CN113433751B - Multicolor electrochromic device and preparation method thereof - Google Patents
Multicolor electrochromic device and preparation method thereof Download PDFInfo
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- CN113433751B CN113433751B CN202110741642.7A CN202110741642A CN113433751B CN 113433751 B CN113433751 B CN 113433751B CN 202110741642 A CN202110741642 A CN 202110741642A CN 113433751 B CN113433751 B CN 113433751B
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- 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
- G02F1/1506—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
- G02F1/1508—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
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- 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
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- 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
- G02F1/155—Electrodes
Abstract
The invention discloses a multi-color electrochromic device, which comprises a transparent working electrode, an insulating isolation column, a Cu counter electrode and a transparent conductive substrate, wherein the transparent working electrode is arranged on the insulating isolation column; the Cu counter electrode is bonded with the transparent conductive substrate; the sealed space surrounded by the transparent working electrode, the transparent conductive base and the insulating isolation column is an electrolyte reaction tank; the electrolyte reaction tank is filled with Bi-Cu ion neutral gel electrolyte; the surface of the transparent working electrode, which is in contact with the electrolyte, is provided with a noble metal nanoparticle modification layer. The invention also discloses a preparation method of the device. The device has the advantages of simple structure, excellent color change performance, energy conservation and color retention, simplifies the preparation process of the device, and obviously reduces the manufacturing period and the cost of the color change device; meanwhile, metal deposition can be realized on the transparent conductive substrate by applying positive voltage, and free reversible switching of the color-changing device in various color states can be realized by changing the voltage magnitude and polarity of reversible metal electrodeposition and the duration time of the applied voltage.
Description
Technical Field
The invention relates to a multicolor electrochromic device, in particular to a multicolor electrochromic device and a preparation method thereof.
Background
The electrochromic glass is a phenomenon that the optical properties of the glass are stable and reversible under the action of an external electric field, and common application fields comprise intelligent windows (CN205121123U), displays (201710001397.X), color-changing energy storage devices (CN106371259A) and the like. Electrochromic devices are increasingly being used in a wide range of applications, such as swiss reinsurance buildings, boeing 787 aircraft portholes, and the like. Sunlight can penetrate through a building glass window or an automobile glass to enable the temperature of an indoor space to rise, so that the environmental temperature is not comfortable, and meanwhile, the energy consumption and the use cost of an indoor air conditioner are increased. In order to reduce energy consumption and save cost, Low-emissivity (Low-E) glass is commonly used to increase the reflectivity of infrared rays and improve the regulation and control of environmental heat. However, the Low-E device needs to plate a plurality of metal thin films or other compound film systems on the glass surface, and a vacuum interlayer structure is adopted to avoid metal oxidation. Most importantly, the Low-e glass cannot actively regulate and control the gradual change of the external environment light. In order to realize the active light control capability of the color-changing device, in the early 80 s of the last century, american scientists and swedish scientists developed a novel intelligent energy-saving window based on electrochromic thin films, which is considered as the starting point of electrochromic research. The electrochromic device is based on a sandwich structure and comprises a conductive substrate, a color-changing layer, a liquid or gel electrolyte, an ion storage layer and a conductive substrate, wherein the color-changing mechanism is an oxidation-reduction reaction caused by ion intercalation (CN 104806128A). However, the color-changing devices are not rich in color-changing colors, and researchers develop organic molecular electrolytes successively to realize multi-color switching. However, organic electrolytes often have high toxicity, and devices need to be tightly sealed to avoid leakage, which is detrimental to the low-cost safe use of the devices. In order to reduce the risk of liquid leakage in the device packaging, a solid electrolyte-based all-solid-state electrochromic device (solid Energy Materials and solid Cells 200 (2019)) 110045 is developed, but because the device adopts an inorganic color-changing material, the color is single, the response color-changing speed is not fast enough, the switching among multiple color states of the device cannot be realized, and the application of the color-changing device in the multifunctional field is also limited. In addition, the conventional electrochromic device is limited to a hard transparent conductive substrate (CN 104806128A) due to the need of depositing a color-changing material in advance and the common high-temperature evaporation method, which limits the application in the flexible color-changing field.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a multi-color electrochromic device which is simple in structure, does not need to pre-deposit an electrochromic film material on a conductive substrate, greatly simplifies the tedious preparation process of a traditional device which needs multiple layers of metal films or compound films, and remarkably reduces the manufacturing cost of the electrochromic device; meanwhile, metal deposition can be realized on the transparent working electrode by applying positive voltage, and free reversible switching of the color-changing device in various optical states can be realized by changing the voltage magnitude and polarity of reversible metal electrodeposition and the duration of the applied voltage.
