CN103688216A - 具有可见光区域透明性的红外调节电活化器件 - Google Patents

具有可见光区域透明性的红外调节电活化器件 Download PDF

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CN103688216A
CN103688216A CN201280032380.6A CN201280032380A CN103688216A CN 103688216 A CN103688216 A CN 103688216A CN 201280032380 A CN201280032380 A CN 201280032380A CN 103688216 A CN103688216 A CN 103688216A
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J·R·雷诺兹
A·L·戴尔
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Abstract

一种电致变色电池，其包含最小变色聚合物(MCCP)和非变色聚合物(NCCP)，其中中性态或氧化态在NIR区域中为高透射性，且氧化态或中性态在NIR区域内的透射率分别显著更低。一种电致变色器件(ECD)，其可包括所述电致变色电池或电致变色电池的组合。所述ECD可为窗户的一部分或者用于窗户的层压体以允许控制所述窗户的IR透射率。

Description

具有可见光区域透明性的红外调节电活化器件
相关申请的交叉引用
本申请要求于2011年6月30日提交的美国临时申请61/502,999的优先权，在此将其全文(包括任何附图、表格或图案)引入作为参考。
发明背景
在节能和温度调节领域中最令人感兴趣的是努力控制红外和热辐射通过建筑如家庭、办公建筑物、飞机和汽车的窗户的透射。用于该类窗户的目前技术通常基于低e玻璃和允许调节所选辐射的材料，包括电致变色、热致变色和光致变色的材料。最适于以主动控制方式进行的节能应用的是基于电致变色材料。这些窗户基于两个透明电极，其上涂覆有电致变色活性材料，其中电解质将所述涂覆的电致变色材料隔开。已开发的电致变色材料包括金属氧化物、小的有机分子和共轭聚合物。这些窗户不能独立于可见光区域调节而可调控制IR透射。
电致变色电池的操作原理与电池组类似，其中例如一个电致变色涂覆的电极为阳极且另一个起对电极，即阴极作用。最高对比度的电池包含位于阳极处的主动显色材料和位于阴极处的电荷平衡材料，其中所述电荷平衡材料显示出与所述显色材料互补的显色性能或者显示出很小或不显示出变色。通常当不对电致变色电池施加电压时，在可见光区域内吸收辐射且所述电池处于显色状态。当对所述电池施加正电压时，获得在可见光区域内具有高透射率的发白状态。
所述电池的操作需要互补性材料，其中一种被氧化且另一种被还原。现有技术的电致变色窗户具有相当高的可见光区域光调节性能，其中长波长(NIR和IR)光学变化最低，其中至少一种材料在器件操作期间总是具有高IR吸收性。因此存在大量可见光调节方式，其中所述窗户在显色和未显色状态之间切换，从而提供有限的私密性和眩光降低效果，但主动调节热辐射的能力低。图1显示了基于处于一个电极处的共轭聚合物电致变色材料(ECP-黑色)和处于对电极处的最小显色材料(MCCP)的典型电致变色器件的调节，其中所述器件在可见光区域内具有高对比度(在555nm处ΔT为40%)，但在NIR具有低对比度(ΔT在1200nm处为18%，在2000nm处为4.2%)。该材料配对导致当所述器件具有最低可见光透射率时具有最大的NIR辐射透射率，该行为与人们对窗户的期望——在温暖的日子调节阳光热量，而在寒冷的日子允许NIR辐射透过且在可见光调节不重要的夜晚进行热控制——相反。
因此，需要可调节IR辐射的器件，其用于建筑和交通工具包括建筑物、汽车和飞机的热量控制。通常在炎热的日子里，希望将室内冷却的成本降至最低。因此，希望具有低IR透射率的窗户。与此相反，在寒冷的日子里，有利的是提供具有高IR透射率的窗户以将室内加热的成本降至最低。因此，希望允许以很小或不具有可见光变化控制IR透射的电致变色电池。
简述
本发明的实施方案涉及用于以透过所述电池的可见光的很小变化控制IR透射的IR调节电致变色电池。所述电池包含最小变色聚合物(MCCP)，其在近IR和/或IR中的透射率变化超过20%(例如在由中性态变化至氧化态时)，但在可见光区域的变化小于15%。所述MCCP与至少一个电极电接触且与非变色聚合物(NCCP)电接触，所述NCPP与至少一个对电极电接触。所述NCCP在可见光、近IR或IR区域内在中性和氧化态之间切换时显示出很小的变化。所述MCCP可为聚(N-取代的亚烷基二氧吡咯)如聚(N-烷基取代的亚乙基二氧吡咯)、聚(N-烷基取代的亚丙基二氧吡咯)或其共聚物。所述NCCP可为在一些或全部重复单元中具有氧化还原活性2,2,6,6-四甲基哌啶-N-氧基(TEMPO)的聚合物。可将聚(2,2,6,6-四甲基哌啶氧基-4-基甲基丙烯酸酯)(PTMA)用作NCCP。
根据本发明的实施方案，电致变色器件(ECD)包括IR调节的电致变色电池。所述ECD可在单个电极上具有MCCP且在单个对电极上具有NCCP。在本发明的另一实施方案中，所述ECD包括两个连接的电致变色电池，其中两种MCCP位于两个阳极上且NCCP位于两个阳极之间的单个阴极之上或之内。所述单个阴极可为多孔性的，其中NCCP位于阴极的孔隙中或者位于阴极的一个或两个面上。所述ECD可为建筑物或交通工具的窗户且可为与窗户连接的层压体。
附图简介
图1显示了现有技术的黑色-至-透明变换电致变色器件在发白状态和显色状态下的透射率对波长的曲线，其中所述器件使用位于玻璃负载的ITO阳极之上的黑色至透射电致变色聚合物(ECP-黑色)和位于玻璃负载的ITO阴极之上的PProDOP-C18(MCCP)构建。
