WO2024082197A1 - Controllable electrochromic device, optical performance regulation and control method therefor, and application thereof - Google Patents
Controllable electrochromic device, optical performance regulation and control method therefor, and application thereof Download PDFInfo
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- WO2024082197A1 WO2024082197A1 PCT/CN2022/126288 CN2022126288W WO2024082197A1 WO 2024082197 A1 WO2024082197 A1 WO 2024082197A1 CN 2022126288 W CN2022126288 W CN 2022126288W WO 2024082197 A1 WO2024082197 A1 WO 2024082197A1
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- optical
- electrochromic device
- electrochromic
- control
- controllable
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
Definitions
- the present invention belongs to the field of optoelectronic technology, and in particular relates to a controllable electrochromic device and an optical performance regulation method and application thereof.
- Electrochromic technology has the advantages of low energy consumption and dynamically adjustable optical properties, so it is widely used. For example, it is used in the fields of adaptive infrared protection, optical camouflage, smart windows, anti-glare rearview mirrors, etc.
- electrochromic devices With the development of modern science and technology, there is an urgent need for high-precision optical control technology of electrochromic devices. Therefore, the development of advanced optical dynamic control technology and its high-precision controllable adjustment method has become a hot topic of research.
- electrochromic devices involve different electrochemical redox reactions in the dynamic optical performance modulation process; on the other hand, conventional optical performance control methods are often based on voltage control, and there is a voltage hysteresis effect, which leads to a decrease in control accuracy and efficiency.
- the existing technology needs to monitor the optical properties of electrochromic devices in real time and continuously, and dynamically obtain the required optical properties based on the external optical performance requirements.
- this process not only causes continuous energy consumption, but also requires additional and complex devices (such as light sensing elements) to monitor the optical performance, which is difficult to meet the requirements of different scenarios for high efficiency, low cost and low energy consumption of optical control technology.
- the existing electrochromic device optical performance control technology mainly uses photosensitive elements to monitor the optical performance of electrochromic devices in real time and continuously, and then feeds back relevant signals to adjust the voltage or current, thereby controlling the electrochromic device to obtain the required optical performance (for example, a control method for electrochromic glass and electrochromic glass disclosed in the patent with application number 202010383716.X, and an electrochromic system, control method and electrochromic rearview mirror disclosed in the patent with application number 201710233384.5). Due to the voltage hysteresis effect when controlling the optical performance of electrochromic devices by adjusting the working voltage, it is difficult to accurately control the optical performance of electrochromic devices. In addition, continuous monitoring of the optical performance of electrochromic devices requires the introduction of additional photosensitive elements and analysis devices, which increases the complexity of the optical control system and increases the cost and energy consumption.
- controllable electrochromic device does not require the introduction of additional photosensitive elements and devices to perform real-time and continuous monitoring of the electrochromic device, which not only reduces the complexity of the regulation system, but also can achieve precise regulation of the optical properties of the electrochromic device, reduce energy consumption, and reduce costs.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
- the present invention proposes a controllable electrochromic device and a method and application for regulating optical properties thereof, wherein the controllable electrochromic device does not require the introduction of additional photosensitive elements.
- the optical properties regulation method does not require the introduction of additional photosensitive elements and devices to continuously monitor the electrochromic device in real time, which not only reduces the complexity of the controllable electrochromic device (the controllable electrochromic device may also be referred to as an electrochromic optical regulation system), but also enables precise regulation of its optical properties, reduces energy consumption, and reduces costs.
- the present invention discloses a controllable electrochromic device that does not rely on additional light sensing elements or devices to monitor the electrochromic device in real time.
- the optical performance of the electrochromic device can be precisely quantitatively controlled.
- the present invention discloses a simple-to-operate optical performance regulation method, which does not require the introduction of additional photosensitive elements or devices to perform real-time and continuous monitoring of the electrochromic device, which not only reduces the complexity of the entire electrochromic optical regulation system, but also can achieve precise regulation of its optical performance, reduce energy consumption, and reduce costs.
- the present invention utilizes the difference in the electric-to-optical conversion efficiency of different redox processes in the electrochromic device during the electrochromic process, combined with the simple control of the effective transfer of charge during the electrochemical redox process, thereby achieving high-precision quantitative regulation of the optical properties of the electrochromic device.
- the optical properties regulation method provided by the present invention is simple in process, easy to operate, and can achieve high-precision regulation.
- a first aspect of the present invention provides a controllable electrochromic device.
- controllable electrochromic device comprising an electrochromic device and a current control device
- the current control device controls the electrochromic device by using the formula shown below:
- OD is the optical density required in the electrochromic process
- OD0 is the initial optical density of the electrochromic device in the electrochromic process
- ⁇ i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process
- Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process
- N is the number of different redox reactions occurring in the electrochromic process
- It is the current density at different times t in the electrochromic process.
- controllable electrochromic device also includes a voltage control device.
- the current control device comprises an electrochemical workstation.
- controllable electrochromic device further comprises a current monitoring device and/or a voltage monitoring device.
- controllable electrochromic device further comprises a photometer.
- the photometer is a UV-Vis-NIR spectrophotometer.
- a controllable electrochromic device comprises an electrochromic device, an electrochemical workstation, and a photometer.
- the electrochromic device comprises at least an electrochromic layer and a conductive substrate layer.
- the electrochromic device further includes an ion conductor layer and an ion storage layer.
- the structure of the electrochromic device is conductive substrate layer/electrochromic layer or conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer.
- the conductive substrate layer may also be called an electron conductor layer.
- the material of the electrochromic layer includes at least one of tungsten oxide, nickel oxide, vanadium oxide, manganese oxide, titanium oxide, lithium manganate, lithium titanate, iridium oxide, polyaniline, polypyrrole, and polythiophene.
- the material of the conductive substrate layer includes at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), nanosilver wire, silver, gold, aluminum, copper, nanocarbon tubes, graphene, and poly(ethylenedioxythiophene).
- ITO indium tin oxide
- FTO fluorine-doped tin oxide
- AZO aluminum-doped zinc oxide
- nanosilver wire silver, gold, aluminum, copper, nanocarbon tubes, graphene, and poly(ethylenedioxythiophene).
- the material of the conductive substrate layer is silver, gold, aluminum, or copper
- the silver, gold, aluminum, or copper may have a porous structure.
- the material of the ion conductor layer includes at least one of carbonate electrolyte, ether electrolyte, sulfone electrolyte, phosphate electrolyte, aqueous electrolyte, lithium niobate, lithium phosphorus oxynitride (LiPON), tantalum oxide, lithium lanthanum zirconium oxide (LLZO), polyethylene oxide polymer electrolyte, and polymethyl methacrylate (PMMA) based polymer electrolyte.
- carbonate electrolyte ether electrolyte, sulfone electrolyte, phosphate electrolyte, aqueous electrolyte, lithium niobate, lithium phosphorus oxynitride (LiPON), tantalum oxide, lithium lanthanum zirconium oxide (LLZO), polyethylene oxide polymer electrolyte, and polymethyl methacrylate (PMMA) based polymer electrolyte.
- ether electrolyte
- the carbonate electrolyte includes at least one of propylene carbonate/LiClO 4 , propylene carbonate/NaClO 4 , and propylene carbonate/Al(ClO 4 ) 3 .
- the ether electrolyte includes at least one of ethylene glycol dimethyl ether/LiTFSI (LiTFSI refers to lithium bis(trifluoromethanesulfonyl imide) and ethylene glycol dimethyl ether/NaTFSI (NaTFSI refers to sodium bis(trifluoromethanesulfonyl imide).
- LiTFSI refers to lithium bis(trifluoromethanesulfonyl imide
- NaTFSI ethylene glycol dimethyl ether/NaTFSI refers to sodium bis(trifluoromethanesulfonyl imide).
- the sulfone electrolyte includes at least one of sulfolane/LiFSI and sulfolane/NaFSI.
- the ether electrolyte includes at least one of ethylene glycol dimethyl ether/LiTFSI and ethylene glycol dimethyl ether/NaTFSI.
- the sulfone electrolyte includes at least one of sulfolane/LiFSI (LiFSI refers to lithium bis(fluorosulfonyl)imide) and sulfolane/NaFSI (NaFSI refers to sodium bis(fluorosulfonyl)imide).
- LiFSI refers to lithium bis(fluorosulfonyl)imide
- NaFSI sodium bis(fluorosulfonyl)imide
- the phosphate ester electrolyte includes at least one of diethyl phosphate/LiFSI and diethyl phosphate/NaFSI.
- the aqueous electrolyte includes at least one of water/ZnSO 4 , water/KCl, and water/ZnCl 2 .
- the material of the ion storage layer includes at least one of tungsten oxide, nickel oxide, vanadium oxide, manganese oxide, titanium oxide, lithium manganate, lithium titanate, iridium oxide, polyaniline, polypyrrole, and polythiophene.
- the thickness of the electrochromic device is 5nm-1100 ⁇ m; further preferably, the thickness of the electrochromic device is 5nm-1000 ⁇ m.
- the thickness of the electrochromic device can specifically be 10nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 2 ⁇ m, 10 ⁇ m, 100 ⁇ m, 1000 ⁇ m.
- the thickness of the electrochromic layer in the electrochromic device is 10nm-1000 ⁇ m; further preferably, the thickness of the electrochromic layer in the electrochromic device is 50nm-1000 ⁇ m.
- the thickness of the electrochromic layer can be 10nm, 50nm, 100nm, 300nm, 500nm, 1 ⁇ m, 10 ⁇ m, 100 ⁇ m, 1000 ⁇ m.
- the electrochemical workstation operates in a two-electrode or three-electrode mode.
- the electrochemical workstation works in a three-electrode mode, wherein the electrochromic device is used as a working electrode, platinum is used as a counter electrode, and Ag/AgCl is used as a reference electrode.
- the electrochemical workstation works in a two-electrode mode, wherein the conductive substrate layer adjacent to the electrochromic layer in the electrochromic device serves as the working electrode, and the conductive substrate layer adjacent to the ion storage layer serves as the counter electrode and the reference electrode.
- a second aspect of the present invention provides a method for regulating the optical properties of a controllable electrochromic device.
