CN102099736A - 具有受控红外反射的电致变色设备 - Google Patents
具有受控红外反射的电致变色设备 Download PDFInfo
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Classifications
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- 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
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- G02F1/153—Constructional details
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
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Abstract
本发明涉及一种具有受控红外反射的电致变色设备，特别是可电控类型的电致变色设备，包括处于承载衬底（1a）和相对衬底（1b）之间的多层堆叠，该承载衬底在红外范围内透明。所述设备的特征在于该多层堆叠顺序地包括：a）形成第一电极的在红外范围内透明的金属网格（3）；b）电致变色功能系统（5），包括离子存储第一电致变色材料层（EC1）、至少一个具有电解功能的层（EL1，EL2），以及第二电致变色材料层（EC2）；c）形成第二电极的能够反射红外辐射的金属层（7）；和d）由热塑性聚合物制成的层压中间层（9）。
Description
技术领域
本发明涉及具有受控红外反射的电致变色设备，尤其意在形成可电控面板，特别是玻璃窗。
背景技术
已知能够反射红外范围中的光的玻璃窗。这样的玻璃窗已经在各种技术领域中得以应用。
因此特别地，所述玻璃窗可以被用作住所的窗户，从而例如确保根据建筑物的各个房间各自对太阳辐射的暴露而对这些房间进行热调节。
当然，所述玻璃窗可以在其它领域中使用，例如特别在航空领域中使用，以例如控制和调节经由航空器的各个窗户进入的红外辐射。
已知电致变色设备包括能够可逆且同时插入离子和电子的电致变色材料层，这些离子和电子的氧化状态对应于插入状态和喷射状态而在这些离子和电子经由适当电源提供时具有独特的颜色，这些状态中的一种比另一种状态具有更高的光透射。电致变色材料通常是基于钨氧化物，并且必须与诸如透明导电层的电子源相接触，并且与诸如离子导电电解液的离子（阳离子或阴离子）源相接触。已知也能够可逆插入阳离子的反电极必须关于电致变色材料层对称地与所述层相关联，从而在宏观上，该电解液看起来是单一的离子介质。所述反电极必须基于颜色为中性或者至少当电致变色层处于有色状态时透明或几乎无色的层。
由于钨氧化物是阴极电致变色材料，即其有色状态对应于最少状态，因此基于镍氧化物或铱氧化物的阳极电致变色材料通常被用于反电极。还提出了使用在所讨论的氧化状态中是光中性的材料，例如铈氧化物或者诸如电子导电聚合物（聚苯胺）或普鲁士蓝的有机材料。
目前，根据所使用的电解液，电致变色系统可以被分为两种类型。
在第一类型中，电解液由此可以处于聚合物或凝胶的形式，例如诸如欧洲专利EP0253713和EP0670346中所描述的质子导电聚合物，或者诸如专利EP0382623、EP0518754和EP0532408中所描述的锂离子导电聚合物。
在第二类型中，电解液也可以基于形成电绝缘的离子导体的矿物质层。这些电致变色系统由此被称作“全固态”系统。读者可以参见欧洲专利EP0867752和EP0831360。
其它类型的电致变色系统是已知的，尤其是例如被称作“全聚合物”电致变色系统的电致变色系统，在该“全聚合物”电致变色系统中两个导电层设置在多层堆叠的任一侧，所述多层堆叠包括阴极着色的聚合物、离子导电的电绝缘聚合物（特别是H+或Li+离子）和最后是阳极着色的聚合物（例如聚苯胺或聚吡咯）。
最后，在本发明的意义上，已知被称作“有源”系统的系统，这些系统将紫罗碱材料和电致变色材料相组合，例如具有顺序：导电电极/具有电致变色属性的矿物层或聚合物/具有紫罗碱属性的层（液体、凝胶或聚合物）/导电电极。
这些基于可逆插入材料的系统的优势尤其在于，这些系统使得可能在比紫罗碱系统更宽的波长范围内对吸收进行调节：它们不仅能够在可见范围，而且尤其能够在红外范围内可变地进行吸收，这能够给予它们有效的光学和/或热作用。
这些各种系统包括将一个或多个电化学有源层夹在中间的两个导电层。现在，当在这两个导电层之间产生电势差时，系统的透射/吸收状态通过该电势差的数值控制，所述透射/吸收状态也被称作系统的透明度水平。
当该系统形成希望被“可电控”的玻璃窗时，当然偏好这些导电层的透明度，以至于它们必须由在薄膜领域通常遇到的厚度范围之内既导电又透明的材料所制成。
