CN107533950B - 用于生产电工薄层的室温方法及按照所述方法获得的薄层序列 - Google Patents

用于生产电工薄层的室温方法及按照所述方法获得的薄层序列 Download PDF

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CN107533950B
CN107533950B CN201680023159.2A CN201680023159A CN107533950B CN 107533950 B CN107533950 B CN 107533950B CN 201680023159 A CN201680023159 A CN 201680023159A CN 107533950 B CN107533950 B CN 107533950B
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帕特里克·林德
丹尼尔·林德
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Abstract

根据现有技术的方法总是要求在升高的温度下的烧结步骤，并且这被认为是有问题的。另外，有问题的是柔性薄层(特别是PV层)往往不能经受这样的温度，并且此外不允许利用工业废热和/或长波光子。这个问题可以使用以下方法解决，其中在固化过程中的另外的反应加速并改进固化。在特别有利的实施例中，具有在其中提供有连续金属颗粒和在上层中的碱溶性硅氧烷部分和金属颗粒的塑料基质的双层序列允许通过在碱溶解期间的组合最终固化来生产可以光伏利用工业废热/长波IR辐射的PV层序列。积极开发工业废热/热/体热在许多领域中提供了明显的、经济上可行的优势。

Description

用于生产电工薄层的室温方法及按照所述方法获得的薄层 序列
技术领域
本发明可以总体上被分类在电工薄层领域。该技术领域在涉及诸位发明人的DE10 2015 102 801中有用地概述。可以从本申请和在此引用的现有技术识别出已知的措施、特征和方法。总体而言，已知所讨论的具有微米范围厚度并且可以在可移动的可折叠的并且可弯曲的载体上灵活地携带的类型的层。因此，AT 36002 E(巴斯夫公司(BASF Corp.)的公开号0 119 051 B2)披露了合适的丙烯酸酯基涂层，其可以用作柔性基材的覆盖物。由本文件可辨识出用于生产这些层的典型的成分、特性和措施。
背景技术
本发明涉及用于生产电工薄层、特别是电工PV层序列的方法。
PV层序列长期以来一直是研究和开发的主题。适当焊接包装并且接触并且还安排在用于大面积发电的太阳能工厂户外的单晶和多晶Si电池是相关技术领域中已确立的产品实例。问题是这些传统电池是刚性的，而且相当非柔性的。在面上延伸的板必须始终在水平面中朝向太阳的位置定向，以确保最佳产率。提供从导电层和开关层通过PV层到覆盖层和保护层携带运送电工薄层的柔性薄层***在这里开始起作用。本申请人在该特定领域是活跃的，并且本申请要求一种用于生产此类层和层复合物的方法以及根据该方法获得的层序列。
所讨论类型的层和PV层序列的保护层和导电层自然是导电和/或柔性的。例如在DE 198 15 291 B4和其中引用的现有技术中披露了适当的导电层和保护层。
所建立的PV导电层和用于生产此类PV层复合物的方法在DE 199 46 712 A1中披露。缺点是存在的溶剂和烧结反应性物质要求150℃或更高的温度以便能够在最终的热固结期间被完全去除；在实际的产品实例中，在此最终的热固结是在450℃下进行的。
鉴于这些问题，EP 2 119 747 B1提出了进行可以通过高反应性金属纳米颗粒在约100℃下烧结以提供不间断的导体轨道的银组合物。然而，即使这种措施不能使得可能在基材上生产电工薄层、特别是PV层序列，而无需烧结步骤：始终必需的是将印刷的薄层加热至约100℃(在示例性实施例中130℃)的烧结温度。
因而，通过本发明解决的问题是克服现有技术的缺点并且提供一种方法以及根据该方法的一种电工薄层，该方法尽管工业过程方案和大的表面积制造可以在不加热至烧结温度下提供是固体的、稳定的并且在其电工技术特性上几乎100％可逆的薄层。
该问题的解决方案根据本文所述的特征实现。由以下描述可识别出有利的实施例。
发明内容
根据本发明，用于生产电工的薄层的室温方法(其中以分散体在面上提供导电和/或半导体的无机附聚物并且硬化以提供层)提供了在室温下进行硬化，并且通过暴露于至少一种试剂加速硬化。
