WO2018023883A1 - 一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试及分析方法 - Google Patents

一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试及分析方法 Download PDF

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WO2018023883A1
WO2018023883A1 PCT/CN2016/102864 CN2016102864W WO2018023883A1 WO 2018023883 A1 WO2018023883 A1 WO 2018023883A1 CN 2016102864 W CN2016102864 W CN 2016102864W WO 2018023883 A1 WO2018023883 A1 WO 2018023883A1
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charge
electrochromic
film
cycle
ads
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严辉
周开岭
汪浩
张永哲
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Beijing University of Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4161—Systems measuring the voltage and using a constant current supply, e.g. chronopotentiometry
    • 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 
    • G02F1/13—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 liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1306—Details
    • G02F1/1309—Repairing; Testing
    • 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
    • G02F2203/00—Function characteristic
    • G02F2203/69—Arrangements or methods for testing or calibrating a device

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  • the invention relates to a test method for testing and analyzing the discoloration mechanism of electrochromic materials by using two-step chronograph analysis technology, and belongs to the field of functional material test and analysis technology.
  • the color-changing material refers to a material that can continuously and reversibly adjust the solar electromagnetic radiation under the influence of external conditions.
  • the discoloration can be divided into photochromism, thermochromism, electrochromism, gas-induced discoloration, and photochromism, among which The color-changing material is one of the hotspots of research in recent years.
  • Electrochromism refers to the phenomenon that the material produces a stable and reversible change in color under the action of an electric field.
  • the valence state and chemical composition will change, so that the reflection and transmission properties of the material change, and the reversible change in color and transparency in appearance properties.
  • the main features are as follows: (1) The injection and extraction of charge in the electrochromic material can be conveniently realized by changing the external voltage or current.
  • the amount of charge injected or extracted directly determines the degree of coloration of the material, and regulates the external voltage or The current can control the degree of coloration of the electrochromic material; (2) by changing the voltage
  • the polarity can be conveniently colored or achromatic; (3)
  • the colored material can maintain a colored state, that is, has a memory function, in the case of cutting off current without occurrence of redox reaction.
  • Electrochromic materials should meet the following technical requirements in practical applications: [1] good electrochemical redox reversibility; [2] short color response time; [3] high color sensitivity; [4] long cycle life; [5] Open circuit memory time is long; [6] good chemical stability.
  • the current research level is still far from the actual demand. This is mainly due to the serious degradation of the performance of the electrochromic film after repeated cycles. The number of cycles plays a decisive role in the application prospect of electrochromic materials.
  • the current characterization technique for electrochromism is mainly cyclic voltammetry to observe and compare the cycle performance of electrochromic thin films, but the mechanism analysis of film cycle attenuation is rare, which is mainly due to the limitations of test techniques.
  • Cyclic voltammetry CV curves can satisfy the researchers' evaluation of film charge storage capacity, cyclic reversibility, and electrochromic efficiency (CE). However, cyclic voltammetry cannot provide information on the mechanism of change in the film in the electrolyte of the electrochromic process. Secondly, the amount of charge involved in the color change process of the electrochromic thin film can be obtained by integrating the CV curve.
  • the response charge (Q) of the electrochemical reaction should include the Faraday charge (the process of the redox reaction occurring in the electrochromic film), the electric double layer charge and discharge charge (electrode) The electric double layer structure formed between the interface with the electrolyte) and the amount of charge consumed in the side reaction process in the electrolyte.
  • the amount of charge obtained by CV is usually attributed to the amount of charge consumed by the color change process, which creates a mistake in the mechanism of the electrochromic reaction process. The root cause comes from the limitations of test technology.
  • the invention uses a multi-cycle double-step chrono-coulomb method to test electrochromic thin film materials.
  • This technology can meet the researcher's need to evaluate the cyclic energy of electrochromic materials and achieve the same evaluation effect as cyclic voltammetry.
