CN114967264A - An electrochromic gel and anti-glare smart glass - Google Patents

Abstract

Translated fromChinese

本发明公开了一种电致变色凝胶，由电致变色材料、离子存储材料、电解质、溶剂和凝胶材料在紫外光固化条件下形成；电致变色材料为紫精化合物；离子存储材料为空穴传输材料，离子存储材料与电致变色材料具有相同变色功能，且变色电压与电致变色材料相反；电解质为锂盐化合物或铵盐化合物；溶剂为碳酸酯类溶剂；凝胶材料是以单体MMA和光引发剂在交联剂作用下，通过紫外光聚合反应形成的交联型聚合物。相比较于现有技术中的全固态电致变色材料，具有较高的离子电导率、变色范围和响应速度，实现稳定性好、响应时间短的高性能防眩光智能玻璃。

The invention discloses an electrochromic gel, which is formed by an electrochromic material, an ion storage material, an electrolyte, a solvent and a gel material under ultraviolet light curing conditions; the electrochromic material is a viologen compound; the ion storage material is The hole transport material, the ion storage material and the electrochromic material have the same color changing function, and the color change voltage is opposite to that of the electrochromic material; the electrolyte is a lithium salt compound or an ammonium salt compound; the solvent is a carbonate solvent; the gel material is a It is a cross-linked polymer formed by the polymerization of monomer MMA and photoinitiator under the action of cross-linking agent by ultraviolet light. Compared with the all-solid-state electrochromic materials in the prior art, it has higher ionic conductivity, color change range and response speed, and realizes high-performance anti-glare smart glass with good stability and short response time.

Description

Translated fromChinese

一种电致变色凝胶和防眩光智能玻璃An electrochromic gel and anti-glare smart glass

技术领域technical field

本发明涉及电致变色材料与器件领域，尤其涉及一种电致变色凝胶和防眩光智能玻璃。The invention relates to the field of electrochromic materials and devices, in particular to an electrochromic gel and an anti-glare smart glass.

背景技术Background technique

电致变色是指材料的光学属性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，具有电致变色性能的材料成为电致变色材料。由电致变色材料所制备的器件具有用户可控制颜色变化的特点，在电致变色智能窗、智能防眩目后视镜、变色太阳镜等领域被广泛使用。Electrochromism refers to the phenomenon in which the optical properties of materials undergo stable and reversible color changes under the action of an external electric field, which manifests as reversible changes in color and transparency in appearance. Materials with electrochromic properties become electrochromic materials. Devices prepared from electrochromic materials have the feature of user-controllable color change, and are widely used in electrochromic smart windows, smart anti-glare rearview mirrors, and color-changing sunglasses.

现有的电致变色材料分别由WO₃和NiO充当电致变色层和离子存储层，然后在电致变色层和离子存储层中制备一层固态的电解质层，提供离子在电致变色层与离子存储层之间的传输提供通道，最终制备出“三明治”结构的全固态电致变色镜；这种全固态电致变色材料使用的电解质一般为固态锂盐，其存在离子电导率不高、变色范围差、器件响应速度慢等一系列问题。The existing electrochromic materials are composed_of WO and NiO as the electrochromic layer and the ion storage layer, respectively, and then a solid electrolyte layer is prepared in the electrochromic layer and the ion storage layer to provide ions between the electrochromic layer and the ion storage layer. The transmission between the ion storage layers provides a channel, and finally an all-solid-state electrochromic mirror with a "sandwich" structure is prepared; the electrolyte used in this all-solid-state electrochromic material is generally a solid-state lithium salt, which has low ionic conductivity, A series of problems such as poor discoloration range and slow device response speed.

为了解决上述问题，本发明提供了一种电致变色凝胶。In order to solve the above problems, the present invention provides an electrochromic gel.

发明内容SUMMARY OF THE INVENTION

本发明克服了现有技术的不足，提供一种电致变色凝胶和防眩光智能玻璃，旨在解决现有技术中的电致变色材料离子电导率不高、变色范围差、器件响应速度慢的问题。The invention overcomes the deficiencies of the prior art, provides an electrochromic gel and an anti-glare smart glass, and aims to solve the problems of low ionic conductivity, poor discoloration range and slow device response speed of electrochromic materials in the prior art The problem.

为达到上述目的，本发明采用的技术方案为：一种电致变色凝胶，其特征在于，由电致变色材料、离子存储材料、电解质和溶剂混合于凝胶材料制备形成；In order to achieve the above purpose, the technical solution adopted in the present invention is: an electrochromic gel, which is characterized in that it is prepared by mixing an electrochromic material, an ion storage material, an electrolyte and a solvent with the gel material;

所述电致变色材料为紫精化合物；The electrochromic material is a viologen compound;

所述离子存储材料为空穴传输材料，所述离子存储材料与所述电致变色材料具有相同变色功能，且变色电压与所述电致变色材料相反；The ion storage material is a hole transport material, the ion storage material has the same color changing function as the electrochromic material, and the color changing voltage is opposite to that of the electrochromic material;

所述电解质为锂盐化合物或铵盐化合物；The electrolyte is a lithium salt compound or an ammonium salt compound;

所述溶剂为碳酸酯类溶剂；The solvent is a carbonate solvent;

所述凝胶材料是以单体MMA和光引发剂在交联剂作用下，通过紫外光聚合反应形成的交联型聚合物。The gel material is a cross-linked polymer formed by the polymerization of monomer MMA and a photoinitiator under the action of a cross-linking agent by ultraviolet light.

本发明一个较佳实施例中，所述紫精化合物为乙基紫精二高氯酸盐、乙基紫精二高氯酸盐、苄基紫精二氯盐或苄基紫精二四氟硼酸盐中的一种。In a preferred embodiment of the present invention, the viologen compound is ethyl viologen diperchlorate, ethyl viologen diperchlorate, benzyl viologen dichloride or benzyl viologen ditetrafluoro A type of borate.

