CN112002777A - 一种柔性钙钛矿薄膜太阳能电池及其制备方法 - Google Patents

一种柔性钙钛矿薄膜太阳能电池及其制备方法 Download PDF

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CN112002777A
CN112002777A CN202010846448.0A CN202010846448A CN112002777A CN 112002777 A CN112002777 A CN 112002777A CN 202010846448 A CN202010846448 A CN 202010846448A CN 112002777 A CN112002777 A CN 112002777A
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赵德威
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Litian Optoelectronic Technology Suzhou Co ltd
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Abstract

本发明公开了一种柔性钙钛矿薄膜太阳能电池，包括框架、含溴薄膜层、超薄氧化锡层、吸收层、柔性衬底层、钙钛矿薄膜层、钾铯离子层、电荷复合层和柔性玻璃层，含溴薄膜层设置在框架最下部，所述电荷复合层设置在钙钛矿薄膜层上，所述电荷复合层呈凹陷结构线性阵列设置有全无机空穴传输层，所述柔性柔性玻璃层密封固定设置在电荷复合层顶部。柔性薄膜叠层太阳能电池，该电池优于传统薄膜太阳能电池，在高海拔部队巡防、野外作战、探险、航天空间飞行器、室内低照度应用场景及小型化轻柔便携式能源供给等领域应用前景广阔。可以在有限空间内更优的组合模块，单个更高电压的模块组合，能够形成更可靠的电池模组，使得能源密度最大化。

