WO2022237066A1 - Microcavity injection type electrochromic device, and manufacturing method therefor and application thereof - Google Patents

Microcavity injection type electrochromic device, and manufacturing method therefor and application thereof Download PDF

Info

Publication number
WO2022237066A1
WO2022237066A1 PCT/CN2021/123446 CN2021123446W WO2022237066A1 WO 2022237066 A1 WO2022237066 A1 WO 2022237066A1 CN 2021123446 W CN2021123446 W CN 2021123446W WO 2022237066 A1 WO2022237066 A1 WO 2022237066A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage bag
microcavity
liquid storage
glass substrate
electrochromic device
Prior art date
Application number
PCT/CN2021/123446
Other languages
French (fr)
Chinese (zh)
Inventor
宁洪龙
张观广
姚日晖
曾璇
叶倩楠
苏国平
熊鑫
姜雅思
梁宏富
彭俊彪
Original Assignee
华南理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华南理工大学 filed Critical 华南理工大学
Publication of WO2022237066A1 publication Critical patent/WO2022237066A1/en

Links

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
    • 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
    • G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
    • 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
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes

Definitions

  • the invention belongs to the field of electrochromic technology, and in particular relates to a microcavity injection type electrochromic device and its preparation method and application.
  • the structure of traditional electrochromic devices is usually: a multi-layer film stack structure of conductive layer/electrochromic layer/electrolyte layer/ion storage layer/conductive layer.
  • the color change principle of this layer-stacked electrochromic device is generally: relying on ions (H + , Li + , Na + , Al 3+ , Zn 2+ , K + , etc.) to move between different layers under the drive of an electric field Intercalation and deintercalation reactions (gain and loss of electrons) occur, causing changes in the valence state or energy band of the electrochromic material, which in turn causes a change in the color of the device.
  • the electrochromic layer and the ion storage layer are solid materials, the ion intercalation and deintercalation process will often cause certain damage to these functional layers, and these damages will gradually accumulate with the repeated operation of the device, which will eventually lead to poor performance of the electrochromic device. decay, or even fail.
  • the current mainstream technologies mainly include: 1) preparing electrochromic layers or ion storage layers of porous and mesoporous materials; 2) using high-valence cations (such as Al 3+ , etc.), reduce the number of ion implantation; 3) use low voltage drive, etc.
  • these current technical means are all around how to slow down this damage, but they cannot fundamentally solve the problem.
  • These film damages are rooted in the traditional electrochromic device structure and discoloration principle, that is, as long as it is based on the multilayer film stack structure and ion intercalation and extraction reactions, the problem of functional film damage cannot be fundamentally solved. How to improve the cycle life of electrochromic devices is an urgent problem to be solved in the industry and academia.
  • the primary purpose of the present invention is to provide a microcavity injection type electrochromic device.
  • Another object of the present invention is to provide a method for preparing the above-mentioned microcavity injection electrochromic device.
  • Another object of the present invention is to provide the application of the above microcavity injection electrochromic device.
  • a microcavity injection type electrochromic device the structure of which includes an electric push rod, a liquid storage bag, a microcavity and an air storage bag;
  • the upper and lower ends of the microcavity are provided with openings, and the structure of the microcavity is a first glass substrate, a first indium tin oxide (ITO) transparent conductive electrode, a first metal tungsten film, glass beads, a second metal tungsten film, and a second metal tungsten film.
  • ITO indium tin oxide
  • ITO Indium tin dioxide
  • the mouth of the liquid storage bag communicates with the opening at the lower end of the microcavity, the mouth of the air storage bag communicates with the opening at the upper end of the microcavity, and the liquid storage bag, the microchamber, and the air storage bag are connected to form a closed space; the liquid storage bag
  • the bag contains electrochromic liquid;
  • the electric push rod is connected with the liquid storage bag, and can act on the liquid storage bag to make the electrochromic liquid flow between the microcavity and the liquid storage bag.
  • the electric push rod is arranged in the normal direction of the liquid storage bag (direction perpendicular to the microcavity) or the bottom of the liquid storage bag, and is connected with the liquid storage bag.
  • the air storage bag is used for storing the air in the microcavity.
  • the electric push rod and the fluid storage bag are wrapped with a casing to form a base.
  • the shell material is acrylonitrile-butadiene-styrene (ABS); the material of the fluid storage bag is styrene-butadiene-styrene block copolymer (SBS), and the volume of the fluid storage bag It is 0.2-0.8L.
  • the air storage bag is wrapped by an outer shell to form a top cover.
  • the shell material is acrylonitrile-butadiene-styrene (ABS); the material of the air storage bag is styrene-butadiene-styrene block copolymer (SBS); the volume of the air storage bag It is 1.5-2.5L.
  • the electrochromic liquid is a 1.5-2.0 mol/L potassium metatungstate aqueous solution.
  • the first glass substrate and the second glass substrate have the same size, with a length of 200-2000 mm and a width of 400-2000 mm.
  • the thicknesses of the first indium tin oxide (ITO) transparent conductive electrode and the second indium tin oxide (ITO) transparent conductive electrode are both 150-300 nm.
  • the thicknesses of the first metal tungsten thin film and the second metal tungsten thin film are both 1-3 nm.
  • the glass microspheres have a diameter of 1-5 ⁇ m.
  • the above-mentioned preparation method of a microcavity injection type electrochromic device comprises the following steps:
  • a first indium tin oxide (ITO) transparent conductive electrode is prepared on the first glass substrate, and a second indium tin oxide (ITO) transparent conductive electrode is prepared on the second glass substrate;
  • step (1) the indium tin oxide (ITO) transparent conductive electrode that step (1) obtains is annealed under air atmosphere;
  • the first glass substrate electrode and the second glass substrate electrode face are pressed together to form a microcavity, and the left and right sides of the microcavity are fused with a laser, and the upper and lower edges are openings to obtain a microcavity;
  • the assembling in step (6) further includes assembling the shell, the electric push rod, and the fluid storage bag into a base, and assembling the shell and the shell into a top cover.
  • the magnetron sputtering process in step (1) is: radio frequency mode, the vacuum environment is 3-10 mTorr, the sputtering power is 50-80 W, and the sputtering time is 5-10 min.
  • the annealing temperature in step (2) is 400-500° C., and the annealing time is 1-2 hours.
  • the magnetron sputtering process in step (3) is a DC mode
  • the vacuum environment is 3-10 mTorr
  • the sputtering power is 25-35 W
  • the sputtering time is 10-20 s.
  • the process of the spin-coating method described in step (4) is: the spin-coating speed is 5000-7000 rpm, the time is 5-10min, the spin-coating liquid is an ethanol dispersion of glass beads, and the solid content is 3-8wt .%.
  • the pressing process in step (5) is: pressure 100-400kPa, pressing plate temperature 400-500°C, pressing time 1-2h;
  • the laser melting process is: excimer laser power 20-50W,
  • the laser beam spot size is 1-4 ⁇ m, and the laser moving speed is 10-20 mm/s.
  • microcavity injection type electrochromic device in the fields of electrochromic smart windows, smart advertising curtain walls, smart partitions and the like.
  • the electric push rod at the base works to squeeze the liquid storage bag, so that the electrochromic liquid in the liquid storage bag is injected into the microcavity until it completely fills the microcavity, and the extruded gas in the microcavity is stored in the gas storage bag on the top cover , to avoid excessive microcavity pressure.
  • the microcavity is filled with the electrochromic liquid, power is supplied to the two electrodes at a voltage of 0.6-0.8V for 10-30s.
  • the anions in the electrochromic liquid obtain electrons from the electrode interface and are reduced, showing a dark blue color.
  • the electric push rod on the base works to expand the liquid storage bag, so that the colored electrochromic liquid in the microcavity is sucked back into the liquid storage bag, and the device quickly returns to transparency.