- a method for controlling the optical properties of a controllable electrochromic device comprises the following steps:
- the current control device is started to use an electrochemical method to effectively transfer charge control on the electrochemical reaction in the electrochromic process of the electrochromic device, thereby achieving quantitative and precise regulation of the optical properties of the electrochromic device.
- the voltage control device is also started, and then an electrochemical method is used to effectively transfer charge control of the electrochemical reaction in the electrochromic process of the electrochromic device.
- the electrochromic device is also monitored by a current monitoring device and/or a voltage monitoring device.
- the electrochemical method includes at least one of cyclic voltammetry, constant current method, constant voltage method, alternating current method, pulse current method, alternating voltage method, pulse voltage method, gradient voltage method, and gradient current method.
- the electrochemical method comprises at least one of cyclic voltammetry, constant current method, constant voltage method, cyclic voltammetry-constant current method, cyclic voltammetry-constant voltage method, constant current method-constant voltage method, cyclic voltammetry-constant voltage method-constant current method.
- Cyclic voltammetry-constant current method means that cyclic voltammetry is first used and then constant current method is used.
- the optical properties include at least one of optical density, optical transmittance, reflectivity, emissivity, and chromaticity.
- the optical wavelength involved in the optical properties includes at least one of the X-ray region, ultraviolet light region, visible light region, infrared light region, microwave region and radio wave region.
- the optical properties of the electrochromic device are tested using a photometer to obtain the desired optical properties.
- a method for controlling the optical properties of a controllable electrochromic device comprises the following steps:
- the optical properties of the electrochromic device are quantitatively and accurately regulated, and the optical properties of the electrochromic device are tested using a photometer to obtain the desired optical properties.
- the formula used for the optical regulation is as follows:
- OD is the optical density (or optical absorbance) required in the electrochromic process
- OD 0 is the initial optical density (or initial optical absorbance) of the electrochromic device in the electrochromic process
- ⁇ i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process
- Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process
- N is the number of different redox reactions occurring in the electrochromic process
- It is the current density at different times t in the electrochromic process.
- the optical density of the electrochromic device can be quantitatively and accurately regulated without the need to introduce additional photosensitive elements or devices to continuously monitor the electrochromic device.
- the optical control precision error of the optical performance control method is less than 5%; further preferably, the optical control precision error of the optical performance control method is less than 4%, even less than 3% or less than 1%.
- the optical control precision error refers to the error between the theoretical value and the measured value.
- the method for preparing the electrochromic device includes at least one of a physical vapor deposition method, a chemical vapor deposition method, an electrochemical method, and a coating method.
- the physical vapor deposition method includes magnetron sputtering or evaporation.
- the physical vapor deposition method is used to prepare the electrochromic device.
- the electrochromic device is prepared by electrochemical method or coating method.
- the electrochromic device can be prepared by electropolymerizing organic monomers and depositing them on a conductive substrate, or by coating the organic material on a conductive substrate by spin coating or scraping.
- a third aspect of the present invention provides an application of the above-mentioned controllable electrochromic device or a method for regulating the optical properties of a controllable electrochromic device.
- the present invention relates to the application of the controllable electrochromic device or the optical performance regulation method in the optoelectronic field.
- the optoelectronic field includes photochromic glass, infrared protection, optical camouflage, smart windows or anti-glare rearview mirrors.
- the controllable electrochromic device of the present invention comprises an electrochromic device and a current control device, wherein the current control device controls the electrochromic device by using the following formula:
- the controllable electrochromic device is an optical performance control system that does not rely on additional photosensitive elements or devices to monitor the electrochromic device in real time.
- the controllable electrochromic device achieves precise quantitative control of the optical performance of the electrochromic device by accurately evaluating the electro-optical conversion efficiency of the electrochromic device in different electrochemical redox processes, and then combining it with precise control of the effective transfer charge density in the continuous electrochemical redox process.
- the optical performance control method of the present invention does not require the introduction of additional light-sensing elements and devices to continuously monitor the electrochromic device in real time, which not only reduces the complexity of the entire electrochromic optical control system, but also can achieve precise control of its optical performance, reduce energy consumption, and reduce costs.
- the optical control accuracy error of the optical performance control method is less than 5%, or even less than 1%.
- FIG1 is a graph showing the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 4 of the present invention;
- FIG2 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 17 of the present invention
- Example 3 shows the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 34 of the present invention
- FIG4 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 35 of the present invention
- Example 5 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value) corresponding to the optical property regulation method of Example 38 of the present invention, as well as the electro-optical conversion efficiency in different redox reaction processes;
- Example 47 of the present invention shows the constant voltage method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 47 of the present invention
- Figure 7 shows the cyclic voltammetry control (theoretical value) and the first-order derivative of the real-time optical density corresponding to the optical property regulation method of Example 45 of the present invention, as well as the effective transfer charge density and optical density (measured value) obtained by the constant current method and time control of Example 46.
- the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.
- Example 1-33 Controllable electrochromic device, optical performance control method
- a controllable electrochromic device comprising an electrochromic device, an electrochemical workstation, and an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer;
- UV-Vis-NIR ultraviolet-visible-near infrared
- the electrochromic device was used as the working electrode of the electrochemical workstation;
- the electrochromic device comprises an electrochromic layer and a conductive base layer.
- the material of the electrochromic layer is tungsten oxide, the conductive base layer is ITO glass, and the electrochromic layer is on the surface of the conductive base layer.
- the preparation method of the electrochromic device is: depositing an electrochromic layer on ITO glass by magnetron sputtering, and the thickness of the electrochromic layer is controlled by the sputtering time of the magnetron sputtering method (depositing a material layer on ITO glass by magnetron sputtering is a conventional technology in the art).
- the optical performance control method of the controllable electrochromic device comprises the following steps:
- the optical properties of the electrochromic device are quantitatively regulated, and the optical properties (optical density) of the electrochromic device are tested using an ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrophotometer to obtain the desired optical properties (optical density).
- UV-Vis-NIR ultraviolet-visible-near-infrared
- OD is the optical density required in the electrochromic process
- OD 0 is the initial optical density of the electrochromic device in the electrochromic process
- ⁇ i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process
- Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, wherein the electro-optical conversion efficiency depends only on the redox reactions occurring in the electrochromic process and the intrinsic physicochemical properties of the material, and has nothing to do with the current density, charge density, etc.
- N is the number of different redox reactions occurring in the electrochromic process
- It is the current density at different times t in the electrochromic process.
- the optical density of the electrochromic device can be quantitatively and accurately regulated without the need to introduce additional photosensitive elements or devices to continuously monitor the electrochromic device.
- the electrochemical workstation operates in a three-electrode mode, wherein the electrochromic device is used as the working electrode, platinum is used as the counter electrode, Ag/AgCl is used as the reference electrode, and LiClO 4 /propylene carbonate solution is used as the electrolyte.
- Example 31 the cyclic voltammetry method is first used to control the coloring of the electrochromic device, and the cut-off voltage is -0.5V (vs. Ag/AgCl). Then, the coloring control is continued by the constant current method, and the cut-off voltage is -1.0V (vs. Ag/AgCl).
- the control wavelength of the electrochromic device is 550nm, a controllable electrochromic device with an optical density of 0.703 can be obtained.
- the present invention adopts the following optical control principle: By evaluating the electro-optical conversion efficiency of tungsten oxide electrochromic materials and precisely controlling the charge during different electrochemical control processes, the optical properties (optical density) of electrochromic devices can be effectively controlled, showing high control accuracy, and the optical density error is generally less than 1%.
- Examples 34-44 change the material type of the electrochromic layer, and the rest of the process is similar to Examples 1-33.
- the specific control parameters and results are shown in Table 2.
- the optical performance control method of the electrochromic device proposed in the present invention when applied to different electrochromic material systems, also exhibits high optical performance control accuracy, and the optical density error is generally less than 1%.
- a controllable electrochromic device comprising an electrochromic device, an electrochemical workstation, and an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer;
- UV-Vis-NIR ultraviolet-visible-near infrared
- the electrochromic device was used as the working electrode of the electrochemical workstation;
- the structure of the electrochromic device is conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer in order; tungsten oxide is used as the electrochromic layer, lithium niobate is used as the ion conductor layer, nickel oxide or lithium manganate is used as the ion storage layer, and ITO glass is used as the conductive substrate layer.
- the electrochromic device is made by magnetron sputtering, and the thickness of each layer of the electrochromic device is controlled by the sputtering time of the magnetron sputtering method.
- the thickness of the conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer is 120nm, 300nm, 200nm, 400nm and 300nm in order.
- the optical performance control method of the controllable electrochromic device comprises the following steps:
- Example 45 the cyclic voltammetry method (scan rate of 0.05 V/s) is used to control the effective transfer charge, and the working voltage range is from -1.5 V to 2.0 V; in Example 46, the constant current method (current density of 0.1 mA/cm 2 ) is used to control the effective transfer charge, and the working voltage range is from -1.5 V to 2.0 V; in Example 47, the constant voltage method (working voltage of -1.5 V) is used to control the effective transfer charge, and the working time lasts for 40 s);
- the optical properties of the electrochromic device are quantitatively regulated, and the optical properties (optical density) of the electrochromic device are tested using an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer to obtain the desired optical properties (optical density).
- UV-Vis-NIR ultraviolet-visible-near infrared
- in-situ optical performance monitoring is used during the electrochemical regulation of the optical properties of the electrochromic device to evaluate the error between the measured optical density and the theoretical value.
- OD is the optical density required in the electrochromic process
- OD 0 is the initial optical density of the electrochromic device in the electrochromic process
- ⁇ i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process
- Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, wherein the electro-optical conversion efficiency depends only on the redox reactions occurring in the electrochromic process and the intrinsic physicochemical properties of the material, and has nothing to do with the current density, charge density, etc.
- N is the number of different redox reactions occurring in the electrochromic process
- It is the current density at different times t in the electrochromic process.
- the optical density of the electrochromic device can be quantitatively and accurately regulated without the need to introduce additional photosensitive elements or devices to continuously monitor the electrochromic device.
- the electrochemical workstation works in a two-electrode mode, in which the conductive substrate layer adjacent to the electrochromic layer in the electrochromic device serves as the working electrode, and the conductive substrate layer adjacent to the ion storage layer serves as the counter electrode and reference electrode.
- control method of the present invention also has a high optical performance control accuracy for the electrochromic device with a multilayer structure, and the optical density error is generally less than 1%.