Description

一种柔性钙钛矿薄膜太阳能电池及其制备方法
技术领域
本发明属于新能源电池技术领域，尤其是涉及一种柔性钙钛矿薄膜太阳能电池制及其制备方法。
背景技术
薄膜电池顾名思义就是将一层薄膜制备成太阳能电池，其用硅量极少，更容易降低成本，同时它既是一种高效能源产品，又是一种新型建筑材料，更容易与建筑完美结合。在国际市场硅原材料持续紧张的背景下，薄膜太阳电池已成为国际光伏市场发展的新趋势和新热点。 已经能进行产业化大规模生产的薄膜电池主要有3种：硅基薄膜太阳能电池、铜铟镓硒薄膜太阳能电池（CIGS）、碲化镉薄膜太阳能电池（CdTe）。
近年来，太阳能光伏电池市场正在向薄膜太阳能光伏产品转移。薄膜太阳能电池的优势在于其产业链的耗能更低，制备材料选择更广泛，制备技术多样，产品的发电效率提升有更大的潜力，产品重量更轻且可柔性化，应用场景更宽泛。
目前市面上钙钛矿电池的缺点是材料有毒，钙钛矿电池材料含有铅，不过铅跟其他类型电池含有的砷、镓、碲、镉相比，简直就是小巫见大巫。而美国西北大学也已研发出一种用锡代替铅的钙钛矿太阳能电池，不过这种电池的转换效率还只有6%，而且材料非常不稳定，目前处于研发初级阶段。我们针对环境保护的严格要求，试制无镉、低铅柔性叠层薄膜太阳能电池，在保护生态环境的前提下，获得稳定、高效、相对环保的柔性薄膜叠层太阳能电池样品。
发明内容
本发明所要解决的技术问题是：提供一种稳定、高效、相对环保的钙钛矿柔性薄膜电池及其制备方法。
为了解决上述技术问题，本发明是通过以下技术方案实现的：一种柔性钙钛矿薄膜太阳能电池，包括框架、含溴薄膜层、超薄氧化锡层、吸收层、柔性衬底层、钙钛矿薄膜层、钾铯离子层、电荷复合层和柔性玻璃层，所述含溴薄膜层设置在框架最下部，所述含溴薄膜层上部设置超薄氧化锡层，所述柔性衬底层设置在超薄氧化锡层上，所述柔性衬底层与超薄氧化锡层之间形成加强区域，所述加强区域内设置吸收层，所述柔性衬底层设置为规则的起伏式结构，所述钾铯离子层间隔设置在柔性衬底层的凸起上，所述钙钛矿薄膜层扣合设置在柔性衬底层上，所述电荷复合层设置在钙钛矿薄膜层上，所述电荷复合层呈凹陷结构线性阵列设置有全无机空穴传输层，所述柔性柔性玻璃层密封固定设置在电荷复合层顶部。
作为优选，所述电荷复合层由超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO复合组成。
作为优选，所述柔性衬底层波峰与波谷的差值为5m～6.3mm。
作为优选，所述全无机空穴传输层的表面均匀设置有直径为0.5mm～0.8mm的凸起点。
作为优选，两个全无机空穴传输层之间的间隔为3cm～5cm。
柔性钙钛矿薄膜太阳能电池的制备方法，包括以下步骤，
A：含溴薄膜层封装设置在框架下部作为基底，将基底输送至集电器腔中，采用磁控溅射将弱取向的多晶膜进行沉积；
B、将金属吸收层采用红外激光加热，并在真空环境下退火后分块封装设置在含溴薄膜层上，各个金属吸收层之间的间隙为2mm～3mm；
C、将柔性衬底层冷却到-20℃～-25℃后粘结设置在各个金属吸收层上；
D、将厚度为3mm～5mm的钾铯离子层在折弯机上折弯为与柔性衬底层、钙钛矿薄膜层相配合的凹陷状结构后，采用分隔式分布的方式固定粘结扣合在柔性衬底层，钙钛矿薄膜层密封设置在柔性衬底层，并且柔性衬底层上设置有与钾铯离子层相配合的凹槽，钾铯离子层顶部粘结在柔性衬底层上的凹槽内，然后进行60℃～80℃加热；
E、电荷复合层中的超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO通过粘合的方式在60℃～80℃的条件下粘结复合组成，所述超薄氧化锡SnO2电子传输层位于最上层，所述铝掺杂氧化锌AZO位于中层，所述氧化铟锡ITO位于最下层；
F、柔性玻璃层在外表面印刷完成后粘合设置在超薄氧化锡SnO2电子传输层上，所述柔性玻璃层与框架之间粘结密封符合。
作为优选，所述步骤C中将柔性衬底层的冷却温度设置为-20℃。
作为优选，所述步骤D中钾铯离子层顶部粘结在柔性衬底层上的凹槽内后进行加热的温度设置68℃。
作为优选，所述步骤D中钾铯离子层顶部粘结在柔性衬底层上的凹槽内后进行60℃～80℃加热的时间为8～10min。
作为优选，所述超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO通过粘合的方式在65℃的条件下粘结复合组成。
与现有技术相比，本发明的有益之处是：柔性薄膜叠层太阳能电池，在特种应用环境中，该电池优于传统薄膜太阳能电池，在高海拔部队巡防、野外作战、探险、航天空间飞行器、室内低照度应用场景及小型化轻柔便携式能源供给等领域应用前景广阔。叠层电池的结构，可以在有限空间内更优的组合模块，单个更高电压的模块组合，能够形成更可靠的电池模组，使得能源密度最大化。
附图说明：
下面结合附图对本发明进一步说明。
图1是柔性钙钛矿薄膜太阳能电池的结构示意图。
具体实施方式：
下面结合具体实施方式对本发明进行详细描述：