  • the technology can also provide the ion, electron transport properties and dynamic changes of the film during the electrochromic electrochemical process from the deep level of the mechanism, which facilitates the research and modification of the electrochromic properties of the film. .
  • the present invention employs an electrochemical workstation to test an electrochromic thin film by a multi-cycle two-step chrono coulometric technique to obtain a Q-t curve.
  • a method for testing cyclic stability of electrochromic materials based on multi-cycle two-step chrono-time analysis technology characterized in that electrochromic thin films are tested by multi-cycle two-step technique, and different cycle periods are calculated or measured respectively.
  • a method for testing and analyzing cyclic stability of electrochromic materials based on multi-cycle two-step chrono-time analysis technology characterized in that the electrochromic film is tested by a multi-cycle double step technique to color a certain period or Fading time
  • the total response charge Q is divided into three parts, namely, the pull charge Q f , the adsorption charge Q ads and the electric double layer charge Q dl .
  • the electrochemical reaction of electrochromic thin films was analyzed as follows: the charge consumed when the electrochromic thin film undergoes electrochemical reaction (ie, the response in the double-step hopping analysis technique)
  • the charge Q comes from three parts:
  • the electrochromic material undergoes a reversible redox reaction under the action of an electric field. Before and after the reaction, it exhibits different structural valence states, which have different absorption and reflection effects on light, so that the color of the material before and after the electric field is different from the macroscopic view. .
  • the charge consumed in this part is defined as the Faraday charge, expressed as Q f ;
  • any two different object contacts will generate an electric potential between the two phases. Since the interface between the working electrode and the electrolyte is energized, excess charge is generated and charge separation occurs, thereby forming an electric double layer and an electric field.
  • the charge and discharge phenomenon of the electric double layer capacitor occurs before and after the action, and the amount of charge involved in the charge and discharge process also constitutes a part of the response charge. This part of the charge is defined as the electric double layer capacitance charge, expressed as Q dl ;
  • the electrolyte active substance adsorbed on the surface of the electrochromic film will be electrolyzed, consuming a part of the charge;
  • the partial charge is recorded as Q ads on the active material adsorbed by the working electrode of the electrochromic thin film;
  • the response charge Q in the entire Q-t curve contains the following three aspects:
  • n is the amount of charge involved in the electrochemical process
  • F is the Faraday constant
  • A is the effective area of the electrochromic working electrode
  • ⁇ is the amount of electrolyte active substance adsorbed on the surface of the working electrode in the adsorption reaction
  • C is The concentration of the electrolyte active material
  • D is the diffusion coefficient of the active material
  • t is the response time
  • the instability of the film structure reduces the ion transport and the adsorption amount of the active material, which is mainly due to the reduction of the film pores. Small, structural damage, need to be modified from the material itself, without considering the conductivity of the film and the substrate.
  • the invention has the advantages that the invention can directly analyze the changes occurring in the film process, and obtain the root cause of the cycle performance, thereby solving the corresponding problem and having a good practical condition. application.
  • the surface morphology of the film and the compactness of the film structure, the rough and porous morphology and the loose structure facilitate the direct contact between the electrolyte and the working electrode, which is beneficial to the electrochemical reaction.
  • the transmission of ions in the process has a large effective area.
  • Fig. 1 is a structural view showing an electrochemical reaction apparatus for a photochromic thin film prepared by the present invention (a NiO electrochromic thin film is taken as an example).
  • Figure 2 shows the Q-t curve obtained by the NiO chronocoulomb method.
  • Figure 4 shows the Q f – cycle number and (Q dl +nFA ⁇ )-cycle number obtained by the NiO chrono-coulomb method.