  • the electrochromic liquid sucked back into the liquid storage bag and the liquid in the liquid storage bag undergo sufficient convection with the deformation of the liquid storage bag, so that the anions are fully rubbed in the solution and lose electrons again, and the electrochromic liquid recovers. transparent.
  • the present invention has the following advantages and beneficial effects:
  • the color change and fading of the electrochromic device of the present invention does not depend on the electrochromic layer at all, so there is no problem of ion erosion.
  • the color change of the present invention does not distinguish between forward voltage and reverse voltage, so the driving is simplified.
  • the core is to obtain an interface with ultra-high surface energy, which can prevent the phenomenon of electrochromic liquid hanging on the wall, while not affecting the overall light transmission and conductivity of the device. .
  • the fading mechanism of the present invention is completely different from that of traditional electrochromic devices.
  • the traditional fading relies on negative bias electrochemical oxidation to cause the electrochromic material to fade, while the present invention relies on the mechanism of coloring anions with different electronegativity and
  • the solvent or the inner surface of the liquid storage bag undergoes friction to exchange and transfer electrons, and loses electrons to be oxidized into colorless high-valent anions.
  • Fig. 1 is the front view of the device of the present invention; wherein 100 refers to the microcavity, 200 refers to the base, 300 refers to the top cover, 210 refers to the liquid storage bag, 220 refers to the electric push rod, and 310 refers to the air storage bag.
  • Fig. 2 is the structure diagram of each layer of the microcavity described in the present invention.
  • 111 refers to the first glass substrate
  • 121 refers to the first ITO conductive electrode
  • 131 refers to the first metal tungsten thin film
  • 140 refers to glass beads
  • 132 refers to the second metal tungsten
  • the thin film, 122 refers to the second ITO conductive electrode
  • 112 refers to the second glass substrate.
  • Fig. 3 is a right view of the device of the present invention; wherein 210 refers to a liquid storage bag, 220 refers to an electric push rod, 100 refers to a microcavity, 310 refers to an air storage bag, and 320 refers to an ABS shell.
  • Fig. 4 is a schematic diagram of the three-dimensional shape of the fluid storage bag of the present invention.
  • Fig. 5 is the transmittance curve of visible light band in the colored state of Example 1.
  • Fig. 6 is the current curve of the coloring process of Example 1.
  • a microcavity injection type electrochromic device its structure includes an electric push rod (220), a liquid storage bag (210), a microcavity (100) and an air storage bag (310);
  • the upper and lower ends of the microcavity are provided with openings, and the structure of the microcavity is a first glass substrate (111), a first indium tin oxide (ITO) transparent conductive electrode (121), a first metal tungsten film (131), a glass microcavity Beads (140), a second metal tungsten thin film (132), a second indium tin oxide (ITO) transparent conductive electrode (122) and a second glass substrate (112), the gap between the glass beads forms a cavity;
  • ITO indium tin oxide
  • ITO indium tin oxide
  • the mouth of the liquid storage bag (210) communicates with the opening of the lower end of the microcavity (100), the opening of the pocket of the air storage bag (310) communicates with the opening of the upper end of the microchamber (100), the mouth of the fluid storage bag (210), the microcavity ( 100), the gas storage bag (310) are connected to form a closed space; the liquid storage bag (210) is equipped with electrochromic liquid;
  • the electric push rod (220) is arranged in the normal direction of the liquid storage bag (210) (perpendicular to the direction of the microcavity) or the bottom of the liquid storage bag (210), and is connected to the liquid storage bag (210);
  • the electric push rod (220) and the fluid storage bag (210) are wrapped with a casing to form a base (200);
  • the casing (320) is made of acrylonitrile-butadiene-styrene (ABS);
  • the fluid storage bag (210) is made of styrene-butadiene-styrene block copolymer (SBS), and the volume of the fluid storage bag (210) is 0.2-0.8L;
  • the air storage bag (310) is wrapped by an outer shell to form a top cover (300); the outer shell is made of acrylonitrile-butadiene-styrene (ABS); the material of the air storage bag (310) is styrene- Butadiene-styrene block copolymer (SBS); the volume of the air storage bag (310) is 1.5-2.5L;
  • the electrochromic solution is an aqueous potassium metatungstate solution of 1.5 to 2.0 mol/L;
  • the size of the first glass substrate (111) and the second glass substrate (112) are the same, the length is 200-2000 mm, and the width is 400-2000 mm;
  • the thicknesses of the first indium tin oxide (ITO) transparent conductive electrode (121) and the second indium tin oxide (ITO) transparent conductive electrode (122) are both 150-300 nm;
  • the thicknesses of the first metal tungsten film (131) and the second metal tungsten film (132) are both 1-3 nm;
  • the diameter of the glass microspheres (140) is 1-5 ⁇ m.
  • Adopt sputtering process DC mode, vacuum environment is 8mTorr, sputtering power is 25W, sputtering time is 10s, deposit a layer of ultra-thin metal tungsten film on the first and second ITO electrodes respectively, the thickness of the film 1nm.
  • the electrode surfaces of the first glass substrate and the second glass substrate are pressed against each other, the pressure is 300kPa, the temperature of the pressing plate is 450°C, and the pressing time is 2h, finally forming a microcavity (glass beads in the middle of the microcavity), and use
  • the excimer laser beam fuses the edges on both sides of the microcavity, the laser power is 40W, the laser beam spot size is 2 ⁇ m, and the laser moving speed is 15mm/s to obtain a microcavity.
  • the structure of the base is: a liquid storage bag made of styrene-butadiene-styrene block copolymer (SBS), the mouth of which is clamped to the opening below the microcavity, completely wrapping the opening slit below the microcavity, and storing
  • SBS styrene-butadiene-styrene block copolymer
  • One side of the liquid storage bag in the normal direction (perpendicular to the direction of the microcavity) is connected to the electric push rod, and the entire base is also made of acrylonitrile-butadiene-benzene.
  • the structure of the top cover is: an air storage bag made of styrene-butadiene-styrene block copolymer (SBS) with a volume of 1.5L. Seams, the entire top cover is also protected by an ABS shell wrap.
  • SBS styrene-butadiene-styrene block copolymer
  • Fig. 1, Fig. 2, Fig. 3 and Fig. 4 have shown the specific structure of embodiment 1.
  • the electric push rod is powered, and the liquid storage bag is squeezed, so that the electrochromic liquid in the liquid storage bag is injected into the microcavity until the microcavity is completely filled, and the extruded gas in the microcavity is stored in the gas storage bag on the top cover.
  • the microcavity is filled with the electrochromic liquid
  • power is supplied to the two electrodes at a voltage of 0.7V for 20s.
  • the anions in the electrochromic liquid obtain electrons from the electrode interface and are reduced, showing a dark blue color.
  • the coloring state of the device The transmission spectrum is shown in Fig. 5, the transmittance at 600nm is about 32%, and it has good light-shielding properties.
  • the current density of the coloring process of the device is shown in Fig. 6 .
  • the electric push rod expands the liquid storage bag, the electrochromic liquid is sucked back into the liquid storage bag, and the device becomes transparent again with a transmittance of 75%.
  • Step 5 It is basically the same as Steps (1)-(7) of Example 1, except that the diameter of the glass microspheres in Step 5 is 5 ⁇ m.
  • the electric push rod is powered, and the liquid storage bag is squeezed, so that the electrochromic liquid in the liquid storage bag is injected into the microcavity until the microcavity is completely filled, and the extruded gas in the microcavity is stored in the gas storage bag on the top cover.
  • the microcavity is filled with the electrochromic liquid
  • power is supplied to the two electrodes with a voltage of 0.7V for 20s.
  • the anions in the electrochromic liquid obtain electrons from the electrode interface and are reduced, showing dark blue, with a transmittance at 600nm. About 13%, has good light-shielding properties.
  • the electric push rod expands the liquid storage bag, the electrochromic liquid is sucked back into the liquid storage bag, and the device becomes transparent again with a transmittance of 75%.