本发明一个较佳实施例中，所述离子存储材料为5,10-二甲基吩嗪、二茂铁或N,N,N',N'-四甲基对苯二胺中的一种。In a preferred embodiment of the present invention, the ion storage material is one of 5,10-dimethylphenazine, ferrocene or N,N,N',N'-tetramethyl-p-phenylenediamine .

本发明一个较佳实施例中，所述电解质为高氯酸锂、六氟磷酸锂、四丁基六氟磷酸铵或四丁基四氟硼酸铵中的一种。In a preferred embodiment of the present invention, the electrolyte is one of lithium perchlorate, lithium hexafluorophosphate, tetrabutylammonium hexafluorophosphate or tetrabutylammonium tetrafluoroborate.

本发明一个较佳实施例中，所述电致变色材料、离子存储材料、电解质、溶剂和凝胶材料的质量占比分别为：1～2％、0.5～1％、10～12％、80～85％、2～3％。In a preferred embodiment of the present invention, the mass proportions of the electrochromic material, ion storage material, electrolyte, solvent and gel material are respectively: 1-2%, 0.5-1%, 10-12%, 80% ~85%, 2~3%.

本发明一个较佳实施例中，所述电致变色材料、离子存储材料和电解质按照摩尔比例为1：1：10。In a preferred embodiment of the present invention, the electrochromic material, the ion storage material and the electrolyte are in a molar ratio of 1:1:10.

本发明一个较佳实施例中，每10g所述凝胶材料不少于0.05M电致变色材料。In a preferred embodiment of the present invention, every 10 g of the gel material is not less than 0.05M electrochromic material.

本发明一个较佳实施例中，所述电致变色材料和所述离子存储材料在电场作用下得失电子时所处的电位大小相等。In a preferred embodiment of the present invention, the electrochromic material and the ion storage material have equal potentials when they gain and lose electrons under the action of an electric field.

本发明一个较佳实施例中，所述苄基紫精二四氟硼酸盐的制备方法，包括以下步骤：In a preferred embodiment of the present invention, the preparation method of the benzyl viologen ditetrafluoroborate comprises the following steps:

S1、加入联吡啶和DMF溶液，搅拌后加入的苄氯，升温至75～80℃并反应12～24小时；其中，每摩尔的联吡啶对应DMF溶液为18～22L，每摩尔的联吡啶对应0.8～1.2摩尔的苄氯；S1, add bipyridine and DMF solution, the benzyl chloride added after stirring, be warmed up to 75～80 ℃ and react for 12～24 hours; Wherein, every mole of bipyridine corresponds to 18～22L of DMF solution, and every mole of bipyridine corresponds to 18～22L 0.8 to 1.2 moles of benzyl chloride;

S2、冷却到室温，将S1所得悬浮物进行减压抽滤，并用乙醚洗涤2～4次；将得到的产物干燥，得到淡黄色固体。S2. Cool to room temperature, filter the suspension obtained in S1 under reduced pressure, and wash with diethyl ether for 2 to 4 times; the obtained product is dried to obtain a light yellow solid.

S3、向S2中淡黄色固体中加入水，搅拌后加入四氟硼酸钠，溶液由淡黄色透明液体变为白色混浊状，在温度25～35℃下反应5～15天；联吡啶与四氟硼酸钠的质量比为1：3～5；S3, add water to the light yellow solid in S2, add sodium tetrafluoroborate after stirring, the solution changes from light yellow transparent liquid to white turbidity, and react at a temperature of 25 to 35 ° C for 5 to 15 days; bipyridine and tetrafluoroborate The mass ratio of sodium borate is 1:3～5;

S4、冷却到室温，将S3所得悬浮物进行减压抽滤，并用水洗涤2～4次；将得到的产物干燥，得到白色固体，即苄基紫精二四氟硼酸盐。S4, cooling to room temperature, performing vacuum suction filtration on the suspension obtained in S3, and washing with water for 2 to 4 times; drying the obtained product to obtain a white solid, namely benzyl viologen ditetrafluoroborate.

一种防眩光智能玻璃，包括两层导电玻璃，设置在所述两层导电玻璃之间的权利要求1-6中任一项所述的电致变色凝胶，以及与所述导电玻璃连接的电源。An anti-glare smart glass, comprising two layers of conductive glass, the electrochromic gel according to any one of claims 1-6 disposed between the two layers of conductive glass, and a power supply.

本发明提供了一种防眩光智能玻璃的制备方法，包括以下步骤：The invention provides a preparation method of anti-glare smart glass, comprising the following steps:

A1、将电致变色凝胶置于器皿中，将导电玻璃置于抽真空装置中，且导电玻璃之间预留的开口向下；A1. Place the electrochromic gel in a vessel, place the conductive glass in a vacuum device, and place the reserved opening between the conductive glass downwards;

A2、抽真空，控制玻璃下降至没入液面以下；向抽真空装置中充入工作气体，将器皿中的电致变色凝胶通过预留的开口压入两导电玻璃内部空间；A2. Vacuum, and control the glass to drop below the submerged liquid level; fill the vacuum device with working gas, and press the electrochromic gel in the vessel into the inner space of the two conductive glasses through the reserved opening;

A3、取出玻璃，用紫外光固化将预留的开口封住，形成防眩光智能玻璃。A3. Take out the glass and seal the reserved opening with UV light curing to form an anti-glare smart glass.

