, X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently selected from hydrogen or C1-C 10 One of the alkyl groups; M + In some embodiments, X is O, each of R1 and R2 is hydrogen, and M +is a proton, and the n-doped organic conductive polymer according to these embodiments is called n-PBDF. The layer including the disclosed n-doped organic conductive polymer can be used as a transparent conductive (TC) layer and / or an ion storage layer and / or an electrochromic layer. In this specification, three specific electrochromic polymers are used for illustrative purposes. It should be understood that the present invention is not limited to these examples. ECP-magenta (ECP-M) is an example magenta ECP. ECP-blue (ECP-B) is an example blue ECP. ECP-black (ECP-BK) is an example black ECP. The structures of example ECP-M, ECP-B and ECP-BK are shown below, respectively, where n is an integer greater than zero.

[0029] Conventional ECDs are composed of seven layers, including two non-conductive layers as substrates, one or two transparent conductive (TC) layers (one for the working electrode and one for the counter electrode) respectively disposed on the substrates, an electrochromic layer as a working electrode (WE), an ion storage layer as a counter electrode (CE), and an electrolyte layer inserted between WE and CE. In the present invention, a layer including the disclosed n-doped organic conductive polymer can be used as a TC layer or / and an ion storage layer or / and an electrochromic layer. In some embodiments, the disclosed n-doped organic conductive polymer can replace the traditional ITO as a large transparent conductor, and a layer including the disclosed n-doped organic conductive polymer can be used as at least one TC layer in an ECD. In some embodiments, a layer including the disclosed n-doped organic conductive polymer can be used as an ion storage layer in an ECD. In some embodiments, a layer including the disclosed n-doped organic conductive polymer can be used as a TC layer and an ion storage layer for a counter electrode, respectively. In some embodiments, a layer including the disclosed n-doped organic conductive polymer can be used as a TC layer and an ion storage layer for a counter electrode at the same time (e.g., integrated into a single layer), so that the number of layers is reduced, thereby simplifying the electrochromic device structure. In some embodiments, the layer including the disclosed n-doped organic conductive polymer can be used as an ion storage layer for the counter electrode and a TC layer for the working electrode, respectively. In some embodiments, the layer including the disclosed n-doped organic conductive polymer can be used as a TC layer and an ion storage layer for the counter electrode (for example, integrated into a single layer) and a TC layer for the working electrode at the same time, so that the number of layers is reduced, thereby simplifying the electrochromic device structure. In some embodiments, the layer including the disclosed n-doped organic conductive polymer can be used as a TC layer and an ion storage layer for the counter electrode and a TC layer for the working electrode, respectively. In some embodiments, the layer including the disclosed n-doped organic conductive polymer can undergo a redox reaction to exhibit electrochromic properties, thereby being used as an electrochromic layer (as a counter electrode, instead of a conventional ion storage layer), which is paired with an electrochromic layer including a p-doped electrochromic material as a working electrode. In some embodiments, the disclosed ECD includes a layer composed of the disclosed n-doped organic conductive polymer. When the layer including the disclosed n-doped organic conductive polymer is used as a TC layer and / or an ion storage layer, in addition to the disclosed n-doped organic conductive polymer, other components that do not significantly affect the optical properties and conductivity of the layer may be included, such as electrolyte salts (e.g., Li + Salt, Na + Salt, TBA +(tetrabutylammonium)) or some stabilizers for adjusting its mechanical properties (such as PEG (polyethylene glycol), polystyrene). When the layer including the disclosed n-doped organic conductive polymer is used as an electrochromic layer, in addition to the disclosed n-doped organic conductive polymer, other components that do not significantly affect the optical properties and conductivity of the layer may be included, such as electrolyte salts (such as Li + Salt, Na + Salt, TBA + (tetrabutylammonium) or some stabilizer that adjusts its mechanical properties (e.g. PEG (polyethylene glycol), polystyrene) or some other n-doped electrochromic material, such as WO3, viologen or n-doped electrochromic polymer). P-doped electrochromic material means a material that undergoes an electrochromic process when oxidized. N-doped electrochromic material means a material that undergoes an electrochromic process when reduced.