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

A microcavity (100) injection type electrochromic device, and a manufacturing method therefor and an application thereof. The structure of the device comprises an electric push rod (220), a liquid storage bag (210), the microcavity (100), and an air storage bag (310); the upper and lower ends of the microcavity (100) are provided with openings; the structure of the microcavity (100) sequentially comprises a first glass substrate (111), a first indium tin oxide (ITO) transparent conductive electrode (121), a first metal tungsten thin film (131), glass microbeads (140), a second metal tungsten thin film (132), a second ITO transparent conductive electrode (122), and a second glass substrate (112); gaps between the glass microbeads (140) form cavities; the liquid storage bag (210), the microcavity (100), and the air storage bag (310) are connected to form a closed space; the liquid storage bag (210) contains an electrochromic solution; the electric push rod (220) is connected to the liquid storage bag (210). Color change and fading of the electrochromic device are completely independent of an electrochromic layer; the fading mechanism is that colored anions having different electronegativities rub against the solvent or the inner surface of the liquid storage bag (210) and thus electron exchange and transfer occurs, and the colored anions lose electrons and are oxidized into colorless high-valence anions; therefore, there is no problem of ion erosion.

Description

一种微腔注入型电致变色器件及其制备方法与应用A microcavity injection type electrochromic device and its preparation method and application 技术领域technical field
本发明属于电致变色技术域，具体涉及一种微腔注入型电致变色器件及其制备方法与应用。The invention belongs to the field of electrochromic technology, and in particular relates to a microcavity injection type electrochromic device and its preparation method and application.
背景技术Background technique
传统的电致变色器件结构通常为：导电层/电致变色层/电解质层/离子储存层/导电层的多层薄膜堆叠结构。这种层层堆叠式的电致变色器件的变色原理一般为：依靠离子(H +,Li +,Na +,Al 3+,Zn 2+,K +等)在电场的驱动下在不同层之间迁移，发生嵌入脱嵌反应(得失电子)，引起电致变色材料的价态或能带的变化，进而引起器件颜色的改变。由于电致变色层、离子储存层是固体材料，离子嵌入脱嵌过程往往会对这些功能层造成一定的损伤，这些损伤随着器件多次循环工作而日渐积累，最终导致电致变色器件的性能衰退，甚至失效。 The structure of traditional electrochromic devices is usually: a multi-layer film stack structure of conductive layer/electrochromic layer/electrolyte layer/ion storage layer/conductive layer. The color change principle of this layer-stacked electrochromic device is generally: relying on ions (H + , Li + , Na + , Al 3+ , Zn 2+ , K + , etc.) to move between different layers under the drive of an electric field Intercalation and deintercalation reactions (gain and loss of electrons) occur, causing changes in the valence state or energy band of the electrochromic material, which in turn causes a change in the color of the device. Since the electrochromic layer and the ion storage layer are solid materials, the ion intercalation and deintercalation process will often cause certain damage to these functional layers, and these damages will gradually accumulate with the repeated operation of the device, which will eventually lead to poor performance of the electrochromic device. decay, or even fail.
为了减少这些离子注入脱嵌导致的薄膜损伤，提升器件的使用寿命，目前的主流技术主要有：1)制备多孔、介孔材料的电致变色层或离子储存层；2)采用高价态的阳离子(如Al 3+等)，减少离子注入数；3)采用低电压驱动等。然而，目前这些技术手段都是围绕着如何减缓这种损伤，却不能从根本上解决问题。这些薄膜损伤根源在于传统的电致变色器件结构和变色原理，即只要是基于多层薄膜堆叠结构和离子嵌入脱出反应，功能薄膜损伤的问题就无法根本解决。如何提高电致变色器件的循环寿命是目前产业界和学术界亟待解决的问题。 In order to reduce the film damage caused by these ion implantation and deintercalation, and improve the service life of the device, the current mainstream technologies mainly include: 1) preparing electrochromic layers or ion storage layers of porous and mesoporous materials; 2) using high-valence cations (such as Al 3+ , etc.), reduce the number of ion implantation; 3) use low voltage drive, etc. However, these current technical means are all around how to slow down this damage, but they cannot fundamentally solve the problem. These film damages are rooted in the traditional electrochromic device structure and discoloration principle, that is, as long as it is based on the multilayer film stack structure and ion intercalation and extraction reactions, the problem of functional film damage cannot be fundamentally solved. How to improve the cycle life of electrochromic devices is an urgent problem to be solved in the industry and academia.
发明内容Contents of the invention
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种微腔注入型电致变色器件。In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a microcavity injection type electrochromic device.
本发明的另一个目的在于提供上述一种微腔注入型电致变色器件的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned microcavity injection electrochromic device.
本发明的再一目的在于提供上述一种微腔注入型电致变色器件的应用。Another object of the present invention is to provide the application of the above microcavity injection electrochromic device.
本发明目的通过以下技术方案实现：The object of the invention is achieved through the following technical solutions:
一种微腔注入型电致变色器件，其结构包括电动推杆、储液袋、微腔和储气袋；A microcavity injection type electrochromic device, the structure of which includes an electric push rod, a liquid storage bag, a microcavity and an air storage bag;
所述微腔上下两端设有开口，微腔结构依次为第一玻璃基板、第一氧化铟锡(ITO)透明导电电极、第一金属钨薄膜、玻璃微珠、第二金属钨薄膜、第二氧化铟锡(ITO)透明导电电极和第二玻璃基板，玻璃微珠间隙形成空腔；The upper and lower ends of the microcavity are provided with openings, and the structure of the microcavity is a first glass substrate, a first indium tin oxide (ITO) transparent conductive electrode, a first metal tungsten film, glass beads, a second metal tungsten film, and a second metal tungsten film. Indium tin dioxide (ITO) transparent conductive electrode and the second glass substrate, the glass bead gap forms a cavity;
所述储液袋袋口与微腔下端开口相通，所述储气袋袋口与微腔上端开口相通，储液袋、微腔、储气袋三者相连形成一个密闭空间；所述储液袋装有电致变色液；The mouth of the liquid storage bag communicates with the opening at the lower end of the microcavity, the mouth of the air storage bag communicates with the opening at the upper end of the microcavity, and the liquid storage bag, the microchamber, and the air storage bag are connected to form a closed space; the liquid storage bag The bag contains electrochromic liquid;
所述电动推杆与储液袋相连，可作用于储液袋使电致变色液在微腔与储液袋之间流动。The electric push rod is connected with the liquid storage bag, and can act on the liquid storage bag to make the electrochromic liquid flow between the microcavity and the liquid storage bag.
优选的，所述电动推杆设置于储液袋法向方向(垂直于微腔的方向)或储液袋底部，且与储液袋相连。Preferably, the electric push rod is arranged in the normal direction of the liquid storage bag (direction perpendicular to the microcavity) or the bottom of the liquid storage bag, and is connected with the liquid storage bag.
所述储气袋用于储装微腔中的空气。The air storage bag is used for storing the air in the microcavity.