The invention also aims to provide a preparation method of the multi-color-state electrochromic device.
The purpose of the invention is realized by the following technical scheme:
a multi-color electrochromic device comprises a transparent working electrode, an insulating isolation column, a Cu counter electrode and a transparent conductive substrate;
the Cu counter electrode is bonded with the transparent conductive substrate;
the sealed space enclosed by the transparent working electrode, the transparent conductive substrate and the insulating isolation column is an electrolyte reaction tank;
the electrolyte reaction tank is filled with Bi-Cu ion neutral gel electrolyte;
the surface of the transparent working electrode, which is in contact with the Bi-Cu ion neutral gel electrolyte, is provided with a noble metal nanoparticle modification layer;
the Cu counter electrode is positioned in the electrolyte reaction tank;
the Bi-Cu ion neutral gel electrolyte comprises:
5 mM-10 mM BiCl 3 12 to 17mM of CuCl 2 0.8-1.2M LiBr, 12-17 mM HCl; also includes vinyl alcohol; the weight of the vinyl alcohol is 8-12% of the total weight of the Bi-Cu ion neutral gel electrolyte.
Preferably, one opening of the insulating isolation column is hermetically bonded with the transparent conductive substrate, and the other opening of the insulating isolation column is hermetically bonded with the transparent working electrode.
Preferably, the noble metal nanoparticles are platinum nanoparticles, gold nanoparticles, silver nanoparticles, iridium nanoparticles, rhodium nanoparticles, or ruthenium nanoparticles.
Preferably, the Cu counter electrode is a Cu net or a Cu metal frame with the mesh number of more than or equal to 400.
Preferably, the multi-color state electrochromic device applies +0.2 to +1V voltage for a transparent state; for the gray state, applying a voltage of-0.5 to-1V and keeping for 8 to 12 s; and for the black state, applying a voltage of-0.5 to-1V and keeping the voltage for 25 to 35 s.
Preferably, the multi-color electrochromic device is biased to-1.4 to-1.6V and kept for 0.3 to 2s, and then is reduced to-0.2 to-0.5V and kept for 25 to 30s, so that a copper mirror state is obtained;
applying a bias voltage of-1.4 to-1.6V and keeping for 20 to 30s to obtain a silver mirror state.
The preparation method of the multi-color electrochromic device comprises the following steps:
(1) pretreating the transparent conductive substrate;
(2) adhering a Cu counter electrode on a transparent conductive substrate;
(3) bonding an opening at one side of the insulating isolation column with the transparent working electrode, and pouring Bi-Cu ion neutral gel electrolyte into the insulating isolation column;
(4) and bonding the surface of the transparent working electrode with the noble metal nanoparticle modification layer with the opening on the other side of the insulating isolation column.
Preferably, the preparation method of the multi-color electrochromic device further comprises the following steps: and (4) depositing an aluminum oxide film on the outer surface of the device obtained in the step (4) by using an ALD (atomic layer deposition) technology.
Preferably, the step (1) of pretreating the transparent conductive substrate specifically comprises:
firstly, cleaning with glass water, and then ultrasonically cleaning in deionized water, acetone and isopropanol for 15-20 min respectively; then blowing the mixture by using high-pressure nitrogen, and treating the mixture in an ultraviolet ozone machine for 30-40 min.
Preferably, the noble metal nanoparticle modification layer is prepared by an electroplating method, atomic layer deposition or magnetron sputtering process.
The electrochemical reaction is utilized in the invention to realize the redox reaction in the Bi-Cu ion neutral gel electrolyte and realize the reversible process of metal deposition and redissolution on the transparent electrode. The step potential method adopted in the invention mainly regulates and controls the nucleation process of the metal particles, realizes the metal particles with different shapes and sizes, and utilizes the local surface plasmon and multiple scattering effect to regulate and control the light transmission state. The step potential simultaneously utilizes the galvanic couple displacement between Bi-Cu elements to realize the continuous regulation and control between Bi and Cu components, simultaneously avoids the rough appearance of metal particles, obtains a more uniform and continuous film and further presents a mirror state.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the multicolor electrochromic device has a simple structure, does not need to pre-deposit electrochromic film materials on a conductive substrate, greatly simplifies the complicated preparation process of the traditional device which needs multiple layers of metal films or compound films, and obviously reduces the manufacturing cost of the electrochromic device.