  • the multi-cycle measurement of the film was carried out by the electrochemical workstation using the double-step chrono-coulomb method. As shown in Fig. 2, the entire phase from the initial stage to the complete decay during the 1500 cycles of the NiO electrochromic film was recorded. Qt data.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试及分析方法，属于功能材料测试分析技术的领域。通过多循环双阶跃技术对电致变色薄膜进行测试，经过分析分别得到抽出电荷量Qex与注入的电荷量Qin，通过两者的比值Qex/Qin能够直接得到薄膜循环的可逆性R＝Qex/Qin值，能够满足研究者对电致变色材料循环性能评估需求。该技术也可以从理论深层次水平将总响应电荷Q分成三个部分，即拉第电荷Qf、吸附电Qads与双电层电荷Qdl。通过比较多循环下Qf及Qdl+nFAΓ的变化情况，判断出反应体系中离子、电子的传输特性及薄膜循环稳定性的影响因素，便于对薄膜电致变色性能及循环寿命研究与改性。

Description

一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试及分析方法 技术领域
本发明涉及一种用双阶跃计时分析技术来测试与分析电致变色材料变色机理的测试方法，属于功能材料测试分析技术的领域。
背景技术
随着工业的迅速发展,能源短缺和环境污染已成为人类社会急需解决的关键问题。发达国家将大量能源应用于建筑物的温度调节,其中空调能耗占首位。因此,采取各种措施降低能耗逐渐成为人们的共识,例如以节能和舒适要求来调节太阳光谱的智能窗,在未来建筑物中有广阔的应用前景,受到了人们的广泛关注。许多物质在受热、光照、外加电场等外界作用时,其颜色会发生变化,即产生致色现象。致变色材料是指在外界条件作用下,能连续可逆的调节太阳电磁辐射的材料,致变色可分为光致变色、热致变色、电致变色、气致变色以及光电致变色等,其中电致变色材料是近年来研究的热点之一。
电致变色是指材料在电场作用下颜色产生稳定可逆变化的现象。当材料在电化学作用下发生电子与离子的注入与抽出时，其价态和化学组分将发生变化，从而使材料的反射与透射性能改变，在外观性能上表现为颜色及透明度的可逆变化。其主要特点如下:(1)电致变色材料中电荷的注入与抽出可以通过外界电压或电流的改变而方便地实现，注入或抽出电荷的多少直接决定了材料的致色程度，调节外界电压或电流可以控制电致变色材料的致色程度；(2)通过改变电压 的极性可以方便地实现着色或消色；(3)已着色的材料在切断电流而不发生氧化还原反应的情况下，可以保持着色状态，即具有记忆功能。电致变色薄膜的优异性能以及在节能方面的应用前景受到人们的普遍关注,符合未来智能材料的发展趋势。
电致变色材料在实际应用中应该满足以下技术要求：[1]良好的电化学氧化还原可逆性；[2]变色响应时间短；[3]变色灵敏度高；[4]循环寿命长；[5]开路记忆时间长；[6]化学稳定性好。然而当前的研究水平与实际需求仍然有很大的差距，这主要归结于电致变色薄膜在多次循环之后性能会发生严重衰减，循环次数对于电致变色材料的应用前景具有决定性的作用。众所周知，当前对于电致变色的表征技术主要是循环伏安法来观察和比较电致变色薄膜的循环性能，但是对于薄膜循环衰减性的机理分析少之又少，这主要归结于测试技术的局限性。。