本发明解决了背景技术中存在的缺陷，本发明具备以下有益效果：The present invention solves the defects existing in the background technology, and the present invention has the following beneficial effects:

(1)本发明提供了一种电致变色凝胶，通过电致变色材料、离子存储材料、电解质、溶剂和凝胶材料配置形成特定浓度和比例的电致变色凝胶，相比较于现有技术中的全固态电致变色材料，具有较高的离子电导率、变色范围和响应速度，实现稳定性好、响应时间短的高性能防眩光智能玻璃。(1) The present invention provides an electrochromic gel, which can form an electrochromic gel with a specific concentration and ratio by configuring an electrochromic material, an ion storage material, an electrolyte, a solvent and a gel material. The all-solid-state electrochromic material in the technology has high ionic conductivity, color change range and response speed, and realizes high-performance anti-glare smart glass with good stability and short response time.

(2)本发明中的离子存储材料需要满足两个条件：1、离子存储材料选择具备相同变色功能的材料，但变色电压需与电致变色材料相反；使得在施加电压时，离子存储材料和电致变色材料同时着色或褪色，从而实现颜色的叠加，增大透过率调制窗口，增强器件的电致变色效果；2、要求具备较高的离子电导率和电子电导率，从而与电致变色材料相配合，保证防眩光智能玻璃具有较快的变色响应速度。3、电致变色材料和离子存储材料在电场作用下得失电子时所处的电位大小相等。(2) The ion storage material in the present invention needs to satisfy two conditions: 1. The ion storage material selects a material with the same color-changing function, but the color-changing voltage needs to be opposite to that of the electrochromic material; so that when a voltage is applied, the ion storage material and The electrochromic material is colored or faded at the same time, so as to realize the superposition of colors, increase the transmittance modulation window, and enhance the electrochromic effect of the device; 2. It is required to have high ionic conductivity and electronic conductivity, so as to be compatible with electrochromic The combination of color-changing materials ensures that the anti-glare smart glass has a faster color-changing response speed. 3. Electrochromic materials and ion storage materials have the same potential when they gain or lose electrons under the action of an electric field.

(3)本发明中制备形成的凝胶电解质，由交联型聚合物骨架和无机电解质组成，交联型聚合物中的羰基侧基可以与碳酸酯类溶剂有很强的相互作用，能够包容大量电解质，具有较高的粘度和离子导电率，并且不易发生挥发、爆炸、泄漏等安全隐患。(3) The gel electrolyte prepared in the present invention is composed of a cross-linked polymer skeleton and an inorganic electrolyte. The carbonyl side groups in the cross-linked polymer can have a strong interaction with carbonate solvents, and can accommodate A large number of electrolytes have high viscosity and ionic conductivity, and are not prone to safety hazards such as volatilization, explosion, and leakage.

附图说明Description of drawings

为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图；In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative work;

图1是本发明的优选实施例的苄基紫精二四氟硼酸盐的合成路径；Fig. 1 is the synthetic route of the benzyl viologen ditetrafluoroborate of the preferred embodiment of the present invention;

图2是本发明的优选实施例的分子4在碳酸丙烯酯的电压扫描图；Fig. 2 is the voltage sweep diagram of molecule 4 in propylene carbonate of the preferred embodiment of the present invention;

图3是本发明的优选实施例的电场作用下电致变色材料的分子结构转变过程图；Fig. 3 is the molecular structure transformation process diagram of the electrochromic material under the action of the electric field of the preferred embodiment of the present invention;

图4是本发明的优选实施例的电场作用下离子存储材料的分子结构转变过程图。FIG. 4 is a diagram of the molecular structure transition process of the ion storage material under the action of the electric field according to the preferred embodiment of the present invention.

具体实施方式Detailed ways

下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

本发明提供一种电致变色凝胶，由电致变色材料、离子存储材料、电解质、溶剂和凝胶材料在紫外光固化条件下形成。The invention provides an electrochromic gel, which is formed from electrochromic material, ion storage material, electrolyte, solvent and gel material under the condition of ultraviolet light curing.

本发明中溶剂为碳酸酯类溶剂，可以是碳酸丙烯酯。碳酸酯类溶剂作为一种胶黏剂，可以改善电解液的粘度；同时其沸点高达242℃，满足防眩光智能玻璃在实际使用中的耐热性需要；另外，碳酸酯类溶剂其是一种高导电性溶剂，锂盐、铵盐均易于溶解在此溶剂中，有利于离子的传输。In the present invention, the solvent is a carbonate-based solvent, which may be propylene carbonate. As an adhesive, carbonate solvent can improve the viscosity of electrolyte; at the same time, its boiling point is as high as 242℃, which meets the heat resistance requirements of anti-glare smart glass in practical use; in addition, carbonate solvent is a kind of High conductivity solvent, lithium salt and ammonium salt are easily dissolved in this solvent, which is beneficial to the transport of ions.

现有的电解质一般为固态电解质、液态电解质或凝胶电解质。固态电解质虽然不存在封装困难、易漏夜挥发等问题，但是其一般采用固态锂盐(LiNbO₃)作为电解质，存在的最大缺点就是离子电导率不高、器件响应速度慢等。液态电解质由于形状体积不固定，易导致变色不均匀、封装困难、易漏夜挥发、易爆炸等安全隐患。本发明中电解质材质鉴于上述碳酸酯类溶剂可以选择较好溶解度的锂盐和铵盐，如高氯酸锂、六氟磷酸锂、四丁基六氟磷酸铵、四丁基四氟硼酸铵等。本发明中优选使用高氯酸锂和四丁基四氟硼酸铵作为电解质。Existing electrolytes are generally solid electrolytes, liquid electrolytes or gel electrolytes. Although solid electrolytes do not have problems such as packaging difficulties and easy leakage and volatilization, they generally use solid lithium salts (LiNbO₃ ) as electrolytes. The biggest drawbacks are low ionic conductivity and slow device response. Liquid electrolytes are prone to safety hazards such as uneven discoloration, difficulty in packaging, easy leakage and volatilization, and easy explosion due to their unstable shape and volume. In the present invention, the electrolyte material can be selected from lithium salts and ammonium salts with better solubility in view of the above carbonate solvents, such as lithium perchlorate, lithium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, and the like. Lithium perchlorate and tetrabutylammonium tetrafluoroborate are preferably used as electrolytes in the present invention.