优选的，所述电动推杆和储液袋用外壳包裹形成底座。所述外壳材质为丙烯腈-丁二烯-苯乙烯(ABS)；所述储液袋的材质为苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)，所述储液袋的容积为0.2～0.8L。Preferably, the electric push rod and the fluid storage bag are wrapped with a casing to form a base. The shell material is acrylonitrile-butadiene-styrene (ABS); the material of the fluid storage bag is styrene-butadiene-styrene block copolymer (SBS), and the volume of the fluid storage bag It is 0.2-0.8L.
优选的，所述储气袋由外壳包裹形成顶盖。所述外壳材质为丙烯腈-丁二烯-苯乙烯(ABS)；所述储气袋的材质为苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)；所述储气袋的容积为1.5～2.5L。Preferably, the air storage bag is wrapped by an outer shell to form a top cover. The shell material is acrylonitrile-butadiene-styrene (ABS); the material of the air storage bag is styrene-butadiene-styrene block copolymer (SBS); the volume of the air storage bag It is 1.5-2.5L.
优选的，所述电致变色液为1.5～2.0mol/L的偏钨酸钾水溶液。Preferably, the electrochromic liquid is a 1.5-2.0 mol/L potassium metatungstate aqueous solution.
优选的，所述第一玻璃基板、第二玻璃基板的尺寸相同，长均为200～2000mm，宽均为400～2000mm。Preferably, the first glass substrate and the second glass substrate have the same size, with a length of 200-2000 mm and a width of 400-2000 mm.
优选的，所述第一氧化铟锡(ITO)透明导电电极、第二氧化铟锡(ITO)透明导电电极的厚度均为150～300nm。Preferably, the thicknesses of the first indium tin oxide (ITO) transparent conductive electrode and the second indium tin oxide (ITO) transparent conductive electrode are both 150-300 nm.
优选的，所述第一金属钨薄膜、第二金属钨薄膜的厚度均为1～3nm。Preferably, the thicknesses of the first metal tungsten thin film and the second metal tungsten thin film are both 1-3 nm.
优选的，所述玻璃微珠的直径为1～5μm。Preferably, the glass microspheres have a diameter of 1-5 μm.
上述一种微腔注入型电致变色器件的制备方法，包括以下步骤：The above-mentioned preparation method of a microcavity injection type electrochromic device comprises the following steps:
(1)采用磁控溅射工艺，在第一玻璃基板上制备第一氧化铟锡(ITO)透明导电电极，在第二玻璃基板上制备第二氧化铟锡(ITO)透明导电电极；(1) Using a magnetron sputtering process, a first indium tin oxide (ITO) transparent conductive electrode is prepared on the first glass substrate, and a second indium tin oxide (ITO) transparent conductive electrode is prepared on the second glass substrate;
(2)将步骤(1)得到的氧化铟锡(ITO)透明导电电极在空气氛围下退火；(2) the indium tin oxide (ITO) transparent conductive electrode that step (1) obtains is annealed under air atmosphere;
(3)采用磁控溅射工艺，在第一氧化铟锡(ITO)透明导电电极和第二氧化铟锡(ITO)透明导电电极上分别制备一层金属钨薄膜；(3) Using a magnetron sputtering process, a layer of metal tungsten thin film is respectively prepared on the first indium tin oxide (ITO) transparent conductive electrode and the second indium tin oxide (ITO) transparent conductive electrode;
(4)采用旋转涂布法在金属钨薄膜表面均匀铺展一层玻璃微珠悬浊液，然后自然风干，得到第一玻璃基板电极和第二玻璃基板电极；(4) Spread a layer of glass bead suspension evenly on the surface of the metal tungsten film by a spin coating method, then air-dry naturally to obtain the first glass substrate electrode and the second glass substrate electrode;
(5)将第一玻璃基板电极和第二玻璃基板电极面相对压合，形成微腔，并用激光将微腔左右两侧边缘熔合，而上下边缘为开口，得到微腔；(5) The first glass substrate electrode and the second glass substrate electrode face are pressed together to form a microcavity, and the left and right sides of the microcavity are fused with a laser, and the upper and lower edges are openings to obtain a microcavity;
(6)将电致变色液装入储液袋，将电动推杆、储液袋、微腔、储气袋组装成微腔注入型电致变色器件。(6) Put the electrochromic liquid into the liquid storage bag, assemble the electric push rod, the liquid storage bag, the microcavity, and the gas storage bag into a microcavity injection type electrochromic device.
优选的，步骤(6)所述组装还包括将外壳和电动推杆、储液袋组装成底座，将外壳和外壳组装成顶盖。Preferably, the assembling in step (6) further includes assembling the shell, the electric push rod, and the fluid storage bag into a base, and assembling the shell and the shell into a top cover.
优选的，步骤(1)所述磁控溅射工艺为：射频模式，真空环境为3～10mTorr，溅射功率为50～80W，溅射时间为5～10min。Preferably, the magnetron sputtering process in step (1) is: radio frequency mode, the vacuum environment is 3-10 mTorr, the sputtering power is 50-80 W, and the sputtering time is 5-10 min.
优选的，步骤(2)所述退火温度为400～500℃，退火时间为1～2h。Preferably, the annealing temperature in step (2) is 400-500° C., and the annealing time is 1-2 hours.
优选的，步骤(3)所述磁控溅射工艺为直流模式，真空环境为3～10mTorr，溅射功率为25～35W，溅射时间为10～20s。Preferably, the magnetron sputtering process in step (3) is a DC mode, the vacuum environment is 3-10 mTorr, the sputtering power is 25-35 W, and the sputtering time is 10-20 s.
优选的，步骤(4)所述旋转涂布法的工艺为：旋转涂布转速为5000～7000 rpm，时间为5～10min，旋涂液为玻璃微珠乙醇分散液，固含量为3～8wt.％。Preferably, the process of the spin-coating method described in step (4) is: the spin-coating speed is 5000-7000 rpm, the time is 5-10min, the spin-coating liquid is an ethanol dispersion of glass beads, and the solid content is 3-8wt .%.
优选的，步骤(5)所述压合工艺为：压强100～400kPa，压板温度400～500℃，压合时间1～2h；所述激光烧熔工艺为：准分子激光功率为20～50W，激光束斑尺寸为1～4μm，激光移速为10～20mm/s。Preferably, the pressing process in step (5) is: pressure 100-400kPa, pressing plate temperature 400-500°C, pressing time 1-2h; the laser melting process is: excimer laser power 20-50W, The laser beam spot size is 1-4 μm, and the laser moving speed is 10-20 mm/s.
上述一种微腔注入型电致变色器件在电致变色智能窗、智能广告幕墙、智能隔板等领域中的应用。The application of the above-mentioned microcavity injection type electrochromic device in the fields of electrochromic smart windows, smart advertising curtain walls, smart partitions and the like.
本发明的工作原理：Working principle of the present invention:
底座的电动推杆工作，挤压储液袋，使储液袋的电致变色液注入到微腔，直到完全充满微腔，微腔里面被挤出的气体存储在顶盖的储气袋中，避免微腔压强过大。当微腔注满电致变色液后，向两个电极供电，电压为0.6～0.8V，持续10～30s，电致变色液中的阴离子从电极界面中获得电子而被还原，呈现深蓝色，实现器件变色过程；当需要器件褪色时，底座的电动推杆工作，扩张储液袋，使微腔中已经着色的电致变色液吸回储液袋中，器件快速恢复透明。同时，被吸回储液袋的电致变色液和储液袋内的液体随着储液袋的形变而发生充分的对流，使阴离子在溶液中充分摩擦而重新失去电子，电致变色液恢复透明。The electric push rod at the base works to squeeze the liquid storage bag, so that the electrochromic liquid in the liquid storage bag is injected into the microcavity until it completely fills the microcavity, and the extruded gas in the microcavity is stored in the gas storage bag on the top cover , to avoid excessive microcavity pressure. When the microcavity is filled with the electrochromic liquid, power is supplied to the two electrodes at a voltage of 0.6-0.8V for 10-30s. The anions in the electrochromic liquid obtain electrons from the electrode interface and are reduced, showing a dark blue color. Realize the discoloration process of the device; when the discoloration of the device is required, the electric push rod on the base works to expand the liquid storage bag, so that the colored electrochromic liquid in the microcavity is sucked back into the liquid storage bag, and the device quickly returns to transparency. At the same time, the electrochromic liquid sucked back into the liquid storage bag and the liquid in the liquid storage bag undergo sufficient convection with the deformation of the liquid storage bag, so that the anions are fully rubbed in the solution and lose electrons again, and the electrochromic liquid recovers. transparent.
与现有技术相比，本发明具有以下优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