- FIG1 shows the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 4 of the present invention
- the ordinate “Area current” on the left side of FIG1(a) represents the area current
- the ordinate “Transmittance” on the right side represents the transmittance
- the abscissa “Potential” represents the electric potential
- “Bleaching” represents fading
- “Coloring” represents coloring.
- the ordinate “Area capacity” on the left side of FIG1(b) represents the area capacity
- the ordinate “Optical density” on the right side represents the optical density
- the abscissa “Potential” represents the electric potential
- “Bleaching” represents fading
- “Coloring” represents coloring.
- FIG2 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transferred charge density and optical density, corresponding to the optical performance control method of Example 17 of the present invention
- the ordinate "Potential” on the left side of FIG2(a) represents the potential
- the ordinate "Transmittance” on the right side represents the transmittance
- the abscissa "Time” represents the time.
- the ordinate "Area capacity” on the left side of FIG2(b) represents the area capacity
- the ordinate "Optical density” on the right side represents the optical density
- the abscissa "Time” represents the time.
- Figure 3 shows the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 34 of the present invention
- the ordinate "Area current” on the left side of Figure 3(a) represents the area current
- the ordinate "Transmittance” on the right side represents the transmittance
- the abscissa "Potential” represents the potential
- “Bleaching” represents fading
- “Coloring” represents coloring.
- FIG4 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transferred charge density and optical density, corresponding to the optical performance control method of Example 35 of the present invention
- the ordinate "Potential” on the left side of FIG4(a) represents the potential
- the ordinate "Transmittance” on the right side represents the transmittance
- the abscissa "Time” represents the time.
- the ordinate "Area capacity” on the left side of FIG4(b) represents the area capacity
- the ordinate "Optical density” on the right side represents the optical density
- the abscissa "Time” represents the time.
- FIG5 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value) corresponding to the optical performance control method of Example 38 of the present invention, as well as the electro-optical conversion efficiency in different redox reaction processes;
- the ordinate "Area current” on the left side of FIG5(a) represents the area current
- the ordinate "Transmittance” on the right side represents the transmittance
- the abscissa "Potential” represents the potential.
- the ordinate "Optical density” on the left side of FIG5(b) represents the optical density
- the abscissa "Area capacity” represents the area capacity.
- FIG6 shows the constant voltage method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density, corresponding to the optical performance control method of Example 47 of the present invention
- the ordinate "Area current” on the left side of FIG6 (a) represents the area current
- the ordinate "Transmittance” on the right side represents the transmittance
- the abscissa "Time” represents the time.
- the ordinate "Area capacity” on the left side of FIG6 (b) represents the area capacity
- the ordinate "Optical density” on the right side represents the optical density
- the abscissa "Time” represents the time.
- FIG7 shows the cyclic voltammetry control (theoretical value) and the first-order derivative of the real-time optical density corresponding to the optical property regulation method of Example 45 of the present invention, as well as the effective transfer charge density and optical density (measured value) obtained by the constant current method and time control of Example 46.
- the ordinate “Area current” on the left side of FIG7(a) represents the area current
- the ordinate “1st-order Derivative of OD” on the right side represents the first-order derivative of the optical density
- the abscissa “Time” represents the time.
- the ordinate “Area capacity” on the left side of FIG7(b) represents the area capacity
- the ordinate “Optical density” on the right side represents the optical density
- the abscissa “Time” represents the time.
- the electro-optical conversion efficiency of electrochromic devices can be accurately evaluated by combining cyclic voltammetry with in-situ optical monitoring.
- the optical properties of electrochromic devices can be precisely controlled by different effective charge transfer control methods such as cyclic voltammetry and constant current method.
- optical property regulation method of the present invention can also be applied to electrochromic devices containing organic-inorganic composite electrochromic materials.
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Abstract
The present invention belongs to the technical field of photoelectricity. Disclosed are a controllable electrochromic device, an optical performance regulation and control method therefor, and application thereof. The controllable electrochromic device comprises an electrochromic device and a current control apparatus, wherein the current control apparatus controls the electrochromic device by using the formula as shown below: formula (I). According to the optical performance regulation and control method in the present invention, it is not necessary to introduce an additional photosensitive element and apparatus to continuously monitor an electrochromic device in real time, such that the complexity of the whole electrochromic optical regulation and control system is reduced, and accurate regulation and control on the optical performance of the electrochromic device can be also achieved, thereby reducing energy consumption and lowering costs. By means of the optical performance regulation and control method, the optical regulation and control precision error is less than 5% and even less than 1%.
Description
本发明属于光电技术领域，特别涉及一种可控电致变色器件及其光学性能调控方法和应用。The present invention belongs to the field of optoelectronic technology, and in particular relates to a controllable electrochromic device and an optical performance regulation method and application thereof.
电致变色技术由于具有能耗低、动态可调控的光学特性等优点，因此应用广泛。例如应用在自适应红外防护、光学伪装、智能窗、防眩目后视镜等领域。随着现代科学技术的发展，对电致变色器件的高精度光学调控技术提出了迫切需求。因此，开发先进的光学动态调控技术及其高精度可控调节方法，已成为研究的热点。然而，电致变色器件光学性能的高精度调控缺乏有效且便捷的方法。一方面，电致变色器件在动态的光学性能调制过程中涉及到不同的电化学氧化还原反应；另一方面，常规的光学性能调控方法往往基于电压调控，存在电压迟滞效应，导致调控精度和效率下降。另外，现有技术中需要对电致变色器件光学性能进行实时持续监测，基于外界的光学性能需求，动态地获得所需要的光学特性。然而，该过程不仅造成持续的能耗，同时需要额外且复杂的装置(例如光感元件)对光学性能进行监测，难以满足不同场景对光学调控技术高效、低成本、低能耗的特征要求。Electrochromic technology has the advantages of low energy consumption and dynamically adjustable optical properties, so it is widely used. For example, it is used in the fields of adaptive infrared protection, optical camouflage, smart windows, anti-glare rearview mirrors, etc. With the development of modern science and technology, there is an urgent need for high-precision optical control technology of electrochromic devices. Therefore, the development of advanced optical dynamic control technology and its high-precision controllable adjustment method has become a hot topic of research. However, there is a lack of effective and convenient methods for high-precision control of the optical properties of electrochromic devices. On the one hand, electrochromic devices involve different electrochemical redox reactions in the dynamic optical performance modulation process; on the other hand, conventional optical performance control methods are often based on voltage control, and there is a voltage hysteresis effect, which leads to a decrease in control accuracy and efficiency. In addition, the existing technology needs to monitor the optical properties of electrochromic devices in real time and continuously, and dynamically obtain the required optical properties based on the external optical performance requirements. However, this process not only causes continuous energy consumption, but also requires additional and complex devices (such as light sensing elements) to monitor the optical performance, which is difficult to meet the requirements of different scenarios for high efficiency, low cost and low energy consumption of optical control technology.
目前已有的电致变色器件光学性能调控技术主要是采用光感元件对电致变色器件的光学性能进行实时持续的监测，进而反馈相关信号调节电压或电流，从而控制电致变色器件，获得所需的光学性能(例如申请号为202010383716.X的专利公开的一种电致变色玻璃的控制方法及电致变色玻璃、申请号为201710233384.5的专利公开的电致变色***、控制方法及电致变色后视镜)。由于通过调节工作电压控制电致变色器件光学性能存在电压迟滞效应，很难对电致变色器件的光学性能进行精准调控。另外，对电致变色器件光学性能实施持续监测，需要引入额外的光感元件与分析装置，增加了光学调控***的复杂度，同时增加了成本与能耗。The existing electrochromic device optical performance control technology mainly uses photosensitive elements to monitor the optical performance of electrochromic devices in real time and continuously, and then feeds back relevant signals to adjust the voltage or current, thereby controlling the electrochromic device to obtain the required optical performance (for example, a control method for electrochromic glass and electrochromic glass disclosed in the patent with application number 202010383716.X, and an electrochromic system, control method and electrochromic rearview mirror disclosed in the patent with application number 201710233384.5). Due to the voltage hysteresis effect when controlling the optical performance of electrochromic devices by adjusting the working voltage, it is difficult to accurately control the optical performance of electrochromic devices. In addition, continuous monitoring of the optical performance of electrochromic devices requires the introduction of additional photosensitive elements and analysis devices, which increases the complexity of the optical control system and increases the cost and energy consumption.
因此，亟需提供一种可控电致变色器件及其光学性能调控方法，该可控电致变色器件不需要引入额外光感元件与装置对电致变色器件进行实时持续监测，不仅降低调控***的复杂度，同时能够实现对电致变色器件光学性能进行精准调控，减少能耗，降低成本的目的。Therefore, there is an urgent need to provide a controllable electrochromic device and a method for regulating its optical properties. The controllable electrochromic device does not require the introduction of additional photosensitive elements and devices to perform real-time and continuous monitoring of the electrochromic device, which not only reduces the complexity of the regulation system, but also can achieve precise regulation of the optical properties of the electrochromic device, reduce energy consumption, and reduce costs.
发明内容Summary of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种可控电致变色器件及其光学性能调控方法和应用，所述可控电致变色器件不需要引入额外光感元件。所述光学性能调控方法不需要引入额外光感元件与装置对电致变色器件进行实时持续监测，不仅降低了可控电致变色器件(所述可控电致变色器件也可称为电致变色光学调控***)的复杂度，同时能够实现对其光学性能的精准调控，减少能耗，降低成本。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a controllable electrochromic device and a method and application for regulating optical properties thereof, wherein the controllable electrochromic device does not require the introduction of additional photosensitive elements. The optical properties regulation method does not require the introduction of additional photosensitive elements and devices to continuously monitor the electrochromic device in real time, which not only reduces the complexity of the controllable electrochromic device (the controllable electrochromic device may also be referred to as an electrochromic optical regulation system), but also enables precise regulation of its optical properties, reduces energy consumption, and reduces costs.
本发明的发明构思为：本发明公开了一种不依赖额外光感元件或装置对电致变色器件实时监测的可控电致变色器件。通过对电致变色器件在不同电化学氧化还原过程中电-光转换效率的精准评估，进而结合在不断电化学氧化还原过程中有效转移电荷密度的精准控制，从而实现电致变色器件光学性能的精确定量调控。The inventive concept of the present invention is: the present invention discloses a controllable electrochromic device that does not rely on additional light sensing elements or devices to monitor the electrochromic device in real time. By accurately evaluating the electro-optical conversion efficiency of the electrochromic device in different electrochemical redox processes, and then combining the precise control of the effective transfer charge density in the continuous electrochemical redox process, the optical performance of the electrochromic device can be precisely quantitatively controlled.
