Measuring device and method for electrochromic material
By designing a simplified electrochromic material measurement device, using cyclic gradient potential and tungsten halogen lamp light source, synchronously measuring the light intensity, current and power of the electrochromic material, the complex structure and cumbersome operation in the prior art are solved, and the problem of complex structure and complicated operation in the existing technology is realized. Quantitative and precise measurement of electrochromic material properties is performed.
Patent Information
- Application Number
- CN202411516668.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-29
- Publication Date
- 2024-12-20
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing electrochromic material measurement devices are complex in structure and cumbersome in operation. They cannot effectively synchronize the light intensity, current, transmittance, power, wavelength and time of the material and their relationships, resulting in the inability to quantify the material performance.
A measurement device including a light source, an electrochromic device module, a collimator, a spectrometer and a silicon diode detector was designed. By setting the cyclic gradient potential, the light generated by the tungsten halogen lamp light source is used to pass through the spectrometer and silicon diode. The detector detects changes in light intensity, and combines the electrochemical workstation to measure current and electricity, and calculates the quantitative relationship between optical density difference and time, current and electricity data.
The quantification of the properties of electrochromic materials is achieved, and the improvement of materials can be scientifically guided, simplified the measurement process and improved the measurement accuracy.
Smart Images
Figure CN119164897A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of photoelectric material measurement, in particular to a device and method for measuring electrochromic materials. Background Art
[0002] Electrochromic materials are energy-saving and environmentally friendly materials that can adjust the potential to obtain material color, effectively filter out light, and reduce energy use. 3 As an electrochromic material, it has been widely studied. Electrochromic smart windows are a new energy-saving technology that can dynamically adjust the lighting and shading performance of houses according to human will. 3 It has become the most widely used electrochromic material due to its advantages such as large color change range and low driving voltage.
[0003] The measuring devices on the market are mainly complex in structure and complicated in operation steps. The present invention presents a new type of measuring device for electrochromic materials, which can solve the problems of difficult operation and complex structure of existing electrochromic testing devices. By building a relatively simple device and setting a cyclic gradient potential, in conjunction with the testing device, it is possible to synchronously measure the light intensity, current, transmittance, amount of electricity, wavelength, time and the relationship between the electrochromic materials, thereby providing a scientific guide for better preparation of electrochromic materials with better performance.
[0004] For example, a testing device for an electrochromic device disclosed in patent publication number CN212134035U includes a light source module, a power module, an illuminance meter, a photometer and a data processing module; the light source module is used to provide a light source for the electrochromic device; the power module is electrically connected to the electrochromic device, and is used to provide a driving voltage for the electrochromic device to change the state of the electrochromic device; the illuminance meter is used to measure the light intensity on the surface of the electrochromic device; the photometer is contacted with the electrochromic device, and is used to perform a spectral scan on the electrochromic device; the data processing module is communicatively connected to the photometer, and is used to read the spectral data output by the photometer and process the spectral data.
[0005] The above-mentioned testing device can measure the illumination intensity of the electrochromic material and the influence of the illumination intensity on the attenuation characteristics of the electrochromic device by a purely physical method, but its structure is complex and it cannot quantify the performance of the electrochromic material. Summary of the invention
[0006] In order to solve the problems existing in the existing electrochromic measurement technology, the purpose of the present invention is to provide a measuring device and method for electrochromic materials, which can realize the synchronous measurement of light intensity, current, transmittance, quantity, wavelength, time and the relationship between them of electrochromic materials.
[0007] To achieve the above object, the present invention is implemented according to the following technical solutions:
[0008] One of the purposes of the present invention is to provide a device for measuring electrochromic materials, comprising a light source, an electrochromic device module,
[0009] The output end of the light source is provided with a first collimator, an aperture, an electrochromic device module, a spectroscope and a silicon diode detector in sequence, the reflected light output end of the spectroscope is provided with a second collimator, and the output end of the second collimator is provided with a spectrometer;
[0010] The electrochromic device module comprises an electrolytic cell, wherein an electrolytic cell base, an electrolytic cell reaction chamber, a quartz glass cover, a working electrode, an electrochromic material, a reference electrode and a counter electrode are arranged in the electrolytic cell. The electrolytic cell base is vertically fixed in the electrolytic cell, the left end face of the electrolytic cell reaction chamber is connected to the left end face of the electrolytic cell base through the working electrode, the quartz glass cover is fixed to the right end face of the electrolytic cell reaction chamber, the electrolytic cell reaction chamber is filled with electrolyte, and the light emitted by the light source passes through the aperture and sequentially passes through the left side wall of the electrolytic cell, the electrolytic cell base, the working electrode, the electrochromic material, the reference electrode and the counter electrode. The electrolytic cell reaction chamber, the quartz glass cover and the right side wall of the electrolytic cell are incident on the incident surface of the spectroscope; the lower end of the reference electrode penetrates the top of the electrolytic cell reaction chamber and extends to the inside of the electrolytic cell reaction chamber, the top end of the counter electrode penetrates the bottom of the electrolytic cell reaction chamber and extends to the inside of the electrolytic cell reaction chamber, and the electrochromic material is fixed on the right end face of the working electrode and is enclosed in the electrolytic cell reaction chamber; the working electrode, the reference electrode, the counter electrode, and the light source are connected to an electrochemical workstation, the electrochemical workstation and the silicon diode detector are connected to a data acquisition device, and the data acquisition device is connected to a computer.
