技术领域Technical field
本发明涉及调光器件技术领域，特别是涉及一种电致变色器件及其制备方法。The present invention relates to the technical field of dimming devices, and in particular to an electrochromic device and a preparation method thereof.
背景技术Background technique
电致变色智能窗是一种重要的建筑节能手段，可在外加电场的作用下发生稳定、可逆的颜色变化的现象，在外观上表现为颜色和透明度的可逆变化。常见的电致变色解决方案为嵌入脱出式的工作原理，利用工作离子在正极或负极材料内部脱嵌时引发的颜色变化实现器件的着色变化。因此，该电致变色器件的结构通常有较多层不同的物种。例如，如图1所示，经典电致变色器件的结构依次包括第一透明基底—第一透明导电层—电致变色层/离子敏化层—电解液层—离子储存层—第二透明导电层—第二透明基底。由于其中的电致变色层和离子储存层(亦有采用两层电致变色层而无需离子储存层的结构)作为固体电极材料须兼顾透明特征、厚度均匀和一定的导电、导离子特性，因此往往需要采用磁控溅射或精密涂布等方式进行施工获得，导致制作工艺的复杂程度大增。新增的工艺步骤带来了良率的下降，尤其是大尺寸电致变色器件制造良率的下降尤其显著。例如，目前市面某主要电致变色器件厂家量产产品的坏点数目≤5个/平方米的产品良率仅为50％。且现有的电致变色器件的着色均匀性、响应速度、着色效率等均不太理想。Electrochromic smart windows are an important means of building energy conservation. They can produce stable and reversible color changes under the action of an external electric field, which appear as reversible changes in color and transparency. A common electrochromic solution is the intercalation-deintercalation working principle, which uses the color change caused by the working ions to deintercalate inside the positive or negative electrode material to achieve the color change of the device. Therefore, the structure of the electrochromic device usually has many layers of different species. For example, as shown in Figure 1, the structure of a classic electrochromic device includes in sequence a first transparent substrate - a first transparent conductive layer - an electrochromic layer/ion sensitized layer - an electrolyte layer - an ion storage layer - a second transparent conductive layer Layer—Second transparent base. Since the electrochromic layer and the ion storage layer (there are also structures that use two electrochromic layers without the ion storage layer), as solid electrode materials, they must have transparent characteristics, uniform thickness, and certain conductive and ion-conducting properties. It is often necessary to use magnetron sputtering or precision coating for construction, which greatly increases the complexity of the production process. The additional process steps have brought about a decrease in yield, especially in the manufacturing of large-size electrochromic devices. For example, the yield rate of mass-produced products by a major electrochromic device manufacturer currently on the market is only 50% if the number of dead pixels is ≤5 per square meter. Moreover, the coloring uniformity, response speed, coloring efficiency, etc. of existing electrochromic devices are not ideal.
因此，如何提升电致变色器件的响应速度和进一步简化和提升器件制作工艺水平是本领域面临的重要挑战。Therefore, how to improve the response speed of electrochromic devices and further simplify and improve the device manufacturing process are important challenges facing this field.
发明内容Contents of the invention
为弥补现有技术的不足，本发明提出一种电致变色器件及其制备方法。In order to make up for the shortcomings of the existing technology, the present invention proposes an electrochromic device and a preparation method thereof.
本发明的技术问题通过以下的技术方案予以解决：The technical problems of the present invention are solved by the following technical solutions:
一种电致变色器件，包括依次叠加的第一透明基底、第一透明电子导电层、电致变色电解液层、第二透明电子导电层和第二透明基底；其中，所述第一透明电子导电层和第二透明电子导电层的四周区域密封围合成密闭空腔，所述电致变色电解液层中的电解液容纳于所述密闭空腔内，所述电解液包括溶剂以及不同金属离子种类的金属盐，所述金属盐根据反应电位的差异分成两组，在对电致变色器件充电时，两组金属盐会分别在第一透明电子导电层和第二透明电子导电层表面沉积为沉积物，在对电致变色器件放电时，所述沉积物会溶解。An electrochromic device, including a first transparent substrate, a first transparent electronic conductive layer, an electrochromic electrolyte layer, a second transparent electronic conductive layer and a second transparent substrate stacked in sequence; wherein, the first transparent electronic The surrounding areas of the conductive layer and the second transparent electronic conductive layer are sealed to form a closed cavity. The electrolyte in the electrochromic electrolyte layer is contained in the closed cavity. The electrolyte includes solvents and different metal ions. Kinds of metal salts, the metal salts are divided into two groups according to the difference in reaction potential. When charging the electrochromic device, the two groups of metal salts will be respectively deposited on the surface of the first transparent electronic conductive layer and the second transparent electronic conductive layer as Deposits that dissolve when the electrochromic device is discharged.
在一些实施例中，所述金属盐中的金属离子包括Mn2+、Co2+、Ag+、Fe2+、Pb2+、Ni2+、Cu2+、Bi3+、Sn2+、Zn2+、Cr3+、Fe3+，所述金属盐中的阴离子包括Cl-、I-、Br-、SO42-、NO3-、ClO4-、PO43-、CF3SO3-、CF3CO2-、CH3COO-、AsF6-、SbF6-、TFSI-、TFO-、(CF3)2PF4-、(CF3)3PF3-、(CF3)4PF2-、(CF3)5PF-、(CF3)6P-、CF3SO3-、C4F9SO3-、CF3CF2SO3-、BF4-。In some embodiments, the metal ions in the metal salt include Mn2+ , Co2+ , Ag+ , Fe2+ , Pb2+ , Ni2+ , Cu2+ , Bi3+ , Sn2+ , Zn2+ , Cr3+ , Fe3+ , the anions in the metal salt include Cl- , I- , Br- , SO42- , NO3- , ClO4- , PO43- , CF3 SO3- , CF3 CO2- , CH3 COO- , AsF6- , SbF6- , TFSI- , TFO- , (CF3 )2 PF4- , (CF3 )3 PF3- , (CF3 )4 PF2- , (CF3 )5 PF- , (CF3 )6 P- , CF3 SO3- , C4 F9 SO3- , CF3 CF2 SO3- , BF4- .
在一些实施例中，所述金属盐包括Zn(CH3COO)2、ZnCl2、ZnSO4、Zn(ClO4)2、Zn(TFSI)2、Zn(CF3SO3)2、Zn(BF4)2、NiSO4、NiCl2、CoCl2、Co(NO3)2、AgNO3、AgClO4、AgAsF6、Cr(NO3)3、Cr2(SO4)3、FeCl3、Fe(TFO)2、CuCl2、CuSO4、Cu(ClO4)2、Mn(CH3COO)2、MnSO4、MnCl2、Bi(CH3COO)3、Bi(NO3)3、Bi(ClO4)3、SnSO4、SnCl2、Pb(NO3)2、Pb(CH3COO)2。In some embodiments, the metal salts include Zn(CH3 COO)2 , ZnCl2 , ZnSO4 , Zn(ClO4 )2 , Zn(TFSI)2 , Zn(CF3 SO3 )2 , Zn(BF4 )2 , NiSO4 , NiCl2 , CoCl2 , Co(NO3 )2 , AgNO3 , AgClO4 , AgAsF6 , Cr(NO3 )3 , Cr2 (SO4 )3 , FeCl3 , Fe(TFO )2 , CuCl2 , CuSO4 , Cu(ClO4 )2 , Mn(CH3 COO)2 , MnSO4 , MnCl2 , Bi(CH3 COO)3 , Bi(NO3 )3 , Bi(ClO4 )3. SnSO4 , SnCl2 , Pb(NO3 )2 , Pb(CH3 COO)2 .