本发明从电致变色技术的电化学调控理论出发，公开了一种操作简单的光学性能调控方法，该光学性能调控方法不需要引入额外光感元件或装置对电致变色器件进行实时持续监测，不仅降低了整个电致变色光学调控***的复杂度，同时能够实现对其光学性能的精准调控，减少能耗，降低成本。Starting from the electrochemical regulation theory of electrochromic technology, the present invention discloses a simple-to-operate optical performance regulation method, which does not require the introduction of additional photosensitive elements or devices to perform real-time and continuous monitoring of the electrochromic device, which not only reduces the complexity of the entire electrochromic optical regulation system, but also can achieve precise regulation of its optical performance, reduce energy consumption, and reduce costs.
本发明利用电致变色过程中电致变色器件中不同氧化还原过程存在的电-光转换效率差异，结合电化学氧化还原过程中有效转移电荷的简单控制，从而实现对电致变色器件光学性能的高精度定量调控。本发明提供的光学性能调控方法过程简单，易于操作，且能实现高精度调控。The present invention utilizes the difference in the electric-to-optical conversion efficiency of different redox processes in the electrochromic device during the electrochromic process, combined with the simple control of the effective transfer of charge during the electrochemical redox process, thereby achieving high-precision quantitative regulation of the optical properties of the electrochromic device. The optical properties regulation method provided by the present invention is simple in process, easy to operate, and can achieve high-precision regulation.
本发明的第一方面提供一种可控电致变色器件。A first aspect of the present invention provides a controllable electrochromic device.
具体的，一种可控电致变色器件，所述可控电致变色器件包括电致变色器件、电流控制装置；Specifically, a controllable electrochromic device, the controllable electrochromic device comprising an electrochromic device and a current control device;
所述电流控制装置通过采用如下所示的公式控制所述电致变色器件：The current control device controls the electrochromic device by using the formula shown below:
其中，OD为电致变色过程中所需的光学密度，OD
0为所述电致变色器件在电致变色过程中的初始光学密度，ε
i为电致变色过程中不同氧化还原反应的电-光转换效率，Q
i为电致变色过程中发生的不同氧化还原反应的有效转移电荷密度，N为电致变色过程中发生的不同氧化还原反应的数量，I
t为电致变色过程中不同时刻t的电流密度。
Wherein, OD is the optical density required in the electrochromic process, OD0 is the initial optical density of the electrochromic device in the electrochromic process, εi is the electro-optical conversion efficiency of different redox reactions in the electrochromic process, Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, N is the number of different redox reactions occurring in the electrochromic process, and It is the current density at different times t in the electrochromic process.
优选的，所述可控电致变色器件中还包括电压控制装置。Preferably, the controllable electrochromic device also includes a voltage control device.
优选的，所述电流控制装置包括电化学工作站。Preferably, the current control device comprises an electrochemical workstation.
优选的，所述可控电致变色器件中还包括电流监测装置和/或电压监测装置。Preferably, the controllable electrochromic device further comprises a current monitoring device and/or a voltage monitoring device.
优选的，所述可控电致变色器件还包括光度计。Preferably, the controllable electrochromic device further comprises a photometer.
优选的，所述光度计为紫外-可见-近红外分光光度计。Preferably, the photometer is a UV-Vis-NIR spectrophotometer.
优选的，一种可控电致变色器件，所述可控电致变色器件包括电致变色器件、电化学工作站、光度计。Preferably, a controllable electrochromic device comprises an electrochromic device, an electrochemical workstation, and a photometer.
优选的，所述电致变色器件至少包括电致变色层和导电基底层。Preferably, the electrochromic device comprises at least an electrochromic layer and a conductive substrate layer.
进一步优选的，所述电致变色器件还包括离子导体层、离子储存层。Further preferably, the electrochromic device further includes an ion conductor layer and an ion storage layer.
优选的，所述电致变色器件的结构为导电基底层/电致变色层或导电基底层/电致变色层/离子导体层/离子储存层/导电基底层。导电基底层也可称为电子导体层。Preferably, the structure of the electrochromic device is conductive substrate layer/electrochromic layer or conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer. The conductive substrate layer may also be called an electron conductor layer.
优选的，所述电致变色层的材料包括氧化钨、氧化镍、氧化钒、氧化锰、氧化钛、锰酸锂、钛酸锂、氧化铱、聚苯胺、聚吡咯、聚噻吩中的至少一种。Preferably, the material of the electrochromic layer includes at least one of tungsten oxide, nickel oxide, vanadium oxide, manganese oxide, titanium oxide, lithium manganate, lithium titanate, iridium oxide, polyaniline, polypyrrole, and polythiophene.
优选的，所述导电基底层的材料包括氧化铟锡(ITO)、掺氟氧化锡(FTO)、掺铝氧化锌(AZO)、纳米银线、银、金、铝、铜、纳米碳管、石墨烯、聚二氧乙基噻吩中的至少一种。当导电基底层的材料为银、金、铝、铜时，银、金、铝、铜可具有多孔结构。Preferably, the material of the conductive substrate layer includes at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), nanosilver wire, silver, gold, aluminum, copper, nanocarbon tubes, graphene, and poly(ethylenedioxythiophene). When the material of the conductive substrate layer is silver, gold, aluminum, or copper, the silver, gold, aluminum, or copper may have a porous structure.
优选的，所述离子导体层的材料包括碳酸酯类电解液、醚类电解液、砜类电解液、磷酸酯类电解液、水系电解液、铌酸锂、锂磷氧氮(LiPON)、氧化钽、锂镧锆氧(LLZO)、聚氧化乙烯基聚合物电解质、聚甲基丙烯酸甲酯(PMMA)基聚合物电解质中的至少一种。Preferably, the material of the ion conductor layer includes at least one of carbonate electrolyte, ether electrolyte, sulfone electrolyte, phosphate electrolyte, aqueous electrolyte, lithium niobate, lithium phosphorus oxynitride (LiPON), tantalum oxide, lithium lanthanum zirconium oxide (LLZO), polyethylene oxide polymer electrolyte, and polymethyl methacrylate (PMMA) based polymer electrolyte.
进一步优选的，所述碳酸酯类电解液包括碳酸丙烯酯/LiClO
4、碳酸丙烯酯/NaClO
4、碳酸丙烯酯/Al(ClO
4)
3中的至少一种。
Further preferably, the carbonate electrolyte includes at least one of propylene carbonate/LiClO 4 , propylene carbonate/NaClO 4 , and propylene carbonate/Al(ClO 4 ) 3 .
进一步优选的，所述醚类电解液包括乙二醇二甲醚/LiTFSI(LiTFSI指双三氟甲磺酰亚胺锂)、乙二醇二甲醚/NaTFSI(NaTFSI指双三氟甲磺酰亚胺钠)中的至少一种。Further preferably, the ether electrolyte includes at least one of ethylene glycol dimethyl ether/LiTFSI (LiTFSI refers to lithium bis(trifluoromethanesulfonyl imide) and ethylene glycol dimethyl ether/NaTFSI (NaTFSI refers to sodium bis(trifluoromethanesulfonyl imide).
进一步优选的，所述砜类电解液包括环丁砜/LiFSI、环丁砜/NaFSI中的至少一种。Further preferably, the sulfone electrolyte includes at least one of sulfolane/LiFSI and sulfolane/NaFSI.
进一步优选的，所述醚类电解液包括乙二醇二甲醚/LiTFSI、乙二醇二甲醚/NaTFSI中的至少一种。Further preferably, the ether electrolyte includes at least one of ethylene glycol dimethyl ether/LiTFSI and ethylene glycol dimethyl ether/NaTFSI.
进一步优选的，所述砜类电解液包括环丁砜/LiFSI(LiFSI指双氟磺酰亚胺锂)、环丁砜/NaFSI(NaFSI指双氟磺酰亚胺钠)中的至少一种。Further preferably, the sulfone electrolyte includes at least one of sulfolane/LiFSI (LiFSI refers to lithium bis(fluorosulfonyl)imide) and sulfolane/NaFSI (NaFSI refers to sodium bis(fluorosulfonyl)imide).
进一步优选的，所述磷酸酯类电解液包括磷酸二乙酯/LiFSI、磷酸二乙酯/NaFSI中的至少一种。Further preferably, the phosphate ester electrolyte includes at least one of diethyl phosphate/LiFSI and diethyl phosphate/NaFSI.
进一步优选的，所述水系电解液包括水/ZnSO
4、水/KCl、水/ZnCl
2中的至少一种。
More preferably, the aqueous electrolyte includes at least one of water/ZnSO 4 , water/KCl, and water/ZnCl 2 .
优选的，所述离子储存层的材料包括氧化钨、氧化镍、氧化钒、氧化锰、氧化钛、锰酸锂、钛酸锂、氧化铱、聚苯胺、聚吡咯、聚噻吩中的至少一种。Preferably, the material of the ion storage layer includes at least one of tungsten oxide, nickel oxide, vanadium oxide, manganese oxide, titanium oxide, lithium manganate, lithium titanate, iridium oxide, polyaniline, polypyrrole, and polythiophene.
优选的，所述电致变色器件的厚度为5nm-1100μm；进一步优选的，所述电致变色器件的厚度为5nm-1000μm。所述电致变色器件的厚度具体可为10nm、100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm、2μm、10μm、100μm、1000μm。Preferably, the thickness of the electrochromic device is 5nm-1100μm; further preferably, the thickness of the electrochromic device is 5nm-1000μm. The thickness of the electrochromic device can specifically be 10nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 2μm, 10μm, 100μm, 1000μm.
优选的，所述电致变色器件中的电致变色层的厚度为10nm-1000μm；进一步优选的，所述电致变色器件中的电致变色层的厚度为50nm-1000μm。具体的，电致变色层的厚度可为10nm、50nm、100nm、300nm、500nm、1μm、10μm、100μm、1000μm。Preferably, the thickness of the electrochromic layer in the electrochromic device is 10nm-1000μm; further preferably, the thickness of the electrochromic layer in the electrochromic device is 50nm-1000μm. Specifically, the thickness of the electrochromic layer can be 10nm, 50nm, 100nm, 300nm, 500nm, 1μm, 10μm, 100μm, 1000μm.