循环伏安法CV曲线能够满足研究者对于薄膜电荷存储能力，循环可逆性，电致变色效率(CE)的评估。但是，循环伏安技术无法提供关于电致变色过程电解液中薄膜所发生的变化机理等相关的信息。其次，通过对CV曲线求积分能够求出电致变色薄膜变色过程中所参与的电荷量。然而，根据电致变色电化学反应装置结构，电化学反应的响应电荷(Q)应该包括法拉第电荷(作用于薄膜电致变色所发生的氧化还原反应的过程)、双电层充电放电电荷(电极和电解液界面之间构成的双电层结构)、电解液中副反应过程的所消耗的电荷量。但是文献中通常将CV所得的电荷量完全归结于变色过程所消耗的电荷量，这对电致变色反应过程的机理产生了一种错误，错误的 根源来源于测试技术的局限性。因此，对测试技术的发展显得格外重要，这将帮助研究者正确的认识电致变色电化学反应过程中电荷反应情况，循环过程中薄膜衰减的根本原因，使得从机理入手，为提高电致变色薄膜的综合性能提供指导。
发明内容
本发明采用多循环双阶跃计时库伦法，对电致变色薄膜材料进行测试。该技术既能够满足研究者对电致变色材料循环性能量的评估需求，起到与循环伏安技术相同的评估效果。同时，该技术也可以从机理的深层次水平分别提供电致变色电化学过程中关于离子，电子传输属性及薄膜在循环过程中动态变化情况，便于对薄膜的电致变色性能进行研究与改性。
为实现这一目的，本发明采用电化学工作站通过多循环双阶跃计时库伦技术对电致变色薄膜进行测试得到Q-t曲线。
一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试方法，其特征在于，通过多循环双阶跃技术对电致变色薄膜进行测试，分别计算或测得不同循环周期的抽出电荷量Qex与注入的电荷量Qin，通过两者的比值Qex/Qin能够直接得到薄膜循环的可逆性R值R＝Qex/Qin，能够满足研究者对电致变色材料循环性能评估需求。从而可以在不需要CV的氧化还原峰的情况下对薄膜的可逆性进行直观的判断。
一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试分析方法，其特征在于，通过多循环双阶跃技术对电致变色薄 膜进行测试，将某一个周期之内着色或褪色时间总响应电荷Q分成三个部分，即拉第电荷Qf、吸附电Qads与双电层电荷Qdl。通过比较多循环下Qf及Qdl+nFAΓ的变化情况，判断出反应体系中离子、电子的传输特性及薄膜循环稳定性的影响因素，便于对薄膜的电致变色性能及循环寿命进行研究与改性。
为了进一步对探究电致变色薄膜循环性能的机理，对电致变色薄膜电化学反应进行分析如下：当电致变色薄膜进行电化学反应时，消耗的电荷(即双阶跃计时分析技术中的响应电荷Q)来源于三部分：
第一部分，电致变色材料在电场的作用下进行可逆的氧化还原反应，反应前后呈现不同的结构价态，对光的吸收、反射作用不同，从而从宏观上表现出电场作用前后材料的颜色不同。此部分所消耗的电荷定义为法拉第电荷，用Qf表示；
第二部分，任何两个不同的物相接触都会在两相间产生电势，由于工作电极与电解液之间界面在通电作用下会产生过剩的电荷、产生电荷分离，从而会形成双电层，电场的作用前后会产生双电层电容的充放电现象，充放电过程所参与的电荷量也构成了响应电荷中的一部分。此部分电荷定义为双电层电容电荷，用Qdl表示；
第三部分，当电极电压或电流大于电解液中活性物质的电解所需要的电压或者电流值，吸附在电致变色薄膜表面的电解液活性物质将发生电解，消耗一部分电荷；因为该部分反应发生在电致变色薄膜工作电极所吸附的活性物质上，该部分电荷记为Qads；
因此整个Q-t曲线中响应电荷Q包含以下三个方面：
Q＝Qf+Qads+Qdl            (1)
根据计时库仑法的基本原理能够求得：
Qads＝nFAΓ               (2)
Qf＝2nFAC(D/π)1/2t1/2             (3)