通常采用掺有杂质的金属氧化物材料，例如掺有氟的锡氧化物（SnO2:F）或者掺有锡的铟氧化物（ITO），该金属氧化物材料可能热沉积到各种衬底上，尤其是通过诸如称作CVD的技术的高温分解而沉积到玻璃上，或者是通过尤其是使用真空喷射技术的冷沉积而沉积到各种衬底上。
然而，已经发现对于它们保持透明的厚度，基于这些材料的层在它们并非充分导电的情况下并未让人完全满意，从而当跨该系统的端子施加适当电压以便使得状态发生必要变化时，该系统的响应时间或切换时间有所增加，并伴有大表面状态的不均匀变化。
更具体地，在例如两个导电层基于掺有锡的铟氧化物（ITO）的情况下，基层或底层大约3至5Ω/平方的电阻系数在顶层的情况下由于其厚度较小而增加至60-70 Ω/平方。特别地，已知如果基层具有约500nm的厚度，则实质上由于多层堆叠中所生成的机械张力的原因，顶层自身仅具有约100nm的厚度。
正是顶层和底层之间的这种电阻系数差导致该设备的切换时间更慢，所述切换时间即该系统从其最为透明的状态切换到其最不透明的状态所需的时间。
所要理解的是，在大多数应用并且尤其在建筑和汽车的玻璃窗部分中，无论其为具有受控透明度还是具有受控反射的电致变色玻璃窗，用户都难以接受这样的缺陷，原因在于该用户希望有尽可能快速和统一的变化。
此外，在许多应用中，尤其是在系统为具有电控反射的红外系统的情况下，关键是要保护该系统免受该系统在其使用期间所暴露于的任何外部攻击，例如特别是诸如恶劣天气的环境攻击，或者诸如冲击或刮擦的机械攻击。
发明内容
本发明的目标是通过提出一种具有可电控红外反射的设备来克服这些各种缺陷，所述设备拥有大约为现有技术十分之一的快速切换时间，该设备在其有色状态和漂白状态之间具有明显的反射差异，此外，该设备被保护免于受到各种类型的外部攻击，在该设备使用期间存在所述设备暴露于所述外部攻击的风险。
因此，本发明的一个主题为一种具有受控红外反射的电致变色设备，特别是可电控类型的电致变色设备，包括处于承载衬底和相对衬底之间的多层堆叠，该承载衬底在红外范围内透明，其特征在于该多层堆叠顺序地包括：
a）形成第一电极的在红外范围内透明的金属网格；
b）电致变色功能系统，包括离子存储第一电致变色材料层、至少一个具有电解功能的层，以及第二电致变色材料层；
c）形成第二电极的能够反射红外辐射的金属层；和
d）由热塑聚合物制成的层压中间层。
优选地，所述衬底将基于蓝宝石，并且所述相对衬底将特别基于玻璃。此外，所述离子存储层优选地将基于铱氧化物。
可以为单层或多层类型的所述金属网格可以基于铝和/或铂和/或钯和/或铜和/或优选地金，和/或基于这些金属的合金，和/或基于钛氮化物。
在本发明的一个实施例中，所述具有电解功能的层将为双层类型，并且将特别基于钽氧化物或钨氧化物。
所述层压中间层可以基于聚乙烯醇缩丁醛（PVB）或乙烯乙烯基/醋酸盐，或者优选地基于聚氨酯（PU）。该层压中间层可以确保将电流送到电极的连接部件得到支持。
本发明的另一个主题是一种具有受控能量耗散的面板，该面板采用根据以上所提到特征之一的设备。
根据另一个方面，本发明的主题是使用如上所述的面板作为建筑玻璃窗、汽车玻璃窗、用于工业交通工具或铁路、海洋和航空公共交通工具、农业交通工具、建筑工地机器的玻璃窗、后视镜和其它镜片、用于图像获取设备的显示器和快门。
附图说明
以下将参考附图通过非限定示例对本发明的一个实施例进行描述，其中：
－图1是根据本发明的具有受控红外反射的电致变色设备的垂直横截面视图；
－图2是用于对所述设备进行密封的器件示例的垂直横截面的示意性视图；和
－图3是示出根据本发明的电致变色设备针对波长在3µm和5µm之间的亮度变化而在有色状态和漂白状态之间的反射变化的曲线。
具体实施方式
图1示出根据本发明的具有受控红外反射的电致变色设备，该电致变色设备尤其意在应用于生产需要对进入的热流量进行调节从而考虑每个窗户对太阳辐射的特定暴露的房间的窗户。
通常，这样的设备由多层堆叠所形成，所述多层堆叠在承载衬底1a和相对衬底1b之间包括在红外范围内透明的金属网格3、电致变色功能系统5、能够反射红外线的金属层7，以及用于对所述设备进行层压的热塑性聚合物片9。
更具体地，该设备由此包括：
－A）在红外范围内，在处于1和30µm之间的波长范围内透明的承载衬底1a，所述衬底尤其基于蓝宝石，但是也可以由硅、锗、锌硫化物、锌硒化物、镉碲化物（CdTe）、钙氟化物、钡氟化物、镁氟化物、对红外线透明的玻璃、或聚乙烯形成；
－B）所述金属网格3优选地由金制成，但是也可以特别由铝、铂、钯或铜制成。根据所讨论的红外光谱范围，该网格也可以基于金属合金或者可以为多层类型。该金属网格还将为所述设备提供电流供应功能；和
－C）所述电致变色功能系统5自身基于两个极端电致变色的电活化层EC1和EC2，在这两个电活化层之间设置有一个或多个具有电解功能的层ELn。