一种根据该方法获得并且作为PV层序列获得的电工薄层序列的特征在于，该薄层序列包括玻璃载体，包括施加在该玻璃载体顶上的电极层，包括施加在该电极层顶上的第一层，该第一层包含塑料基质中的铝颗粒，包括施加在该第一层顶上的第二层，该第二层包含作为至少部分碱性的玻璃状层的在玻璃状网络中的至少硅-氧桥，并且还包含作为无机附聚物的至少部分碱溶解的铝颗粒，包括施加在该第二层顶上并具有接触电极的透明覆盖电极，其中进而如此制备的PV层序列在长波和极长波长红外范围内表现出光伏效应。
根据本发明，用于生产电工的薄层的室温方法(其中以分散体在面上提供导电和/或半导体的无机附聚物并且硬化以提供一个层)的特征在于在室温下进行硬化，并且通过暴露于至少一种试剂加速硬化。
优选地，该方法的特征在于，形成PV层序列。
优选地，该方法的特征在于，施加作为至少一个基层的包含至少一种金属或金属化合物的层，其中该至少一种金属或其化合物选自下组，该组由以下项组成：钢、锌、锡、银、铜、铝、镍、铅、铁。
优选地，该方法的特征在于，施加并且至少部分硬化作为导电基层的至少一个金属导电和/或半导体层。
优选地，该方法的特征在于，作为载体，使用在面上延伸的材料网，该材料网由至少一种选自以下材料组的材料组成，该组由以下项组成：玻璃、塑料、聚碳酸酯、塑料膜、金属合金、电机块合金、换热器管合金、换热器合金、换热器焊接合金、陶瓷、工业陶瓷、天然石、大理石、粘土陶瓷、屋顶瓦陶瓷、层压木材、地板材料、铝、楼梯铝合金、印刷电路板复合物、集成电路外壳材料、处理器外壳化合物。
优选地，该方法的特征在于，第一层的无机附聚物是分布在塑料基质中的金属或金属化合物，这些金属或金属化合物的金属类型选自下组，该组由以下项组成：铍、硼铝、镓、铟、硅、锗、锡、铅、砷、锑、硒、碲、铜、银、金、锌、铁、铬、锰、钛、锆。
优选地，该方法的特征在于，第二层的无机附聚物是被安排分布在至少部分无机基质中的金属或金属化合物，其中这些金属或金属化合物的金属类型选自下组，该组由以下项组成：铍、硼铝、镓、铟、硅、锗、锡、铅、砷、锑、硒、碲、铜、银、金、锌、铁、铬、锰、钛、锆。
优选地，该方法的特征在于，在作为无机基质的层中，使用包含作为该玻璃状氧化基质的至少一种链形成或改性元件的基质，该元件选自下组，该组由以下项组成：硼、磷、硅、砷、硫、硒、碲、无定形形式的碳、石墨改性的碳、碳纳米管形式的碳、多壁碳纳米管形式的碳、巴明敏斯特(Buckminster)富勒烯形式的碳、钙、钠、铝、铅、镁、钡、钾、锰、锌、锡、锑、铈、锆、钛、锶、镧、钍、钇、氟、氯、溴、碘。
优选地，该方法的特征在于
-将导电电极层施加在载体顶上，
-将分布在塑料基质中的金属或金属化合物作为第一层中的无机附聚物施加在电极层顶上，
-将至少部分强碱性或强酸性氧化基质中的无机金属附聚物的第二层施加在第一层顶上，其中
-在施加和硬化期间，这些金属附聚物与该强酸性或碱性基质反应，其中该基质还进而与该第一层的金属附聚物反应，
-在硬化和反应期间，形成光伏活性结，
-该第二层设置有透明覆盖电极和/或接触电极，并且
-适当地接触该光伏活性层序列并且焊接包装为PV层序列。
附图说明
附图参照原则草图展示了：
图1，包含在顶面上的塑料基质的PV双层的SEM平面图，该塑料基质包含硅氧烷部分以及被携带并且部分溶解在其中的Al片，该PV双层被施加并且硬化在包含相同Al片的纯的预硬化的塑料基质的顶上；
图2，根据图1的SEM图像的放大部分；
图3，根据图1和2的PV双层的底面的SEM图像；
图4a，由PV双层测量光伏分接(tappable)电位，其可以仅由围绕PV双层放置的热水产生，作为从46℃降至31℃的水/电池的温度的函数，表明起始值、变化和相应的最终值；
图4b，作为根据所提供的现有技术的波长的函数的在空气中的H2O的光吸收最大值，用于阐明图4a所示的行为。
具体实施方式
在有利的实施例中，通过根据本发明的方法作为PV层序列获得的电工薄层序列的特征在于，该薄层序列
-包括玻璃载体，
-包括施加在该玻璃载体顶上的电极层，该电极层包括银，
-包括施加在该电极层顶上的第一层，该第一层包含塑料基质中的铝颗粒，
-包括施加在该第一层顶上的第二层，该第二层包含作为至少部分碱性的玻璃状层的在玻璃状网络中的至少硅-氧桥，并且还包含作为无机附聚物的至少部分碱溶解的铝颗粒，
-包括施加在该第二层顶上并具有接触电极的透明覆盖电极，其中进而