[0011] Preferably, the light source is a halogen tungsten lamp light source HL-2000, and the wavelength of the light generated is 350nm-1050nm.
[0012] Preferably, the angle between the light path emitted by the light source and the beam splitter is 45 degrees.
[0013] The second object of the present invention is to provide a method for measuring an electrochromic material, using the above-mentioned electrochromic material measuring device for measurement, and the specific steps are as follows:
[0014] S1. Assemble the electrolytic cell and inject electrolyte into the reaction chamber of the electrolytic cell so that a reaction will occur when the electrochemical workstation inputs a potential;
[0015] S2, the working electrode, the reference electrode, and the counter electrode are connected to an electrochemical workstation respectively, and the potential and information are sent through the electrochemical workstation. The electrochemical workstation and the silicon diode detector are connected to a data acquisition device, and the data acquisition device is connected to a computer;
[0016] S3. Turn on the computer, electrochemical workstation and light source, set different negative potential data through the computer, set the sampling speed and the total measurement time; after starting the operation, a reaction cycle is generated. During the operation, the installed electrochromic material will show electrochromic performance and will change color. The light beam remains on. After the color change, the intensity of the light passing through changes. The light is split at the position of the spectroscope. The light intensity before and after the light changes through the electrochromic material is detected by a silicon diode detector. The spectral information before and after the light changes through the electrochromic material is measured by a spectrometer, and the current and quantity of the electrolytic cell reaction chamber are measured by the electrochemical workstation; the computer calculates the quantitative relationship between the optical density difference and the time, current and quantity data based on the collected data.
[0017] Compared with the prior art, the present invention uses the light generated by the halogen tungsten lamp light source HL-2000 as the detection light for studying the performance of the electrochromic material, passes through the collimator and the spectroscope, and after the light beam passes through the electrochromic material and changes color, it reaches the silicon diode light detector, and the light intensity before and after the light changes color after passing through the electrochromic material is detected by the silicon diode detector, and the spectrum information before and after the light changes color after passing through the electrochromic material is measured by the spectrometer, and the current and quantity of the electrolytic cell reaction chamber are measured by the chemical workstation; the computer calculates the quantitative relationship between the optical density difference and the time, current and quantity data according to the collected data, so that the performance of the electrochromic material can be quantified, so that the performance of the electrochromic material can be judged through the deficiencies presented by the data of the electrochromic material, and further can scientifically guide us to improve the electrochromic material. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is a structural schematic diagram of the present invention.
[0019] Figure 2 In the range of -0.6 VRHE to 0.6 VRHE, the program is set to change the potential every ten seconds. 3 The current density, charge, and optical density difference of the film change synchronously with time.
[0020] Figure 3 The electrochromic material WO changes from 0.6VRHE to -0.6BRHE potential 3 The change in optical density of a thin film due to different potentials.
[0021] Figure 4 In order to conduct electrochromic material WO at different scanning rates 3 Cyclic voltammetry curves of the films.
[0022] Figure 5 WO is an electrochromic material 3The degree of absorption of light of different wavelengths by a film under different parameters and different potentials.
[0023] Figure 6 WO is an electrochromic material 3 The relationship between the charge and the optical density difference of the film periodic test results. DETAILED DESCRIPTION
[0024] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not used to limit the invention.