在一些实施例中，所述电解液中的金属离子的浓度为0.1-20mol/L，优选为0.1-15mol/L。In some embodiments, the concentration of metal ions in the electrolyte is 0.1-20 mol/L, preferably 0.1-15 mol/L.
在一些实施例中，所述电解液中还包括质子来源物，所述质子来源物为硫酸、盐酸、硝酸、高氯酸、乙酸的一种；优选地，所述电解液中的质子的浓度为0.1-4.0mol/L，更优选0.1-2.0mol/L。In some embodiments, the electrolyte also includes a proton source, and the proton source is one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, and acetic acid; preferably, the concentration of protons in the electrolyte It is 0.1-4.0mol/L, more preferably 0.1-2.0mol/L.
在一些实施例中，所述电解液为水系电解液、凝胶电解液、有机电解液或混合电解液。In some embodiments, the electrolyte is an aqueous electrolyte, a gel electrolyte, an organic electrolyte or a mixed electrolyte.
在一些实施例中，当所述电解液为水系电解液时，所述溶剂为水；In some embodiments, when the electrolyte is an aqueous electrolyte, the solvent is water;
当所述电解液为凝胶电解液时，所述溶剂包括聚合物凝胶；优选地，所述聚合物胶凝为PMMA(聚甲基丙烯酸甲酯)凝胶、PVA(聚乙烯醇)凝胶、PAM(聚丙烯酰胺)凝胶、PAA(聚丙烯酸)凝胶、PVDF(聚偏二氟乙烯)凝胶、PEG(聚乙二醇)凝胶、PEO(聚环氧乙烷)凝胶、PVP(聚乙烯吡咯烷酮)凝胶、HEC(羟乙基纤维素)凝胶、HMC(羟甲基纤维素)凝胶中的一种，优选地，所述聚合物胶凝为聚乙烯醇凝胶、羟乙基纤维素凝胶、羟甲基纤维素凝胶中的一种；When the electrolyte is a gel electrolyte, the solvent includes a polymer gel; preferably, the polymer gel is PMMA (polymethyl methacrylate) gel, PVA (polyvinyl alcohol) gel. Gel, PAM (polyacrylamide) gel, PAA (polyacrylic acid) gel, PVDF (polyvinylidene fluoride) gel, PEG (polyethylene glycol) gel, PEO (polyethylene oxide) gel , one of PVP (polyvinylpyrrolidone) gel, HEC (hydroxyethylcellulose) gel, and HMC (hydroxymethylcellulose) gel. Preferably, the polymer gel is polyvinyl alcohol gel. One of glue, hydroxyethyl cellulose gel, and hydroxymethyl cellulose gel;
当所述电解液为有机电解液时，所述溶剂为醇类溶剂、醚类溶剂、酮类溶剂、酯类溶剂、酰胺类溶剂、亚砜或砜类溶剂中的至少一种，其中：所述醇类溶剂优选为甲醇、乙醇、乙二醇、异丙醇、正丁醇、异丁醇、丙二醇、丁二醇、丙三醇中的至少一种；所述醚类溶剂优选为1,3-二氧五环、1,4-二氧六环、乙二醇丁醚、乙二醇单甲醚、乙二醇单乙醚、乙二醇甲乙醚、乙二醇二乙醚中的至少一种；所述酮类溶剂优选为丁酮、甲基异丁基酮、环己酮、苯乙酮、苯丙酮、乙酰丙酮中的至少一种；所述酯类溶剂优选为乙酸乙酯、乙酸丁酯、乙酸苯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、碳酸亚乙烯酯、碳酸丙烯酯中的至少一种；所述酰胺类溶剂优选为N,N-二甲基甲酰胺，N,N-二甲基乙酰胺，N-甲基吡咯烷酮中的至少一种；所述亚砜或砜类溶剂优选为二甲基亚砜；优选地，当所述电解液为有机电解液时，所述溶剂为乙醇、乙二醇单甲醚、乙二醇甲乙醚、环己酮、乙酰丙酮、碳酸甲乙酯、碳酸乙烯酯、碳酸二甲酯、二甲基亚砜中的至少一种；When the electrolyte is an organic electrolyte, the solvent is at least one of alcohol solvents, ether solvents, ketone solvents, ester solvents, amide solvents, sulfoxides or sulfone solvents, wherein: The alcohol solvent is preferably at least one of methanol, ethanol, ethylene glycol, isopropanol, n-butanol, isobutanol, propylene glycol, butylene glycol, and glycerol; the ether solvent is preferably 1, At least one of 3-dioxane, 1,4-dioxane, ethylene glycol butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol diethyl ether. species; the ketone solvent is preferably at least one of butanone, methyl isobutyl ketone, cyclohexanone, acetophenone, phenylacetone, and acetylacetone; the ester solvent is preferably ethyl acetate, acetic acid At least one of butyl ester, phenyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, and propylene carbonate; the amide solvent is preferably N, N -At least one of dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; the sulfoxide or sulfone solvent is preferably dimethyl sulfoxide; preferably, when the When the electrolyte is an organic electrolyte, the solvent is ethanol, ethylene glycol monomethyl ether, ethylene glycol methyl ethyl ether, cyclohexanone, acetylacetone, methyl ethyl carbonate, ethylene carbonate, dimethyl carbonate, dimethyl carbonate, etc. At least one of the acyl sulfones;
当所述电解液为混合电解液时，所述溶剂为乙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙二醇、丙三醇中的至少一种与水的混合。When the electrolyte is a mixed electrolyte, the solvent is a mixture of at least one of ethanol, isopropyl alcohol, n-butanol, isobutanol, ethylene glycol, propylene glycol, and glycerol and water.
在一些实施例中，所述第一透明基底和所述第二透明基底的材质各自独立地为氧化物玻璃、非氧化物玻璃、聚酯薄膜、聚丙烯酸酯、聚碳酸酯、聚烃中的一种；In some embodiments, the first transparent substrate and the second transparent substrate are each independently made of oxide glass, non-oxide glass, polyester film, polyacrylate, polycarbonate, or polyhydrocarbon. A sort of;
所述第一透明电子导电层和所述第二透明电子导电层的材料各自独立地为金属氧化物、掺杂金属氧化物、金属网格、金属纳米线、合金、碳材料、透明导电聚合物、导电聚合物与金属纳米线复合、导电聚合物与金属网格复合中的一种；优选地，所述第一透明电子导电层和所述第二透明电子导电层的材料各自独立地为氧化铟锡、掺氟氧化锡、氧化锌、Cu金属网格、纳米银线、碳纳米管薄膜、石墨烯薄膜、PEDOT:PSS混合透明电极中的一种。The materials of the first transparent electronic conductive layer and the second transparent electronic conductive layer are each independently metal oxide, doped metal oxide, metal grid, metal nanowire, alloy, carbon material, transparent conductive polymer , a composite of conductive polymer and metal nanowires, a composite of conductive polymer and metal mesh; preferably, the materials of the first transparent electronic conductive layer and the second transparent electronic conductive layer are independently oxidized One of indium tin, fluorine-doped tin oxide, zinc oxide, Cu metal mesh, nanosilver wire, carbon nanotube film, graphene film, PEDOT:PSS hybrid transparent electrode.