-如此制备的PV层序列在长波和极长波长红外范围内表现出光伏效应。
在另一个有利的实施例中，将用于外部区域的丙烯酸酯基涂漆与铝片(用于具有银外观的涂漆的涂漆工业的颜料添加)混合，均化，并且将第一层沉积在具有约10cm×10cm的面积的玻璃载体上，该载体预先用半透明的导电金属层涂覆。将包含铝片的丙烯酸酯基层在空气中在室温下预硬化5分钟。随后，将相同的丙烯酸酯基涂漆的第二混合物用铝片制备，与二氧化硅溶胶混合，并且在冷却的搅拌器中用氢氧化钠水溶液调节至碱性pH并且均化。将仍反应的混合物作为第二层施加在第一预硬化层顶上，并且均匀且覆盖地分布。其中铝至少部分溶解的平行反应加速了两层的最终硬化。由此获得的层复合物在其顶面上设置有由来自Busch的室温导电银制成的指状电极。如图1所示，在扫描电子显微镜图像(SEM)中，由此获得的其顶面上的层的特征在于其中碱溶解的水玻璃提供硅氧烷部分的塑料基质。在该基质中携带的Al片溶解并且牢固地整合到塑料基质中。如图2所传授的，这些Al片通过塑料层到达表面，并允许由通过接触点和短电解质桥导电地互连的Al片制成的支架的直接电接触。使用手术刀分离塑料双层的柔性部分显示出该双层作为柔性的固体的可去除的复合物存在；通过SEM在其底面上测试所去除的部分。如图3在SEM图像中所示出的，在底面上也存在Al片，并且与半透明电极的相界面面接触并允许电接触。
该双层的顶面设置有由来自Busch的室温导电银制成的指状电极，并且与透明粘附地可结合的ITO膜补充地面接触。随后，将覆盖电极和底面电极接触，并研究电池的PV活性。最初通过具有可见光的冷光LED光源研究该双层的PV活性。光伏电流是弱至不存在的。在1至4秒的短预热阶段后用卤素灯照射时，测量超过100mV的明显的光伏电位差异。有可能使用恒定负载来操作LED自行车灯。该问题产生于这是否可归因于珀尔帖效应。为了测试这一点，整个接触的电池在顶面和底面上设置热电偶，焊接包装在具有实施的接触线的水密真空袋中并完全浸没在10升热水中。在约5分钟的加热时间后，所有热电偶的温度是相同的。在覆盖电极与底面电极之间的光伏电位差是显著的，并且成比例地依赖于现在随着水的温度而缓慢下降的电池温度。在起始值、最终值和测量值之间发生的变化用数字记录并且在图4a的图形中再现。如图4a所示出的，来自PV双层的光伏分接电位的测量显示出对于从46℃至31℃下降的水的温度成比例的依赖性：温度越低，可分接电位越低。然而，周围的水确保在这里不会测量到温度梯度，这在珀尔帖元件中将要求然后可测量的塞贝克效应。完全被均匀加热的水包围的电池的温度不显示梯度。
出人意料地，披萨炉中去除和未包装的电池的验证显示，在电池与披萨炉的热壁的距离处高达50℃下，没有足够的热辐射到达电池。如图4b所示出的，作为波长的函数的空气中H2O的已知光吸收最大值在5至10微米的波长范围内是显著的。
诸位发明人相信，特定地热水相应地在该波长范围内发出，并且因此在所选择的实验装置中以最高的效率提供具有适当能量的光子。测量结果清楚地表明在长波至远IR范围内超过5微米的可用带隙。然而，这也意味着相反地，在高热入射辐射下，足够的热辐射将需要穿透细胞周围的薄空气层并且能够产生电流。这被证实：在热炉石与双层之间具有2cm的空气间隙的在80℃下的披萨炉中，如以上描述的生产和接触的双层清楚并且明显地输送可测量的电流，其在冷却期间再次与温度成比例地下降并且在约60℃下失去控制。目前生产的双层序列使得有可能实现长波至极长波轻光分数直至远IR辐射的有利光伏利用，这种范围在现有技术中是不利地被忽略并且未研究的波长范围。当将上述电池连接到电压表上并用放置在其上的平手加热时，建立与相应的可测量的表面温度成比例的电位差。特别地，工业废热和/或体热可以有用地并且有效地用目前生产的PV层序列利用。
工业实用性
这是根据现有技术的方法的一个问题，这些方法总是需要在高温下的烧结步骤。另一个问题是柔性薄层、特别是PV层经常不能容许此类温度，并且另外不允许利用工业废热和/或长波光子。
这些问题的解决方案可以通过以下方法提供，其中在硬化期间加速另外的反应并且改善硬化。这特别有利地允许包含塑料基质的双层序列，其中遍及金属颗粒并且在顶层中存在碱溶解的硅氧烷部分并且存在金属颗粒，其中通过在碱溶解期间的相互最终硬化使得有可能产生工业废热/长波IR辐射通过光伏手段变得可利用的PV层序列。工业废热/热/体热的有效利用在许多领域提供了明显的经济优势。