(2) The multicolor electrochromic device can realize the continuity and chemical component regulation of the metal film by a step potential method, and realize a copper mirror state and a silver mirror state on the same device. According to different applied bias voltages, five different color states can be presented, namely a transparent state, a gray state, a black state, a silver mirror state and a copper mirror state.
(3) The multicolor electrochromic device has good reversible cycling stability. Reversible switching of the device between different optical states is achieved through a step potential method, and the initial modulation capacity of over 70% can be maintained in the optical modulation range after 200 cycles.
(4) The Bi-Cu ion neutral gel electrolyte used in the invention is green, nontoxic and environment-friendly.
(5) The multi-color electrochromic device has high flexible compatibility; due to the adoption of a low-temperature method (below 200 ℃), the device flexible substrate has high compatibility, and the device still can show good optical modulation capability and performance stability after being bent for more than 50 circles. The invention is also applicable to flexible substrates (such as PET or PEN substrates) and can realize the construction of flexible electrochromic devices.
(6) According to the multi-color electrochromic device, the noble metal nanoparticle modification layer is deposited on the surface of the transparent working electrode, so that the nucleation uniformity of metal under voltage regulation is improved, and the coloring uniformity and the mirror reflectivity of the device are improved.
(7) The multicolor electrochromic device provided by the invention has the advantages that the transparent conductive substrate is subjected to ozone treatment, the hydrophilicity between the surface of the transparent conductive substrate and the electrolyte is improved, and the cycle stability and the uniformity of the device are facilitated.
Drawings
Fig. 1 is a schematic structural diagram of a multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of a transparent conductive substrate in a gray state of a multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of a transparent conductive substrate in a black state of a multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 4 is a Scanning Electron Microscope (SEM) photograph of the transparent conductive substrate in the copper mirror state of the multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 5 is a Scanning Electron Microscope (SEM) photograph of a transparent conductive substrate in a silver mirror state of a multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 6 is an electrochemical voltammetry characteristic (a) and a modulated transmission spectrum (b) of a multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 7 is a transmission mode spectral modulation curve of a multi-color electrochromic device prepared in example 1 of the present invention.
Fig. 8 is an atomic force microscope image of a multi-color electrochromic device prepared in example 2 of the present invention in a gray state.
Fig. 9 is an atomic force microscope image of a multi-color electrochromic device prepared in example 2 of the present invention in a black state.
Fig. 10 is an atomic force microscope image of a multi-color electrochromic device prepared in example 2 of the present invention in a copper mirror state.
Fig. 11 is an atomic force microscope image of a multi-color electrochromic device prepared in example 2 of the present invention in a silver mirror state.
Fig. 12 is a graph of the light reflection spectrum of a multi-colored electrochromic device prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The multi-color electrochromic device prepared in this embodiment is shown in fig. 1, and includes a transparent working electrode 2, an insulating isolation column 3, a Cu counter electrode 4 and a transparent conductive substrate 5, which are coated in a device sealing layer 1; the Cu counter electrode is bonded with the transparent conductive substrate; one opening of the insulating isolation column is hermetically bonded with the transparent conductive substrate, and the other opening of the insulating isolation column is hermetically bonded with the transparent working electrode; the sealed space enclosed by the transparent working electrode, the transparent conductive substrate and the insulating isolation column is an electrolyte reaction tank; the electrolyte reaction tank is filled with Bi-Cu ion neutral gel electrolyte 6; the surface of the transparent working electrode, which is in contact with the Bi-Cu ion electrolyte, is provided with a noble metal nanoparticle modification layer.
The preparation method of the multi-color electrochromic device of the embodiment is as follows:
(1) commercial ITO glass (sheet resistance-10-15 omega/□) is used as a transparent conductive substrate, and is sequentially cleaned by glass water and ultrasonically cleaned in deionized water, acetone and isopropanol for 15min respectively; the cleaned substrate was blow-dried with nitrogen and pre-treated in an ultraviolet ozone machine for a period of 30 min.
(2) Preparing the Bi-Cu neutral gel electrolyte. The mixture ratio of the mixed solution is as follows: 5mM BiCl 3 15mM of CuCl 2 And 1M LiBr, 15mM HCl, mixed with 10% by weight of vinyl alcohol (PVA), the molecular weight of PVA being 88000. Then, the mixture was stirred magnetically for 6 hours and mixed uniformly for use.