本发明中电致变色材料为紫精化合物，本发明中优选乙基紫精二高氯酸盐、乙基紫精二高氯酸盐、苄基紫精二氯盐或苄基紫精二四氟硼酸盐中的一种。In the present invention, the electrochromic material is a viologen compound, and in the present invention, ethyl viologen diperchlorate, ethyl viologen diperchlorate, benzyl viologen dichloride or benzyl viologen ditetrachloride are preferred One of the fluoroborates.

本发明中电致变色材料为紫精化合物。紫精类材料的电致变色机理为：当紫精在外加电场的作用下于电解液中发生两步还原反应，第一步是正二价联吡啶阳离子获得一个电子被还原为正一价自由基阳离子，第二步是该自由基再得到一个电子被还原为零价的中性态紫精。正二价的紫精几乎是无色的，中性态的紫精呈现出浅黄色，而自由基阳离子紫精由于光电子能够在整个联吡啶平面内转移，因此该状态的紫精具有极大的摩尔吸光系数，从而表现出较深的蓝紫色着色状态。当外加电场撤去时，被还原的自由基阳离子态紫精会与电解液中的物质进行电子交换而被氧化为正二价阳离子状态导致颜色消失。上述可逆过程即为紫精类材料的电致变色机理，可以看出紫精的电致变色过程中最重要的就是自由基阳离子的生成。In the present invention, the electrochromic material is a viologen compound. The electrochromic mechanism of viologen materials is as follows: when viologen undergoes a two-step reduction reaction in the electrolyte under the action of an external electric field, the first step is that the positive divalent bipyridine cation obtains an electron and is reduced to a positive monovalent radical. The second step is that the free radical gets an electron and is reduced to a neutral state viologen of zero valence. The positive divalent viologen is almost colorless, the neutral state viologen shows a light yellow color, and the free radical cation viologen can transfer photoelectrons in the entire bipyridine plane, so the viologen in this state has an extremely large molar Absorption coefficient, thus showing a darker blue-violet coloring state. When the applied electric field is removed, the reduced free radical cationic viologen will exchange electrons with the substances in the electrolyte and be oxidized to a positive divalent cation state, resulting in the disappearance of the color. The above reversible process is the electrochromic mechanism of viologen materials. It can be seen that the most important thing in the electrochromic process of viologen is the generation of free radical cations.

本发明中优选紫精化合物为乙基紫精二高氯酸盐、乙基紫精二高氯酸盐、苄基紫精二氯盐或苄基紫精二四氟硼酸盐中的一种。其中，本发明中的苄基紫精二四氟硼酸盐以吡啶阳离子为母体，合成如图1所示的分子4。其结构中的四氟硼酸根离子不仅与上述电解质中的阴离子保持一致，其体积还与联吡啶阳离子体积相接近，可以使其容易地溶解在碳酸丙烯酯溶剂中。In the present invention, the preferred viologen compound is one of ethyl viologen diperchlorate, ethyl viologen diperchlorate, benzyl viologen dichloride or benzyl viologen ditetrafluoroborate . Among them, the benzyl viologen ditetrafluoroborate in the present invention takes pyridine cation as the parent, and the molecule 4 shown in FIG. 1 is synthesized. The tetrafluoroborate ion in its structure is not only consistent with the anion in the above electrolyte, but also has a volume close to that of the bipyridine cation, which can be easily dissolved in propylene carbonate solvent.

苄基紫精二四氟硼酸盐(分子4)的合成步骤为：加入124.8g(0.8mol)联吡啶和16LDMF(N，N-二甲基甲酰胺)溶液，搅拌后加入的1.844L(16mol)的苄氯；升温至75～80℃，在此温度条件下反应12～24小时；反应完成后，冷却到室温；将所得悬浮物进行减压抽滤，并将得到的滤饼用乙醚洗涤2～4次；将得到的产物干燥，得到300g淡黄色固体，即分子3。向分子3中加入水，搅拌后加入500g四氟硼酸钠，溶液由淡黄色透明液体变为白色混浊状。在温度25～35℃下反应5～15天后，将所得悬浮物减压抽滤，并将得到的滤饼用水洗涤2～4次；将得到的产物干燥，得到白色固体，即分子4。产率86％。1H NMR(400MHz，CDCl3)，δ：7.41(dd，J＝10.3Hz，14H)，7.17(d，J＝7.2Hz，4H)，4.15(d，J＝7.1Hz，4H)。The synthesis step of benzyl viologen ditetrafluoroborate (molecule 4) is: adding 124.8g (0.8mol) bipyridine and 16LDMF (N,N-dimethylformamide) solution, adding 1.844L ( 16mol) of benzyl chloride; be warmed up to 75～80 ℃, react 12～24 hours under this temperature condition; After the reaction is completed, cool down to room temperature; Washed 2 to 4 times; the obtained product was dried to obtain 300 g of a pale yellow solid, namely molecule 3. Water was added to molecule 3, and after stirring, 500 g of sodium tetrafluoroborate was added, and the solution changed from light yellow transparent liquid to white turbidity. After reacting at a temperature of 25-35°C for 5-15 days, the obtained suspension was filtered under reduced pressure and the obtained filter cake was washed with water 2-4 times; the obtained product was dried to obtain a white solid, namely molecule 4. Yield 86%. 1H NMR (400 MHz, CDCl3), δ: 7.41 (dd, J=10.3 Hz, 14H), 7.17 (d, J=7.2 Hz, 4H), 4.15 (d, J=7.1 Hz, 4H).