在一些实施例中，所述第一透明基底和所述第二透明基底的厚度各自独立地为0.05mm-5.00mm，优选为0.10mm-1.00mm；In some embodiments, the thickness of the first transparent substrate and the second transparent substrate are each independently 0.05mm-5.00mm, preferably 0.10mm-1.00mm;
所述第一透明电子导电层和所述第二透明电子导电层的厚度各自独立地为1nm-1000nm，优选为10nm-200nm；The thickness of the first transparent electronic conductive layer and the second transparent electronic conductive layer is each independently 1 nm-1000 nm, preferably 10 nm-200 nm;
所述第一透明电子导电层和所述第二透明电子导电层的方阻各自为0.01-200Ω/□。Each of the first transparent electronically conductive layer and the second transparent electronically conductive layer has a sheet resistance of 0.01-200Ω/□.
本发明还提出了上述的电致变色器件的制备方法，包括如下步骤：The present invention also proposes a method for preparing the above-mentioned electrochromic device, which includes the following steps:
(1)分别从已形成在第一透明基底上的第一透明电子导电层与已形成在第二透明基底上的第二透明电子导电层上引出电极引线，再用密封胶将所述第一透明电子导电层和第二透明电子导电层的四周区域密封围合以在所述第一透明电子导电层和第二透明电子导电层之间形成空腔并预留注液口；(1) Lead electrode leads from the first transparent electronic conductive layer formed on the first transparent substrate and the second transparent electronic conductive layer formed on the second transparent substrate respectively, and then seal the first transparent electronic conductive layer with sealant The surrounding areas of the transparent electronic conductive layer and the second transparent electronic conductive layer are sealed and enclosed to form a cavity between the first transparent electronic conductive layer and the second transparent electronic conductive layer and reserve a liquid injection port;
(2)待密封胶固化后，通过所述注液口将电解液注入所述空腔内，并用密封胶密封注液口，待密封胶固化后得到所述电致变色器件。(2) After the sealant solidifies, inject the electrolyte into the cavity through the liquid injection port, and seal the liquid injection port with the sealant. After the sealant solidifies, the electrochromic device is obtained.
本发明与现有技术对比的有益效果包括：The beneficial effects of the present invention compared with the prior art include:
本发明通过第一透明电子导电层和第二透明电子导电层夹电致变色电解液层的设置，其中第一透明电子导电层和第二透明电子导电层分别作为阴极集流体和阳极集流体能够同时触发电致变色电解液层中不同种类的金属离子的沉积或溶解，在第一透明电子导电层和第二透明电子导电层上同时发生沉积或溶解来达到变色的效果，且金属离子在第一透明电子导电层和第二透明电子导电层上所发生的氧化还原反应互为彼此平衡电荷，从而省去了离子储存层，此外，由于一组金属离子形成的金属氧化物的导电性远低于另一组金属离子形成的金属或金属合金，因此在沉积过程中不会发生电场集聚效应，使得整个电致变色器件内部的电场分布趋于均匀化，并表现出均匀的变色效果。因此，本发明具有优异的着色均匀性、响应速度、着色效率，并提升了电致变色器件寿命，有效提升了电致变色器件的生产效率和良率，降低制作成本，有效改善整体层状结构的厚度。区别于传统电致变色器件的结构(例如包括依次叠加的第一透明基底、第一透明电子导电层、电致变色层、电解液层、离子存储层、第二透明电子导电层和第二透明基底)，本发明省去了电致变色层和离子储存层的制作步骤，制作工艺仅包括注液和封边等较少的步骤，简化了电致变色器件的制作工艺，减少了设备投入和材料成本，并降低能耗。The present invention adopts the arrangement of a first transparent electronic conductive layer and a second transparent electronic conductive layer sandwiching an electrochromic electrolyte layer, wherein the first transparent electronic conductive layer and the second transparent electronic conductive layer serve as cathode current collectors and anode current collectors respectively. The deposition or dissolution of different types of metal ions in the electrochromic electrolyte layer is triggered simultaneously. The deposition or dissolution occurs simultaneously on the first transparent electronic conductive layer and the second transparent electronic conductive layer to achieve the discoloration effect, and the metal ions are deposited or dissolved on the first transparent electronic conductive layer and the second transparent electronic conductive layer. The redox reactions occurring on the first transparent electronic conductive layer and the second transparent electronic conductive layer balance each other's charges, thus eliminating the need for an ion storage layer. In addition, the conductivity of the metal oxide formed by a group of metal ions is much lower. A metal or metal alloy formed from another group of metal ions, so there will be no electric field concentration effect during the deposition process, making the electric field distribution inside the entire electrochromic device uniform and showing a uniform discoloration effect. Therefore, the present invention has excellent coloring uniformity, response speed, and coloring efficiency, and improves the service life of electrochromic devices, effectively improves the production efficiency and yield of electrochromic devices, reduces production costs, and effectively improves the overall layered structure. thickness. It is different from the structure of traditional electrochromic devices (for example, it includes a first transparent substrate, a first transparent electronic conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a second transparent electronic conductive layer and a second transparent layer) that are stacked in sequence. substrate), the present invention eliminates the manufacturing steps of the electrochromic layer and the ion storage layer, and the manufacturing process only includes few steps such as liquid injection and edge sealing, simplifying the manufacturing process of the electrochromic device, reducing equipment investment and material costs, and reduce energy consumption.
本发明实施例中的其他有益效果将在下文中进一步述及。Other beneficial effects in embodiments of the present invention will be further described below.
附图说明Description of the drawings
图1是传统的电致变色器件的结构示意图；Figure 1 is a schematic structural diagram of a traditional electrochromic device;
图2是本发明实施例中电致变色器件的结构示意图；Figure 2 is a schematic structural diagram of an electrochromic device in an embodiment of the present invention;
图3是本发明实施例中电致变色器件的着色图；Figure 3 is a coloring diagram of an electrochromic device in an embodiment of the present invention;
图4是本发明实施例中电致变色器件的褪色图；Figure 4 is a fading diagram of an electrochromic device in an embodiment of the present invention;
图5是本发明实施例中电致变色器件在400-800nm波长处的透过率光谱；Figure 5 is the transmittance spectrum of the electrochromic device at the wavelength of 400-800nm in the embodiment of the present invention;
图6是本发明实施例中在460nm处的透过率响应曲线；Figure 6 is the transmittance response curve at 460nm in the embodiment of the present invention;
图7是本发明实施例中在初始状态和循环工作2000次后的透过率光谱图。Figure 7 is a transmittance spectrum chart in the initial state and after 2000 cycles of operation in the embodiment of the present invention.
具体实施方式Detailed ways
下面对照附图并结合优选的实施方式对本发明作进一步说明。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。The present invention will be further described below with reference to the accompanying drawings and preferred embodiments. It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of this application can be combined with each other.
需要说明的是，本实施例中的左、右、上、下、顶、底等方位用语，仅是互为相对概念，或是以产品的正常使用状态为参考的，而不应该认为是具有限制性的。It should be noted that the orientation terms such as left, right, up, down, top, and bottom in this embodiment are only relative concepts to each other, or are based on the normal use state of the product, and should not be considered as having Restrictive.