(3) The Cu metal frame is used as a counter electrode and attached to the transparent conductive substrate to form good contact so as to realize uniform electric field regulation.
(4) And taking the other transparent electrode as a transparent working electrode, and performing noble metal nanoparticle surface treatment by adopting a two-electrode electroplating method, wherein the specific method comprises the following steps: platinum particles are deposited on the surface of the conductive electrode, and the graphite electrode is used as a counter electrode. Mixing chloroplatinic acid (0.08ml) with deionized water (125ml) as electrolyte, electroplating at constant current for 300s, and maintaining current density at-0.25 mAcm -2 。
(5) An insulating isolation column (Spacer) with a thickness of 300- 2 ) And (3) bonding the working electrode, wherein the main function is to separate the working electrode from the counter electrode, and simultaneously uniformly filling the neutral gel electrolyte prepared in the step (2), so that bubbles are prevented from being generated in the process.
(6) And (5) modifying the transparent electrode with the noble metal particles, filling the transparent electrode in the step (5), and sealing the transparent electrode in a complementary manner, wherein hot melt adhesive or epoxy resin is adopted, so that the problems of air bubbles, electrolyte leakage and the like in the process are avoided.
(7) Packaging the device: and (4) depositing an alumina film with the thickness of 5nm outside the device prepared in the step (6) by using an ALD (atomic layer deposition) technology to protect and package the surface of the device. The deposition parameters were as follows: the precursor source was Trimethylaluminum (TMA) and the deposition conditions were: the chamber temperature was 85 ℃ and the chamber pressure was 9Pa, and the growth cycle was 53 times.
In the multi-color electrochromic device of the present embodiment, for the transparent state, a voltage of +0.8V is applied; for the gray state, the voltage is applied at-0.8V and held for 10 s; for the black state, a voltage of-0.8V was applied for 25 s. Applying a bias of-1.6V and holding for 0.5s, followed by a reduction to-0.4V and holding for 30s to obtain a copper colored mirror state; and applying a bias voltage of-1.6V and keeping for 20-30 s to obtain a silver mirror state.
Fig. 2 to 5 are Scanning Electron Microscope (SEM) photographs of the transparent conductive substrate in a gray state, a black state, a copper mirror state, and a silver mirror state of the multi-color electrochromic device prepared in this embodiment, respectively. As can be seen, FIG. 2 corresponds to a gray state film with very small particles having an average size of less than 100nm, and FIG. 3 corresponds to a black state film with larger particles having an average particle size of greater than 200 nm. For the silver mirror state of fig. 4, the surface of the film is smooth and very continuous, and for the copper state of fig. 5, the surface of the film has smaller particles but high density and has certain roughness.
Fig. 6 shows the electrochemical voltammetry characteristics (a) and modulated transmission spectrum (b) of the multi-color electrochromic device prepared in this example. As can be seen, the voltage window applied to the device ranged from-0.8V to 0.8V, and during the reverse sweep from 0V to-0.8V, a first reduction peak position of about-0.5V was observed due to Cu 2+ And Bi 3+ The co-deposition of (b) forms a Cu-Bi alloy thin film, so that the transmittance of the device is decreased. When the applied voltage is swept from-0.8V to the forward voltage, the transmittance of the b-plot begins to increase when the applied voltage is about +0.2V, and forms an oxidation peak at about +0.5V, corresponding to the dissolution of the Cu-Bi alloy thin film, which is reoxidized to Cu 2+ And Bi 3+ 。
Fig. 7 is a transmission mode spectral modulation curve of a multi-color electrochromic device prepared in this example. It can be seen that the device can be reversibly switched from a transparent state to a black state, and the maximum light modulation range is greater than 75%.
The preparation method of the embodiment is to realize reversible redox reaction of the ionic electrolyte at room temperature, and proposes to realize reversible free switching of the color-changing device between five different optical states by using a step potential method, so that the device shows good high reflectivity, wide light modulation range and long cycle stability, and simultaneously shows long-time color retention capacity under zero bias, and the flexible substrate is good in compatibility. The preparation method is suitable for the fields of low-energy consumption flexible electrochromic intelligent windows, anti-dazzling rearview mirrors, aircraft portholes, flexible display and the like, and provides an efficient, feasible and low-cost application scheme for low-cost electrochromic devices and industrialization thereof.