[0025] like Figure 1 As shown, this embodiment exemplarily shows a device for measuring electrochromic materials, including a light source 900 and an electrochromic device module;
[0026] In this embodiment, the light source is a halogen tungsten lamp HL-2000, the wavelength of the light generated is 350nm-1050nm, and it is in a constant light state after the power is turned on, and is used to emit a light beam; the output end of the light source 900 is provided with a first collimator 800, an aperture 700, an electrochromic device module, a spectroscope 400 and a silicon diode detector 300 in sequence, and the reflected light output end of the spectroscope 400 is provided with a second collimator 200, and the angle between the light path emitted by the light source 100 and the spectroscope 400 is 45 degrees, and the first collimator 800 and the second collimator 200 are used to convert the passing light beam into parallel light; the aperture 700 is used to obtain a light beam that is parallel to the electrochromic device by adjusting the diameter of the light source. The aperture is the same size as the color-changing material, so that the light source can pass smoothly and be detected; the spectroscope 400 is used to split the light beam passing through the material into two paths, horizontal and vertical, which is convenient for measuring most data; the silicon diode detector 300 is used to detect the actual light intensity of the light source before and after the electrochromic device module changes color; the output end of the second collimator 200 is provided with a spectrometer 500. In this embodiment, the spectrometer 500 uses a USB4000 fiber optic spectrometer, which is used to pass the light separated by the spectroscope 400 and then connect to a computer to measure the spectral information of the electrochromic device module before and after the color change in real time; in the following embodiments, WO 3 Thin films as electrochromic materials.
[0027] The electrochromic device module includes an electrolytic cell 100, which is provided with an electrolytic cell base 110, an electrolytic cell reaction chamber 120, a quartz glass cover 130, a working electrode 140, an electrochromic material 170, a reference electrode 150 and a counter electrode 160. In this embodiment, the working electrode 140 is made of copper sheet, the reference electrode 150 is made of Ag / AgCl, and the counter electrode 160 is made of platinum wire; the electrolytic cell base 110 is vertically fixed in the electrolytic cell 100, the left end face of the electrolytic cell reaction chamber 120 is connected to the left end face of the electrolytic cell base 110 through the working electrode 140, the quartz glass cover 130 is fixed to the right end face of the electrolytic cell reaction chamber 120, and the electrolytic cell reaction chamber 120 is filled with an electrolyte, and in this embodiment, 0.1 mol / L HNO 3 As an electrolyte, the light emitted by the light source 100 passes through the aperture 700 and then sequentially passes through the left wall of the electrolytic cell 100, the electrolytic cell base 100, the working electrode 140, the electrochromic material 170, the electrolytic cell reaction chamber 120, the quartz glass cover 130 and the right side wall of the electrolytic cell 100 to the incident surface of the spectroscope 400; the lower end of the reference electrode 150 extends through the top of the electrolytic cell reaction chamber 120 to the inside of the electrolytic cell reaction chamber, the top end of the counter electrode 160 extends through the bottom of the electrolytic cell reaction chamber 120 to the inside of the electrolytic cell reaction chamber, the electrochromic material 170 is fixed on the right end surface of the working electrode 140 and is enclosed in the electrolytic cell reaction chamber 120; the working electrode 140, the reference electrode 150, the counter electrode 160, and the light source 900 are connected to the electrochemical workstation, the electrochemical workstation and the silicon diode detector 300 are connected to the data acquisition device 600, and the data acquisition device 600 is connected to a computer (not shown in the figure).
[0028] The electrolytic cell 100 is used to generate a reaction, and is program-controlled by an electrochemical workstation and a connected computer to achieve potential changes, thereby generating a reaction in the electrolytic cell; the light intensity before and after the light changes color through the electrochromic material is detected by a silicon diode, and the spectral information of the electrochromic material before and after the color change is measured by a spectrometer, and the current and quantity of the electrolytic cell reaction chamber are measured by the electrochemical workstation; the computer calculates the quantitative relationship between the optical density difference and the time, current, and quantity data based on the collected data.
[0029] Specifically, the measurement is performed using the above-mentioned electrochromic material measuring device, and the specific steps are as follows:
[0030] S1. Assemble the electrolytic cell 100 and inject 0.1 mol / L HNO into the electrolytic cell reaction chamber 120. 3 As an electrolyte, it causes a reaction when the electrochemical workstation inputs a potential;
[0031] S2, the working electrode 140, the reference electrode 150, and the counter electrode 160 are respectively connected to an electrochemical workstation, and the potential and information are sent through the electrochemical workstation. The electrochemical workstation and the silicon diode detector 300 are connected to a data acquisition device 600, and the data acquisition device 600 is connected to a computer;
[0032] S3, turn on the computer, electrochemical workstation, light source 900, set different negative potential data through the computer, set the sampling speed and the total measurement time; after starting the operation, a reaction cycle is generated. During the operation, the installed WO 3 The film will show electrochromic properties, and will change color. The light beam will remain in the open state. After the color change, the intensity of the light passing through will change. The light will be split at the position of the beam splitter 400, and the light will be detected by the silicon diode detector 300 through the WO 3 The light intensity before and after the film changes color is measured by the spectrometer 500. 3 The spectral information of the film before and after color change is collected, and the current and quantity of the electrolytic cell reaction chamber are measured by a chemical workstation; the computer calculates the quantitative relationship between the optical density difference and the time, current, and quantity data based on the collected data; the calculation formula of the optical density difference is:
[0033]
[0034] Where: I 0 is the light intensity before the light passes through the electrolyte, and I is the light intensity after the light passes through the electrolyte.