如图2所示，本发明具体实施方式提出了一种电致变色器件，其包括依次叠加的第一透明基底、第一透明电子导电层、电致变色电解液层、第二透明电子导电层和第二透明基底，其中第一透明电子导电层和第二透明电子导电层的四周区域密封围合成密闭空腔，电致变色电解液层中的电解液容纳于密闭空腔内，电解液包含两种以上金属离子，具体包括溶剂以及不同金属离子种类的金属盐，所述金属盐根据反应电位的差异分成两组，在对电致变色器件充电时，两组金属盐会分别在第一透明电子导电层和第二透明电子导电层表面沉积为沉积物，在对电致变色器件放电时，所述沉积物会溶解。As shown in Figure 2, the specific embodiment of the present invention proposes an electrochromic device, which includes a first transparent substrate, a first transparent electronic conductive layer, an electrochromic electrolyte layer, and a second transparent electronic conductive layer that are stacked in sequence. and a second transparent substrate, wherein the surrounding areas of the first transparent electronic conductive layer and the second transparent electronic conductive layer are sealed to form a closed cavity, and the electrolyte in the electrochromic electrolyte layer is contained in the closed cavity, and the electrolyte contains Two or more metal ions specifically include solvents and metal salts of different metal ion types. The metal salts are divided into two groups according to the difference in reaction potential. When charging the electrochromic device, the two groups of metal salts will be in the first transparent state respectively. The electron conductive layer and the second transparent electron conductive layer are deposited on the surface as deposits that dissolve when the electrochromic device is discharged.
相对于传统的电致变色器件，本发明的电致变色器件具有无电极结构的特点。本发明提出的电致变色器件新结构和新的制作方法取消了传统电致变色器件的电极和离子储存层的制作步骤，有效改善整体层状结构的厚度、简化制作工艺、提高电致变色效率。在上述电致变色电解液层中，电解液中的不同种类的金属离子可以分别在第一透明导电层和第二透明导电层实现可逆电沉积和溶解。电解液中的不同金属离子种类的金属盐作为光活性物质，用于电致变色，金属盐(包含不同金属离子种类的金属盐，即金属盐中具有至少两种金属离子)根据反应电位的差异分成两组，不同种类的金属离子为可以分别在第一透明电子导电层和第二透明电子导电层实现可逆电沉积和溶解，具体地，在对电致变色器件充电时，两组金属盐会同步分别在第一透明电子导电层和第二透明电子导电层表面沉积为沉积物(一组金属盐发生氧化反应沉积为金属氧化物，另一组金属盐发生还原反应沉积为金属或金属合金)，从而电致变色器件着色，在对电致变色器件放电时，沉积物会溶解(即沉积的金属氧化物、金属或金属合金会转化为可溶的物质)，从而电致变色器件褪色。Compared with traditional electrochromic devices, the electrochromic device of the present invention has the characteristics of an electrodeless structure. The new structure and new manufacturing method of the electrochromic device proposed by the present invention eliminate the manufacturing steps of the electrode and ion storage layer of the traditional electrochromic device, effectively improve the thickness of the overall layered structure, simplify the manufacturing process, and improve the electrochromic efficiency. . In the electrochromic electrolyte layer, different types of metal ions in the electrolyte can be reversibly electrodeposited and dissolved in the first transparent conductive layer and the second transparent conductive layer respectively. Metal salts of different metal ion types in the electrolyte are used as photoactive substances for electrochromism. The metal salts (including metal salts of different metal ion types, that is, there are at least two metal ions in the metal salt) vary according to the difference in reaction potential. Divided into two groups, different types of metal ions can achieve reversible electrodeposition and dissolution in the first transparent electronic conductive layer and the second transparent electronic conductive layer respectively. Specifically, when charging the electrochromic device, the two groups of metal salts will Simultaneously depositing deposits on the surfaces of the first transparent electronic conductive layer and the second transparent electronic conductive layer respectively (one group of metal salts undergoes an oxidation reaction to deposit into metal oxides, and the other group of metal salts undergoes a reduction reaction to deposit into metals or metal alloys) , so that the electrochromic device is colored. When the electrochromic device is discharged, the deposits will dissolve (that is, the deposited metal oxide, metal or metal alloy will be converted into soluble substances), so that the electrochromic device will fade.
在优选的实施例中，金属盐中的金属离子包括Mn2+、Co2+、Ag+、Fe2+、Pb2+、Ni2+、Cu2+、Bi3+、Sn2+、Zn2+、Cr3+、Fe3+；，金属盐中的阴离子包括Cl-、I-、Br-、SO42-、NO3-、ClO4-、PO43-、CF3SO3-、CF3CO2-、CH3COO-、AsF6-、SbF6-、TFSI-、TFO-、(CF3)2PF4-、(CF3)3PF3-、(CF3)4PF2-、(CF3)5PF-、(CF3)6P-、CF3SO3-、C4F9SO3-、CF3CF2SO3-、BF4-。进一步优选地，不同金属离子种类的金属盐的阴离子相同。In a preferred embodiment, the metal ions in the metal salt include Mn2+ , Co2+ , Ag+ , Fe2+ , Pb2+ , Ni2+ , Cu2+ , Bi3+ , Sn2+ , Zn2+ , Cr3+ , Fe3+ ;, the anions in the metal salt include Cl- , I- , Br- , SO42- , NO3- , ClO4- , PO43- , CF3 SO3- , CF3 CO2- , CH3 COO- , AsF6- , SbF6- , TFSI- , TFO- , (CF3 )2 PF4- , (CF3 )3 PF3- , (CF3 )4 PF2- , (CF3 )5 PF- , (CF3 )6 P- , CF3 SO3- , C4 F9 SO3- , CF3 CF2 SO3- , BF4- . It is further preferred that the anions of the metal salts of different metal ion species are the same.
在进一步优选的实施例中，上述可以发生氧化反应沉积为金属氧化物的一组金属盐中的金属离子可以选自Mn2+、Co2+、Ag+、Fe2+、Pb2+、Ni2+；上述可以发生还原反应沉积为金属或金属合金的另一组金属盐中的金属离子可以选自Cu2+、Bi3+、Pb2+、Sn2+、Zn2+、Cr3+、Fe2+、Fe3+、Co2+、Ni2+，两组金属盐根据各物质反应的电极电势进行匹配，选择合适的正极和负极反应，使二者符合可逆的沉积和溶解即可，此外，两组金属盐中的金属离子的配比足以满足正负极反应的容量匹配，一般会添加过量的浓度。在优选的实施例中，金属盐包括Zn(CH3COO)2、ZnCl2、ZnSO4、Zn(ClO4)2、Zn(TFSI)2、Zn(CF3SO3)2、Zn(BF4)2、NiSO4、NiCl2、CoCl2、Co(NO3)2、AgNO3、AgClO4、AgAsF6、Cr(NO3)3、Cr2(SO4)3、FeCl3、Fe(TFO)2、CuCl2、CuSO4、Cu(ClO4)2、Mn(CH3COO)2、MnSO4、MnCl2、Bi(CH3COO)3、Bi(NO3)3、Bi(ClO4)3、SnSO4、SnCl2、Pb(NO3)2、Pb(CH3COO)2。In a further preferred embodiment, the metal ions in the above-mentioned group of metal salts that can undergo oxidation reactions and be deposited as metal oxides can be selected from Mn2+ , Co2+ , Ag+ , Fe2+ , Pb2+ , Ni2+ ; the metal ions in another group of metal salts that can undergo reduction reactions and be deposited as metals or metal alloys can be selected from Cu2+ , Bi3+ , Pb2+ , Sn2+ , Zn2+ , Cr3+ , Fe2+ , Fe3+ , Co2+ , Ni2+ , the two groups of metal salts are matched according to the electrode potential of each substance reaction, and the appropriate positive and negative electrode reactions are selected so that they meet reversible deposition and dissolution. , In addition, the ratio of metal ions in the two sets of metal salts is sufficient to meet the capacity matching of the positive and negative electrode reactions, and an excess concentration is generally added. In preferred embodiments, the metal salts include Zn(CH3 COO)2 , ZnCl2 , ZnSO4 , Zn(ClO4 )2 , Zn(TFSI)2 , Zn(CF3 SO3 )2 , Zn(BF4 )2 , NiSO4 , NiCl2 , CoCl2 , Co(NO3 )2 , AgNO3 , AgClO4 , AgAsF6 , Cr(NO3 )3 , Cr2 (SO4 )3 , FeCl3 , Fe(TFO)2. CuCl2 , CuSO4 , Cu(ClO4 )2 , Mn(CH3 COO)2 , MnSO4 , MnCl2 , Bi(CH3 COO)3 , Bi(NO3 )3 , Bi(ClO4 )3 , SnSO4 , SnCl2 , Pb(NO3 )2 , Pb(CH3 COO)2 .