其中，n为电化学过程中参与电荷的数量，F为法拉第常数，A为电致变色工作电极的有效作用面积，Γ为参与吸附反应中吸附在工作电极表面电解液活性物质的量，C为电解液活性物质的浓度，D为活性物质的扩散系数，t为响应时间；
其中Q通过仪器检测到，实际Qf＝Q-Qads-Qdl。
比较等式(1)(2)(3)可知，通过对Q-t1/2作图能够得到以k＝2nFAC(D/π)1/2为斜率，Qads+Qdl为截距一条直线。因此，通过数学处理能够得到实际响应电荷中Qf，通过附图截距得到Qdl+nFAΓ的实际值。对一个特定的电致变色材料及电化学反应体系，法拉第电荷Qf与电极的有效面积A成正比；若所得实际10个循环周期之内Qf衰减超过60％，同时Qdl+nFAΓ的实际值衰减超过60％，则认为薄膜与衬底之间结合力差而脱落。
若相同的周期之内Qdl+nFAΓ的实际值衰减百分比大于Qf衰减百分比，则认为薄膜结构的不稳定性对离子传输及活性物质吸附性量的减小，这主要来源于薄膜孔洞的减小，结构破坏，需要从材料本身进行改性处理，而不需要考虑薄膜与衬底的导电性问题。
本发明的优点：本发明能直接分析出薄膜过程中所发生的变化，得出循环性能好坏的根本原因，从而解决相应问题，具有很好的实际 应用。影响电极有效面积A有两个方面的因素：1、薄膜的表面形貌与薄膜结构的致密程度，多空粗糙的形貌及疏松的结构有利于电解液与工作电极直接接触，利于电化学反应过程中离子的传输，有效面积较大。2、电极基底与电致变色薄膜的界面接触电阻，薄膜的导电性越好，薄膜与基底的结合性越好，电荷传输也有利，薄膜的有效面积也就越大。
附图说明
图1为本发明所制备致变色薄膜进行电化学反应装置的结构图(NiO电致变色薄膜为例)。
图2NiO计时库仑法所得到的Q-t曲线图
图3NiO计时库仑法所得到的R图
图4NiO计时库仑法所得到的Qf–循环次数与(Qdl+nFAΓ)-循环次数图
具体实施方式
下面结合附图和具体实施方式，进一步阐明本发明的实质性特点和显著优点，本发明决非仅局限于所陈述的实施例。
1).制备电致变色薄膜，然后与电解液、参比电极、对铂片电极组合成电致变色电化学反应体系。
2).用电化学工作站用双阶跃计时库伦法对薄膜进行多循环测量，记录电致变色薄膜多循环过程中由起始阶段到完全衰减的整个阶段的Q-t数据；
3).分析出Q-t数据中Qex与Qin的值，求出薄膜循环的可逆性R 值(R＝Qex/Qin)；
4).选取适当循环间隔的Q-t曲线，作Q-t1/2数学转换处理，求出对应循环次数下Q-t1/2直线的斜率及Q轴截距，分别对应Qf与Qdl+nFAΓ；
4).将所选循环次数下的Qf与Qdl+nFAΓ分别对循环次数进行作图处理得到Qf-循环次数与(Qdl+nFAΓ)-循环次数图；
5).将所得到的Qf及Qdl+nFAΓ随之循环次数的变化趋势及变化的先后及速率进行对比，分析出薄膜过程中所发生的变化机理，得出循环性能好坏的根本原因。
实施例1
多循环双节约技术在NiO电致变色薄膜中的应用
1).制备通过sol-gel法在ITO导电玻璃衬底上制备出NiO电致变色薄膜，然后与KOH电解液、Ag/AgCl参比电极、铂片电极作对电极组合成电致变色电化学反应体系。
2).用电化学工作站用双阶跃计时库伦法对薄膜进行多循环测量，如图2所示，记录了NiO电致变色薄膜1500个循环过程中由起始阶段到完全衰减的整个阶段的Q-t数据。
3).分析出Q-t数据中Qb与Qc的值，求出薄膜循环的可逆性R值(R＝Qex/Qin)如图3所示。能够发现，随着循环的进行薄膜的R值不断减小，说明该薄膜具有较差的循环性能。
4).每隔100个循环选取响应循环次数的Q-t曲线，作Q-t1/2数学转换处理，求出对应循环次数下Q-t1/2直线的斜率及Q轴截距，分 别对应Qf与Qdl+nFAΓ。