Example 2
The multi-color electrochromic device prepared by the embodiment comprises a transparent working electrode, an insulating isolation column, a Cu counter electrode and a transparent conductive substrate, wherein the transparent working electrode, the insulating isolation column, the Cu counter electrode and the transparent conductive substrate are coated in a device sealing layer; the Cu counter electrode is bonded with the transparent conductive substrate; one opening of the insulating isolation column is hermetically bonded with the transparent conductive substrate, and the other opening of the insulating isolation column is hermetically bonded with the transparent working electrode; the sealed space enclosed by the transparent working electrode, the transparent conductive substrate and the insulating isolation column is an electrolyte reaction tank; the electrolyte reaction tank is filled with Bi-Cu ion neutral gel electrolyte; the surface of the transparent working electrode, which is in contact with the Bi-Cu ion electrolyte, is provided with a noble metal nanoparticle modification layer.
The preparation method of the multi-color electrochromic device of the embodiment is as follows:
(1) adopting commercial I PET/ITO (sheet resistance-15 omega/□) as a transparent conductive substrate, sequentially cleaning with glass water, and ultrasonically cleaning in deionized water, acetone and isopropanol for 15min respectively; the cleaned substrate was blow-dried with nitrogen and pre-treated in an ultraviolet ozone machine for 40 min.
(2) Preparing a Bi-Cu neutral ion electrolyte. Mixing formulationThe ratio is as follows: 10mM BiCl 3 15mM of CuCl 2 And 1M LiBr, 15mM HCl mixed with 12% by weight vinyl alcohol (PVA) having a molecular weight of 120000. Then, the mixture was stirred magnetically for 8 hours and mixed uniformly for use.
(3) The Cu metal net (the sheet resistance is less than 5 omega/□) is used as a counter electrode, and a 3M adhesive tape with the thickness of 800 micrometers is selected to be attached to the transparent conductive substrate to form good contact so as to realize uniform electric field regulation.
(4) And taking the other transparent electrode as a transparent working electrode to carry out surface treatment on the noble metal nanoparticles, wherein the specific method comprises the following steps: platinum particles are deposited on a transparent conductive substrate using a platinum source selected from trimethyl (methylcyclopentadienyl) platinum and oxygen. High-purity nitrogen is selected as carrier gas, and the pressure of the cavity is controlled to be 4-6 mbar. The reaction temperature range is 250-300 ℃. To ensure sufficient vapor pressure, the platinum source was heated to 65 ℃; the pipeline is heated to 80 ℃, the pulse time of the platinum precursor is 1.2s, and the nitrogen purging time is 3 s.
(5) An insulating isolation column (Spacer) with a thickness of 300- 2 ) And (3) bonding the working electrode, wherein the main function is to separate the working electrode from the counter electrode, and simultaneously uniformly filling the neutral gel electrolyte prepared in the step (2), so that bubbles are prevented from being generated in the process.
(6) And (5) modifying the transparent electrode with the noble metal particles, filling the transparent electrode in the step (5), and sealing the transparent electrode in a complementary manner, wherein hot melt adhesive or epoxy resin is adopted, so that the problems of air bubbles, electrolyte leakage and the like in the process are avoided.
(7) Packaging the device: and (5) depositing an aluminum oxide film with the thickness of 5nm outside the device prepared in the step (6) by using an ALD technology, and protecting and packaging the surface of the device. The deposition parameters were as follows: the precursor source was Trimethylaluminum (TMA) and the deposition conditions were: the chamber temperature was 85 ℃ and the chamber pressure was 9Pa, and the growth cycle was 53 times.
In the multi-color electrochromic device of the present embodiment, for the transparent state, a voltage of +0.2V is applied; for the gray state, the voltage is applied at-0.8V and held for 12 s; for the black state, a voltage of-0.5V was applied for 35 s. Applying a bias of-1.4V and holding for 2s, followed by a reduction to-0.4V and holding for 30s to obtain a copper mirror state; a bias of-1.4V was applied and maintained for 30s to obtain a silver mirror state.
Fig. 8 to 11 are atomic force microscope images of the multi-color electrochromic device prepared in this embodiment in a gray state, a black state, a copper mirror state, and a silver mirror state, respectively, and the respective roughness values are 31.013 nm, 40.293 nm, 13.742 nm, and 24.82 nm, respectively, which shows that, for the gray state and the black state, the roughness value of the film surface has a stronger scattering effect on light, and particularly, the local plasmon light absorption enhancement effect corresponding to the nanoparticles. For the mirror state, the lower the surface roughness, the stronger the corresponding reflection effect, which appears as a mirror state.