[0035] To further verify the feasibility of this implementation, perform the following operations:
[0036] Before the reaction time was 20 s, the working potential was 0.6 V. When the reaction time was 20 s, the electrochemical workstation started periodic operation, and the working potential changed from 0.6 V to -0.2 V, and the potential was negative. The electrolytic cell reacted, and WO 3 The film will undergo an oxidation reaction, and the valence state of the tungsten ion will change from +6 to +4. The electrochromic material will change color from transparent to dark blue, so most of the light from the light source is blocked. The sensor reflects the light density difference ΔOD. Due to the electrochemical reaction, the current density and the amount of electricity also change synchronously. In this process, all data will be transmitted to the data acquisition output end for collection.
[0037] During the reaction time of 30-40s, the electrochemical workstation was programmed to change the working potential to 0.6V, so that various data changed synchronously.
[0038] During the reaction time of 40-50 s, the working potential became -0.3 V. The reaction continued.
[0039] During the reaction time of 50-60 s, the working potential became 0.6 V. The reaction continued.
[0040] During the reaction time of 60-70 s, the working potential became -0.4 V. The reaction continued.
[0041] Similarly, when the potential changes from -0.6V to 0.6V, a cycle ends. 3 The film can maintain its transparent state due to the feedback of positive potential. Under negative potential, the electron migration rate of tungsten ions increases as the potential becomes more negative, and the tungsten ions are oxidized more thoroughly, showing a synchronous increase in optical density, current density, and charge, and all data are reflected synchronously.
[0042] At -0.6V RHE to 0.6V RHE In the following example, the program is set to change the potential every ten seconds. 3 The current density, charge, and optical density difference ΔOD of the film change synchronously with time. Figure 2 As shown, at 0.6VRHE to -0.6V RHE WO under potential change 3 The change in optical density of the film due to different potentials is as follows: Figure 3 The computer is based on Figure 2 and Figure 3 The data can be used to plot the relationship between wavelength and optical density difference using the optical density difference formula.
[0043] Cyclic voltammetry is an effective way to evaluate the ability of thin films to insert and extract hydrogen ions. Cyclic voltammetry testing can reveal the electrochemical behavior. Figure 4 The voltage window was between -0.6 V and +0.6 V, and different scan rates (20 mV s -1 , 50mV s -1 , 100mV s -1 , 200mV s -1 ). At different rates in 0.1 M HNO 3 In each cycle scan, when H ions are inserted, WO 3 The film appears blue, and when hydrogen ions are extracted, WO 3 The film becomes transparent. 3 When the film was cathodically polarized in the electrolytic cell, it turned blue, indicating that W ions were inserted into WO 3 In the film. Different from other documents, the WO in this embodiment 3The film produced two peaks during the cathodic polarization process, indicating that W ions underwent two oxidation reactions during this process. Due to the influence of the potential rate change, this situation was caused by the deposition time being too short or too long, and WO 3 The film is highly sensitive to current density, and it can be seen that WO 3 When the film is deposited for 1500s, the anode and cathode current density peaks of the sample are shifted to positive and negative potentials, respectively, resulting in smaller peak separation between oxidation and reduction, which means faster charge transfer kinetics. Thus, the present invention can be used to obtain the synchronous relationship between the scan rate and the current density and optical density difference, and reveal the reaction mechanism.
[0044] By studying the WO 3 The film was tested and the test results were as follows Figure 5 As shown by Figure 5 It can be seen that by testing WO with different thicknesses 3 The film was tested in the same manner as described above. The electrochromic material testing device of the present invention was used to compare the changes in optical density under different potentials, which can intuitively explain the WO 3 The absorption degree of the film at different thicknesses and different potentials for wavelength light can be concluded from data analysis. The optical density change reaches a peak when the deposition time is 1500s and 1800s. This is because at the appropriate thickness, WO 3 The particles at the film interface are relatively uniform, which is conducive to ion conduction on the surface and more conducive to electron conduction at the interface. The overall change in optical density is first increased and then decreased. This intuitive testing method can guide us to understand that the performance is best when the deposition time is 1500s, so as to scientifically guide WO 3 Modification and research of thin films.