4).将所选循环次数下的Qf与Qdl+nFAΓ分别对循环次数进行作图处理得到Qf-Cycle number与(Qdl+nFAΓ)-Cycle numbe图，如图4所示。
5).将所得到的Qf及Qdl+nFAΓ随循环次数的变化趋势及变化的先后及速率进行对比，发现Qf及Qdl+nFAΓ同时随着循环次数的增加在第10次循环发生了迅速的衰减，根据等式(2)(3)，说明次数薄膜的有效面积A在短暂的循环之后发生了快速的衰减，这说明在基底与薄膜的结合处发生了瞬间的脱落导致薄膜的快速失效，而在实验过程中我们也很清楚地发现了薄膜在第10次循环时发生了脱落现象。这说明需要通过工艺来调节薄膜与衬底的结合程度，才能够增加薄膜的循环寿命。从图4可以看出来薄膜脱落，实际也是脱落的。

Claims (3)

  1. 一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性测试方法，其特征在于，通过多循环双阶跃技术对电致变色薄膜进行测试，分别计算或测得不同循环周期的抽出电荷量Qex与注入的电荷量Qin，通过两者的比值Qex/Qin能够直接得到薄膜循环的可逆性R值R＝Qex/Qin。
  2. 一种基于多循环双阶跃计时分析技术的电致变色材料循环稳定性分析方法，其特征在于，通过多循环双阶跃技术对电致变色薄膜进行测试，将某一个周期之内着色或褪色时间总响应电荷Q分成三个部分，即拉第电荷Qf、吸附电Qads与双电层电荷Qdl；通过比较多循环下Qf及Qdl+nFAΓ的变化情况，判断出反应体系中离子、电子的传输特性及薄膜循环稳定性的影响因素；
    第一部分，电致变色材料在电场的作用下进行可逆的氧化还原反应，反应前后呈现不同的结构价态，对光的吸收、反射作用不同，从而从宏观上表现出电场作用前后材料的颜色不同；此部分所消耗的电荷定义为法拉第电荷，用Qf表示；
    第二部分，任何两个不同的物相接触都会在两相间产生电势，由于工作电极与电解液之间界面在通电作用下会产生过剩的电荷、产生电荷分离，从而会形成双电层，电场的作用前后会产生双电层电容的充放电现象，充放电过程所参与的电荷量也构成了响应电荷中的一部分；此部分电荷定义为双电层电容电荷，用Qdl表示；
    第三部分，当电极电压或电流大于电解液中活性物质的电解所需要的电压或者电流值，吸附在电致变色薄膜表面的电解液活性物质将发生电解，消耗一部分电荷；因为该部分反应发生在电致变色薄膜工作电极所吸附的活性物质上，该部分电荷记为Qads。
  3. 按照权利要求2的方法，其特征在于，
    整个Q-t曲线中响应电荷Q包含以下三个方面：
    Q＝Qf+Qads+Qdl   (1)
    根据计时库仑法的基本原理求得：
    Qads＝nFAΓ   (2)
    Qf＝2nFAC(D/π)1/2t1/2   (3)
    其中，n为电化学过程中参与电荷的数量，F为法拉第常数，A为电致变色工作电极的有效作用面积，Γ为参与吸附反应中吸附在工作电极表面电解液活性物质的量，C为电解液活性物质的浓度，D为活性物质的扩散系数，t为响应时间；
    其中Q通过仪器检测到，实际Qf＝Q-Qads-Qdl；
    比较等式(1)(2)(3)，通过对Q-t1/2作图能够得到以k＝2nFAC(D/π)1/2为斜率，Qads+Qdl为截距一条直线；通过数学处理能够得到实际响应电荷中Qf，通过截距得到Qdl+nFAΓ的实际值；对一个特定的电致变色材料及电化学反应体系，法拉第电荷Qf与电极的有效面积A成正比；若所得实际10个循环周期之内Qf衰减超过60％，同时Qdl+nFAΓ的实际值衰减超过60％，则认为薄膜与衬底之间结合力差而脱落。
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