Fig. 12 is a graph of the light reflection spectrum of the multi-color electrochromic device prepared in this example. As can be seen, the reflectivity of the mirror state is the greatest in both the ultraviolet and visible regions, while the reflectivity of the gray and black states is slightly higher, and the reflectivity of the transparent state is the lowest, with the transparent state reflection mainly coming from the transparent PET/ITO glass reflection.
The noble metal nanoparticles of the above embodiments may also be gold nanoparticles, silver nanoparticles, iridium nanoparticles, rhodium nanoparticles, or ruthenium nanoparticles; the noble metal nanoparticles may also be prepared by magnetron sputtering processes or other processes.
The Cu counter electrode of the above embodiment can also be other Cu nets with mesh number larger than or equal to 400.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A multi-color electrochromic device is characterized by comprising a transparent working electrode, an insulating isolation column, a Cu counter electrode and a transparent conductive substrate;
the Cu counter electrode is bonded with the transparent conductive substrate;
the sealed space enclosed by the transparent working electrode, the transparent conductive substrate and the insulating isolation column is an electrolyte reaction tank;
the electrolyte reaction tank is filled with Bi-Cu ion neutral gel electrolyte;
the surface of the transparent working electrode, which is in contact with the Bi-Cu ion neutral gel electrolyte, is provided with a noble metal nanoparticle modification layer; the noble metal nanoparticles are platinum nanoparticles, gold nanoparticles, silver nanoparticles, iridium nanoparticles, rhodium nanoparticles or ruthenium nanoparticles;
the Cu counter electrode is positioned in the electrolyte reaction tank;
the Bi-Cu ion neutral gel electrolyte comprises:
5mM to 10mM BiCl 3 12 to 17mM of CuCl 2 0.8-1.2M LiBr, 12-17 mM HCl; also includes vinyl alcohol; the weight of the vinyl alcohol is 8-12% of the total weight of the Bi-Cu ion neutral gel electrolyte.
2. The multi-color electrochromic device according to claim 1, wherein the insulating spacers have openings on one side hermetically bonded to the transparent conductive substrate and openings on the other side hermetically bonded to the transparent working electrode.
3. The multi-color electrochromic device according to claim 1, wherein the Cu counter electrode is a Cu mesh or Cu metal frame with a mesh number of not less than 400.
4. The multi-color electrochromic device according to claim 1, wherein for a transparent state, the voltage is applied at +0.2 to + 1V; for the gray state, applying a voltage of-0.5 to-1V and keeping for 8 to 12 s; and for the black state, applying a voltage of-0.5 to-1V and keeping the voltage for 25 to 35 s.
5. The multi-color electrochromic device according to claim 1, wherein the multi-color electrochromic device is biased at-1.4 to-1.6V for 0.3 to 2s, and then is reduced to-0.2 to-0.5V for 25 to 30s to obtain a copper mirror state;
applying bias voltage of-1.4 to-1.6V and keeping for 20-30 s to obtain a silver mirror state.
6. A method of making a multi-color electrochromic device according to any of claims 1 to 5, comprising the steps of:
(1) pretreating the transparent conductive substrate;
(2) adhering a Cu counter electrode on a transparent conductive substrate;
(3) bonding an opening at one side of the insulating isolation column with the transparent working electrode, and pouring Bi-Cu ion neutral gel electrolyte into the insulating isolation column;
(4) and bonding the surface of the transparent working electrode with the noble metal nanoparticle modification layer with the opening on the other side of the insulating isolation column.
7. The method of making a multi-color electrochromic device according to claim 6, further comprising the steps of: and (5) depositing an aluminum oxide film on the outer surface of the device obtained in the step (4) by using an ALD (atomic layer deposition) technology.
8. The method for preparing a multi-color electrochromic device according to claim 6, wherein the transparent conductive substrate is pretreated in step (1), specifically:
firstly, washing with glass water, and then ultrasonically washing in deionized water, acetone and isopropanol for 15-20 min respectively; then blowing the mixture by using high-pressure nitrogen, and treating the mixture in an ultraviolet ozone machine for 30-40 min.
9. The method of claim 6, wherein the noble metal nanoparticle modification layer is formed by electroplating, atomic layer deposition, or magnetron sputtering.
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