Claims (4)

1.一种用于生产电工薄层的室温方法，其中以分散体平面地提供导电和/或半导体的无机金属附聚物并且将其硬化以提供层，该方法的特征在于
-在室温下进行该硬化并且
-通过暴露于至少一种试剂来加速该硬化，
其中，形成PV层序列，
其中，施加作为至少一个第一层的包含至少一种金属的层，其中该至少一种金属选自下组，该组由以下项组成：钢、锌、锡、银、铜、铝、镍、铅、铁，
其中，施加并且至少部分硬化作为第二层的至少一个金属导电和/或半导体层，
其中，第一层的无机金属附聚物是分布在塑料基质中的金属或金属化合物，这些金属或金属化合物的金属类型选自下组，该组由以下项组成：铍、硼、铝、镓、铟、硅、锗、锡、铅、砷、锑、硒、碲、铜、银、金、锌、铁、铬、锰、钛、锆，
其中，第二层的无机金属附聚物是被安排分布在至少部分无机基质中的金属或金属化合物，其中这些金属或金属化合物的金属类型选自下组，该组由以下项组成：铍、硼、铝、镓、铟、硅、锗、锡、铅、砷、锑、硒、碲、铜、银、金、锌、铁、铬、锰、钛、锆，
其中，在第二层中，作为无机基质使用包含作为玻璃状氧化基质的至少一种链形成或改性元素的基质，该元素选自下组，该组由以下项组成：硼、磷、硅、砷、硫、硒、碲、无定形形式的碳、石墨改性的碳、碳纳米管形式的碳、多壁碳纳米管形式的碳、巴明敏斯特富勒烯形式的碳、钙、钠、铝、铅、镁、钡、钾、锰、锌、锡、锑、铈、锆、钛、锶、镧、钍、钇、氟、氯、溴、碘。
2.如权利要求1所述的方法，其特征在于，作为载体，使用平面地延伸的材料网，该材料网由至少一种选自以下材料组的材料组成，该组由以下项组成：玻璃、塑料、聚碳酸酯、塑料膜、金属合金、电机块合金、换热器管合金、换热器合金、换热器焊接合金、陶瓷、工业陶瓷、天然石、大理石、粘土陶瓷、屋顶瓦陶瓷、层压木材、地板材料、铝、楼梯铝合金、铂复合物、集成电路外壳材料、处理器外壳化合物。
3.如权利要求1或2所述的方法，其特征在于
-将导电电极层施加在载体顶上，
-将分布在塑料基质中的金属或金属化合物作为第一层中的无机金属附聚物施加在导电电极层顶上，
-将至少部分强碱性或强酸性氧化基质中的无机金属附聚物的第二层施加在该第一层顶上，其中
-在施加和硬化期间，第二层的无机金属附聚物与该强碱性或强酸性氧化基质反应，其中该强碱性或强酸性氧化基质还进而与该第一层的无机金属附聚物反应，
-在硬化和反应期间，形成光伏活性层序列，
-该第二层设置有透明覆盖电极和/或接触电极，并且
-适当地接触该光伏活性层序列并且焊接包装为PV层序列。
4.一种作为如前述权利要求中任一项所述的PV层序列获得的电工薄层序列，其特征在于，该薄层序列包括
-玻璃载体，
-施加在该玻璃载体顶上的电极层，该电极层包括银，
-施加在该电极层顶上的第一层，该第一层包含塑料基质中的铝颗粒，
-施加在该第一层顶上的第二层，该第二层包含作为至少部分碱性的玻璃状层的在玻璃状网络中的至少硅-氧桥，并且还包含作为无机金属附聚物的至少部分碱溶解的铝颗粒，
-施加在该第二层顶上并具有接触电极的透明覆盖电极，其中进而
-如此制备的PV层序列在长波和极长波长红外范围内表现出光伏效应。
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