层EC1和EC2包括以下至少一个单独使用或混合使用的化合物：钨氧化物、铌氧化物、锡氧化物、铋氧化物、钒氧化物、镍氧化物、铱氧化物、锑氧化物、钽氧化物和/或附加的金属，例如钛、铼或钴，并且具有电解功能的层EL实际上可以通过组合至少一个基于以下材料的层而形成，所述材料从钽氧化物、钨氧化物、钼氧化物、锑氧化物、铌氧化物、铬氧化物、钴氧化物、钛氧化物、锡氧化物、镍氧化物和锌氧化物中选择，可选地与铝、锆、铝或硅形成合金，可选地与铝氮化物或硅氮化物形成合金，可选地与铝或硼、硼氮化物、铝氮化物或钒氧化物形成合金，可选地与铝或锡锌氧化物形成合金，这些氧化物中的至少一种可选地被氢化或氮化。
在本发明的当前实施例中，所述电致变色功能系统5由此包括：
－阳极电致变色材料的第一层EC1，由含水的铱氧化物IrOxHy所制成，厚度为70nm；
－具有电解功能的钨氧化物WO3第一层EL1，厚度为100nm；
－具有电解功能的含水钽第二层EL2，厚度为100nm；和
－基于钨氧化物HxWO3的阴极电致变色材料的第二层EC2，厚度为380nm；
－D）能够反射红外线的金属层7将在所述设备的工作光谱范围内进行优化。将特别基于金的该金属层由此也可以基于高度导电的金属氧化物，例如掺有铝或氟、掺有SnO2-ZnO、掺有铝、掺有铂、掺有钯或掺有铜的锌氧化物。根据本发明，该金属层提供两种功能，即红外辐射反射功能和给电致变色层的电流供应功能；和
－E）所述热塑性聚合物片9意在出于获得层压玻璃窗的目的而对所述设备进行层压。优选地，所述热塑性聚合物片9可以为聚氨酯（PU）片，但是也可以基于聚乙烯醇缩丁醛（PVB）或乙烯乙烯基/醋酸盐（EVA）。有利地，该聚合物片可以实现针对向电致变色层EC1和EC2提供电流的连接部件的支持功能。可选地，衬底1a的外表面将被涂以抗反射层12。
根据本发明，根据所述设备意在提供的结果，当然可以以各种方式配置电致变色功能系统5。
如图2所示，根据本发明的设备被提供以能够从外部和内部对该设备密封的器件，并且由此包括与两个衬底1a和1b的内表面相接触的第一外围密封11，该第一外围密封11被设计为作为针对外部化学攻击的屏障以及作为针对蒸汽形式的水的屏障。
所述设备还包括第二外围密封13，该第二外围密封13也与两个衬底1a和1b的内表面相接触并且位于第一密封11的外围上。其形成液态水无法渗透的屏障，并且提供了机械强化外围凹槽的器件，以防止薄的衬底在层压或连续处理操作期间出现破损。
本发明是特别有利的，原因在于其无需使用TCO，即用于向电致变色层提供电流的透明导电氧化物，该氧化物是一般电致变色设备切换速度低的原因。
根据本发明对玻璃窗进行的测量由此为具有3×3
cm2面积的玻璃窗获得1秒量级的切换时间，为30×30
cm2面积获得7秒量级的切换时间，而为1 m2面积获得50秒量级的切换时间。
此外，如图3所示，根据本发明的具有受控红外反射的电致变色设备的有色状态和漂白状态之间的反射变化是有效的，原因在于，该反射变化对于具有3nm和5nm之间波长的红外辐射约为15％。
Claims (11)
1. 一种具有受控红外反射的电致变色设备，特别是可电控类型的电致变色设备，包括处于承载衬底（1a）和相对衬底（1b）之间的多层堆叠，该承载衬底（1a）在红外范围内透明，其特征在于该多层堆叠顺序地包括：
a）形成第一电极的在红外范围内透明的金属网格（3），
b）电致变色功能系统（5），包括离子存储第一电致变色材料层（EC1）、至少一个具有电解功能的层（EL1，EL2），以及第二电致变色材料层（EC2），
c）形成第二电极的能够反射红外辐射的金属层（7），和
d）由热塑性聚合物制成的层压中间层（9），
e）衬底（1a）和相对衬底（1b）特别是包括蓝宝石或硅或锗或锌硫化物或锌硒化物或镉碲化物或钙氟化物，或者钡氟化物或镁氟化物，或者对红外线透明的玻璃，或者聚乙烯。
2. 如权利要求1所述的具有受控红外反射的电致变色设备，其特征在于所述衬底（1a）基于蓝宝石，并且所述相对衬底（1b）基于玻璃。
3. 如权利要求1所述的具有受控红外反射的电致变色设备，其特征在于所述金属网格（3）可以为单层或多层类型并且可以基于铝和/或铂和/或钯和/或铜和/或优选地金，和/或基于这些金属的合金，和/或基于钛氮化物。
4. 如之前任一项权利要求所述的具有受控红外反射的电致变色设备，其特征在于离子存储层（EC1）基于铱氧化物。
5. 如之前任一项权利要求所述的具有受控红外反射的电致变色设备，其特征在于具有电解功能的层为双层类型。
6. 如权利要求5所述的具有受控红外反射的电致变色设备，其特征在于电解层（EL1，EL2）基于钽氧化物和钨氧化物。
7. 如之前任一项权利要求所述的具有受控红外反射的电致变色设备，其特征在于所述层压中间层（9）基于聚乙烯醇缩丁醛（PVB）或乙烯乙烯基/醋酸盐，或者优选地基于聚氨酯（PU）。