[0030] In the present invention, the disclosed n-doped organic conductive polymer shows low sheet resistance, high optical transparency and large voltage window for most EC materials, which makes the disclosed n-doped organic conductive polymer an organic transparent conductor for ECD. In addition, the disclosed n-doped organic conductive polymer is mechanically flexible and can be easily applied to roll-to-roll manufacturing and flexible ECDs, which is comparable to the traditional transparent conductor ITO. In the ECD disclosed in the present invention, when the layer including the disclosed n-doped organic conductive polymer is used as both an ion storage layer and a TC layer for a counter electrode, the ECD structure can be simplified, and thus the ECD can be manufactured at a lower cost and with increased production volume. Therefore, the disclosed technology can provide high-performance ECDs at a lower cost.

[0031] In one aspect, the disclosed electrochromic device includes a layer comprising the disclosed n-doped organic conductive polymer that does not undergo redox reactions and remains transparent in the applied device voltage window. The disclosed electrochromic device configurations are of three main different types. Individual example configurations from each type are shown and discussed below.

[0032] The first type of disclosed electrochromic devices has at least one TC layer comprising the disclosed n-doped organic conductive polymer. Figure 1As shown, such an example configuration may have: a first insulating substrate 102; a first conductive layer 104, which includes the disclosed n-doped organic conductive polymer, disposed on the first insulating substrate 102; an ion storage layer 106, which is disposed on the first conductive layer 104; an electrolyte layer 108, which is disposed on the ion storage layer 106; an electrochromic layer 110, which is disposed on the electrolyte layer 108; a second conductive layer 112, which is disposed on the electrochromic layer 110; a second insulating substrate 114, which is disposed on the second conductive layer 112; and a circuit 116, which controls 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 referred to as a TC layer). In some embodiments, both the first conductive layer and the second conductive layer are transparent (for these disclosed ECDs, there are two TC layers). 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. In some embodiments, the first conductive layer 104 may include a transparent conductor (such as ITO) without the disclosed n-doped organic conductive polymer, while the second conductive layer 112 includes the disclosed n-doped organic conductive polymer. In some embodiments, both the first conductive layer 104 and the second conductive layer 112 include the disclosed n-doped organic conductive polymer. In some embodiments, at least one of the first conductive layer 104 and the second conductive layer 112 is composed of the disclosed n-doped organic conductive polymer.

[0033] The disclosed n-doped organic conductive polymer can be used as a high-performance transparent conductor. To demonstrate this, n-PBDF is used as an example n-doped organic conductive polymer, and its optical transmittance, conductivity and sheet resistance at various thicknesses are studied. FIG. 2(A) is a graph showing the conductivity of films with a thickness of 16 nm to 94 nm. The conductivity of the film increases with the increase of the film thickness. When the thickness is around 94 nm, the conductivity can reach 6100 S / cm. The optical transmittance of the n-PBDF film is described in FIG. 2(B). As shown in FIG. 2(B), the n-PBDF film shows high transmittance in the visible light region (e.g., 400-700 nm). The high conductivity of the film and the high transmittance in the visible light region indicate that the disclosed n-doped organic conductive polymer is suitable for use as a transparent conductor. This is more obvious in FIG. 2(C), where the sheet resistance and optical transmittance are plotted together with the film thickness. At 550nm wavelength, where the human eye is most sensitive, the optimized n-PBDF film exhibits a low sheet resistance of 45Ω / sq and high transmittance (T 550 >80%), which is comparable to the conventional transparent conductor ITO. Thus, the disclosed n-doped organic conductive polymers are established as high performance transparent conductors.

