CN115477768A - 一种调光材料组合物及调光器件 - Google Patents
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Abstract
本发明涉及一种调光材料组合物及调光器件,所述组合物是一种包含MOFs纳米粒子、粘度调控剂及分散剂的悬浮液,所述调光材料组合物应用于调光器件有效解决了现有调光器件光学动态范围窄、响应速度慢、变色慢的技术问题。
Description
技术领域
本发明涉及调光材料组合物技术领域,尤其涉及一种调光材料组合物及调光器件。
背景技术
光阀是可以控制光透过性的装置。常见的光阀主要分为热致变色系统、光致变色系统及电致变色系统。其中电致变色系统进一步可分类为聚合物分散液晶系统(PDLC,如美国专利US3585381)、电化学变色系统(EC,如美国专利US9581877)及悬浮颗粒系统(SPD,如美国专利US6606185)。虽然上述技术已趋于成熟,如PDLC已经实现商业化,但当前的产品在透过率、经济效率(节能)、便捷操作性、可调性、成本等方面依然存在着不同程度的缺点,EC(电致变色)通过氧化还原反应实现变色调光,但响应速度较慢(~5min/m2),且玻璃尺寸越大,变色越慢,容易出现变色不均匀的现象。因此核心材料的开发对光阀领域的发展依然非常重要。
由于SPD调光技术不仅兼具EC和PDLC调光玻璃的优势,而且还具有组装结构简单、无极调光、瞬时变色、能耗小、制备成本低、产品安全可靠、可用基材范围广等特点,因此该技术理论上为最为理想的智能调光技术,市场前景极为广阔。在SPD中,其核心材料的必要条件是粒子具有不等轴形状。其次,这类材料需要在一定条件下能够形成胶体分散体系且具有高轴径比。因此,具有一维或者二维结构的纳米线、纳米棒、纳米带、纳米椎及纳米薄片是SPD核心材料形貌的首选。目前已经发现碳纳米管、石墨烯、TiO2纳米线)、V2O5纳米棒等材料可以作为SPD材料(Nanotechnology, 2014, 25, 415703;Optical Materials, 2015,46, 418-422;RSC Advance, 2013, 3, 10414-10419)。但由于这些无机材料由于存在组分单一、光学动态范围窄、稳定性不高等缺陷,导致实际的应用范围十分有限。
有机-金属框架(MOFs)是一类具有配位结构明确、大比表面积、高孔隙率、易修饰等特点的多孔性有机-无机杂化材料。由于这类材料结构中的金属离子和有机配体的可选择性广泛,形貌易控且结构容易修饰,金属配位节点可近似认为无机结构单元,因此这类材料在传感、光学、催化、气体存储与分离等方面具有巨大的应用潜力。
发明内容
本发明的目的在于提供一种调光材料组合物,所述调光材料组合物应用于SPD调光器件解决现有技术中调光器件光学动态范围窄、响应速度慢、变色慢的技术问题。
为实现上述目的,本申请提供了一种调光材料组合物,所述组合物是一种包含MOFs纳米粒子、粘度调控剂及分散剂的悬浮液,由于作为悬浮粒子的MOFs纳米粒子的稳定性高,比表面积大、高孔隙率、表面易修饰、结构形貌可控等特性,在一定条件下能够形成胶体分散体系,因此将其应用于调光器件可有效解决调光器件中存在的光透过率变化范围窄、响应速度慢的技术问题。
作为本申请的进一步改进,所述悬浮液中:
MOFs纳米粒子质量分数范围为 0.1%-50%,
粘度调控剂质量分数范围为 0.1%-20%,
分散剂质量分数范围为 30%-99.8%。
作为本申请的进一步改进,所述MOFs纳米粒子的微观形貌选自片状、棒状、线状中的一种或多种。
作为本申请的进一步改进,所述MOFs纳米粒子微观形貌棒状的轴径比范围为4-100。
作为本申请的进一步改进,所述MOFs纳米粒子中金属离子选自Mg2+、Ca2+、Co2+、Fe2 +、Zn2+、Mn2+、Ni2+、Cd2+、Cu2+、Co3+、Al3+、Fe3+、Mn3+、Cr3+、Zr4+、Ti4+中的一种或多种,但不仅仅限于上述金属离子。
作为本申请的进一步改进,所述MOFs纳米粒子的中有机配体选自卟啉衍生物、共轭苯衍生物及吡嗪衍生物中的一种或多种,但不仅仅限于上述有机配体。
作为本申请的进一步改进,所述卟啉衍生物选自四(4-羧基苯基)卟啉(TCPP)、四(4-羟基苯基)卟啉、四氨基酞菁、四羧酸基酞菁中的一种或多种。