8. 如之前任一项权利要求所述的具有受控红外反射的电致变色设备，其特征在于所述层压中间层（9）确保将电流送到电极（3，7）的连接部件得到支持。
9. 一种具有受控能量耗散的面板，其特征在于该面板使用如之前任一项权利要求所述的设备。
10. 如权利要求9所述的面板，其特征在于该面板由玻璃窗构成。
11. 如权利要求9和10之一所述的面板作为建筑玻璃窗、汽车玻璃窗、用于工业交通工具或铁路、海洋和航空公共交通工具、农业交通工具、建筑工地机器的玻璃窗、后视镜和其它镜片、用于图像获取设备的显示器和快门的使用。
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| ES (1) | ES2390819T3 (zh) |
| FR (1) | FR2934062B1 (zh) |
| WO (1) | WO2010007303A1 (zh) |
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2008
- 2008-07-17 FR FR0854865A patent/FR2934062B1/fr not_active Expired - Fee Related
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2009
- 2009-07-10 JP JP2011517969A patent/JP5711122B2/ja not_active Expired - Fee Related
- 2009-07-10 EA EA201170210A patent/EA019444B1/ru not_active IP Right Cessation
- 2009-07-10 WO PCT/FR2009/051392 patent/WO2010007303A1/fr active Application Filing
- 2009-07-10 DK DK09784514.3T patent/DK2307926T3/da active
- 2009-07-10 US US13/054,089 patent/US8102587B2/en not_active Expired - Fee Related
- 2009-07-10 CN CN2009801277907A patent/CN102099736B/zh not_active Expired - Fee Related
- 2009-07-10 EP EP09784514A patent/EP2307926B1/fr not_active Not-in-force
- 2009-07-10 ES ES09784514T patent/ES2390819T3/es active Active
- 2009-07-10 KR KR1020117000911A patent/KR20110043595A/ko not_active Application Discontinuation
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| CN108828867A (zh) * | 2018-06-29 | 2018-11-16 | 信利光电股份有限公司 | 一种电致变色后视镜及其制作方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| FR2934062A1 (fr) | 2010-01-22 |
| US8102587B2 (en) | 2012-01-24 |
| EP2307926A1 (fr) | 2011-04-13 |
| EA201170210A1 (ru) | 2011-06-30 |
| US20110181939A1 (en) | 2011-07-28 |
| ES2390819T3 (es) | 2012-11-16 |
| EP2307926B1 (fr) | 2012-07-04 |
| WO2010007303A1 (fr) | 2010-01-21 |
| DK2307926T3 (da) | 2012-10-08 |
| CN102099736B (zh) | 2013-07-17 |
| KR20110043595A (ko) | 2011-04-27 |
| JP2011528131A (ja) | 2011-11-10 |
| JP5711122B2 (ja) | 2015-04-30 |
| EA019444B1 (ru) | 2014-03-31 |
| FR2934062B1 (fr) | 2010-08-13 |
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