[0034] In order to simplify the demonstration of the disclosed n-doped organic conductive polymer as a TC layer in an ECD, a three-electrode electrochromic device 300 is used. As shown in the schematic diagram in FIG3(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 FIG3(B), the working electrode WE includes a piece of glass or PET as a substrate, a layer of the disclosed n-doped organic conductive polymer as a transparent conductor, and a layer of an electrochromic material (e.g., ECP-B) as an electrochromic layer. In one embodiment, a T is first coated on a bare glass substrate. 550 (Transmittance at wavelength 550nm)>85% and R s (sheet resistance) < 80Ω / sq. An example of an n-doped organic conductive polymer n-PBDF layer is then coated with an electrochromic layer, such as ECP-B. The slide is then immersed in a liquid electrolyte to create a 3-electrode electrochromic device. In one embodiment, upon application of a positive potential up to 0.7V (relative to Ag / AgCl), ECP-B is gradually oxidized and becomes transmissive. This process was captured in the spectroelectrochemical measurement of ECP-B on the n-PBDF / substrate structure as shown in FIG4(B). As the applied voltage increases, the transmittance of ECP-B in the visible region (e.g., 400-700nm) increases. The same measurements were performed when ITO was used as the transparent electrode, and very similar electrochromic responses were recorded. FIG4(A) shows the CV measurement results of ECP-B on ITO / substrate, ECP-B on n-PBDF / substrate, and n-PBDF itself measured on a platinum button working electrode. The ECP-B electrochromic layer shows that ECP-B has the same oxidation starting point on ITO and n-PBDF transparent conductors, which is about -0.2V (relative to Ag / AgCl), which is about 0.8V lower than the oxidation starting point of n-PBDF (0.58V relative to Ag / AgCl). Therefore, when the voltage applied to n-PBDF is lower than 0.58V, n-PBDF does not undergo redox reaction. In summary, these results show that the disclosed n-doped organic conductive polymer can be used as a TC layer in an electrochromic device, and does not negatively affect the optical and electrical properties of the electrochromic device, which is comparable to inorganic TC (such as ITO).

[0035] In addition to transparency, the disclosed n-doped organic conductive polymer also exhibits high charge density. Demonstration is performed using an example n-doped organic conductive polymer n-PBDF. As shown in FIG5(A), the specific volume capacitance (C*) of the n-PBDF film is measured by recording cyclic voltammograms at different scan rates in a 0.2M TBA-TFSI (PC) electrolyte. According to the cyclic voltammogram, the non-zero current plateau in the range of -0.2V to +0.4V represents the double-layer capacitance. As shown in FIG5(B), the linear increase in current density with scan rate also confirms the capacitive behavior. Both high transmittance and large charge capacity ensure that the disclosed n-doped organic conductive polymer can be used as an ion storage material in an ECD.

[0036] A second type of disclosed electrochromic device has a layer comprising the disclosed n-doped organic conductive polymer as an ion storage layer. Figure 6 An example ECD scheme having a layer including the disclosed n-doped organic conductive polymer as an ion storage layer is shown in FIG. 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 including the disclosed n-doped organic conductive polymer disposed on the first conductive layer 604; an electrolyte layer 608 disposed on the ion storage layer 606 including the disclosed n-doped organic conductive polymer; 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 a circuit 616 that controls the electrochromic device 600. The disclosed n-doped organic conductive polymer layer is used as an ion storage layer and can work with an inorganic or organic electrochromic material in the electrochromic layer 610 (working electrode). In some embodiments, the ion storage layer 606 is composed of the disclosed n-doped organic conductive polymer. 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.

[0037] In order to demonstrate the performance of the layer including the disclosed n-doped organic conductive polymer as an ion storage layer (counter electrode) in an electrochromic device, ECP-B is used as an example ECP as a working electrode at the electrochromic layer, and an example n-doped organic conductive polymer n-PBDF is used in the following ECD embodiments. 0.2M in 1:1 PEGDA:PC cross-linked in situ is used as an electrolyte layer 608. The disclosed n-PBDF film is used as an ion storage layer 606 for the counter electrode. FIG. 7(A) is a diagram describing the transmission spectrum of the disclosed electrochromic device. The transmission spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the colored state and the faded state. FIG. 7(B) shows the conversion kinetics from the step potential fast chronoamperometry (SPFC), which shows that the electrochromic device achieves a rapid conversion from 5% to 55% at 612nm. These results show that the disclosed n-doped organic conductive polymer is excellent as an ion storage material for electrochromic devices.