本发明中的离子存储材料需要满足两个条件：1、离子存储材料选择具备相同变色功能的材料，但变色电压需与电致变色材料相反；2、要求具备较高的离子电导率和电子电导率，从而与电致变色材料相配合，保证防眩光智能玻璃具有较快的变色响应速度。3、电致变色材料和离子存储材料在电场作用下得失电子时所处的电位大小相等。The ion storage material in the present invention needs to meet two conditions: 1. The ion storage material is selected to have the same color-changing function, but the color-changing voltage needs to be opposite to that of the electrochromic material; 2. Higher ionic conductivity and electronic conductivity are required. rate, so as to cooperate with electrochromic materials to ensure that the anti-glare smart glass has a fast color change response speed. 3. Electrochromic materials and ion storage materials have the same potential when they gain or lose electrons under the action of an electric field.

由于电致变色材料为典型的n型有机半导体材料，电场作用下可以得到电子，而相对应的离子存储材料则一般为p型材料，电场作用下可以失去电子。Since electrochromic materials are typical n-type organic semiconductor materials, electrons can be obtained under the action of an electric field, while the corresponding ion storage materials are generally p-type materials, which can lose electrons under the action of an electric field.

如图3和图4所示，示出了在电场作用下电致变色材料和离子存储材料的分子结构转变过程。其中，电致变色材料由正离子得到电子变为中性物质时显示明显的颜色(由无色到墨绿色)，而离子存储材料由中性物质失去电子变为正离子时显示出明显的颜色(由无色到墨绿色)，因而其变色电压相反。As shown in Fig. 3 and Fig. 4, the molecular structure transition process of electrochromic material and ion storage material under the action of electric field is shown. Among them, electrochromic materials show obvious color (from colorless to dark green) when positive ions gain electrons and become neutral substances, while ion storage materials show obvious colors when they lose electrons from neutral substances and become positive ions (from colorless to dark green), so its color change voltage is opposite.

本发明中还提供一种电致变色材料和离子存储材料的确定方式：通过电化学测试确定电致变色材料和离子存储材料得失电子时所处的电位，通过比较找出电位大小相等或相接近的的电致变色材料和离子存储材料，即可组成阴极材料和阳极材料。The present invention also provides a method for determining the electrochromic material and the ion storage material: determine the potential at which the electrochromic material and the ion storage material gain or lose electrons through electrochemical testing, and find out the potentials are equal or close to each other through comparison. The electrochromic materials and ion storage materials can be composed of cathode materials and anode materials.

电场作用下，电致变色材料由正离子转变为电中性材料，为了防止体系中多余的阴离子在电场作用下做定向的移动，需要向体系中加入离子存储材料(电场作用下变为正离子)来稳定阴离子，从而提高体系的稳定性。Under the action of the electric field, the electrochromic material changes from positive ions to electrically neutral materials. In order to prevent the excess anions in the system from moving directionally under the action of the electric field, it is necessary to add ion storage materials to the system (they become positive ions under the action of the electric field). ) to stabilize the anion, thereby improving the stability of the system.

本发明离子存储材料为空穴传输材料，空穴传输材料的变色电压与电致变色材料相反。由于紫精的电致变色在电场作用下易得电子，所以离子存储材料应该选择为在相同电场条件下易失去电子的有机物。其中，本发明中的空穴传输材料为5,10-二甲基吩嗪、N,N,N',N'-四甲基对苯二胺、二茂铁等有机物中的一种。The ion storage material of the present invention is a hole transport material, and the color change voltage of the hole transport material is opposite to that of the electrochromic material. Since the electrochromism of viologen is easy to obtain electrons under the action of an electric field, the ion storage material should be selected as an organic substance that is easy to lose electrons under the same electric field condition. Wherein, the hole transport material in the present invention is one of organic substances such as 5,10-dimethylphenazine, N,N,N',N'-tetramethyl-p-phenylenediamine and ferrocene.

本发明中凝胶材料是以单体MMA和光引发剂在交联剂作用下，通过紫外光聚合反应形成的交联型聚合物。其中，交联型凝胶聚合物不仅可以与上述碳酸丙烯酯溶剂有很强的相互作用，还能够包容大量的电解质。甲基丙烯酸甲酯MMA具有原料丰富、易合成等优点。In the present invention, the gel material is a cross-linked polymer formed by the polymerization of the monomer MMA and the photoinitiator under the action of the cross-linking agent by ultraviolet light. Among them, the cross-linked gel polymer can not only have a strong interaction with the above-mentioned propylene carbonate solvent, but also can accommodate a large amount of electrolyte. Methyl methacrylate MMA has the advantages of abundant raw materials and easy synthesis.

本发明中交联型聚合物的制备过程由单体MMA、光引发剂(2-羟基-2-甲基-1-苯基丙酮，HMPP)、溶剂、交联剂(乙氧基化三羟甲基丙烷三丙烯酸酯，ETPTA)，通过紫外光聚合反应形成一种以化学键相互作用的网络结构。用上述方法合成的交联型聚合物(PMMA-ETPTA)由于聚甲基丙烯酸甲酯PMMA中的羰基侧基，可以与上述碳酸酯类溶剂有很强的相互作用，能够包容大量的液体电解质，具有对电极有较好的界面稳定性，和与电解液相容性好等特殊的优点。The preparation process of the cross-linked polymer in the present invention is composed of monomer MMA, photoinitiator (2-hydroxy-2-methyl-1-phenylacetone, HMPP), solvent, cross-linking agent (ethoxylated trihydroxyl) Methylpropane triacrylate, ETPTA), forms a network structure that interacts with chemical bonds by UV photopolymerization. The cross-linked polymer (PMMA-ETPTA) synthesized by the above method can have a strong interaction with the above-mentioned carbonate solvents due to the carbonyl side groups in polymethyl methacrylate PMMA, and can accommodate a large amount of liquid electrolytes, It has the special advantages of good interfacial stability to the electrode and good compatibility with the electrolyte.