优选的，所述电化学工作站的工作方式包括二电极或三电极。Preferably, the electrochemical workstation operates in a two-electrode or three-electrode mode.
优选的，当所述电致变色器件的结构为导电基底层/电致变色层时，电化学工作站的工作方式为三电极。其中电致变色器件作为工作电极，铂作为对电极，以Ag/AgCl为参比电极。Preferably, when the structure of the electrochromic device is conductive substrate layer/electrochromic layer, the electrochemical workstation works in a three-electrode mode, wherein the electrochromic device is used as a working electrode, platinum is used as a counter electrode, and Ag/AgCl is used as a reference electrode.
优选的，当所述电致变色器件的结构为导电基底层/电致变色层/离子导体层/离子储存层/导电基底层时，电化学工作站的工作方式为二电极。其中电致变色器件中紧邻电致变色层的导电基底层作为工作电极，紧邻离子储存层的导电基底层作为对电极与参比电极。Preferably, when the structure of the electrochromic device is conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer, the electrochemical workstation works in a two-electrode mode, wherein the conductive substrate layer adjacent to the electrochromic layer in the electrochromic device serves as the working electrode, and the conductive substrate layer adjacent to the ion storage layer serves as the counter electrode and the reference electrode.
本发明的第二方面提供一种可控电致变色器件的光学性能调控方法。A second aspect of the present invention provides a method for regulating the optical properties of a controllable electrochromic device.
具体的，一种可控电致变色器件的光学性能调控方法，包括以下步骤：Specifically, a method for controlling the optical properties of a controllable electrochromic device comprises the following steps:
启动所述电流控制装置，采用电化学方法对所述电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制；从而实现对所述电致变色器件的光学性能的定量精确调控。The current control device is started to use an electrochemical method to effectively transfer charge control on the electrochemical reaction in the electrochromic process of the electrochromic device, thereby achieving quantitative and precise regulation of the optical properties of the electrochromic device.
优选的，启动所述电流控制装置的同时，还启动电压控制装置，然后采用电化学方法对所述电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制。Preferably, when the current control device is started, the voltage control device is also started, and then an electrochemical method is used to effectively transfer charge control of the electrochemical reaction in the electrochromic process of the electrochromic device.
优选的，对所述电致变色器件还采用电流监测装置和/或电压监测装置进行监测。Preferably, the electrochromic device is also monitored by a current monitoring device and/or a voltage monitoring device.
优选的，所述电化学方法包括循环伏安法、恒电流法、恒电压法、交变电流法、脉冲电流法、交变电压法、脉冲电压法、梯度电压法、梯度电流法中的至少一种。Preferably, the electrochemical method includes at least one of cyclic voltammetry, constant current method, constant voltage method, alternating current method, pulse current method, alternating voltage method, pulse voltage method, gradient voltage method, and gradient current method.
进一步优选的，所述电化学方法包括循环伏安法、恒电流法、恒电压法、循环伏安法-恒电流法、循环伏安法-恒电压法、恒电流法-恒电压法、循环伏安法-恒电压法-恒电流法中的至少一种。循环伏安法-恒电流法表示先采用循环伏安法，然后采用恒电流法。Further preferably, the electrochemical method comprises at least one of cyclic voltammetry, constant current method, constant voltage method, cyclic voltammetry-constant current method, cyclic voltammetry-constant voltage method, constant current method-constant voltage method, cyclic voltammetry-constant voltage method-constant current method. Cyclic voltammetry-constant current method means that cyclic voltammetry is first used and then constant current method is used.
优选的，所述光学性能包括光学密度、光学透过率、反射率、发射率、色度中的至少一种。Preferably, the optical properties include at least one of optical density, optical transmittance, reflectivity, emissivity, and chromaticity.
优选的，所述光学性能涉及的光学波长包括X射线区、紫外光区、可见光区、红外光区、微波区以及无线电波区中的至少一种。Preferably, the optical wavelength involved in the optical properties includes at least one of the X-ray region, ultraviolet light region, visible light region, infrared light region, microwave region and radio wave region.
优选的，利用光度计测试电致变色器件的光学性能，从而获得所需的光学性能。Preferably, the optical properties of the electrochromic device are tested using a photometer to obtain the desired optical properties.
优选的，一种可控电致变色器件的光学性能调控方法，包括以下步骤：Preferably, a method for controlling the optical properties of a controllable electrochromic device comprises the following steps:
启动电化学工作站，采用电化学方法对电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制；Start the electrochemical workstation and use electrochemical methods to effectively transfer charge control of the electrochemical reaction in the electrochromic process of the electrochromic device;
结合光学调控原理，对电致变色器件的光学性能进行定量精准调控，利用光度计测试电致变色器件的光学性能，从而获得所需的光学性能。Combined with the principle of optical regulation, the optical properties of the electrochromic device are quantitatively and accurately regulated, and the optical properties of the electrochromic device are tested using a photometer to obtain the desired optical properties.
优选的，所述光学调控采用的公式如下：Preferably, the formula used for the optical regulation is as follows:
其中，OD为电致变色过程中所需的光学密度(或称为光学吸收度)，OD
0为所述电致变色器件在电致变色过程中的初始光学密度(或称为初始光学吸收度)，ε
i为电致变色过程中不同氧化还原反应的电-光转换效率，Q
i为电致变色过程中发生的不同氧化还原反应的有效转移电荷密度，N为电致变色过程中发生的不同氧化还原反应的数量，I
t为电致变色过程中不同时刻t的电流密度。通过光学控制原理所示式子，基于对电化学调控过程中电荷的控制以及电压范围的监测，电致变色器件的光学密度能够被定量精确地调控，而不需要引入额外光感元件或装置对电致变色器件进行实施持续监测。
Wherein, OD is the optical density (or optical absorbance) required in the electrochromic process, OD 0 is the initial optical density (or initial optical absorbance) of the electrochromic device in the electrochromic process, ε i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process, Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, N is the number of different redox reactions occurring in the electrochromic process, and It is the current density at different times t in the electrochromic process. Through the formula shown in the optical control principle, based on the control of the charge in the electrochemical regulation process and the monitoring of the voltage range, the optical density of the electrochromic device can be quantitatively and accurately regulated without the need to introduce additional photosensitive elements or devices to continuously monitor the electrochromic device.
优选的，所述光学性能调控方法的光学调控精度误差小于5％；进一步优选的，所述光学性能调控方法的光学调控精度误差小于4％，甚至小于3％或小于1％。光学调控精度误差指理论值与实测值之间的误差。Preferably, the optical control precision error of the optical performance control method is less than 5%; further preferably, the optical control precision error of the optical performance control method is less than 4%, even less than 3% or less than 1%. The optical control precision error refers to the error between the theoretical value and the measured value.
优选的，制备所述电致变色器件的方法包括物理气相沉积法、化学气相沉积法、电化学法、涂覆法中的至少一种。Preferably, the method for preparing the electrochromic device includes at least one of a physical vapor deposition method, a chemical vapor deposition method, an electrochemical method, and a coating method.
进一步优选的，所述物理气相沉积法包括磁控溅射法或蒸镀法。当电致变色层的材料为无机物时，采用物理气相沉积法来制备电致变色器件。Further preferably, the physical vapor deposition method includes magnetron sputtering or evaporation. When the material of the electrochromic layer is an inorganic substance, the physical vapor deposition method is used to prepare the electrochromic device.
当电致变色层的材料为有机物时，采用电化学法、涂覆法来制备电致变色器件。例如可通过对有机物单体电聚合并沉积在导电基底上制备电致变色器件，或采用旋涂或刮涂将有机物涂覆在导电基底上来制备电致变色器件。When the material of the electrochromic layer is organic, the electrochromic device is prepared by electrochemical method or coating method. For example, the electrochromic device can be prepared by electropolymerizing organic monomers and depositing them on a conductive substrate, or by coating the organic material on a conductive substrate by spin coating or scraping.
本发明的第三方面提供上述可控电致变色器件或可控电致变色器件的光学性能调控方法的应用。A third aspect of the present invention provides an application of the above-mentioned controllable electrochromic device or a method for regulating the optical properties of a controllable electrochromic device.
具体的，本发明涉及上述可控电致变色器件或上述光学性能调控方法在光电领域中的应用。Specifically, the present invention relates to the application of the controllable electrochromic device or the optical performance regulation method in the optoelectronic field.
优选的，所述光电领域包括变色玻璃、红外防护、光学伪装、智能窗或防眩目后视镜。Preferably, the optoelectronic field includes photochromic glass, infrared protection, optical camouflage, smart windows or anti-glare rearview mirrors.
相对于现有技术，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
(1)本发明所述可控电致变色器件包括电致变色器件、电流控制装置，所述电流控制装置通过采用如下所示的公式控制所述电致变色器件：
所述可控电致变色器件是一种不依赖额外光感元件或装置对电致变色器件实时监测的光学性能调控***。所述可控电致变色器件通过对电致变色器件在不同电化学氧化还原过程中电-光转换效率的精准评估，进而结合在不断电化学氧化还原过程中有效转移电荷密度的精准控制，从而实现电致变色器件光学性能的精确定量调控。
(1) The controllable electrochromic device of the present invention comprises an electrochromic device and a current control device, wherein the current control device controls the electrochromic device by using the following formula: The controllable electrochromic device is an optical performance control system that does not rely on additional photosensitive elements or devices to monitor the electrochromic device in real time. The controllable electrochromic device achieves precise quantitative control of the optical performance of the electrochromic device by accurately evaluating the electro-optical conversion efficiency of the electrochromic device in different electrochemical redox processes, and then combining it with precise control of the effective transfer charge density in the continuous electrochemical redox process.
(2)本发明所述光学性能调控方法不需要引入额外光感元件与装置对电致变色器件进行实时持续监测，不仅降低了整个电致变色光学调控***的复杂度，同时能够实现对其光学性能的精准调控，减少能耗，降低成本。所述光学性能调控方法的光学调控精度误差小于5％，甚至小于1％。(2) The optical performance control method of the present invention does not require the introduction of additional light-sensing elements and devices to continuously monitor the electrochromic device in real time, which not only reduces the complexity of the entire electrochromic optical control system, but also can achieve precise control of its optical performance, reduce energy consumption, and reduce costs. The optical control accuracy error of the optical performance control method is less than 5%, or even less than 1%.