图2显示了用于本发明实施方案的电池中的位于ITO电极上的A)聚(N-十八烷基-亚丙基二氧吡咯)(PProDOP-N-C18)和B)聚(2,2,6,6-四甲基哌啶基氧基-4-基甲基丙烯酸酯)(PTMA)的喷涂-流延膜在中性和氧化电位下的百分透射率对波长的曲线。
图3显示了A)具有MCCP作为IR活性阳极电致变色材料和NCCP作为阴极材料的本发明实施方案的2电极电池；和B)在一对阳极上具有MCCP且在双面透射阴极上具有NCCP的本发明实施方案的3电极电致变色器件(ECD)。
图4显示了根据本发明实施方案的A)图3A所示的2电极电池和B)图3B所示的3电极电池在中性和氧化态下的MCCP(PProDOP-N-C18)阳极和NCCP(PTMA)阴极材料的复合光谱。
详细公开内容
本发明的实施方案涉及一种电致变色电池，其在中性和氧化态之间切换期间在可见光区域内的透射率相差很小(具有很小或者不具有可见光电致变色性)，但当在中性和氧化态之间切换时具有大的可调NIR和IR变化。本发明实施方案的电化学电池通过使用沉积在阳极上的IR电致变色的最小颜色变化聚合物(MCCP)的器件活性组分和沉积在所述电池的阴极上的非变色聚合物(NCCP)而获得该NIR和IR电致变色行为，所述NCCP在可见光和红外区域内均不具有活性。在本发明的实施方案中，所述MCCP为聚(N-取代的亚烷基二氧吡咯)。所述聚(N-取代的亚烷基二氧吡咯)可为聚(N-烷基二氧吡咯)，其中所述N-烷基可为被烷基、磺酸化物、芳基或腈官能团封端的C1-C30烷基。N-取代可为低聚醚或聚醚取代基，例如N-[(CH2CH2O)x-(CHCH3CH2O)y]nR，其中x和y独立地平均为0-20，n为1-20，且R为H、烷基、芳基、腈基或聚磺酸化物基团，其中所述聚磺酸化物基团为与碱金属或铵离子配对的离子，或者用C1-C20烷基烷基化。所述亚烷基二氧吡咯可为取代或未取代的亚乙基二氧吡咯、亚丙基二氧吡咯、亚丁基二氧吡咯或类似衍生物。所述NCCP可为具有氧化还原活性2,2,6,6-四甲基哌啶-N-氧基(TEMPO)的聚合物，例如聚降冰片烯、聚甲基丙烯酸酯、聚丙烯酰胺或聚交酯，尤其例如为聚(2,2,6,6-四甲基哌啶基氧基-4-基甲基丙烯酸酯)(PTMA)。
在本发明的示例性实施方案中，所述MCCP可为聚(N-十八烷基-亚丙基二氧吡咯)(PProDOP-N-C18)且所述NCCP可为PTMA。示例性电致变色电池的阳极显色MCCP的光谱电化学特性示于图2a中，其中在中性和氧化态之间具有很小的可见光区域调节效应(在555nm处ΔT为7.5%)，但在1600nm处的NIR内观察到34%的显著更大的差异。如图2b所示，所述NCCP，即PTMA在光谱的可见光或IR部分内不显示出光学调节性能。
在本发明的实施方案中，可将所述MCCP和NCCP组合在简单的2电极电致变色器件(ECD)中，如图3A对包含PProDOP-N-C18和PTMA的电池所示的那样。图2的中性和氧化光谱的求和表明ECD(如图3A所示)具有图4A所示的光谱特性，其中在1600nm处的NIR对比度为26%，且在555nm处的可见光区域具有10%的对比度。对该ECD而言，氧化状态下的可见光和NIR辐射的吸收大于中性状态下的吸收。
在本发明的另一实施方案中，可构建图3B所示的3电极电致变色器件以提高电池的对比度。所述3电极ECD具有两个MCCP(PProDOP-N-C18)涂覆的阳极，其与中间阴极连接，所述阴极在每一侧上均涂覆有NCCP(PTMA)。所述3电极ECD为通过使用共用对电极连接的两个2电极电致变色电池的光学等效物。从图4B可以看出，与图4A所示的单个2电极电致变色电池相比，以此方式提高了IR和NIR区域内的对比度，其中所述3电极器件在1600nm处的NIR对比度翻倍，达到52%，而在555nm处的对比度仅提高14%。
本发明实施方案的电致变色电池和器件包括至少一个位于阳极和阴极上的聚合物之间的电解质层。所述电解质层可为凝胶电解质、固体电解质或离子液体。在本发明的一个实施方案中，所述电解质层为凝胶电解质，如含有聚甲基丙烯酸甲酯和LiClO4盐的碳酸亚丙酯(PC)溶液。在本发明的另一实施方案中，所述电解质层为固态电解质。固态电解质包括极性聚合物主体，如聚氧化乙烯、聚氧化丙烯、甲氧基乙氧基乙氧基取代的聚磷腈、聚醚基聚氨酯和能溶解金属盐并得到离子传导性配合物的其他类似聚合物。典型的金属盐包括碱金属阳离子，包括Li+、Na+、K+和Cs+，其具有非亲核性的阴离子，包括但不限于四氟硼酸根、高氯酸根、三氟甲磺酸根和双(三氟甲磺酰基)酰亚胺。通常获得10-5-10-4S/cm的室温电导率，这对本发明的大多数应用场合而言是足够的。
在本发明的示例性实施方案中，与MCCP和NCCP接触的电极包含氧化铟锡(ITO)，如果ITO具有低表面电阻，则其限制了NIR和中IR区域中的透射率。如从图2所观察到的那样，尽管很小，但由于薄ITO电极的反射，NIR和IR区域内的透射率损失一些。
本发明实施方案的ECD可为窗户的一部分，其中一个或两个电极的基材可为具有高可见光和NIR光透射率的玻璃。所述ECD可为图3A所示的2电极器件或图3B所示的3电极器件。所述基材可为玻璃或塑料材料。在本发明的实施方案中，窗户可包括两个或多个ECD。在本发明的一个实施方案中，所述ECD为柔性层压体，其中电极的基材为柔性塑料。柔性塑料包括聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚苯硫醚(PPS)、聚碳酸酯(PC)、聚砜、聚醚砜、聚甲基丙烯酸甲酯(PMMA)、聚丁二烯、聚异戊二烯和/或聚硅氧烷。
应理解的是，本文所述的实例和实施方案仅出于示意性目的，且本领域技术人员在参照本文下能获得各种改变或变型的启示，所述改变或变型包含在本申请的主旨和范围之内。