作为本申请的进一步改进,所述共轭苯衍生物选自对苯二甲酸、均苯三甲酸、4,4'-联苯二甲酸的一种或多种。
作为本申请的进一步改进,所述吡嗪衍生物选自2,5-吡嗪二羧酸、2,3-吡嗪二羧酸、2,6-吡嗪二羧酸的一种或多种。
作为本申请的进一步改进,所述粘度调控剂选自纤维素酯、聚丙烯酸酯中的一种或多种。
作为本申请的进一步改进,所述纤维素酯选自为硝化纤维素、醋酸纤维素、丙酸纤维素、醋酸丁酯纤维素的一种或多种。
作为本申请的进一步改进,所述聚丙烯酸酯选自聚甲基丙烯酸甲酯、聚甲基丙烯酸异丁酯(PMMA)、聚甲基丙烯酸乙酯的一种或多种。
作为本申请的进一步改进,所述分散液选自PDMS(聚二甲基硅氧烷)、DOA(己二酸二辛酯)、DOS(癸二酸二辛酯)、DINP(邻苯二甲酸二异壬酯)、DOP(邻苯二甲酸二辛酯)、BBP(邻苯二甲酸丁基苄酯)、DOTP(对苯二甲酸二辛酯)、TOTM(偏苯三酸三异辛酯)、D13P(邻苯二甲酸双十三酯)中的一种或多种,但不仅仅限于上述分散液。
为实现上述目的,本申请还提供了一种调光器件,所述调光器件包括第一透明导电层、第二透明导电层以及位于所述第一透明导电层和所述第二透明导电层之间的调光材料层,所述调光材料层包含上述调光材料组合物。
作为本申请的进一步改进,所述第一透明导电层与所述第二透明导电层之间的间隙范围为1μm-100μm。
作为本申请的进一步改进,所述第一透明导电层及所述第二透明导电层为透明导电层。
作为本申请的进一步改进,所述第一透明导电层远离所述调光材料层的一侧设置有第一透明基板,所述第二透明导电层远离所述调光材料层的一侧设置有第二透明基板。
本申请提供的调光材料组合物,所述组合物是一种包含MOFs纳米粒子、粘度调控剂及分散剂的悬浮液,本申请还提供了包含上述调光材料组合物的调光器件。本发明提供的悬浮液应用于调光器件的接通状态比断开状态具有更宽的光学动态范围,且响应速度快。
附图说明
图1为一实施例调光器件;
图2为一实施例调光器件;
图3为一实施例通电前,MOFs无序排列,器件呈现着色态;
图4为一实施例通电后,MOFs有序排列,器件呈现透明态;
图5 为预备例2 MOFs材料扫描电镜图;
图6为预备例2 MOFs材料XRD图;
图7为预备例6 MOFs材料扫描电镜图;
图8为预备例6 MOFs材料XRD图;
图中:1、调光材料层;2、第一透明导电层;3、第二透明导电层;4、第一透明基板;5、第二透明基板;6、MOFs纳米粒子。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚,下面将结合本申请具体实施例及附图对本申请技术方案进行清楚、完整地描述。显然,所描述的实施例仅是本申请一部分实施例,而不是全部的实施例,不用来限制本发明的范围。基于本申请中的实施例,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,都属于本申请保护的范围。
为制备光学动态范围宽、响应速度快的调光器件,本申请提供一种调光材料组合物,所述组合物是一种包含MOFs纳米粒子、粘度调控剂及分散剂的悬浮液。作为本申请优选的实施例,所述悬浮液中MOFs纳米粒子质量分数范围为0.1%-50%,当MOFs纳米粒子质量分数低于0.1%,暗态的透过率越大,但透明态的透过率不等值上升,当MOFs纳米粒子质量分数大于50%,暗态的透过率越小,同时透明态的透过率同样也会变小。粘度调控剂质量分数范围为 0.1%-20%,所述粘度调控其主要作用是增加材料的分散性,降低材料团聚,添加不同的粘度控制剂需要添加不同的量,粘度太小,响应速度快,但材料很容易沉降,因此一定要选择添加高于某一限度的量方能得到相应的悬浮液;粘度过大,则响应很慢。分散剂质量分数范围为30%-99.8%,所述分散剂主要作用是分散MOFs粒子和溶解粘度调控剂。作为本申请的优选实施例所述MOFs纳米粒子的轴径比范围为4-100。作为本申请优选的实施例所述MOFs纳米粒子中金属离子选自Zn2+、Cu2+、Ni2+,Co3+、Zr4+,但不仅仅限于上述金属离子。作为本申请的优选实施例所述MOFs纳米粒子的中有机配体选自四(4-羧基苯基)卟啉(TCPP)、对苯二甲酸及2,5-吡嗪二羧酸,但不仅仅限于上述有机配体。