在优选的实施例中，电解液中的金属离子的浓度为0.1-20mol/L，优选为0.1-15mol/L。In a preferred embodiment, the concentration of metal ions in the electrolyte is 0.1-20 mol/L, preferably 0.1-15 mol/L.
在优选的实施例中，电解液中的质子的浓度为0.1-4.0mol/L，优选0.1-2.0mol/L。In a preferred embodiment, the concentration of protons in the electrolyte is 0.1-4.0 mol/L, preferably 0.1-2.0 mol/L.
在优选的实施例中，所述电解液中还包括质子来源物，电解液中的质子来源物为硫酸、盐酸、硝酸、高氯酸、乙酸的一种；优选地，所述电解液中的质子的浓度为0.1-4.0mol/L，更优选0.1-2.0mol/L。In a preferred embodiment, the electrolyte also includes a proton source, and the proton source in the electrolyte is one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, and acetic acid; preferably, the proton source in the electrolyte The concentration of protons is 0.1-4.0 mol/L, more preferably 0.1-2.0 mol/L.
在优选的实施例中，电解液为液态电解液(如水系电解液、有机电解液或混合电解液)或凝胶电解液。In a preferred embodiment, the electrolyte is a liquid electrolyte (such as an aqueous electrolyte, an organic electrolyte or a mixed electrolyte) or a gel electrolyte.
在优选的实施例中，当电解液为水系电解液时，其溶剂为水。In a preferred embodiment, when the electrolyte is an aqueous electrolyte, the solvent is water.
在优选的实施例中，当所述电解液为凝胶电解液时，所述溶剂包括聚合物凝胶；优选地，所述聚合物胶凝为PMMA(聚甲基丙烯酸甲酯)凝胶、PVA(聚乙烯醇)凝胶、PAM(聚丙烯酰胺)凝胶、PAA(聚丙烯酸)凝胶、PVDF(聚偏二氟乙烯)凝胶、PEG(聚乙二醇)凝胶、PEO(聚环氧乙烷)凝胶、PVP(聚乙烯吡咯烷酮)凝胶、HEC(羟乙基纤维素)凝胶、HMC(羟甲基纤维素)凝胶中的一种，优选地，所述聚合物胶凝为聚乙烯醇凝胶、羟乙基纤维素凝胶、羟甲基纤维素凝胶中的一种。In a preferred embodiment, when the electrolyte is a gel electrolyte, the solvent includes a polymer gel; preferably, the polymer gel is PMMA (polymethylmethacrylate) gel, PVA (polyvinyl alcohol) gel, PAM (polyacrylamide) gel, PAA (polyacrylic acid) gel, PVDF (polyvinylidene fluoride) gel, PEG (polyethylene glycol) gel, PEO (polyethylene glycol) gel, One of ethylene oxide) gel, PVP (polyvinylpyrrolidone) gel, HEC (hydroxyethylcellulose) gel, HMC (hydroxymethylcellulose) gel, preferably, the polymer Gelation is one of polyvinyl alcohol gel, hydroxyethyl cellulose gel, and hydroxymethyl cellulose gel.
在优选的实施例中，当所述电解液为有机电解液时，所述溶剂为醇类溶剂、醚类溶剂、酮类溶剂、酯类溶剂、酰胺类溶剂、亚砜或砜类溶剂中的至少一种，其中：所述醇类溶剂优选为甲醇、乙醇、乙二醇、异丙醇、正丁醇、异丁醇、丙二醇、丁二醇、丙三醇中的至少一种；所述醚类溶剂优选为1,3-二氧五环、1,4-二氧六环、乙二醇丁醚、乙二醇单甲醚、乙二醇单乙醚、乙二醇甲乙醚、乙二醇二乙醚中的至少一种；所述酮类溶剂优选为丁酮、甲基异丁基酮、环己酮、苯乙酮、苯丙酮、乙酰丙酮中的至少一种；所述酯类溶剂优选为乙酸乙酯、乙酸丁酯、乙酸苯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、碳酸亚乙烯酯、碳酸丙烯酯中的至少一种；所述酰胺类溶剂优选为N,N-二甲基甲酰胺，N,N-二甲基乙酰胺，N-甲基吡咯烷酮中的至少一种；所述亚砜或砜类溶剂优选为二甲基亚砜；优选地，当所述电解液为有机电解液时，所述溶剂为乙醇、乙二醇单甲醚、乙二醇甲乙醚、环己酮、乙酰丙酮、碳酸甲乙酯、碳酸乙烯酯、碳酸二甲酯、二甲基亚砜中的至少一种。In a preferred embodiment, when the electrolyte is an organic electrolyte, the solvent is an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, an amide solvent, a sulfoxide or a sulfone solvent. At least one, wherein: the alcoholic solvent is preferably at least one of methanol, ethanol, ethylene glycol, isopropanol, n-butanol, isobutanol, propylene glycol, butylene glycol, and glycerol; Ether solvents are preferably 1,3-dioxane, 1,4-dioxane, ethylene glycol butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol At least one of alcohol diethyl ethers; the ketone solvent is preferably at least one of butanone, methyl isobutyl ketone, cyclohexanone, acetophenone, phenylacetone, and acetylacetone; the ester solvent Preferably, it is at least one of ethyl acetate, butyl acetate, phenyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, and propylene carbonate; the amide The solvent is preferably at least one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; the sulfoxide or sulfone solvent is preferably dimethyl sulfoxide ; Preferably, when the electrolyte is an organic electrolyte, the solvent is ethanol, ethylene glycol monomethyl ether, ethylene glycol methyl ethyl ether, cyclohexanone, acetylacetone, ethyl methyl carbonate, ethylene carbonate, At least one of dimethyl carbonate and dimethyl sulfoxide.
在优选的实施例中，当电解液为混合电解液时，溶剂为乙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙二醇、丙三醇中的至少一种与水的混合。In a preferred embodiment, when the electrolyte is a mixed electrolyte, the solvent is a mixture of at least one of ethanol, isopropyl alcohol, n-butanol, isobutanol, ethylene glycol, propylene glycol, and glycerol and water. .