Claims (15)

1.一种IR调节电致变色电池，其包含与至少一个电极接触的最小变色聚合物(MCCP)和与至少一个对电极接触的非变色聚合物(NCCP)，其中当从中性变化至氧化态时，所述MCCP在近IR和/或IR区域内的透射率变化超过20%，但在可见光区域内的变化小于15%，且其中所述NCCP在由中性变化至氧化态时，在可见光、近IR或IR区域内的透射率变化很小或不变化。
2.根据权利要求1的电致变色电池，其中所述MCCP为聚(N-取代的亚烷基二氧吡咯)。
3.根据权利要求2的电致变色电池，其中所述聚(N-取代的亚烷基二氧吡咯)为聚(N-烷基取代的亚乙基二氧吡咯)、聚(N-烷基取代的亚丙基二氧吡咯)或其共聚物。
4.根据权利要求2的电致变色电池，其中所述聚(N-取代的亚烷基二氧吡咯)为聚(N-十八烷基-亚丙基二氧吡咯)(PProDOP-N-C18)。
5.根据权利要求1的电致变色电池，其中所述NCCP为包含氧化还原活性2,2,6,6-四甲基哌啶-N-氧基(TEMPO)的聚合物。
6.根据权利要求5的电致变色电池，其中所述包含化还原活性2,2,6,6-四甲基哌啶-N-氧基(TEMPO)的聚合物为聚(2,2,6,6-四甲基哌啶基氧基-4-基甲基丙烯酸酯)(PTMA)。
7.一种电致变色器件(ECD)，其包括至少一个根据权利要求1的电致变色电池。
8.根据权利要求7的ECD，其中所述电致变色电池包含位于单个电极上的MCCP和位于单个对电极上的NCCP。
9.根据权利要求7的ECD，其中将两个电致变色电池连接，其包含位于两个电极上的两种MCCP和位于所述两个电极之间的单个对电极之上或之内的NCCP。
10.根据权利要求9的ECD，其中所述对电极为多孔性的且所述NCCP位于所述对电极的孔隙中和/或位于其一个或两个面上。
11.根据权利要求7的ECD，其中将两个电致变色电池连接，其包含位于两个电极上的两种NCCP和位于所述两个电极之间的单个对电极之上或之内的MCCP。
12.根据权利要求11的ECD，其中所述对电极为多孔性的且所述MCCP位于所述对电极的孔隙中和/或位于其一个或两个面上。
13.根据权利要求7的ECD，其中所述MCCP包括聚(N-烷基取代的亚烷基二氧吡咯)且所述NCCP包括PTMA。
14.根据权利要求7的ECD，其中所述器件为建筑物或交通工具的窗户。
15.根据权利要求7的ECD，其中所述器件为用于窗户的层压体。
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