[0045] Furthermore, for WO 3 The film is periodically tested. The test method on the electrochromic material testing device of the present invention is consistent with the above description, and the data of the difference between the electric quantity and the optical density are collected by a computer, so that the relationship between the two can be drawn, which is conducive to the development of related research. The results are as follows Figure 6 As shown by Figure 6 It can be seen that the response of the difference between the charge and the optical density is the most positive when the deposition time is 1500s and 1800s, while a "platform" will appear in other cases. The reason for the platform is that WO 3 The film thickness leads to insufficient electron conduction at the material interface, and this platform is not conducive to extending the life of the material. Therefore, the present invention can intuitively explain the life of the material.
[0046] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. All technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims
1. A device for measuring electrochromic materials, comprising a light source (900), an electrochromic device module, Features: The output end of the light source (900) is provided with a first collimator (800), an aperture (700), an electrochromic device module, a spectroscope (400) and a silicon diode detector (300) in sequence; the reflected light output end of the spectroscope (400) is provided with a second collimator (200); and the output end of the second collimator (200) is provided with a spectrometer (500); The electrochromic device module comprises an electrolytic cell (100), wherein the electrolytic cell (100) is provided with an electrolytic cell base (110), an electrolytic cell reaction chamber (120), a quartz glass cover (130), a working electrode (140), an electrochromic material (170), a reference electrode (150) and a counter electrode (160); the electrolytic cell base (110) is vertically fixed in the electrolytic cell (100); the left end surface of the electrolytic cell reaction chamber (120) is connected to the left end surface of the electrolytic cell base (110) through the working electrode (140); the quartz glass cover (130) is fixed to the right end surface of the electrolytic cell reaction chamber (120); the electrolytic cell reaction chamber (120) is filled with electrolyte; and light emitted by the light source (100) passes through an aperture (700) and then sequentially passes through the left side wall of the electrolytic cell (100), the electrolytic cell base (100), the working electrode (140), The electrochromic material (170), the electrolytic cell reaction chamber (120), the quartz glass cover (130) and the right side wall of the electrolytic cell (100) are incident on the incident surface of the spectroscope (400); the lower end of the reference electrode (150) penetrates the top of the electrolytic cell reaction chamber (120) and extends to the inside of the electrolytic cell reaction chamber, the top end of the counter electrode (160) penetrates the bottom of the electrolytic cell reaction chamber (120) and extends to the inside of the electrolytic cell reaction chamber, the electrochromic material (170) is fixed on the right end surface of the working electrode (140) and is enclosed in the electrolytic cell reaction chamber (120); the working electrode (140), the reference electrode (150), the counter electrode (160) and the light source (900) are connected to an electrochemical workstation, the electrochemical workstation and the silicon diode detector (300) are connected to a data acquisition device (600), and the data acquisition device (600) is connected to a computer.
2. The measuring device for electrochromic material according to claim 1, Features: The light source is a halogen tungsten lamp light source HL-2000, and the wavelength of the light generated is 350nm-1050nm.
3. The measuring device for electrochromic material according to claim 1, Features: The angle between the light path emitted by the light source (100) and the beam splitter (400) is 45 degrees.
4. A method for measuring electrochromic materials, It is characterized in that The measurement is performed using the measuring device for electrochromic materials as described in any one of claims 1 to 3, and the specific steps are as follows: S1. Assemble the electrolytic cell and inject electrolyte into the reaction chamber of the electrolytic cell so that a reaction will occur when the electrochemical workstation inputs a potential; S2, the working electrode, the reference electrode, and the counter electrode are connected to an electrochemical workstation respectively, and the potential and information are sent through the electrochemical workstation. The electrochemical workstation and the silicon diode detector are connected to a data acquisition device, and the data acquisition device is connected to a computer; S3. Turn on the computer, electrochemical workstation and light source, set different negative potential data through the computer, set the sampling speed and the total measurement time; after starting the operation, a reaction cycle is generated. During the operation, the installed electrochromic material will show electrochromic performance and will change color. The light beam remains on. After the color change, the intensity of the light passing through changes. The light is split at the position of the spectroscope. The light intensity before and after the light changes through the electrochromic material is detected by a silicon diode detector. The spectral information before and after the light changes through the electrochromic material is measured by a spectrometer, and the current and quantity of the electrolytic cell reaction chamber are measured by the electrochemical workstation; the computer calculates the quantitative relationship between the optical density difference and the time, current and quantity data based on the collected data.