为制备光学动态范围宽,响应速度快的调光器件,本申请提供了一种包含上述所述的调光材料组合物的调光材料层及包含所述调光材料层的调光器件,作为本申请的优选实施例,所述调光器件包括第一透明导电层、第二透明导电层以及位于所述第一透明导电层和所述第二透明导电层之间的上述所述调光材料层,所述第一透明导电层远离所述调光材料层的一侧设置有第一透明基板,所述第二透明导电层远离所述调光材料层的一侧设置有第二透明基板。所述第一透明导电层与所述第二透明导电层之间的间隙范围为1μm-100μm,1μm以下的盒子预留空间太小,影响悬浮粒子的自由旋转和粒子的单位浓度,导致暗态的透光率变高,动态范围变窄;间隙过大则不仅会增加驱动电压,同时器件在制作工艺、体系暗态到透明态的动态范围以及雾度等方面均为受到影响。
本申请还提供了一系列优选的MOFs纳米粒子的制备方法,如下:
预备例1:
将2.4mg的硝酸铜,40μL三氟乙酸及10mgPVP溶解在9mL的DMF中,加入3mL乙醇,搅匀后逐滴加入3mL四(4-羧基苯基)卟啉的DMF溶液。随后将混合溶液放入高压反应釜中,80℃反应4小时。反应产物用乙醇洗涤,最终离心得到的MOFs材料Ⅰ为Cu-TCPP纳米片。
预备例2:
将0.35 g ZrCl4,0.5 g 2,5-吡嗪二羧酸溶解在30 mL DMF中,充分溶解,随后将溶液置于50 mL水热反应釜中,120℃反应12 h。反应产物用DMF洗涤,最终离心得到的MOFs材料Ⅱ为Zr-H2PzDC纳米片。微观形貌如图5所示的扫描电镜图,图6为其相应的XRD图。
预备例3:
将0.75mmol的对苯二甲酸溶解到32mL的DMF中,加入2mL乙醇及2mL超纯水。随后加入0.75mmol的氯化镍,完全溶解后加入0.8mL的三乙胺,搅拌得到均一溶胶状悬浮液。随后将悬浮液在40kHz环境下超声反应8小时,得到的固体用水和乙醇分别洗涤5次,离心得到绿色的MOFs材料Ⅲ为Ni-BDC纳米片。
预备例4:
将0.75mmol的对苯二甲酸溶解到32mL的DMF中,加入2mL乙醇及2mL超纯水。随后加入0.5mmol的氯化镍及0.25mmmol的硝酸钴,完全溶解后加入0.8mL的三乙胺,搅拌得到均一溶胶状悬浮液。随后将悬浮液在40kHz环境下超声反应8小时,得到的固体用水和乙醇分别洗涤5次,离心得到墨绿色的MOFs材料Ⅳ为Ni/Co-BDC纳米片。
预备例5:
将0.35 g ZnI2,0.75 g I2,0.5 g 2,5-吡嗪二羧酸溶解在30 mL DMF中,充分溶解,随后将溶液置于50 mL水热反应釜中,180℃反应12 h。反应产物用DMF洗涤,最终离心得到的MOFs材料Ⅴ为Zn-H2PzDC纳米片。
预备例6:
将0.35 g ZrCl4,0.75 g I2,0.49 g KI,0.3 g PVP溶解在30 mL DMF中,充分溶解,随后将溶液置于100 mL三口瓶中,150℃回流反应12 h。反应产物用DMF洗涤,最终离心得到的MOFs材料Ⅵ为Zr/I2-H2PzDC纳米棒,纳米棒的长径比最大为100,最小为4,平均值为38。微观形貌如图7所示的扫描电镜图,图8为其相应的XRD图。
实施例1-8:
将预备例1-6中的MOFs纳米粒子分散在含有粘度调控剂的分散液中,然后将分散液封装入第一透明导电层及第二透明导电层之间形成调光材料层,在所述第一透明导电层远离调光材料层一侧还设置有第一透明基板,在所述第二透明导电层远离调光材料层一侧还设置有第二透明基板制成调光器件,具体调光材料组合物的组分质量分数及包含上述调光材料组合物的调光器件测试结果见表1。
对比例1:
将二氧化钛纳米线(TiO2,商业品)的分散在含有粘度调控剂的分散液中,然后将分散液封装入第一透明导电层及第二透明导电层之间形成调光材料层,所述第一透明导电层远离调光材料层一侧还设置有第一透明基板,在所述第二透明导电层远离调光材料层一侧还设置有第二透明基板制成调光器件。组分含量及测试结果见表1。
对比例2-4
将预备例6分散在含有粘度调控剂的分散液中,然后将分散液封装入第一透明导电层及第二透明导电层之间形成调光材料层,所述第一透明导电层远离调光材料层一侧还设置有第一透明基板,在所述第二透明导电层远离调光材料层一侧还设置有第二透明基板制成调光器件。测试结果见表1。