实施例一Example 1

本实施例对上述提供的电致变色凝胶的配方选择，配制出多种浓度和比例的电致变色凝胶体系，如(电致变色材料：离子存储材料：电解质)/(溶剂+凝胶材料)＝(0.01M:0.01M:0.1M)/(80g+10g)、(电致变色材料：离子存储材料：电解质)/(溶剂+凝胶材料)＝(0.005M:0.005M:0.05M)/(80g+10g)、(电致变色材料：离子存储材料：电解质)/(溶剂+凝胶材料)＝(0.05M:0.05M:0.5M)/(80g+10g)。当电致变色材料浓度为0.01M和0.005M时，电场作用下其颜色只能从无色或浅绿或浅黄色转变为浅绿色，远远没有达到墨绿色的变色范围。本实施例中优选(电致变色材料：离子存储材料：电解质)/(溶剂+凝胶材料)＝(0.05M:0.05M:0.5M)/(80g+10g)，此时电场作用下其颜色从无色或浅绿或浅黄色转变为墨绿色。In this example, the formulation of the electrochromic gel provided above is selected, and electrochromic gel systems with various concentrations and ratios are prepared, such as (electrochromic material: ion storage material: electrolyte)/(solvent + gel) material)=(0.01M:0.01M:0.1M)/(80g+10g), (electrochromic material: ion storage material: electrolyte)/(solvent+gel material)=(0.005M:0.005M:0.05M )/(80g+10g), (electrochromic material: ion storage material: electrolyte)/(solvent+gel material)=(0.05M:0.05M:0.5M)/(80g+10g). When the concentration of electrochromic material is 0.01M and 0.005M, its color can only change from colorless or light green or light yellow to light green under the action of electric field, which is far from the color change range of dark green. In this embodiment, it is preferable that (electrochromic material: ion storage material: electrolyte)/(solvent+gel material)=(0.05M:0.05M:0.5M)/(80g+10g), at this time, its color under the action of electric field From colorless or light green or light yellow to dark green.

样品1Sample 1

本实施例中电致变色凝胶采用以下方法制备：将0.05M的乙基紫精二高氯酸盐、0.05M的5,10-二甲基吩嗪、0.5M的高氯酸锂混合，取80g碳酸丙烯酯和10gPMMA-ETPTA，搅拌加热后，形成溶解为均相的黏性液体。In this example, the electrochromic gel was prepared by the following method: mixing 0.05M ethyl viologen diperchlorate, 0.05M 5,10-dimethylphenazine, and 0.5M lithium perchlorate, Take 80g of propylene carbonate and 10g of PMMA-ETPTA, stir and heat to form a homogeneous viscous liquid.

样品2Sample 2

本实施例中电致变色凝胶采用以下方法制备：将0.05M的乙基紫精二高氯酸盐、0.05M的二茂铁、0.5M的高氯酸锂混合，取80g碳酸丙烯酯和10gPMMA-ETPTA，搅拌加热后，形成溶解为均相的黏性液体。In this example, the electrochromic gel was prepared by the following method: mixing 0.05M ethyl viologen diperchlorate, 0.05M ferrocene, and 0.5M lithium perchlorate, taking 80g of propylene carbonate and 10g PMMA-ETPTA, after stirring and heating, it forms a viscous liquid that dissolves into a homogeneous phase.

样品3Sample 3

本实施例中电致变色凝胶采用以下方法制备：将0.05M的乙基紫精二高氯酸盐、0.05M的N,N,N',N'-四甲基对苯二胺、0.5M的高氯酸锂混合，取80g碳酸丙烯酯和10gPMMA-ETPTA，搅拌加热后，形成溶解为均相的黏性液体。In this example, the electrochromic gel was prepared by the following method: 0.05M ethyl viologen diperchlorate, 0.05M N,N,N',N'-tetramethyl-p-phenylenediamine, 0.5M Mix M with lithium perchlorate, take 80g of propylene carbonate and 10g of PMMA-ETPTA, stir and heat to form a homogeneous viscous liquid.

样品4Sample 4

本实施例中电致变色凝胶采用以下方法制备：将0.05M的苄基紫精二氯盐、0.05M的5,10-二甲基吩嗪、0.5M的高氯酸锂混合，取80g碳酸丙烯酯和10gPMMA-ETPTA，搅拌加热后，形成溶解为均相的黏性液体。In this example, the electrochromic gel was prepared by the following method: mix 0.05M benzyl viologen dichloride, 0.05M 5,10-dimethylphenazine, and 0.5M lithium perchlorate, take 80 g Propylene carbonate and 10g PMMA-ETPTA, after stirring and heating, formed a viscous liquid that was dissolved into a homogeneous phase.

样品5Sample 5

本实施例中电致变色凝胶采用以下方法制备：将0.05M的苄基紫精二四氟硼酸盐、0.05M的5,10-二甲基吩嗪、0.5M的四丁基四氟硼酸铵混合，取80g碳酸丙烯酯和10gPMMA-ETPTA，搅拌加热后，形成溶解为均相的黏性液体。In this example, the electrochromic gel was prepared by the following method: 0.05M benzyl viologen ditetrafluoroborate, 0.05M 5,10-dimethylphenazine, 0.5M tetrabutyl tetrafluoroborate Ammonium borate is mixed, 80g of propylene carbonate and 10g of PMMA-ETPTA are taken, and after stirring and heating, a homogeneous viscous liquid is formed.