图1为本发明实施例4光学性能调控方法对应的循环伏安法控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；FIG1 is a graph showing the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 4 of the present invention;
图2为本发明实施例17光学性能调控方法对应的恒电流法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；FIG2 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 17 of the present invention;
图3为本发明实施例34光学性能调控方法对应的循环伏安法控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；3 shows the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 34 of the present invention;
图4为本发明实施例35光学性能调控方法对应的恒电流法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；FIG4 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 35 of the present invention;
图5为本发明实施例38光学性能调控方法对应的恒电流法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及在不同氧化还原反应过程中的电-光转换效率；5 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value) corresponding to the optical property regulation method of Example 38 of the present invention, as well as the electro-optical conversion efficiency in different redox reaction processes;
图6为本发明实施例47光学性能调控方法对应的恒电压法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；6 shows the constant voltage method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 47 of the present invention;
图7为本发明实施例45光学性能调控方法对应的循环伏安法控制(理论值)与实时光学密度的一阶导数，以及实施例46恒电流法与时间控制获得的有效转移电荷密度及光学密度(实测值)。Figure 7 shows the cyclic voltammetry control (theoretical value) and the first-order derivative of the real-time optical density corresponding to the optical property regulation method of Example 45 of the present invention, as well as the effective transfer charge density and optical density (measured value) obtained by the constant current method and time control of Example 46.
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。 需要指出的是，以下实施例对本发明要求的保护范围不构成限制作用。In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.
实施例1-33：可控电致变色器件、光学性能调控方法Example 1-33: Controllable electrochromic device, optical performance control method
一种可控电致变色器件，包括电致变色器件、电化学工作站、紫外-可见-近红外(UV-Vis-NIR)分光光度计；A controllable electrochromic device, comprising an electrochromic device, an electrochemical workstation, and an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer;
电致变色器件作为电化学工作站的工作电极；The electrochromic device was used as the working electrode of the electrochemical workstation;
电致变色器件包括电致变色层和导电基底层，电致变色层的材料为氧化钨，导电基地层为ITO玻璃，电致变色层在导电基底层表面。The electrochromic device comprises an electrochromic layer and a conductive base layer. The material of the electrochromic layer is tungsten oxide, the conductive base layer is ITO glass, and the electrochromic layer is on the surface of the conductive base layer.
电致变色器件的制备方法为：在ITO玻璃上通过磁控溅射法来沉积电致变色层，电致变色层的厚度通过磁控溅射法的溅射时间控制(通过磁控溅射法在ITO玻璃上沉积材料层是本领域常规技术)。The preparation method of the electrochromic device is: depositing an electrochromic layer on ITO glass by magnetron sputtering, and the thickness of the electrochromic layer is controlled by the sputtering time of the magnetron sputtering method (depositing a material layer on ITO glass by magnetron sputtering is a conventional technology in the art).
上述可控电致变色器件的光学性能调控方法，包括以下步骤：The optical performance control method of the controllable electrochromic device comprises the following steps:
启动电化学工作站，采用电化学方法对电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制；Start the electrochemical workstation and use electrochemical methods to effectively transfer charge control of the electrochemical reaction in the electrochromic process of the electrochromic device;
结合光学调控原理，对电致变色器件的光学性能进行定量调控，利用紫外-可见-近红外(UV-Vis-NIR)分光光度计测试电致变色器件的光学性能(光学密度)，从而获得所需的光学性能(光学密度)。Combined with the principle of optical regulation, the optical properties of the electrochromic device are quantitatively regulated, and the optical properties (optical density) of the electrochromic device are tested using an ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrophotometer to obtain the desired optical properties (optical density).
光学调控采用的公式如下：The formula used for optical control is as follows:
其中，OD为电致变色过程中所需的光学密度，OD
0为所述电致变色器件在电致变色过程中的初始光学密度，ε
i为电致变色过程中不同氧化还原反应的电-光转换效率，Q
i为电致变色过程中发生的不同氧化还原反应的有效转移电荷密度，其中电-光转换效率仅取决于电致变色过程中所发生的氧化还原反应与材料本征物化特性，与电流密度、电荷密度等无关，N为电致变色过程中发生的不同氧化还原反应的数量，I
t为电致变色过程中不同时刻t的电流密度。通过光学控制原理所示式子，基于对电化学调控过程中电荷的控制以及电压范围的监测，电致变色器件的光学密度能够被定量精确地调控，而不需要引入额外光感元件或装置对电致变色器件进行实施持续监测。
Wherein, OD is the optical density required in the electrochromic process, OD 0 is the initial optical density of the electrochromic device in the electrochromic process, ε i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process, Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, wherein the electro-optical conversion efficiency depends only on the redox reactions occurring in the electrochromic process and the intrinsic physicochemical properties of the material, and has nothing to do with the current density, charge density, etc., N is the number of different redox reactions occurring in the electrochromic process, and It is the current density at different times t in the electrochromic process. Through the formula shown in the optical control principle, based on the control of the charge in the electrochemical regulation process and the monitoring of the voltage range, the optical density of the electrochromic device can be quantitatively and accurately regulated without the need to introduce additional photosensitive elements or devices to continuously monitor the electrochromic device.
电化学工作站的工作方式为三电极，其中电致变色器件作为工作电极，铂作为对电极， 以Ag/AgCl为参比电极，LiClO
4/碳酸丙烯酯溶液作为电解液。
The electrochemical workstation operates in a three-electrode mode, wherein the electrochromic device is used as the working electrode, platinum is used as the counter electrode, Ag/AgCl is used as the reference electrode, and LiClO 4 /propylene carbonate solution is used as the electrolyte.
实施例1-33采用上述方法对电致变色器件的光学性能(光学密度)调控过程中的参数及结果如表1所示(表1中的光学密度理论值通过上述式子计算得到，光学密度实测值通过紫外-可见-近红外(UV-Vis-NIR)分光光度计测得)。The parameters and results of the process of regulating the optical properties (optical density) of the electrochromic device using the above method in Examples 1-33 are shown in Table 1 (the theoretical optical density value in Table 1 is calculated by the above formula, and the actual optical density value is measured by an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer).
以实施例31为例，先采用循环伏安法对电致变色器件进行着色控制，截止电压是-0.5V(vs.Ag/AgCl)，然后通过恒电流法继续进行着色控制，截止电压为-1.0V(vs.Ag/AgCl)，电致变色器件的调控波长为550nm时，即可得到光学密度为0.703的可控电致变色器件。Taking Example 31 as an example, the cyclic voltammetry method is first used to control the coloring of the electrochromic device, and the cut-off voltage is -0.5V (vs. Ag/AgCl). Then, the coloring control is continued by the constant current method, and the cut-off voltage is -1.0V (vs. Ag/AgCl). When the control wavelength of the electrochromic device is 550nm, a controllable electrochromic device with an optical density of 0.703 can be obtained.
表1：实施例1-33调控参数及结果Table 1: Control parameters and results of Examples 1-33
从表1可以看出，本发明采用如下光学调控原理：
通过对氧化钨电致变色材料电-光转换效率评估以及不同电化学法控制过程中电荷的精准调控，可有效控制电致变色器件的光学性能(光学密度)，表现出很高的调控精度，光学密度误差普遍小于1％。
As can be seen from Table 1, the present invention adopts the following optical control principle: By evaluating the electro-optical conversion efficiency of tungsten oxide electrochromic materials and precisely controlling the charge during different electrochemical control processes, the optical properties (optical density) of electrochromic devices can be effectively controlled, showing high control accuracy, and the optical density error is generally less than 1%.
实施例34-44：可控电致变色器件、光学性能调控方法Examples 34-44: Controllable electrochromic device, optical performance control method
与实施例1-33相比，实施例34-44改变电致变色层的材料种类，其余过程与实施例1-33类似，具体调控参数及结果如表2所示。Compared with Examples 1-33, Examples 34-44 change the material type of the electrochromic layer, and the rest of the process is similar to Examples 1-33. The specific control parameters and results are shown in Table 2.
表2：实施例34-44调控参数及结果Table 2: Control parameters and results of Examples 34-44
由表2可知，本发明提出的电致变色器件的光学性能调控方法，应用于不同的电致变色材料体系，同样表现出很高的光学性能调控精度，光学密度误差普遍小于1％。As can be seen from Table 2, the optical performance control method of the electrochromic device proposed in the present invention, when applied to different electrochromic material systems, also exhibits high optical performance control accuracy, and the optical density error is generally less than 1%.
实施例45-60：可控电致变色器件、光学性能调控方法Examples 45-60: Controllable electrochromic device, optical performance control method
一种可控电致变色器件，包括电致变色器件、电化学工作站、紫外-可见-近红外(UV-Vis-NIR)分光光度计；A controllable electrochromic device, comprising an electrochromic device, an electrochemical workstation, and an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer;
电致变色器件作为电化学工作站的工作电极；The electrochromic device was used as the working electrode of the electrochemical workstation;
电致变色器件的结构依次为导电基底层/电致变色层/离子导体层/离子储存层/导电基底层；氧化钨作为电致变色层，铌酸锂作为离子导体层，氧化镍或锰酸锂作为离子储存层，ITO玻璃作为导电基底层。电致变色器件通过磁控溅射法制得，电致变色器件各层的厚度通过磁控溅射法的溅射时间控制。导电基底层/电致变色层/离子导体层/离子储存层/导电基底层的厚度依次为120nm、300nm、200nm、400nm与300nm。The structure of the electrochromic device is conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer in order; tungsten oxide is used as the electrochromic layer, lithium niobate is used as the ion conductor layer, nickel oxide or lithium manganate is used as the ion storage layer, and ITO glass is used as the conductive substrate layer. The electrochromic device is made by magnetron sputtering, and the thickness of each layer of the electrochromic device is controlled by the sputtering time of the magnetron sputtering method. The thickness of the conductive substrate layer/electrochromic layer/ion conductor layer/ion storage layer/conductive substrate layer is 120nm, 300nm, 200nm, 400nm and 300nm in order.