表1
由上述实施例及对比例可知MOFs以外的材料,效果差,光学动态范围窄,当MOFs纳米粒子质量分数低于0.1%,暗态的透过率越大,但透明态的透过率不等值上升,当MOFs纳米粒子质量分数大于50%,暗态的透过率越小,同时透明态的透过率同样也会变小。粘度调控剂质量分数范围为0.1%-20%,所述粘度调控其主要作用是增加材料的分散性,降低材料团聚,添加不同的粘度控制剂需要添加不同的量,粘度太小,响应速度快,但材料很容易沉降,粘度太大响应时间慢。本发明提供的悬浮液应用于调光器件的接通状态比断开状态具有更宽的光学动态范围,且响应速度快。
虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施方式中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明,它们并非用以限制本发明的保护范围,凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。
Claims (17)
1.一种调光材料组合物,其特征在于,所述组合物是一种包含MOFs纳米粒子、粘度调控剂及分散剂的悬浮液。
2.根据权利要求1所述调光材料组合物,其特征在于,所述悬浮液中:
MOFs纳米粒子质量分数范围为 0.1%-50%,
粘度调控剂质量分数范围为 0.1%-20%,
分散剂质量分数范围为 30%-99.8%。
3.根据权利要求1所述的调光材料组合物,其特征在于,所述MOFs纳米粒子的微观形貌选自片状、棒状、线状中的一种或多种。
4.根据权利要求3所述的调光材料组合物,其特征在于,所述MOFs纳米粒子微观形貌棒状的轴径比范围为4-100。
5.根据权利要求1所述的调光材料组合物,其特征在于,所述MOFs纳米粒子中金属离子选自Mg2+、Ca2+、Co2+、Fe2+、Zn2+、Mn2+、Ni2+、Cd2+、Cu2+、Co3+、Al3+、Fe3+、Mn3+、Cr3+、Zr4+、Ti4+中的一种或多种。
6.根据权利要求1所述的调光材料组合物,其特征在于,所述MOFs纳米粒子的中有机配体选自卟啉衍生物、共轭苯衍生物及吡嗪衍生物中的一种或多种。
7.根据权利要求6所述的调光材料组合物,其特征在于,所述卟啉衍生物选自四(4-羧基苯基)卟啉(TCPP)、四(4-羟基苯基)卟啉、四氨基酞菁、四羧酸基酞菁中的一种或多种。
8.根据权利要求6所述的调光材料组合物,其特征在于,所述共轭苯衍生物选自对苯二甲酸、均苯三甲酸、4,4'-联苯二甲酸的一种或多种。
9.根据权利要求6所述的调光材料组合物,其特征在于,所述吡嗪衍生物选自2,5-吡嗪二羧酸、2,3-吡嗪二羧酸、2,6-吡嗪二羧酸的一种或多种。
10.根据权利要求1所述的调光材料组合物,其特征在于,所述粘度调控剂选自纤维素酯、聚丙烯酸酯中的一种或多种。
11.根据权利要求10所述的调光材料组合物,其特征在于,所述纤维素酯选自为硝化纤维素、醋酸纤维素、丙酸纤维素、醋酸丁酯纤维素的一种或多种。
12.根据权利要求10所述的调光材料组合物,其特征在于,所述聚丙烯酸酯选自聚甲基丙烯酸甲酯、聚甲基丙烯酸异丁酯、聚甲基丙烯酸乙酯的一种或多种。
13.根据权利要求1所述的调光材料组合物,其特征在于,所述分散液选自PDMS、DOA、DOS、DINP、DOP、BBP、DOTP、TOTM、D13P中的一种或多种。
14.一种调光器件,所述调光器件包括第一透明导电层、第二透明导电层以及位于所述第一透明导电层和所述第二透明导电层之间的调光材料层,其特征在于,所述调光材料层包含权利要求1-13任一项所述的调光材料组合物。
15.根据权利要求14所述的调光器件,其特征在于,所述第一透明导电层与所述第二透明导电层之间的间隙范围为1μm-100μm。
16.根据权利要求14所述的调光器件,其特征在于,所述第一透明导电层及所述第二透明导电层为透明导电层。
17.根据权利要求14所述的调光器件,其特征在于,所述第一透明导电层远离所述调光材料层的一侧设置有第一透明基板,所述第二透明导电层远离所述调光材料层的一侧设置有第二透明基板。
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