在优选的实施例中，第一透明基底和第二透明基底的材质各自独立地为氧化物玻璃、非氧化物玻璃(包括硫系玻璃和卤化物玻璃)、聚酯薄膜、聚丙烯酸酯、聚碳酸酯、聚烃中的一种；优选地，氧化物玻璃包括硅酸盐玻璃、硼酸盐玻璃、磷酸盐玻璃；优选地，聚酯薄膜包括聚对苯二甲酸乙二醇酯薄膜、聚甲基丙烯酸甲酯薄膜；优选地，玻璃透光度范围为50％-99％，优选范围为80％-99％，玻璃雾度范围为0.1％-10％，优选范围为0.1％-3.0％。In a preferred embodiment, the materials of the first transparent substrate and the second transparent substrate are independently oxide glass, non-oxide glass (including chalcogenide glass and halide glass), polyester film, polyacrylate, polyester One of carbonate and polyhydrocarbon; preferably, the oxide glass includes silicate glass, borate glass, and phosphate glass; preferably, the polyester film includes polyethylene terephthalate film, polyethylene terephthalate film, Methyl methacrylate film; preferably, the glass transmittance range is 50%-99%, the preferred range is 80%-99%, the glass haze range is 0.1%-10%, the preferred range is 0.1%-3.0% .
在优选的实施例中，第一透明基底和所述第二透明基底的厚度各自独立地为0.05mm-5.00mm，优选为0.10mm-1.00mm。In a preferred embodiment, the thicknesses of the first transparent substrate and the second transparent substrate are each independently 0.05mm-5.00mm, preferably 0.10mm-1.00mm.
在优选的实施例中，第一透明电子导电层和所述第二透明电子导电层的材料各自独立地为金属氧化物、掺杂金属氧化物、金属网格、金属纳米线、合金、碳材料、透明导电聚合物、导电聚合物与金属纳米线复合、导电聚合物与金属网格复合中的一种；优选地，所述第一透明电子导电层和所述第二透明电子导电层的材料各自独立地为氧化铟锡、掺氟氧化锡、氧化锌、Cu金属网格、纳米银线、碳纳米管薄膜、石墨烯薄膜、PEDOT:PSS混合透明电极中的一种。In a preferred embodiment, the materials of the first transparent electronic conductive layer and the second transparent electronic conductive layer are independently metal oxides, doped metal oxides, metal meshes, metal nanowires, alloys, and carbon materials. , one of transparent conductive polymer, conductive polymer and metal nanowire composite, conductive polymer and metal mesh composite; preferably, the materials of the first transparent electronic conductive layer and the second transparent electronic conductive layer Each is independently one of indium tin oxide, fluorine-doped tin oxide, zinc oxide, Cu metal mesh, nanosilver wire, carbon nanotube film, graphene film, and PEDOT:PSS hybrid transparent electrode.
在优选的实施例中，第一透明电子导电层和所述第二透明电子导电层的厚度各自独立地为1nm-1000nm，优选为10nm-200nm；第一透明电子导电层和所述第二透明电子导电层的方阻各自为0.01-200Ω/□。In a preferred embodiment, the thicknesses of the first transparent electronic conductive layer and the second transparent electronic conductive layer are each independently 1 nm-1000 nm, preferably 10 nm-200 nm; the thickness of the first transparent electronic conductive layer and the second transparent electronic conductive layer The square resistance of the electronic conductive layer is each 0.01-200Ω/□.
本发明具体实施方式还提出一种电致变色器件的制备方法，其包括如下步骤：Specific embodiments of the present invention also provide a method for preparing an electrochromic device, which includes the following steps:
(1)分别从已形成在第一透明基底上的第一透明电子导电层与已形成在第二透明基底上的第二透明电子导电层上引出电极引线，再用密封胶将所述第一透明电子导电层和第二透明电子导电层的四周区域密封围合以在所述第一透明电子导电层和第二透明电子导电层之间形成空腔并预留注液口；(1) Lead electrode leads from the first transparent electronic conductive layer formed on the first transparent substrate and the second transparent electronic conductive layer formed on the second transparent substrate respectively, and then seal the first transparent electronic conductive layer with sealant The surrounding areas of the transparent electronic conductive layer and the second transparent electronic conductive layer are sealed and enclosed to form a cavity between the first transparent electronic conductive layer and the second transparent electronic conductive layer and reserve a liquid injection port;
例如可以通过OCA光学胶作为围堰对第一透明基底和第一透明电子导电层形成的整体上进行贴合，再将第二透明基底和第二透明电子导电层形成的整体对准覆盖在OCA光学胶的一面，使得第一透明电子导电层和第二透明电子导电层之间形成空腔并预留注液口，在粘贴过程中，可以利用压力控制设备对器件进行压力施加，使其粘结更牢固；For example, OCA optical glue can be used as a cofferdam to bond the entire body formed by the first transparent substrate and the first transparent electronic conductive layer, and then the entire body formed by the second transparent substrate and the second transparent electronic conductive layer can be aligned and covered on the OCA On one side of the optical glue, a cavity is formed between the first transparent electronic conductive layer and the second transparent electronic conductive layer and a liquid injection port is reserved. During the pasting process, the pressure control device can be used to apply pressure to the device to make it adhere. Knots are stronger;
(2)待密封胶固化后，通过注液口将电解液注入空腔内，并用密封胶(例如可以是有机硅密封胶)密封注液口，待密封胶固化(例如在室温下固化2h)后得到所述电致变色器件。(2) After the sealant solidifies, inject the electrolyte into the cavity through the injection port, seal the injection port with sealant (for example, it can be silicone sealant), and wait for the sealant to solidify (for example, cure at room temperature for 2 hours) Finally, the electrochromic device is obtained.
在一个示例中，电致变色器件的制备方法可以为：将丁基橡胶圈固定在的第一透明电子导电层，橡胶圈厚度设置为1-5mm，橡胶圈宽度设置为1-3mm，将第二透明电子导电层的正对面贴在橡胶圈的另一面，并分别引出电极引线，用密封胶将四周密封并保留注液口，待固化好后，通过的注液口将电解液注入空腔内，待密封胶固化5-6小时后制备完成。In one example, the preparation method of the electrochromic device can be as follows: fix the butyl rubber ring on the first transparent electronic conductive layer, set the thickness of the rubber ring to 1-5mm, set the width of the rubber ring to 1-3mm, and set the first transparent electronic conductive layer to The opposite side of the two transparent electronic conductive layers is attached to the other side of the rubber ring, and the electrode leads are drawn out respectively. The surroundings are sealed with sealant and the liquid injection port is retained. After curing, the electrolyte is injected into the cavity through the liquid injection port. Within 5-6 hours, the preparation is completed after the sealant has cured.
以下通过具体实施例，对本发明做进一步阐述。The present invention will be further described below through specific examples.