上述可控电致变色器件的光学性能调控方法，包括以下步骤：The optical performance control method of the controllable electrochromic device comprises the following steps:
启动电化学工作站，采用电化学方法对电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制(例如实施例45中，采用循环伏安法(扫速为0.05V/s)对有效转移电荷进行控制，工作电压范围从-1.5V到2.0V；实施例46中，采用恒电流法(电流密度为0.1mA/cm
2)对有效转移电荷进行控制，工作电压范围从-1.5V到2.0V；实施例47中，采用恒电压法(工作电压为-1.5V)对有效转移电荷进行控制，工作时间持续40s)；
Start the electrochemical workstation, and use an electrochemical method to control the effective transfer charge of the electrochemical reaction in the electrochromic process of the electrochromic device (for example, in Example 45, the cyclic voltammetry method (scan rate of 0.05 V/s) is used to control the effective transfer charge, and the working voltage range is from -1.5 V to 2.0 V; in Example 46, the constant current method (current density of 0.1 mA/cm 2 ) is used to control the effective transfer charge, and the working voltage range is from -1.5 V to 2.0 V; in Example 47, the constant voltage method (working voltage of -1.5 V) is used to control the effective transfer charge, and the working time lasts for 40 s);
结合光学调控原理，对电致变色器件的光学性能进行定量调控，利用紫外-可见-近红外(UV-Vis-NIR)分光光度计测试电致变色器件的光学性能(光学密度)，从而获得所需的光学性能(光学密度)。为了体现本发明调控方法的先进性，在电致变色器件光学性能的电化学法调控过程中，采用原位光学性能监测，评估实测光学密度与理论值的误差。Combined with the optical regulation principle, the optical properties of the electrochromic device are quantitatively regulated, and the optical properties (optical density) of the electrochromic device are tested using an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer to obtain the desired optical properties (optical density). In order to reflect the advanced nature of the regulation method of the present invention, in-situ optical performance monitoring is used during the electrochemical regulation of the optical properties of the electrochromic device to evaluate the error between the measured optical density and the theoretical value.
光学控制采用的公式如下：The formula used for optical control is as follows:
其中，OD为电致变色过程中所需的光学密度，OD
0为所述电致变色器件在电致变色过程中的初始光学密度，ε
i为电致变色过程中不同氧化还原反应的电-光转换效率，Q
i为电致变色过程中发生的不同氧化还原反应的有效转移电荷密度，其中电-光转换效率仅取决于电致变色过程中所发生的氧化还原反应与材料本征物化特性，与电流密度、电荷密度等无关，N为电致变色过程中发生的不同氧化还原反应的数量，I
t为电致变色过程中不同时刻t的电流密度。通过光学控制原理所示式子，基于对电化学调控过程中电荷的控制以及电压范围的监测，电致变色器件的光学密度能够被定量精确地调控，而不需要引入额外光感元件或装置对电致变色器件进行实施持续监测。
Wherein, OD is the optical density required in the electrochromic process, OD 0 is the initial optical density of the electrochromic device in the electrochromic process, ε i is the electro-optical conversion efficiency of different redox reactions in the electrochromic process, Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, wherein the electro-optical conversion efficiency depends only on the redox reactions occurring in the electrochromic process and the intrinsic physicochemical properties of the material, and has nothing to do with the current density, charge density, etc., N is the number of different redox reactions occurring in the electrochromic process, and It is the current density at different times t in the electrochromic process. Through the formula shown in the optical control principle, based on the control of the charge in the electrochemical regulation process and the monitoring of the voltage range, the optical density of the electrochromic device can be quantitatively and accurately regulated without the need to introduce additional photosensitive elements or devices to continuously monitor the electrochromic device.
电化学工作站的工作方式为二电极，其中电致变色器件中紧邻电致变色层的导电基底层作为工作电极，紧邻离子储存层的导电基底层作为对电极与参比电极。The electrochemical workstation works in a two-electrode mode, in which the conductive substrate layer adjacent to the electrochromic layer in the electrochromic device serves as the working electrode, and the conductive substrate layer adjacent to the ion storage layer serves as the counter electrode and reference electrode.
实施例45-60采用上述方法对电致变色器件的光学性能(光学密度)调控过程中的参数及结果如表3所示(表3中的光学密度理论值通过上述式子计算得到，光学密度实测值通过紫外-可见-近红外(UV-Vis-NIR)分光光度计测得，表中M表示mol/L)。The parameters and results of the process of regulating the optical properties (optical density) of the electrochromic device using the above method in Examples 45-60 are shown in Table 3 (the theoretical optical density value in Table 3 is calculated by the above formula, and the actual optical density value is measured by an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer, and M in the table represents mol/L).
表3：实施例45-60调控参数及结果Table 3: Control parameters and results of Examples 45-60
从表3可知，本发明的调控方法对具有多层结构的电致变色器件也具有很高的光学性能调控精度，光学密度误差普遍小于1％。As can be seen from Table 3, the control method of the present invention also has a high optical performance control accuracy for the electrochromic device with a multilayer structure, and the optical density error is generally less than 1%.
图1为本发明实施例4光学性能调控方法对应的循环伏安法控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；图1(a)左侧纵坐标“Area current”表示面积电流，右侧纵坐标“Transmittance”表示透过率，横坐标“Potential”表示电势，“Bleaching”表示褪色，“Coloring”表示着色。图1(b)左侧纵坐标“Area capacity”表示面积容量，右侧纵坐标“Optical density”表示光学密度，横坐标“Potential”表示电势，“Bleaching”表示褪色，“Coloring”表示着色。FIG1 shows the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 4 of the present invention; the ordinate “Area current” on the left side of FIG1(a) represents the area current, the ordinate “Transmittance” on the right side represents the transmittance, the abscissa “Potential” represents the electric potential, “Bleaching” represents fading, and “Coloring” represents coloring. The ordinate “Area capacity” on the left side of FIG1(b) represents the area capacity, the ordinate “Optical density” on the right side represents the optical density, the abscissa “Potential” represents the electric potential, “Bleaching” represents fading, and “Coloring” represents coloring.
图2为本发明实施例17光学性能调控方法对应的恒电流法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；图2(a)左侧纵坐标“Potential”表示电势，右侧纵坐标“Transmittance”表示透过率，横坐标“Time”表示时间。图2(b)左侧纵坐标“Area capacity”表示面积容量，右侧纵坐标“Optical density”表示光学密度，横坐标“Time”表示时间。FIG2 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transferred charge density and optical density, corresponding to the optical performance control method of Example 17 of the present invention; the ordinate "Potential" on the left side of FIG2(a) represents the potential, the ordinate "Transmittance" on the right side represents the transmittance, and the abscissa "Time" represents the time. The ordinate "Area capacity" on the left side of FIG2(b) represents the area capacity, the ordinate "Optical density" on the right side represents the optical density, and the abscissa "Time" represents the time.
图3为本发明实施例34光学性能调控方法对应的循环伏安法控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；图3(a)左侧纵坐标“Area current”表示面积电流，右侧纵坐标“Transmittance”表示透过率，横坐标“Potential”表示电势，“Bleaching”表示褪色，“Coloring”表示着色。图3(b)左侧纵坐标“Area Current”表示面积电流，右侧纵坐标“Derivative of OD”表示光学密度的导数，横坐标“Potential”表示电势。Figure 3 shows the cyclic voltammetry control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density corresponding to the optical property regulation method of Example 34 of the present invention; the ordinate "Area current" on the left side of Figure 3(a) represents the area current, the ordinate "Transmittance" on the right side represents the transmittance, the abscissa "Potential" represents the potential, "Bleaching" represents fading, and "Coloring" represents coloring. The ordinate "Area Current" on the left side of Figure 3(b) represents the area current, the ordinate "Derivative of OD" on the right side represents the derivative of the optical density, and the abscissa "Potential" represents the potential.
图4为本发明实施例35光学性能调控方法对应的恒电流法与时间控制(理论值)与实时 监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；图4(a)左侧纵坐标“Potential”表示电势，右侧纵坐标“Transmittance”表示透过率，横坐标“Time”表示时间。图4(b)左侧纵坐标“Area capacity”表示面积容量，右侧纵坐标“Optical density”表示光学密度，横坐标“Time”表示时间。FIG4 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transferred charge density and optical density, corresponding to the optical performance control method of Example 35 of the present invention; the ordinate "Potential" on the left side of FIG4(a) represents the potential, the ordinate "Transmittance" on the right side represents the transmittance, and the abscissa "Time" represents the time. The ordinate "Area capacity" on the left side of FIG4(b) represents the area capacity, the ordinate "Optical density" on the right side represents the optical density, and the abscissa "Time" represents the time.
图5为本发明实施例38光学性能调控方法对应的恒电流法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及在不同氧化还原反应过程中的电-光转换效率；图5(a)左侧纵坐标“Area current”表示面积电流，右侧纵坐标“Transmittance”表示透过率，横坐标“Potential”表示电势。图5(b)左侧纵坐标“Optical density”表示光学密度，横坐标“Area capacity”表示面积容量。FIG5 shows the constant current method and time control (theoretical value) and real-time monitored optical transmittance (measured value) corresponding to the optical performance control method of Example 38 of the present invention, as well as the electro-optical conversion efficiency in different redox reaction processes; the ordinate "Area current" on the left side of FIG5(a) represents the area current, the ordinate "Transmittance" on the right side represents the transmittance, and the abscissa "Potential" represents the potential. The ordinate "Optical density" on the left side of FIG5(b) represents the optical density, and the abscissa "Area capacity" represents the area capacity.
图6为本发明实施例47光学性能调控方法对应的恒电压法与时间控制(理论值)与实时监测的光学透过率(实测值)，以及有效转移电荷密度及光学密度；图6(a)左侧纵坐标“Area current”表示面积电流，右侧纵坐标“Transmittance”表示透过率，横坐标“Time”表示时间。图6(b)左侧纵坐标“Area capacity”表示面积容量，右侧纵坐标“Optical density”表示光学密度，横坐标“Time”表示时间。FIG6 shows the constant voltage method and time control (theoretical value) and real-time monitored optical transmittance (measured value), as well as the effective transfer charge density and optical density, corresponding to the optical performance control method of Example 47 of the present invention; the ordinate "Area current" on the left side of FIG6 (a) represents the area current, the ordinate "Transmittance" on the right side represents the transmittance, and the abscissa "Time" represents the time. The ordinate "Area capacity" on the left side of FIG6 (b) represents the area capacity, the ordinate "Optical density" on the right side represents the optical density, and the abscissa "Time" represents the time.