第一，和传统的多层薄膜型电致变色器件有本质不同，本发明的电致变色器件变色和褪色完全不依赖电致变色层，因此不存在离子侵蚀的问题。First, it is essentially different from traditional multilayer thin-film electrochromic devices. The color change and fading of the electrochromic device of the present invention does not depend on the electrochromic layer at all, so there is no problem of ion erosion.
第二，本发明变色不区分正向电压和反向电压，因此驱动上得以简化。Second, the color change of the present invention does not distinguish between forward voltage and reverse voltage, so the driving is simplified.
第三，采用在ITO电极上镀超薄金属钨薄膜的技术，核心是获得超高表面能的界面，抑制电致变色液挂壁的现象发生，同时不影响器件的整体透光性和导电性。Third, adopt the technology of plating ultra-thin metal tungsten film on the ITO electrode. The core is to obtain an interface with ultra-high surface energy, which can prevent the phenomenon of electrochromic liquid hanging on the wall, while not affecting the overall light transmission and conductivity of the device. .
第四，本发明褪色机理与传统电致变色器件完全不同，传统褪色是依赖负偏压电化学氧化而使电致变色材料褪色，而本发明依赖机理的是电负性不同的着色态阴离子和溶剂或储液袋内表面发生摩擦而发生电子交换转移，失去电子氧化成无色的高价态阴离子。Fourth, the fading mechanism of the present invention is completely different from that of traditional electrochromic devices. The traditional fading relies on negative bias electrochemical oxidation to cause the electrochromic material to fade, while the present invention relies on the mechanism of coloring anions with different electronegativity and The solvent or the inner surface of the liquid storage bag undergoes friction to exchange and transfer electrons, and loses electrons to be oxidized into colorless high-valent anions.
附图说明Description of drawings
图1为本发明所述器件正视图；其中100指微腔，200指底座，300指顶盖，210指储液袋，220指电动推杆，310指储气袋。Fig. 1 is the front view of the device of the present invention; wherein 100 refers to the microcavity, 200 refers to the base, 300 refers to the top cover, 210 refers to the liquid storage bag, 220 refers to the electric push rod, and 310 refers to the air storage bag.
图2为本发明所述微腔各层结构示意图；其中111指第一玻璃基板，121指第一ITO导电电极，131指第一金属钨薄膜，140指玻璃微珠，132指第二金属钨薄膜，122指第二ITO导电电极，112指第二玻璃基板。Fig. 2 is the structure diagram of each layer of the microcavity described in the present invention; Wherein 111 refers to the first glass substrate, 121 refers to the first ITO conductive electrode, 131 refers to the first metal tungsten thin film, 140 refers to glass beads, and 132 refers to the second metal tungsten The thin film, 122 refers to the second ITO conductive electrode, and 112 refers to the second glass substrate.
图3为本发明器件右视图；其中210指储液袋，220指电动推杆，100指微腔，310指储气袋，320指ABS外壳。Fig. 3 is a right view of the device of the present invention; wherein 210 refers to a liquid storage bag, 220 refers to an electric push rod, 100 refers to a microcavity, 310 refers to an air storage bag, and 320 refers to an ABS shell.
图4为本发明所述储液袋的三维形状示意图。Fig. 4 is a schematic diagram of the three-dimensional shape of the fluid storage bag of the present invention.
图5为实施例1着色状态可见光波段透射率曲线。Fig. 5 is the transmittance curve of visible light band in the colored state of Example 1.
图6为实施例1着色过程电流曲线。Fig. 6 is the current curve of the coloring process of Example 1.
具体实施方式Detailed ways
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be further described in detail below with reference to the examples and drawings, but the implementation of the present invention is not limited thereto.
本发明实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。In the embodiment of the present invention, if no specific conditions are indicated, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The raw materials, reagents, etc. of manufacturers not indicated are all conventional products that can be purchased from the market.
本发明所述一种微腔注入型电致变色器件，其结构包括电动推杆(220)、储液袋(210)、微腔(100)和储气袋(310)；A microcavity injection type electrochromic device according to the present invention, its structure includes an electric push rod (220), a liquid storage bag (210), a microcavity (100) and an air storage bag (310);
所述微腔上下两端设有开口，微腔结构依次为第一玻璃基板(111)、第一氧化铟锡(ITO)透明导电电极(121)、第一金属钨薄膜(131)、玻璃微珠(140)、第二金属钨薄膜(132)、第二氧化铟锡(ITO)透明导电电极(122)和第二玻璃基板(112)，玻璃微珠间隙形成空腔；The upper and lower ends of the microcavity are provided with openings, and the structure of the microcavity is a first glass substrate (111), a first indium tin oxide (ITO) transparent conductive electrode (121), a first metal tungsten film (131), a glass microcavity Beads (140), a second metal tungsten thin film (132), a second indium tin oxide (ITO) transparent conductive electrode (122) and a second glass substrate (112), the gap between the glass beads forms a cavity;
所述储液袋(210)袋口与微腔(100)下端开口相通，所述储气袋(310) 袋口与微腔(100)上端开口相通，储液袋(210)、微腔(100)、储气袋(310)三者相连形成一个密闭空间；所述储液袋(210)装有电致变色液；The mouth of the liquid storage bag (210) communicates with the opening of the lower end of the microcavity (100), the opening of the pocket of the air storage bag (310) communicates with the opening of the upper end of the microchamber (100), the mouth of the fluid storage bag (210), the microcavity ( 100), the gas storage bag (310) are connected to form a closed space; the liquid storage bag (210) is equipped with electrochromic liquid;
所述电动推杆(220)设置于储液袋(210)法向方向(垂直于微腔的方向)或储液袋(210)底部，且与储液袋(210)相连；The electric push rod (220) is arranged in the normal direction of the liquid storage bag (210) (perpendicular to the direction of the microcavity) or the bottom of the liquid storage bag (210), and is connected to the liquid storage bag (210);
所述电动推杆(220)和储液袋(210)用外壳包裹形成底座(200)；所述外壳(320)材质为丙烯腈-丁二烯-苯乙烯(ABS)；所述储液袋(210)的材质为苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)，所述储液袋(210)的容积为0.2～0.8L；The electric push rod (220) and the fluid storage bag (210) are wrapped with a casing to form a base (200); the casing (320) is made of acrylonitrile-butadiene-styrene (ABS); the fluid storage bag (210) is made of styrene-butadiene-styrene block copolymer (SBS), and the volume of the fluid storage bag (210) is 0.2-0.8L;
所述储气袋(310)由外壳包裹形成顶盖(300)；所述外壳材质为丙烯腈-丁二烯-苯乙烯(ABS)；所述储气袋(310)的材质为苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)；所述储气袋(310)的容积为1.5～2.5L；The air storage bag (310) is wrapped by an outer shell to form a top cover (300); the outer shell is made of acrylonitrile-butadiene-styrene (ABS); the material of the air storage bag (310) is styrene- Butadiene-styrene block copolymer (SBS); the volume of the air storage bag (310) is 1.5-2.5L;
所述电致变色液为1.5～2.0mol/L的偏钨酸钾水溶液；The electrochromic solution is an aqueous potassium metatungstate solution of 1.5 to 2.0 mol/L;
所述第一玻璃基板(111)、第二玻璃基板(112)的尺寸相同，长均为200～2000mm，宽均为400～2000mm；The size of the first glass substrate (111) and the second glass substrate (112) are the same, the length is 200-2000 mm, and the width is 400-2000 mm;
所述第一氧化铟锡(ITO)透明导电电极(121)、第二氧化铟锡(ITO)透明导电电极(122)的厚度均为150～300nm；The thicknesses of the first indium tin oxide (ITO) transparent conductive electrode (121) and the second indium tin oxide (ITO) transparent conductive electrode (122) are both 150-300 nm;