本实施例将两块长为Xcm，宽为Ycm的ITO(氧化铟锡)玻璃分别用肥皂水、丙酮、异丙醇超声清洗15分钟，然后烘干以备用。接着在其中一块ITO玻璃四周均匀的涂上一层固化剂(在ITO玻璃窄的一边留一个长度为1cm的开口)，然后将第二块ITO玻璃覆盖在第一块ITO玻璃上，并控制其厚度为Zcm，然后将其放置在烘箱中烘烤12小时，进而得到容积为XYZ的空间，此空间用于罐装上述电致变色凝胶。In this embodiment, two pieces of ITO (indium tin oxide) glass with a length of Xcm and a width of Ycm are respectively ultrasonically cleaned with soapy water, acetone and isopropanol for 15 minutes, and then dried for later use. Then apply a layer of curing agent evenly around one of the ITO glass (leaving an opening with a length of 1cm on the narrow side of the ITO glass), then cover the second piece of ITO glass on the first piece of ITO glass, and control its The thickness is Zcm, and then it is placed in an oven to bake for 12 hours, thereby obtaining a space with a volume of XYZ, which is used for canning the above electrochromic gel.

具体罐装的方法为：将上述样品1～5中制备的电致变色凝胶放置在器皿中，将玻璃挂置在一个可以抽真空的装置中，且预留的开口朝下。抽真空直至真空度为10^-6Pa，然后控制玻璃缓慢下降直至其没入液面以下；往腔体中冲入氮气，将器皿中的液体通过预留的开口压入玻璃内部空间。待电致变色凝胶完全充满玻璃内部空间后，取出玻璃，用光固化胶将预留的开口封住，形成对电致变色凝胶的罐装。紫外光固化不仅可以封住防眩光玻璃的封口，还可以将单体聚合成PMMA-ETPTA。The specific canning method is as follows: placing the electrochromic gel prepared in the above samples 1 to 5 in a vessel, and hanging the glass in a device that can be evacuated with the reserved opening facing down. Evacuate until the vacuum degree is 10^-6 Pa, and then control the glass to slowly descend until it is submerged below the liquid level; flush nitrogen into the cavity, and press the liquid in the vessel into the inner space of the glass through the reserved opening. After the electrochromic gel completely fills the inner space of the glass, the glass is taken out, and the reserved opening is sealed with light-curing glue to form a can for the electrochromic gel. UV curing not only seals the anti-glare glass, but also polymerizes the monomers into PMMA-ETPTA.

将上述罐装形成的玻璃外侧连接电源，形成防眩光智能玻璃。将样品1～5的防眩光智能玻璃施加1.2V电压，得到如下表中的变色范围。The outer side of the glass formed by the above canning is connected to a power source to form an anti-glare smart glass. Apply a voltage of 1.2V to the anti-glare smart glass of samples 1 to 5 to obtain the discoloration range in the following table.

表1样品1～5中电致变色凝胶的配置和变色范围Table 1 Configuration and discoloration range of electrochromic gels in samples 1 to 5

如上表1可知，N,N,N',N'-四甲基对苯二胺、二茂铁在氧化后呈现的颜色和上述分子4颜色存在差别，而5,10-二甲基吩嗪氧化后可以跟分子4呈现相同的颜色。由于本发明中离子存储材料最好是选择具备相同变色功能的材料，但变色电压需与电致变色材料相反。施加电压时，二者同时着色或褪色，从而实现颜色的叠加，增大透过率调制窗口，增强器件的电致变色效果。因此本实施例优选5,10-二甲基吩嗪充当离子存储材料。As can be seen from Table 1 above, the color of N,N,N',N'-tetramethyl-p-phenylenediamine and ferrocene after oxidation is different from the color of the above-mentioned molecule 4, while 5,10-dimethylphenazine After oxidation, it can show the same color as molecule 4. Since the ion storage material in the present invention is preferably a material with the same color changing function, the color changing voltage needs to be opposite to that of the electrochromic material. When a voltage is applied, the two are colored or faded at the same time, thereby realizing the superposition of colors, increasing the transmittance modulation window, and enhancing the electrochromic effect of the device. Therefore, in this embodiment, 5,10-dimethylphenazine is preferably used as the ion storage material.

将0.5M的高氯酸锂和四丁基四氟硼酸铵各自加入80g碳酸丙烯酯溶液中，发现高氯酸锂在常温条件下溶解相对困难，需要在100℃加热条件下约2小时才能溶解完成。而四丁基四氟硼酸铵在常温条件下可以在1分钟之内快速溶解完成，并且其电导率测试为5.53ms/cm。基于此，本实施例四丁基四氟硼酸铵将作为电解质添加到电致变色体系中。0.5M lithium perchlorate and tetrabutylammonium tetrafluoroborate were added to 80g propylene carbonate solution respectively. It was found that lithium perchlorate was relatively difficult to dissolve under normal temperature conditions, and it took about 2 hours to dissolve under 100 ℃ heating conditions. Finish. The tetrabutylammonium tetrafluoroborate can be rapidly dissolved within 1 minute under normal temperature conditions, and its conductivity test is 5.53ms/cm. Based on this, in this example, tetrabutylammonium tetrafluoroborate will be added to the electrochromic system as an electrolyte.