[0038] A third type of disclosed electrochromic device has a layer including the disclosed n-doped organic conductive polymer that functions as both a TC layer and an ion storage layer. Figure 8An example configuration of an electrochromic device 800 is shown in FIG. 800 includes: a first insulating substrate 802; a layer 804 including the disclosed n-doped organic conductive polymer, which is disposed on the first insulating substrate 802; an electrolyte layer 806, which is disposed on the layer 804 including the disclosed n-doped organic conductive polymer; an electrochromic layer 808, which is disposed on the electrolyte layer 806; a TC layer 810, which is disposed on the electrochromic layer 808; and a second insulating substrate 812, which is disposed on the conductive layer 810. The conductive layer 810 may include or be composed of the disclosed n-doped organic conductive polymer, or may be a TC layer without the disclosed n-doped organic conductive polymer, such as ITO, or may be a reflective conductive layer, such as a metal. The electrochromic device 800 also includes a circuit 814 for controlling the electrochromic device 800. In this example device 800, a single layer 804 including the disclosed n-doped organic conductive polymer is used as both a TC layer and an ion storage layer for a counter electrode, thereby simplifying the device structure, lowering costs, and increasing production volume. In some embodiments, due to changes in other components in each layer, the layer 804 including the disclosed n-doped organic conductive polymer can be divided into two separate layers, wherein one layer including the disclosed n-doped organic conductive polymer is used as a TC layer, and the other layer including the disclosed n-doped organic conductive polymer is used as an ion storage layer. The TC layer 810 can also include or consist of the disclosed n-doped organic conductive polymer, or can be a TC layer without the disclosed n-doped organic conductive polymer, such as ITO. In some embodiments, the layer 804 including the disclosed n-doped organic conductive polymer can be divided into two separate layers, wherein one layer includes the disclosed n-doped organic conductive polymer as an ion storage layer, and the other TC layer does not have the disclosed n-doped organic conductive polymer, such as ITO, and the TC layer 810 can also include or consist of the disclosed n-doped organic conductive polymer. In some embodiments, the disclosed electrochromic devices have a layer composed of the disclosed n-doped organic conductive polymer that functions as both a TC layer and an ion storage layer.

[0039] In one embodiment, an example n-doped organic conductive polymer n-PBDF is assembled into an electrochromic device using ECP-B as an electrochromic layer 808 (working electrode), 0.2M TBATFSI in an in-situ cross-linked 1:1 PEGDA:PC as an electrolyte layer 806, an n-PBDF film as a transparent conductive layer 810 for the working electrode 808, and an n-PBDF layer 804. The n-PBDF layer 804 is used as both a transparent conductor and an ion storage layer for the counter electrode. The optical properties of the electrochromic device are illustrated in Figures 9(A) and 9(B). Figure 9(A) is a diagram describing the transmission spectrum of the electrochromic device. The transmission spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the coloring state and the fading state. The conversion kinetics from the step potential fast SPFC are shown in Figure 9(B), which shows that the electrochromic device achieves a fast conversion from 18% to 70% at 612nm. These results demonstrate that the disclosed n-doped organic conducting polymers work well as transparent conductors and ion storage materials for counter electrodes.

[0040] The above-mentioned structural configuration can also be applied to other types of ECP. For example, the ECP-B of the electrochromic layer 808 can be replaced by ECP-M or ECP-BK. The optical properties of the electrochromic device with the electrochromic layer 808 of ECP-M are illustrated in Figures 10(A) and 10(B). Figure 10(A) is a diagram describing the transmission spectrum of the electrochromic device. The transmission spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the colored state and the faded state. The conversion dynamics from the step potential fast SPFC are shown in Figure 10(B), which shows that the electrochromic device achieves a rapid conversion from 22% to 78% at 550nm. These results show that the disclosed n-doped organic conductive polymer is excellent as a transparent conductor and an ion storage material of the ECP-M electrochromic layer 808.

[0041] The optical performance of an electrochromic device having an ECP-BK electrochromic layer 808 is illustrated in Figures 11(A) and 11(B). Figure 11(A) is a diagram describing the transmission spectrum of the electrochromic device. The transmission spectrum shows a large change during the coloring process, indicating that the electrochromic device successfully switches between the colored state and the faded state. The conversion dynamics from the step potential fast SPFC are shown in Figure 11(B), which shows that the electrochromic device achieves a rapid conversion from 7% to 40% at 550nm. These results show that the disclosed n-doped organic conductive polymers also work well as transparent conductors and / or ion storage materials for the ECP-BK electrochromic layer 808.