所述第一金属钨薄膜(131)、第二金属钨薄膜(132)的厚度均为1～3nm；The thicknesses of the first metal tungsten film (131) and the second metal tungsten film (132) are both 1-3 nm;
所述玻璃微珠(140)的直径为1～5μm。The diameter of the glass microspheres (140) is 1-5 μm.
实施例1Example 1
(1)将水溶性的偏钨酸钾溶解到去离子水中，并搅拌至充分溶解，配制浓度为1.5mol/L的电致变色液。(1) Dissolve water-soluble potassium metatungstate in deionized water and stir until fully dissolved to prepare an electrochromic solution with a concentration of 1.5mol/L.
(2)在选取长1600mm，宽1000mm的玻璃基板，采用溅射工艺：射频模式，真空环境为8mTorr，溅射功率为60W，溅射时间为10min，在第一玻璃基板上制备第一氧化铟锡(ITO)透明导电电极，在第二玻璃基板上制备第二ITO电极，ITO电极厚度均为250nm。(2) Selecting a glass substrate with a length of 1600 mm and a width of 1000 mm, using a sputtering process: radio frequency mode, a vacuum environment of 8 mTorr, a sputtering power of 60 W, and a sputtering time of 10 min to prepare the first indium oxide on the first glass substrate Tin (ITO) transparent conductive electrodes, the second ITO electrode is prepared on the second glass substrate, and the thickness of the ITO electrodes is 250nm.
(3)将步骤2得到的ITO透明导电电极在空气氛围下退火吗，退火温度为 450℃，退火时间为2h。(3) Anneal the ITO transparent conductive electrode obtained in step 2 in an air atmosphere, the annealing temperature is 450°C, and the annealing time is 2h.
(4)采用溅射工艺：直流模式，真空环境为8mTorr，溅射功率为25W，溅射时间为10s，在第一和第二ITO电极上分别沉积一层超薄金属钨薄膜，薄膜的厚度为1nm。(4) Adopt sputtering process: DC mode, vacuum environment is 8mTorr, sputtering power is 25W, sputtering time is 10s, deposit a layer of ultra-thin metal tungsten film on the first and second ITO electrodes respectively, the thickness of the film 1nm.
(5)采用旋转涂布法，在超薄金属钨薄膜电极上均匀铺展一层玻璃微珠悬浊液，旋转涂布转速为7000rpm，时间为10min，旋涂液为玻璃微珠乙醇分散液，固含量为5wt.％，玻璃微珠直径为1μm，然后自然风干。(5) Adopt the spin-coating method, evenly spread one deck glass bead suspension on the ultra-thin metal tungsten thin film electrode, the spin-coating speed is 7000rpm, the time is 10min, and the spin-coating liquid is glass bead ethanol dispersion liquid, The solid content is 5wt.%, the diameter of the glass microspheres is 1 μm, and then air-dried naturally.
(6)将第一玻璃基板和第二玻璃基板电极面相对压合，压强为300kPa，压板温度为450℃，压合时间为2h，最终形成微腔(玻璃微珠在微腔中间)，并用准分子激光束将微腔两侧边缘熔合，激光功率为40W，激光束斑尺寸为2μm，激光移速为15mm/s，得到微腔。(6) The electrode surfaces of the first glass substrate and the second glass substrate are pressed against each other, the pressure is 300kPa, the temperature of the pressing plate is 450°C, and the pressing time is 2h, finally forming a microcavity (glass beads in the middle of the microcavity), and use The excimer laser beam fuses the edges on both sides of the microcavity, the laser power is 40W, the laser beam spot size is 2μm, and the laser moving speed is 15mm/s to obtain a microcavity.
(7)将电致变色液装入储液袋，将电动推杆、储液袋、外壳组装成底座，将储气袋和外壳组装成顶盖，将底座中的储气袋、顶盖中的储气袋与微腔组装成微腔注入型电致变色器件。具体的，底座结构为：一个苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)材质的储液袋，其袋口钳制于微腔下方开口，完全包裹微腔下方开口狭缝，储液袋装入电致变色液，溶积为0.5L，储液袋法向方向(垂直于微腔的方向)的一侧和电动推杆相连，整个底座还由丙烯腈-丁二烯-苯乙烯(ABS)塑料外壳包裹保护。顶盖结构为：一个苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)材质的储气袋，容积为1.5L，其袋口钳制于微腔上方开口，完全包裹微腔上方开口狭缝，整个顶盖还由ABS外壳包裹保护。(7) Put the electrochromic liquid into the liquid storage bag, assemble the electric push rod, the liquid storage bag, and the shell into a base, assemble the air storage bag and the shell into a top cover, and put the air storage bag in the base, the top cover The gas storage bag and the microcavity are assembled into a microcavity injection type electrochromic device. Specifically, the structure of the base is: a liquid storage bag made of styrene-butadiene-styrene block copolymer (SBS), the mouth of which is clamped to the opening below the microcavity, completely wrapping the opening slit below the microcavity, and storing The liquid bag is filled with electrochromic liquid, and the solution volume is 0.5L. One side of the liquid storage bag in the normal direction (perpendicular to the direction of the microcavity) is connected to the electric push rod, and the entire base is also made of acrylonitrile-butadiene-benzene. Vinyl (ABS) plastic shell wrap protection. The structure of the top cover is: an air storage bag made of styrene-butadiene-styrene block copolymer (SBS) with a volume of 1.5L. Seams, the entire top cover is also protected by an ABS shell wrap.
图1，图2、图3和图4展示了实施例1的具体结构。Fig. 1, Fig. 2, Fig. 3 and Fig. 4 have shown the specific structure of embodiment 1.
电致变色测试：Electrochromic test:
电动推杆供电，挤压储液袋，使储液袋的电致变色液注入到微腔，直到完全充满微腔，微腔里面被挤出的气体存储在顶盖的储气袋中。当微腔注满电致变色液后，向两个电极供电，电压为0.7V，持续20s，电致变色液中的阴离子从电极界面中获得电子而被还原，呈现深蓝色，器件的着色态透射光谱如图5 所示，在600nm处透射率约为32％，具有良好的遮光特性。器件的着色过程电流密度如图6所示。电动推杆扩张储液袋，电致变色液被吸回储液袋，器件恢复透明，透射率为75％。The electric push rod is powered, and the liquid storage bag is squeezed, so that the electrochromic liquid in the liquid storage bag is injected into the microcavity until the microcavity is completely filled, and the extruded gas in the microcavity is stored in the gas storage bag on the top cover. When the microcavity is filled with the electrochromic liquid, power is supplied to the two electrodes at a voltage of 0.7V for 20s. The anions in the electrochromic liquid obtain electrons from the electrode interface and are reduced, showing a dark blue color. The coloring state of the device The transmission spectrum is shown in Fig. 5, the transmittance at 600nm is about 32%, and it has good light-shielding properties. The current density of the coloring process of the device is shown in Fig. 6 . The electric push rod expands the liquid storage bag, the electrochromic liquid is sucked back into the liquid storage bag, and the device becomes transparent again with a transmittance of 75%.
实施例2Example 2
与实施例1步骤(1)～(7)基本一致，不同在于：步骤5的玻璃微珠直径为5μm。It is basically the same as Steps (1)-(7) of Example 1, except that the diameter of the glass microspheres in Step 5 is 5 μm.
电致变色测试：Electrochromic test:
电动推杆供电，挤压储液袋，使储液袋的电致变色液注入到微腔，直到完全充满微腔，微腔里面被挤出的气体存储在顶盖的储气袋中。当微腔注满电致变色液后，向两个电极供电，电压为0.7V，持续20s，电致变色液中的阴离子从电极界面中获得电子而被还原，呈现深蓝，在600nm处透射率约为13％，具有良好的遮光特性。电动推杆扩张储液袋，电致变色液被吸回储液袋，器件恢复透明，透射率为75％。The electric push rod is powered, and the liquid storage bag is squeezed, so that the electrochromic liquid in the liquid storage bag is injected into the microcavity until the microcavity is completely filled, and the extruded gas in the microcavity is stored in the gas storage bag on the top cover. When the microcavity is filled with the electrochromic liquid, power is supplied to the two electrodes with a voltage of 0.7V for 20s. The anions in the electrochromic liquid obtain electrons from the electrode interface and are reduced, showing dark blue, with a transmittance at 600nm. About 13%, has good light-shielding properties. The electric push rod expands the liquid storage bag, the electrochromic liquid is sucked back into the liquid storage bag, and the device becomes transparent again with a transmittance of 75%.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