同时，经过测试发现，分子4在碳酸丙烯酯中的溶解度可以满足电致变色体系的应用。于是将分子4溶解在碳酸丙烯酯溶液中，进而测试了其电化学性能，如图2所示。分子4在负电压的扫描方向显示出两个明显的可逆峰，这主要是由于分子4中两个吡啶阳离子可以在不同的电压下得到一个电子所引起的，因此分子4是一个典型的还原性分子。并且随着还原时间的延长，电极处的物质有无色变为深绿色，即还原后的分子4为深绿色物质。因此，本实施例中优选苄基紫精二四氟硼酸盐作为电致变色凝胶的电致变色材料。At the same time, after testing, it was found that the solubility of molecule 4 in propylene carbonate can meet the application of electrochromic system. Then, molecule 4 was dissolved in propylene carbonate solution, and its electrochemical performance was tested, as shown in Figure 2. Molecular 4 shows two distinct reversible peaks in the scanning direction of negative voltage, which is mainly caused by the fact that two pyridinium cations in Molecular 4 can obtain one electron at different voltages, so Molecular 4 is a typical reducing molecular. And with the prolongation of the reduction time, the substance at the electrode changes from colorless to dark green, that is, the reduced molecule 4 is a dark green substance. Therefore, in this embodiment, benzyl viologen ditetrafluoroborate is preferred as the electrochromic material of the electrochromic gel.

本实施例对制备好的防眩光智能玻璃施加一个1.2V的电压，为了测试不同样品的变色时间，即从开始变化到稳定颜色所需的时间。发现防眩光智能玻璃由最初的颜色到各自的深色的变色时间为23s～73s，其中样品5由最初的无色透明状态变为墨绿色的变色时间甚至只需23s，远远快于对比1中大于90s的变色时间。因此，相对于现有技术中的全固态电致材料，本发明中提供的电致变色凝胶的变色范围更大，且响应更快。In this example, a voltage of 1.2V is applied to the prepared anti-glare smart glass, in order to test the discoloration time of different samples, that is, the time required from the beginning of the change to the stable color. It was found that the discoloration time of the anti-glare smart glass from the initial color to the respective dark color was 23s to 73s, and the discoloration time of the sample 5 from the initial colorless and transparent state to the dark green even only took 23s, which was much faster than that of the comparison 1. Medium discoloration time greater than 90s. Therefore, compared with the all-solid electro-materials in the prior art, the electrochromic gel provided in the present invention has a larger discoloration range and a faster response.

以上依据本发明的理想实施例为启示，通过上述的说明内容，相关人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定技术性范围。The ideal embodiments of the present invention are inspired by the above, and relevant persons can make various changes and modifications without departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, and the technical scope must be determined according to the scope of the claims.

Claims (10)

1. The electrochromic gel is characterized by being prepared by mixing an electrochromic material, an ion storage material, an electrolyte and a solvent in a gel material;

the electrochromic material is a viologen compound;

the ion storage material is a hole transport material, the ion storage material and the electrochromic material have the same color change function, and the color change voltage is opposite to that of the electrochromic material;

the electrolyte is a lithium salt compound or an ammonium salt compound;

the solvent is a carbonate solvent;

the gel material is a cross-linked polymer formed by ultraviolet photopolymerization reaction of a monomer MMA and a photoinitiator under the action of a cross-linking agent.

2. An electrochromic gel in accordance with claim 1, wherein: the viologen compound is one of ethyl viologen diperchlorate, benzyl viologen dichloride or benzyl viologen diperfluoroborate.

3. An electrochromic gel in accordance with claim 1, wherein: the ion storage material is one of 5, 10-dimethylphenazine, ferrocene or N, N, N ', N' -tetramethyl-p-phenylenediamine.

4. An electrochromic gel in accordance with claim 1, wherein: the electrolyte is one of lithium perchlorate, lithium hexafluorophosphate, tetrabutylammonium hexafluorophosphate or tetrabutylammonium tetrafluoroborate.

5. An electrochromic gel in accordance with claim 1, wherein: the electrochromic material, the ion storage material, the electrolyte, the solvent and the gel material are respectively in mass ratio as follows: 1-2%, 0.5-1%, 10-12%, 80-85%, 2-3%.

6. An electrochromic gel in accordance with claim 1, wherein: the electrochromic material, the ion storage material and the electrolyte are mixed according to a molar ratio of 1: 1: 10.

7. an electrochromic gel in accordance with claim 6, wherein: not less than 0.05M electrochromic material per 10g of said gel material.

8. An electrochromic gel in accordance with claim 1, wherein: the preparation method of the benzyl viologen ditetrafluoroborate comprises the following steps:

s1, adding bipyridyl and a DMF solution, stirring, adding benzyl chloride, heating to 75-80 ℃, and reacting for 12-24 hours;

s2, cooling to room temperature, carrying out vacuum filtration on the suspended substance obtained in the S1, and washing for 2-4 times by using ether; the resulting product was dried to give a pale yellow solid.

S3, adding water into the light yellow solid in the S2, stirring, adding sodium tetrafluoroborate, changing the solution from light yellow transparent liquid into white turbid liquid, and reacting for 5-15 days at the temperature of 25-35 ℃;

s4, cooling to room temperature, carrying out vacuum filtration on the suspended substance obtained in the S3, and washing with water for 2-4 times; the resulting product was dried to give a white solid, i.e., benzyl viologen ditetrafluoroborate.

9. An anti-glare smart glass comprising two layers of conductive glass, the electrochromic gel of any one of claims 1-8 disposed between the two layers of conductive glass, and a power source connected to the conductive glass.

10. The method for preparing the anti-glare intelligent glass according to claim 9, wherein the method comprises the following steps:

a1, placing the electrochromic gel in a vessel, placing the conductive glass in a vacuumizing device, and enabling an opening reserved between the conductive glass to face downwards;

a2, vacuumizing, and controlling the glass to fall below the liquid level; filling working gas into the vacuumizing device, and pressing electrochromic gel in the utensil into the inner spaces of the two conductive glasses through the reserved opening;

and A3, taking out the glass, and sealing the reserved opening by ultraviolet curing to form the anti-glare intelligent glass.

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