[0042] Both inorganic and organic electrochromic materials can be used in the electrochromic layer in the electrochromic device disclosed herein. In some embodiments, the electrochromic layer in the electrochromic device disclosed herein includes WO3, NiO, IrO2, V2O5, isoindigo, polydecyl viologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers including 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. One or more of the acceptor units include benzothiadiazole, benzotriazole, or pyrrolopyrrole dione. Different types of electrolyte materials (such as liquid electrolytes, gel electrolytes, or solid electrolytes) can be used in the electrolyte layer in the electrochromic device disclosed herein. In some embodiments, the electrolyte layer in the electrochromic device disclosed herein includes a solid electrolyte or a gel electrolyte.

[0043] Both inorganic and organic ion storage materials can be used in the ion storage layer in the electrochromic device disclosed herein. In some embodiments, when the ion storage layer does not include the disclosed n-doped organic conductive polymer, the ion storage layer in the electrochromic device disclosed herein includes one or more oxides of metal elements of Groups 4-12, or a mixture of these oxides, or one of these oxides doped with any other metal oxide. Substrates 102 and 114 can be any insulating substrate, such as glass or plastic. Substrates 102 and 114 can be flexible to accommodate roll-to-roll manufacturing processes.

[0044] In another aspect, the present invention also relates to the use of the disclosed n-doped organic conductive polymer as an electrochromic layer. The example organic conductive polymer PBDF and the example n-doped organic conductive polymer n-PBDF are redox pairs. Therefore, they can potentially be used as electrochromic materials. The example n-doped organic conductive polymer n-PBDF in 0.2M TBA-TFSI in PC was subjected to spectroelectrochemical characterization. Fig.12 As shown, n-PBDF can undergo redox reaction and present a color with maximum absorbance around 850 nm, and the absorbance increases with the increase of applied voltage. Fig.13The construction of an electrochromic device 1300 according to an example embodiment is described, which uses the disclosed n-doped organic conductive polymer as the electrochromic material for the counter electrode. The electrochromic device 1300 includes: a first insulating substrate 1302; a first conductive layer 1304, which is disposed on the first insulating substrate 1302; a first electrochromic layer 1306, which includes the disclosed n-doped organic conductive polymer, disposed on the first conductive layer 1304; an electrolyte layer 1308, which is disposed on the first electrochromic layer 1306 including the disclosed n-doped organic conductive polymer; a second electrochromic layer 1310, which includes a p-doped electrochromic material, disposed on the electrolyte layer 1308; a second conductive layer 1312, which is disposed on the second electrochromic layer 1310 including the p-doped electrochromic material; and a second insulating substrate 1314, which is disposed on the second conductive layer 1312. In some embodiments, one of the first conductive layer 1304 and the second conductive layer 1312 may include 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 include the disclosed n-doped organic conductive polymer because the disclosed n-doped organic conductive polymer may be colored under the applied voltage window of such a dual polymer ECD as exemplified herein. The disclosed n-doped organic conductive polymer in the first electrochromic layer 1306 is used as an n-doped ECP. The electrochromic device 1300 also includes a circuit 1316 for manipulating the electrochromic device 1300. In some embodiments, the first electrochromic layer 1306 is composed of the disclosed n-doped organic conductive polymer.

[0045] Both inorganic and organic p-doped electrochromic materials can 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 of NiO, IrO2, V2O5, isoindigo, polydecyl viologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers including 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 an acceptor unit, the acceptor unit including benzothiadiazole, benzotriazole, or diketopyrrolopyrrole. In some embodiments, the p-doped electrochromic material is a p-doped electrochromic polymer. Different types of electrolyte materials (e.g., liquid electrolytes, gel electrolytes, or solid electrolytes) can be used in the electrolyte layer 1308 in the electrochromic device disclosed herein. In some embodiments, electrolyte layer 1308 in the electrochromic devices disclosed herein includes a solid electrolyte or a gel electrolyte.