  1. 一种微腔注入型电致变色器件，其特征在于，结构包括电动推杆、储液袋、微腔和储气袋；A microcavity injection type electrochromic device, characterized in that the structure includes an electric push rod, a liquid storage bag, a microcavity and an air storage bag;
    所述微腔上下两端设有开口，微腔结构依次为第一玻璃基板、第一氧化铟锡透明导电电极、第一金属钨薄膜、玻璃微珠、第二金属钨薄膜、第二氧化铟锡透明导电电极和第二玻璃基板，玻璃微珠间隙形成空腔；The upper and lower ends of the microcavity are provided with openings, and the structure of the microcavity is a first glass substrate, a first indium tin oxide transparent conductive electrode, a first metal tungsten film, glass beads, a second metal tungsten film, and a second indium oxide The tin transparent conductive electrode and the second glass substrate form a cavity in the gap between the glass beads;
    所述储液袋袋口与微腔下端开口相通，所述储气袋袋口与微腔上端开口相通，储液袋、微腔、储气袋三者相连形成一个密闭空间；所述储液袋装有电致变色液；The mouth of the liquid storage bag communicates with the opening at the lower end of the microcavity, the mouth of the air storage bag communicates with the opening at the upper end of the microcavity, and the liquid storage bag, the microchamber, and the air storage bag are connected to form a closed space; the liquid storage bag The bag contains electrochromic liquid;
    所述电动推杆与储液袋相连。The electric push rod is connected with the liquid storage bag.
  2. 根据权利要求1所述一种微腔注入型电致变色器件，其特征在于，所述玻璃微珠的直径为1～5μm。The microcavity injection type electrochromic device according to claim 1, wherein the diameter of the glass microsphere is 1-5 μm.
  3. 根据权利要求1所述一种微腔注入型电致变色器件，其特征在于，所述电致变色液为1.5～2.0mol/L的偏钨酸钾水溶液。The microcavity injection type electrochromic device according to claim 1, wherein the electrochromic liquid is a 1.5-2.0 mol/L potassium metatungstate aqueous solution.
  4. 根据权利要求1所述一种微腔注入型电致变色器件，其特征在于，所述电动推杆设置于储液袋法向方向或储液袋底部，且与储液袋相连；The microcavity injection type electrochromic device according to claim 1, wherein the electric push rod is arranged in the normal direction of the liquid storage bag or at the bottom of the liquid storage bag, and is connected to the liquid storage bag;
    所述电动推杆和储液袋用外壳包裹形成底座；The electric push rod and the liquid storage bag are wrapped with a casing to form a base;
    所述储气袋由外壳包裹形成顶盖。The air storage bag is wrapped by the shell to form a top cover.
  5. 根据权利要求1所述一种微腔注入型电致变色器件，其特征在于，所述第一氧化铟锡透明导电电极、第二氧化铟锡透明导电电极的厚度均为150～300nm；The microcavity injection type electrochromic device according to claim 1, wherein the thicknesses of the first indium tin oxide transparent conductive electrode and the second indium tin oxide transparent conductive electrode are both 150-300 nm;
    所述第一金属钨薄膜、第二金属钨薄膜的厚度均为1～3nm。The thicknesses of the first metal tungsten thin film and the second metal tungsten thin film are both 1-3 nm.
  6. 根据权利要求4所述一种微腔注入型电致变色器件，其特征在于，所述第一玻璃基板、第二玻璃基板的尺寸相同，长均为200～2000mm，宽均为400～2000mm；The microcavity injection type electrochromic device according to claim 4, characterized in that the first glass substrate and the second glass substrate have the same size, the length is 200-2000mm, and the width is 400-2000mm;
    所述储液袋的材质为苯乙烯-丁二烯-苯乙烯嵌段共聚物；The material of the liquid storage bag is styrene-butadiene-styrene block copolymer;
    所述储液袋的容积为0.2～0.8L；The volume of the liquid storage bag is 0.2-0.8L;
    所述储气袋的材质为苯乙烯-丁二烯-苯乙烯嵌段共聚物；The material of the air storage bag is styrene-butadiene-styrene block copolymer;
    所述储气袋的容积为1.5～2.5L；The volume of the air storage bag is 1.5-2.5L;
    所述外壳材质均为丙烯腈-丁二烯-苯乙烯。The shell material is all acrylonitrile-butadiene-styrene.
  7. 权利要求1～6任一项所述一种微腔注入型电致变色器件的制备方法，其特征在于，包括以下步骤：The preparation method of a microcavity injection type electrochromic device according to any one of claims 1 to 6, characterized in that it comprises the following steps:
    (1)采用磁控溅射工艺，在第一玻璃基板上制备第一氧化铟锡透明导电电极，在第二玻璃基板上制备第二氧化铟锡透明导电电极；(1) Using a magnetron sputtering process, preparing a first indium tin oxide transparent conductive electrode on the first glass substrate, and preparing a second indium tin oxide transparent conductive electrode on the second glass substrate;
    (2)将步骤(1)得到的氧化铟锡透明导电电极在空气氛围下退火；(2) annealing the indium tin oxide transparent conductive electrode obtained in step (1) under air atmosphere;
    (3)采用磁控溅射工艺，在第一氧化铟锡透明导电电极和第二氧化铟锡透明导电电极上分别制备一层金属钨薄膜；(3) Using a magnetron sputtering process to prepare a layer of metal tungsten film on the first indium tin oxide transparent conductive electrode and the second indium tin oxide transparent conductive electrode respectively;
    (4)采用旋转涂布法在金属钨薄膜表面均匀铺展一层玻璃微珠悬浊液，然后自然风干，得到第一玻璃基板电极和第二玻璃基板电极；(4) Spread a layer of glass bead suspension evenly on the surface of the metal tungsten film by a spin coating method, then air-dry naturally to obtain the first glass substrate electrode and the second glass substrate electrode;
    (5)将第一玻璃基板电极和第二玻璃基板电极面相对压合，形成微腔，并用激光将微腔左右两侧边缘熔合，而上下边缘为开口，得到微腔；(5) The first glass substrate electrode and the second glass substrate electrode face are pressed together to form a microcavity, and the left and right sides of the microcavity are fused with a laser, and the upper and lower edges are openings to obtain a microcavity;
    (6)将电致变色液装入储液袋，将电动推杆、储液袋、微腔、储气袋组装成微腔注入型电致变色器件。(6) Put the electrochromic liquid into the liquid storage bag, assemble the electric push rod, the liquid storage bag, the microcavity, and the gas storage bag into a microcavity injection type electrochromic device.
  8. 根据权利要求7所述一种微腔注入型电致变色器件的制备方法，其特征在于，步骤(6)所述组装还包括将外壳和电动推杆、储液袋组装成底座，将外壳和外壳组装成顶盖。A method for preparing a microcavity injection type electrochromic device according to claim 7, characterized in that the assembling in step (6) also includes assembling the shell, the electric push rod, and the liquid storage bag into a base, and assembling the shell and The shells are assembled into a top cover.
  9. 根据权利要求7所述一种微腔注入型电致变色器件的制备方法，其特征在于，步骤(1)所述磁控溅射工艺为：射频模式，真空环境为3～10mTorr，溅射功率为50～80W，溅射时间为5～10min；According to the preparation method of a microcavity injection type electrochromic device according to claim 7, it is characterized in that, the magnetron sputtering process described in step (1) is: radio frequency mode, vacuum environment is 3 ~ 10mTorr, sputtering power 50~80W, sputtering time is 5~10min;
    步骤(2)所述退火温度为400～500℃，退火时间为1～2h；The annealing temperature in step (2) is 400-500°C, and the annealing time is 1-2h;
    步骤(3)所述磁控溅射工艺为直流模式，真空环境为3～10mTorr，溅射 功率为25～35W，溅射时间为10～20s；The magnetron sputtering process described in step (3) is a DC mode, the vacuum environment is 3～10mTorr, the sputtering power is 25～35W, and the sputtering time is 10～20s;
    步骤(4)所述旋转涂布法的工艺为：旋转涂布转速为5000～7000rpm，时间为5～10min，旋涂液为玻璃微珠乙醇分散液，固含量为3～8wt.％；The process of the spin-coating method in step (4) is: the spin-coating speed is 5000-7000rpm, the time is 5-10min, the spin-coating liquid is an ethanol dispersion of glass beads, and the solid content is 3-8wt.%.
    步骤(5)所述压合工艺为：压强100～400kPa，压板温度400～500℃，压合时间1～2h；所述激光烧熔工艺为：准分子激光功率为20～50W，激光束斑尺寸为1～4μm，激光移速为10～20mm/s。The pressing process in step (5) is: pressure 100-400kPa, pressing plate temperature 400-500°C, pressing time 1-2h; the laser melting process is: excimer laser power 20-50W, laser beam spot The size is 1-4μm, and the laser moving speed is 10-20mm/s.
  10. 权利要求1～6任一项所述一种微腔注入型电致变色器件在电致变色智能窗、智能广告幕墙、智能隔板领域中的应用。Application of the microcavity injection electrochromic device described in any one of claims 1 to 6 in the fields of electrochromic smart windows, smart advertising curtain walls, and smart partitions.
PCT/CN2021/123446 2021-05-08 2021-10-13 Microcavity injection type electrochromic device, and manufacturing method therefor and application thereof WO2022237066A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110498074.2A CN113359361B (en) 2021-05-08 2021-05-08 Microcavity-injected electrochromic device and preparation method and application thereof
CN202110498074.2 2021-05-08