实施例1Example 1
电致变色器件的结构包括依次叠加的第一透明基底、第一透明电子导电层、电致变色电解液层、第二透明电子导电层和第二透明基底；OCA光学胶将第一透明电子导电层和第二透明电子导电层的四周区域密封围合成密闭空腔，电致变色电解液层中的电解液容纳于密闭空腔内，电解液是具有第一透明电子导电层和第二透明电子导电层同步沉积溶解功能的电解液，其中，电解液包括1M的Zn(CH3COO)2、0.5M的Mn(CH3COO)2、0.5M CH3COOH和去离子水，第一透明基底和第一透明电子导电层的整体采用FTO导电玻璃，第二透明电子导电层和第二透明基底的整体也采用同样的FTO导电玻璃，本例中，具体地，为在玻璃基底上磁控溅射FTO层或者也可以直接购买得到制作好的玻璃-FTO基底，FTO层厚度为200nm，方阻为7Ω/□。The structure of the electrochromic device includes a first transparent substrate, a first transparent electronic conductive layer, an electrochromic electrolyte layer, a second transparent electronic conductive layer and a second transparent substrate that are stacked in sequence; the OCA optical glue conducts the first transparent electron The surrounding areas of the electrochromic electrolyte layer and the second transparent electron conductive layer are sealed to form a closed cavity. The electrolyte in the electrochromic electrolyte layer is contained in the closed cavity. The electrolyte has a first transparent electron conductive layer and a second transparent electron conductive layer. The conductive layer simultaneously deposits an electrolyte with dissolving function, wherein the electrolyte includes 1M Zn(CH3 COO)2 , 0.5M Mn(CH3 COO)2 , 0.5M CH3 COOH and deionized water, the first transparent substrate The whole body of the first transparent electronic conductive layer is made of FTO conductive glass, and the whole body of the second transparent electronic conductive layer and the second transparent substrate is also made of the same FTO conductive glass. In this example, specifically, it is magnetron sputtering on the glass substrate. Inject the FTO layer or you can directly purchase the prepared glass-FTO substrate. The thickness of the FTO layer is 200nm and the square resistance is 7Ω/□.
电致变色器件的制备方法包括如下步骤：The preparation method of the electrochromic device includes the following steps:
所需材料：丙酮、无水乙醇、去离子水、乙酸锌(Zn(CH3COO)2，分析纯)、乙酸锰(Mn(CH3COO)2，分析纯)、乙酸(CH3COOH)、FTO导电玻璃、OCA光学胶、有机硅密封胶。制作步骤如下：Materials required: acetone, absolute ethanol, deionized water, zinc acetate (Zn(CH3C OO)2 , analytical grade), manganese acetate (Mn(CH3 COO)2 , analytical grade), acetic acid (CH3 COOH) , FTO conductive glass, OCA optical glue, silicone sealant. The production steps are as follows:
(1)FTO导电玻璃的清洗：分别用丙酮、无水乙醇、去离子水超声清洗10分钟。(1) Cleaning of FTO conductive glass: Ultrasonic cleaning with acetone, absolute ethanol, and deionized water for 10 minutes respectively.
(2)电解液的制备：量取一定量的去离子水作为溶剂，加入1M的Zn(CH3COO)2、0.5M的Mn(CH3COO)2和0.5M CH3COOH搅拌均匀所得溶液即为电解液。(2) Preparation of electrolyte: Measure a certain amount of deionized water as the solvent, add 1M Zn(CH3 COO)2 , 0.5M Mn(CH3 COO)2 and 0.5M CH3 COOH and stir the resulting solution evenly. That is the electrolyte.
(3)电致变色器件的组装：将两块清洗好的FTO导电玻璃导电面相对贴合用OCA光学胶进行固定密封形成空腔并预留出注液口，其中空腔的大小由OCA光学胶的厚度(OCA光学胶的厚度为125-500μm)控制。将制备的电解液注入到空腔内，最后用有机硅密封胶进行封口和胶封。(3) Assembly of the electrochromic device: Place two cleaned FTO conductive glass conductive surfaces against each other and use OCA optical glue to fix and seal them to form a cavity and reserve a liquid injection port. The size of the cavity is determined by OCA Optical The thickness of the glue (the thickness of OCA optical glue is 125-500μm) is controlled. Inject the prepared electrolyte into the cavity, and finally seal it with silicone sealant.
如图3和图4所示，实施例1制得的电致变色器件在褪色态和着色态的实物照片对比。可以看到，电致变色器件可以在完全透明和完全不透光之间切换，如图5所示，着色态时可以实现对可见光波段(400-800nm)全部隔绝，展示了较宽范围的光调制，器件在460nm处得到最大透过率差值为90.3％。此外如图6所示，该器件展现出非常高的可逆性，对此我们进行了实时的光谱检测，本发明实施例提出的电致变色器件可以在透明态和着色态不断地可逆切换。一般来说，在变色过程中将达到最大透过率变化的90％所需要的时间定义为着色响应时间和褪色响应时间。通过记录器件在特定电压条件下工作的透过率随时间变化，可以计算出器件的响应时间为着色时间15s，褪色时间60s。如图7所示，对本发明实施例提出的电致变色器件的循环稳定性同样进行了测试，器件在初始状态和循环了2000次之后光调制能力无明显衰退，这说明了本发明实施例提出的电致变色器件具有优良的循环稳定性。As shown in Figures 3 and 4, physical photos of the electrochromic device produced in Example 1 are compared in the faded state and the colored state. It can be seen that the electrochromic device can switch between completely transparent and completely opaque, as shown in Figure 5. In the colored state, it can completely isolate the visible light band (400-800nm), demonstrating a wide range of light. Modulated, the device obtains a maximum transmittance difference of 90.3% at 460nm. In addition, as shown in Figure 6, the device exhibits very high reversibility, for which we conducted real-time spectral detection. The electrochromic device proposed in the embodiment of the present invention can continuously and reversibly switch between the transparent state and the colored state. Generally speaking, the time required to reach 90% of the maximum transmittance change during the discoloration process is defined as the coloring response time and fading response time. By recording the change in transmittance of the device over time when operating under specific voltage conditions, the response time of the device can be calculated as the coloring time of 15s and the fading time of 60s. As shown in Figure 7, the cycle stability of the electrochromic device proposed in the embodiment of the present invention was also tested. The device showed no significant decline in light modulation capability in the initial state and after 2000 cycles. This illustrates that the electrochromic device proposed in the embodiment of the present invention did not decline significantly. The electrochromic device has excellent cycling stability.
实施例2Example 2
与实施例1的区别在于，本实施例中的电解液包括0.1M的BiCl3、0.1M的CuCl2、0.5M的MnCl2、1M HCl和去离子水。The difference from Embodiment 1 is that the electrolyte in this embodiment includes 0.1M BiCl3 , 0.1M CuCl2 , 0.5M MnCl2 , 1M HCl and deionized water.
电致变色器件的制备方法包括如下步骤：The preparation method of the electrochromic device includes the following steps:
所需材料：丙酮、无水乙醇、去离子水、氯化铋(BiCl3，99％)、氯化铜(CuCl2，分析纯)、氯化锰(MnCl2，分析纯)、浓盐酸(HCl，质量分数37％-38％)、FTO导电玻璃、OCA光学胶、有机硅密封胶。Materials required: acetone, absolute ethanol, deionized water, bismuth chloride (BiCl3 , 99%), copper chloride (CuCl2 , analytical grade), manganese chloride (MnCl2 , analytical grade), concentrated hydrochloric acid ( HCl, mass fraction 37%-38%), FTO conductive glass, OCA optical glue, silicone sealant.
制作步骤如下：The production steps are as follows:
(1)FTO导电玻璃的清洗：分别用丙酮、无水乙醇、去离子水超声清洗10分钟。(1) Cleaning of FTO conductive glass: Ultrasonic cleaning with acetone, absolute ethanol, and deionized water for 10 minutes respectively.