[0046] To demonstrate the performance of the disclosed n-doped organic conductive polymers as EC layers, an example n-doped organic conductive polymer, n-PBDF, was paired with an example p-doped polymer, PEDOT:PSS, to fabricate a dual polymer electrochromic device. In one embodiment, n-PBDF was assembled into an electrochromic device using PEDOT:PSS as the p-doped ECP, 0.2M TBATFSI in in-situ cross-linked 1:1 PEGDA:PC as the electrolyte, and n-PBDF as the n-doped ECP. Fig.13 A schematic diagram is drawn in . As shown in Figure 14(A) (only a few voltages are shown as examples), spectroelectrochemical measurements were recorded between -0.5V and 1.5V in increments of 0.2V. On one electrode, n-PBDF loses electrons upon oxidation and returns to a neutral state, accompanied by an increase in the absorption peak near 850nm. On the other electrode, PEDOT:PSS is reduced and returns to a neutral state, accompanied by an increase in the absorption peak near 700nm. The electrochromic device shows fast switching kinetics and a high optical contrast of 50%. As shown in Figure 14(B), the electrochromic device reaches a faded state within 0.2s at an applied voltage of -0.5V and becomes colored within 3s at an applied voltage of 1.5V. The device shows 1900cm 2 The high coloring efficiency of 1.17 W / C is the highest value recorded in known electrochromic devices.

[0047] The above description of the present invention is provided for the purpose of illustration and description. The description is not intended to be exhaustive of the present invention or to limit the present invention to the precise form disclosed. The breadth and scope of the present invention should not be limited by any of the above exemplary embodiments. Many modifications and changes will be apparent to those skilled in the art. Modifications and changes include any relevant combination of the disclosed features. The embodiments are selected and described in order to best explain the principles of the present invention and its practical application, so that other technical personnel in the art can understand the various embodiments of the present invention and the various modifications suitable for the specific purposes envisioned. The scope of the present invention is intended to be defined by the appended claims and their equivalents.

Claims

1. An electrochromic device, comprising: a first insulating substrate; A first conductive layer, which is disposed on the first insulating substrate; an ion storage layer, which is 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; as well as a second insulating substrate, which is disposed on the second conductive layer; Wherein, 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 comprises a layer having a chemical formula n-doped organic conductive polymer, wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently selected from hydrogen or C1-C 10 One of the alkyl groups; M + It is a cation.

2. The electrochromic device according to claim 1, wherein: X is O, each of R1 and R2 is hydrogen, M + It's a proton.

3. The electrochromic device according to claim 1, wherein: 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 is composed of the n-doped organic conductive polymer.

4. The electrochromic device according to claim 1, wherein: The first conductive layer and the ion storage layer each include the n-doped organic conductive polymer and are integrated into a single layer.

5. The electrochromic device according to claim 1, wherein: The electrochromic layer includes one or more of WO3, NiO, IrO2, V2O5, isoindigo, polydecyl viologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers including 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, wherein the acceptor units include benzothiadiazole, benzotriazole, or dione pyrrolopyrrole.

6. The electrochromic device according to claim 1, wherein: The electrolyte layer includes a solid electrolyte or a gel electrolyte.

7. The electrochromic device according to claim 1, wherein: When the ion storage layer does not include the n-doped organic conductive polymer, the ion storage layer includes one or more oxides of Group 4-12 metal elements, or a mixture of the oxides, or one of the oxides doped with any other metal oxide.

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

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

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

11. An electrochromic device, comprising: a first insulating substrate; A first conductive layer, which is disposed on the first insulating substrate; A first electrochromic layer is disposed on the first conductive layer and comprises a chemical formula n-doped organic conductive polymer, wherein X is O, S or Se; each of m and n is an integer greater than zero; each of R1 and R2 is independently selected from hydrogen or C1-C 10 One of the alkyl groups; M + It is a cation; an electrolyte layer disposed on the first electrochromic layer; a second electrochromic layer disposed on the electrolyte layer and comprising a p-doped electrochromic material; a second conductive layer disposed on the second electrochromic layer; and The second insulating substrate is disposed on the second conductive layer.

12. The electrochromic device according to claim 11, wherein: X is O, each of R1 and R2 is hydrogen, M + It's a proton.

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

14. The electrochromic device according to claim 11, wherein: The p-doped electrochromic material includes one or more of NiO, IrO2, V2O5, isoindigo, polydecyl viologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers including 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, wherein the acceptor units include benzothiadiazole, benzotriazole, or dione pyrrolopyrrole.

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

16. The electrochromic device according to claim 11, wherein: The electrolyte layer includes a solid electrolyte or a gel electrolyte.

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

18. The electrochromic device according to claim 17, wherein: The inorganic conductive material includes indium tin oxide or metal.

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

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

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