Publications (1)

Publication Number Publication Date
WO2022237066A1 true WO2022237066A1 (en) 2022-11-17

Family

ID=77525916

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/123446 WO2022237066A1 (en) 2021-05-08 2021-10-13 Microcavity injection type electrochromic device, and manufacturing method therefor and application thereof

Country Status (2)

Country Link
CN (1) CN113359361B (en)
WO (1) WO2022237066A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113359361B (en) * 2021-05-08 2022-10-25 华南理工大学 Microcavity-injected electrochromic device and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108363256A (en) * 2018-04-26 2018-08-03 广东工业大学 A kind of electrochromic device and preparation method thereof
CN109501677A (en) * 2018-11-27 2019-03-22 陆玮 A kind of new-energy automobile rearview mirror
CN109581776A (en) * 2019-01-02 2019-04-05 华南理工大学 A kind of low cost electrochromic device and preparation method thereof
CN209888748U (en) * 2019-03-06 2020-01-03 信利光电股份有限公司 Electrochromic rearview mirror
CN112162440A (en) * 2020-09-25 2021-01-01 华南理工大学 Electrochromic device and preparation method and application thereof
WO2021049772A1 (en) * 2019-09-11 2021-03-18 주식회사 스위스 Electrochromic device having low-resistance transparent electrode structure
CN113359361A (en) * 2021-05-08 2021-09-07 华南理工大学 Microcavity-injected electrochromic device and preparation method and application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216349A (en) * 1991-09-06 1995-08-15 Donnelly Corp Electrochemichromic solution, its preparation, method of using it, and device produced by using it
JPH11282023A (en) * 1998-03-30 1999-10-15 Nippon Mitsubishi Oil Corp Production of electrochromic element
CN101510038B (en) * 2009-03-16 2010-12-01 浙江大学 Method for producing full-solid electrochromic device
TW201222117A (en) * 2010-11-26 2012-06-01 J Touch Corp Touch-controlled electrochromic device
CN102608820B (en) * 2011-01-19 2014-06-04 介面光电股份有限公司 Touch type electrochromic device
CN105236019B (en) * 2015-11-17 2018-05-29 周晓青 A kind of vapour-pressure type squeeze fluid device
CN107765491A (en) * 2017-11-29 2018-03-06 信利光电股份有限公司 A kind of electrochromism module and preparation method thereof and rearview mirror
CN110888280A (en) * 2019-11-18 2020-03-17 爱卓智能科技(上海)有限公司 Frameless electrochromic rearview mirror structure
CN112081514B (en) * 2020-08-27 2021-04-13 哈尔滨工业大学 Electrochromic intelligent window without conductive glass

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108363256A (en) * 2018-04-26 2018-08-03 广东工业大学 A kind of electrochromic device and preparation method thereof
CN109501677A (en) * 2018-11-27 2019-03-22 陆玮 A kind of new-energy automobile rearview mirror
CN109581776A (en) * 2019-01-02 2019-04-05 华南理工大学 A kind of low cost electrochromic device and preparation method thereof
CN209888748U (en) * 2019-03-06 2020-01-03 信利光电股份有限公司 Electrochromic rearview mirror
WO2021049772A1 (en) * 2019-09-11 2021-03-18 주식회사 스위스 Electrochromic device having low-resistance transparent electrode structure
CN112162440A (en) * 2020-09-25 2021-01-01 华南理工大学 Electrochromic device and preparation method and application thereof
CN113359361A (en) * 2021-05-08 2021-09-07 华南理工大学 Microcavity-injected electrochromic device and preparation method and application thereof

Also Published As

Publication number Publication date
CN113359361A (en) 2021-09-07
CN113359361B (en) 2022-10-25

Similar Documents

Publication Publication Date Title
WO2022237066A1 (en) Microcavity injection type electrochromic device, and manufacturing method therefor and application thereof
CN103771724B (en) Full solid thin film electrochomeric glass and preparation method thereof
EP2470953B1 (en) Electrochromic device and assembly incorporating the same
CN202953940U (en) All-solid film electrochromic glass
TWI679483B (en) Improved electronically controlled all-solid-state intelligent dimming product and its glass window
CN111095094B (en) Method for preparing electrochromic device
EP3823930A1 (en) Electrochromic material and method of manufacturing thereof
CN110095911B (en) Preparation method of electrochromic device
Mashkov et al. Effect of ligand treatment on the tuning of infrared plasmonic indium tin oxide nanocrystal electrochromic devices
CN112162440B (en) Electrochromic device and preparation method and application thereof
TWI604254B (en) Method for fabricating electrochromic device
TW201319705A (en) Hydrogenated films used in solid-state electrochromic (EC) device structure and process methods
CN107045242A (en) Electrochromic structure and forming method thereof
TWI550331B (en) Method for fabricating an all-solid-state electrochromic device
CN113189822A (en) Electrochromic device and preparation method thereof
JPS6020754B2 (en) electrolytic display cell
TW201012292A (en) Electrochromic device and fabrication method thereof
CN114296284B (en) Passive self-driven electrochromic device and preparation method and application thereof
TWI832093B (en) Preparation method of electrochromic ion storage membrane
Yoshimura Metal Hydrides for Smart‐Window Applications
CN206236745U (en) A kind of safety-type lithium battery pole piece structure
CN114967267A (en) Transparent state to full black state electrochromic device
CN116534899A (en) Tungsten oxide nanocrystalline, functional glass, electrochromic device and preparation method
WO2022010429A2 (en) Innovation in high performance electro-chromic device manufacturing method
CN117821911A (en) Aluminum ion group solid electrolyte film, preparation method and application thereof, electrochromic device and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21941632

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21941632

Country of ref document: EP

Kind code of ref document: A1