(2)电解液的制备：取0.1M BiCl3用浓盐酸(HCl，质量分数37％-38％)溶解后，再加入去离子水慢慢稀释，以防Bi离子水解为沉积物，稀释到酸浓度为1M，再加0.1M的CuCl2、0.5M的MnCl2，搅拌均匀所得溶液即为电解液(2) Preparation of electrolyte: Dissolve 0.1MBiCl3 with concentrated hydrochloric acid (HCl, mass fraction 37%-38%), then add deionized water to slowly dilute it to prevent Bi ions from hydrolyzing into sediments, dilute to The acid concentration is 1M, add 0.1M CuCl2 and 0.5M MnCl2 , stir evenly, and the resulting solution is the electrolyte.
(3)电致变色器件的组装：同实施例1(3) Assembly of electrochromic device: same as Example 1
本实施例的器件可以在褪色态和着色态之间切换，着色态时可以实现对可见光波段(400-800nm)全部隔绝，展示了较宽范围的光调制，器件在460nm处得到最大透过率差值为90.3％。一般来说，在变色过程中将达到最大透过率变化的90％所需要的时间定义为着色响应时间和褪色响应时间。通过记录器件在特定电压条件下工作的透过率随时间变化，可以计算出器件的响应时间为着色时间9s，褪色时间33s。对本实施例器件的循环稳定性同样进行了测试，器件在初始状态和循环了5000次之后光调制能力无明显衰退，这说明了本实施例的电致变色器件具有优良的循环稳定性。The device of this embodiment can switch between the faded state and the tinted state. In the tinted state, it can completely isolate the visible light band (400-800nm), demonstrating a wide range of light modulation. The device obtains the maximum transmittance at 460nm. The difference is 90.3%. Generally speaking, the time required to reach 90% of the maximum transmittance change during the discoloration process is defined as the coloring response time and fading response time. By recording the change in transmittance of the device over time when operating under specific voltage conditions, it can be calculated that the response time of the device is 9s for coloring and 33s for fading. The cycle stability of the device in this embodiment was also tested. There was no significant decline in the light modulation capability of the device in the initial state and after 5,000 cycles, which illustrates that the electrochromic device in this embodiment has excellent cycle stability.
实施例3Example 3
与实施例1的区别在于，本实施例中的电解液包括0.1M的CuSO4、1M的MnSO4、1M的硫酸、3g的PVA和去离子水。The difference from Example 1 is that the electrolyte in this example includes 0.1M CuSO4 , 1M MnSO4 , 1M sulfuric acid, 3g PVA and deionized water.
电致变色器件的制备方法包括如下步骤：The preparation method of the electrochromic device includes the following steps:
所需材料：丙酮、无水乙醇、去离子水、硫酸铜(CuSO4，分析纯)、硫酸锰(MnSO4，分析纯)、硫酸(H2SO4，质量分数98％)、聚乙烯醇(PVA)、FTO导电玻璃、OCA光学胶、有机硅密封胶。Materials required: acetone, absolute ethanol, deionized water, copper sulfate (CuSO4 , analytical grade), manganese sulfate (MnSO4 , analytical grade), sulfuric acid (H2 SO4 , mass fraction 98%), polyvinyl alcohol (PVA), FTO conductive glass, OCA optical glue, silicone sealant.
制作步骤如下：The production steps are as follows:
(1)FTO导电玻璃的清洗：分别用丙酮、无水乙醇、去离子水超声清洗10分钟(1) Cleaning of FTO conductive glass: ultrasonic cleaning with acetone, absolute ethanol, and deionized water for 10 minutes respectively
(2)电解液的制备：取0.1M的CuSO4、1M的MnSO4、1M的硫酸、3g的PVA，加入30ml去离子水后90℃搅拌2h。(2) Preparation of electrolyte: Take 0.1M CuSO4 , 1M MnSO4 , 1M sulfuric acid, and 3g PVA, add 30 ml of deionized water, and stir at 90°C for 2 hours.
(3)电致变色器件的组装：同实施例1(3) Assembly of electrochromic device: same as Example 1
本实施例的器件可以在褪色态和着色态之间切换，着色态时可以实现对可见光波段(400-800nm)全部隔绝，展示了较宽范围的光调制，器件在460nm处得到最大透过率差值为90.3％。一般来说，在变色过程中将达到最大透过率变化的90％所需要的时间定义为着色响应时间和褪色响应时间。通过记录器件在特定电压条件下工作的透过率随时间变化，可以计算出器件的响应时间为着色时间19s，褪色时间121s。对本本实施例的器件的循环稳定性同样进行了测试，器件在初始状态和循环了10000次之后光调制能力无明显衰退，这说明了本本实施例的器件具有优良的循环稳定性。The device of this embodiment can switch between the faded state and the tinted state. In the tinted state, it can completely isolate the visible light band (400-800nm), demonstrating a wide range of light modulation. The device obtains the maximum transmittance at 460nm. The difference is 90.3%. Generally speaking, the time required to reach 90% of the maximum transmittance change during the discoloration process is defined as the coloring response time and fading response time. By recording the change in transmittance of the device over time when operating under specific voltage conditions, the response time of the device can be calculated as the coloring time of 19s and the fading time of 121s. The cycle stability of the device of this embodiment was also tested. There was no significant decline in the light modulation capability of the device in the initial state and after 10,000 cycles, which illustrates that the device of this embodiment has excellent cycle stability.
综上所述，本发明可以有效的提升电致变色器件的生产效率和良率、降低制作成本、提高电致变色效率和响应速度。To sum up, the present invention can effectively improve the production efficiency and yield of electrochromic devices, reduce production costs, and improve electrochromic efficiency and response speed.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的技术人员来说，在不脱离本发明构思的前提下，还可以做出若干等同替代或明显变型，而且性能或用途相同，都应当视为属于本发明的保护范围。The above content is a further detailed description of the present invention in combination with specific preferred embodiments, and it cannot be concluded that the specific implementation of the present invention is limited to these descriptions. For those skilled in the technical field to which the present invention belongs, several equivalent substitutions or obvious modifications can be made without departing from the concept of the present invention, and the same performance or use should be regarded as belonging to the protection scope of the present invention.
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| CN202310874857.5ACN116841094A (en) | 2023-07-17 | 2023-07-17 | An electrochromic device and its preparation method |
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| CN118778316A (en)* | 2024-06-26 | 2024-10-15 | 电子科技大学 | An electrolyte for zinc-based electrochromic devices |
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120243068A1 (en)* | 2011-03-25 | 2012-09-27 | J Touch Corporation | Electrochromic apparatus |
| CN104375350A (en)* | 2014-10-31 | 2015-02-25 | 合肥博一环保科技有限公司 | Multifunctional controllable electrochromic device and manufacturing method thereof |
| CN116047826A (en)* | 2023-02-06 | 2023-05-02 | 华南师范大学 | An all-liquid electrochromic device using heavy water as a solvent and its preparation method |
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| US20120243068A1 (en)* | 2011-03-25 | 2012-09-27 | J Touch Corporation | Electrochromic apparatus |
| CN104375350A (en)* | 2014-10-31 | 2015-02-25 | 合肥博一环保科技有限公司 | Multifunctional controllable electrochromic device and manufacturing method thereof |
| CN116047826A (en)* | 2023-02-06 | 2023-05-02 | 华南师范大学 | An all-liquid electrochromic device using heavy water as a solvent and its preparation method |
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| CN118778316A (en)* | 2024-06-26 | 2024-10-15 | 电子科技大学 | An electrolyte for zinc-based electrochromic devices |
| CN118778316B (en)* | 2024-06-26 | 2025-04-08 | 电子科技大学 | Electrolyte for zinc-based electrochromic device |
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