图7为本发明实施例45光学性能调控方法对应的循环伏安法控制(理论值)与实时光学密度的一阶导数，以及实施例46恒电流法与时间控制获得的有效转移电荷密度及光学密度(实测值)。图7(a)左侧纵坐标“Area current”表示面积电流，右侧纵坐标“1st-order Derivative of OD”表示光学密度的一阶导数，横坐标“Time”表示时间。图7(b)左侧纵坐标“Area capacity”表示面积容量，右侧纵坐标“Optical density”表示光学密度，横坐标“Time”表示时间。FIG7 shows the cyclic voltammetry control (theoretical value) and the first-order derivative of the real-time optical density corresponding to the optical property regulation method of Example 45 of the present invention, as well as the effective transfer charge density and optical density (measured value) obtained by the constant current method and time control of Example 46. The ordinate “Area current” on the left side of FIG7(a) represents the area current, the ordinate “1st-order Derivative of OD” on the right side represents the first-order derivative of the optical density, and the abscissa “Time” represents the time. The ordinate “Area capacity” on the left side of FIG7(b) represents the area capacity, the ordinate “Optical density” on the right side represents the optical density, and the abscissa “Time” represents the time.
从图1-7中可以看出，通过结合循环伏安法与原位光学监测能够准确的评估电致变色器件的电-光转换效率。在此基础上，通过循环伏安法、恒电流法等不同的有效传输电荷控制方法能够对电致变色器件的光学性能进行精准控制。As can be seen from Figures 1-7, the electro-optical conversion efficiency of electrochromic devices can be accurately evaluated by combining cyclic voltammetry with in-situ optical monitoring. On this basis, the optical properties of electrochromic devices can be precisely controlled by different effective charge transfer control methods such as cyclic voltammetry and constant current method.
本发明的光学性能调控方法也可适用于含有机-无机复合电致变色材料的电致变色器件。The optical property regulation method of the present invention can also be applied to electrochromic devices containing organic-inorganic composite electrochromic materials.
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims (17)
- 一种可控电致变色器件，其特征在于，所述可控电致变色器件包括电致变色器件、电流控制装置；A controllable electrochromic device, characterized in that the controllable electrochromic device comprises an electrochromic device and a current control device;所述电流控制装置通过采用如下所示的公式控制所述电致变色器件：The current control device controls the electrochromic device by using the formula shown below:
其中，OD为电致变色过程中所需的光学密度，OD 0为所述电致变色器件在电致变色过程中的初始光学密度，ε i为电致变色过程中不同氧化还原反应的电-光转换效率，Q i为电致变色过程中发生的不同氧化还原反应的有效转移电荷密度，N为电致变色过程中发生的不同氧化还原反应的数量，I t为电致变色过程中不同时刻t的电流密度。 Wherein, OD is the optical density required in the electrochromic process, OD0 is the initial optical density of the electrochromic device in the electrochromic process, εi is the electro-optical conversion efficiency of different redox reactions in the electrochromic process, Qi is the effective transfer charge density of different redox reactions occurring in the electrochromic process, N is the number of different redox reactions occurring in the electrochromic process, and It is the current density at different times t in the electrochromic process. - 根据权利要求1所述的可控电致变色器件，其特征在于，所述电致变色器件至少包括电致变色层和导电基底层。The controllable electrochromic device according to claim 1 is characterized in that the electrochromic device comprises at least an electrochromic layer and a conductive substrate layer.
- 根据权利要求1所述的可控电致变色器件，其特征在于，所述可控电致变色器件中还包括电压控制装置。The controllable electrochromic device according to claim 1 is characterized in that the controllable electrochromic device also includes a voltage control device.
- 根据权利要求1所述的可控电致变色器件，其特征在于，所述电流控制装置包括电化学工作站。The controllable electrochromic device according to claim 1 is characterized in that the current control device comprises an electrochemical workstation.
- 根据权利要求1所述的可控电致变色器件，其特征在于，所述可控电致变色器件中还包括电流监测装置和/或电压监测装置。The controllable electrochromic device according to claim 1 is characterized in that the controllable electrochromic device also includes a current monitoring device and/or a voltage monitoring device.
- 根据权利要求1-5任一项所述的可控电致变色器件，其特征在于，所述可控电致变色器件还包括光度计。The controllable electrochromic device according to any one of claims 1 to 5, characterized in that the controllable electrochromic device also includes a photometer.
- 根据权利要求6所述的可控电致变色器件，其特征在于，所述光度计为紫外-可见-近红外分光光度计。The controllable electrochromic device according to claim 6 is characterized in that the photometer is a UV-visible-near infrared spectrophotometer.
- 权利要求1-7中任一项所述的可控电致变色器件的光学性能调控方法，其特征在于，包括以下步骤：The method for controlling the optical properties of a controllable electrochromic device according to any one of claims 1 to 7, characterized in that it comprises the following steps:启动所述电流控制装置，采用电化学方法对所述电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制；从而实现对所述电致变色器件的光学性能的定量精确调控。The current control device is started to use an electrochemical method to effectively transfer charge control on the electrochemical reaction in the electrochromic process of the electrochromic device, thereby achieving quantitative and precise regulation of the optical properties of the electrochromic device.
- 根据权利要求8所述的光学性能调控方法，其特征在于，启动所述电流控制装置的同时，还启动电压控制装置，然后采用电化学方法对所述电致变色器件电致变色过程中的电化学反应进行有效转移电荷控制。The optical property control method according to claim 8 is characterized in that, when the current control device is started, the voltage control device is also started, and then an electrochemical method is used to effectively transfer charge control of the electrochemical reaction in the electrochromic process of the electrochromic device.
- 根据权利要求8所述的光学性能调控方法，其特征在于，对所述电致变色器件还采用 电流监测装置和/或电压监测装置进行监测。The optical property control method according to claim 8 is characterized in that the electrochromic device is also monitored by a current monitoring device and/or a voltage monitoring device.
- 根据权利要求8所述的光学性能调控方法，其特征在于，所述电化学方法包括循环伏安法、恒电流法、恒电压法、交变电流法、脉冲电流法、交变电压法、脉冲电压法、梯度电压法、梯度电流法中的至少一种。The optical property control method according to claim 8 is characterized in that the electrochemical method includes at least one of cyclic voltammetry, constant current method, constant voltage method, alternating current method, pulse current method, alternating voltage method, pulse voltage method, gradient voltage method, and gradient current method.
- 根据权利要求8所述的光学性能调控方法，其特征在于，所述电化学方法包括循环伏安法、恒电流法、恒电压法、循环伏安法-恒电流法、循环伏安法-恒电压法、恒电流法-恒电压法、循环伏安法-恒电压法-恒电流法中的至少一种。The optical property control method according to claim 8 is characterized in that the electrochemical method includes at least one of cyclic voltammetry, constant current method, constant voltage method, cyclic voltammetry-constant current method, cyclic voltammetry-constant voltage method, constant current method-constant voltage method, and cyclic voltammetry-constant voltage method-constant current method.
- 根据权利要求8所述的光学性能调控方法，其特征在于，所述光学性能包括光学密度、光学透过率、反射率、发射率、色度中的至少一种。The optical property control method according to claim 8 is characterized in that the optical property includes at least one of optical density, optical transmittance, reflectivity, emissivity, and chromaticity.
- 根据权利要求8所述的光学性能调控方法，其特征在于，所述光学性能涉及的光学波长包括X射线区、紫外光区、可见光区、红外光区、微波区以及无线电波区中的至少一种。The optical property control method according to claim 8 is characterized in that the optical wavelength involved in the optical property includes at least one of the X-ray region, ultraviolet light region, visible light region, infrared light region, microwave region and radio wave region.
- 根据权利要求8所述的光学性能调控方法，其特征在于，对所述电致变色器件的光学性能进行定量调控后，利用所述光度计测试电致变色器件的光学性能，获得所需的光学性能。The optical property control method according to claim 8 is characterized in that after the optical property of the electrochromic device is quantitatively controlled, the optical property of the electrochromic device is tested using the photometer to obtain the desired optical property.
- 权利要求8-15中任一项所述的光学性能调控方法，其特征在于，所述光学性能调控方法的光学调控精度误差小于5％。The optical performance control method according to any one of claims 8 to 15 is characterized in that the optical control accuracy error of the optical performance control method is less than 5%.
- 权利要求1-7中任一项所述的可控电致变色器件或权利要求8-16中任一项所述的光学性能调控方法在光电领域中的应用；优选的，所述光电领域包括变色玻璃、红外防护、光学伪装、智能窗或防眩目后视镜。Application of the controllable electrochromic device according to any one of claims 1 to 7 or the optical property regulation method according to any one of claims 8 to 16 in the optoelectronic field; preferably, the optoelectronic field includes photochromic glass, infrared protection, optical camouflage, smart windows or anti-glare rearview mirrors.
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| US20160266410A1 (en) * | 2013-11-20 | 2016-09-15 | Ashwin-Ushas Corporation, Inc. | Method and apparatus for control of electrochromic devices |
| CN107422566A (en) * | 2017-09-18 | 2017-12-01 | 北京工业大学 | A kind of control method based on the transmission of electrochromic material structure intermediate ion and ion storage |
| CN108427232A (en) * | 2018-04-03 | 2018-08-21 | 华南理工大学 | A kind of method and system that electrochomeric glass passes through internet-based control colour switching |
| CN113504684A (en) * | 2021-06-15 | 2021-10-15 | 合肥威迪变色玻璃有限公司 | Current integral differential control-based electrochromic glass coloring and fading method |
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| US20160266410A1 (en) * | 2013-11-20 | 2016-09-15 | Ashwin-Ushas Corporation, Inc. | Method and apparatus for control of electrochromic devices |
| CN107422566A (en) * | 2017-09-18 | 2017-12-01 | 北京工业大学 | A kind of control method based on the transmission of electrochromic material structure intermediate ion and ion storage |
| CN108427232A (en) * | 2018-04-03 | 2018-08-21 | 华南理工大学 | A kind of method and system that electrochomeric glass passes through internet-based control colour switching |
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