如图1所示的一种柔性钙钛矿薄膜太阳能电池，包括框架1、含溴薄膜层2、超薄氧化锡层3、吸收层4、柔性衬底层5、钙钛矿薄膜层6、钾铯离子层7、电荷复合层8和柔性玻璃层9，所述含溴薄膜层2设置在框架1最下部，所述含溴薄膜层2上部设置超薄氧化锡层3，所述柔性衬底层5设置在超薄氧化锡层3上，所述柔性衬底层5与超薄氧化锡层3之间形成加强区域，所述加强区域内设置吸收层4，所述柔性衬底层5设置为规则的起伏式结构，所述钾铯离子层7间隔设置在柔性衬底层5的凸起上，所述钙钛矿薄膜层6扣合设置在柔性衬底层5上，所述电荷复合层8设置在钙钛矿薄膜层6上，所述电荷复合层8呈凹陷结构线性阵列设置有全无机空穴传输层81，所述柔性柔性玻璃层9密封固定设置在电荷复合层8顶部。通过电池的吸光、传输材料的优化整合、器件结构的构筑，解决柔性薄膜太阳能电池制备中存在的问题，通过多物理场耦合模型，构建光子、电子协同调控机制，设计纳米结构，增加纳米结构的陷光能力，提高太阳能电池的光吸收效率，优化太阳能电池光电性能，解决制备过程中高质量成膜的制备技术问题，包括柔性透明导电电极的成膜制备技术、钙钛矿纳米薄膜的成膜制备技术以及叠层太阳能电池中间层薄膜制备技术等关键核心技术，制备高效率柔性薄膜叠层太阳能电池器件。
所述电荷复合层8由超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO复合组成。叠层结构已被证明是超越Shockley-Queisser辐射效率的有效途径，钙钛矿-钙钛矿(全钙钛矿)叠层电池的理论效率可达40%。研究全钙钛矿叠层太阳能电池技术，利用组分工程和界面工程，采用低温无损双氧化物层来制备中间连接层，最小化光电损失，解决子电池效率低、中间连接层制作工艺复杂的问题，提高整体光电转化效率。所述柔性衬底层5波峰与波谷的差值为5m～6.3mm。所述全无机空穴传输层81的表面均匀设置有直径为0.5mm～0.8mm的凸起点。两个全无机空穴传输层81之间的间隔为3cm～5cm。
柔性钙钛矿薄膜太阳能电池的制备方法，包括以下步骤，
A：含溴薄膜层封装设置在框架下部作为基底，将基底输送至集电器腔中，采用磁控溅射将弱取向的多晶膜进行沉积；
B、将金属吸收层采用红外激光加热，并在真空环境下退火后分块封装设置在含溴薄膜层上，各个金属吸收层之间的间隙为2mm～3mm；
C、将柔性衬底层冷却到-20℃～-25℃后粘结设置在各个金属吸收层上；
D、将厚度为3mm～5mm的钾铯离子层在折弯机上折弯为与柔性衬底层、钙钛矿薄膜层相配合的凹陷状结构后，采用分隔式分布的方式固定粘结扣合在柔性衬底层，钙钛矿薄膜层密封设置在柔性衬底层，并且柔性衬底层上设置有与钾铯离子层相配合的凹槽，钾铯离子层顶部粘结在柔性衬底层上的凹槽内，然后进行60℃～80℃加热；
E、电荷复合层中的超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO通过粘合的方式在60℃～80℃的条件下粘结复合组成，所述超薄氧化锡SnO2电子传输层位于最上层，所述铝掺杂氧化锌AZO位于中层，所述氧化铟锡ITO位于最下层；
F、柔性玻璃层在外表面印刷完成后粘合设置在超薄氧化锡SnO2电子传输层上，所述柔性玻璃层与框架之间粘结密封符合。所述步骤C中将柔性衬底层的冷却温度设置为-20℃。所述步骤D中钾铯离子层顶部粘结在柔性衬底层上的凹槽内后进行加热的温度设置68℃。所述步骤D中钾铯离子层顶部粘结在柔性衬底层上的凹槽内后进行60℃～80℃加热的时间为8～10min。所述超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO通过粘合的方式在65℃的条件下粘结复合组成。
宽带隙电池：利用界面工程，首次在非浸润性表面的空穴传输聚合物上制备常规带隙钙钛矿（1.6eV），通过对宽带隙钙钛矿（1.75eV）掺杂添加剂和溶剂处理，增大晶粒尺寸、降低缺陷态密
度及电荷复合几率，提高电池的稳态效率到
17%，为此前报道的该类电池的世界最高水平。
2）非铅纯锡电池：提出新制备方法和界面工程，首次将反型结构引入到纯锡钙钛矿电池，获得6.22%效率，达到了当时国际领先水平。
3）窄带隙电池：首次采用反型结构及全新生长1.25eV窄带隙钙钛矿的方法，创新性地提出了生长大晶粒、长载流子寿命的厚锡铅混合窄带隙钙钛矿的方法，首次获得了经权威第三方认证机构（Newport Corporation）认证的17%转换效率，为此前报道的窄带隙钙钛矿电池的世界最高值。
4）通过光调控设计，完善宽带隙钙钛矿电池的半透明电极，将全钙钛矿并联叠层电池的稳态效率提高到23%，通过构筑有效中间连接层和窄带隙子电池的提高，实现了全钙钛矿串联叠层电池的效率首次超过21%，寿命达到80小时，效率老化至初始值的85%。
5）提出了一种新型超薄、超平整、低光学损耗、热稳定、室温下长时间稳定、高柔性银膜的制备方法，即通过在银的沉积过程中掺入少量的铝。国际上首次报道在超薄（4nm）银膜上制备高效柔性太阳能电池。完成了可见光范围内透光率>60%的金属铝纳米结构透明导电电极的制备。
6）研发出一种新型高疏水性钙钛矿材料，在提升电池效率的同时大大提高了产品稳定性，该新材料的性能还在进一步的优化和完善中。研发的新型电池500小时后仍保持初始效率的90%，为开发大面积化稳定产品提供了奠定了基础和有力保障。
柔性薄膜叠层太阳能电池，在特种应用环境中，该电池优于传统薄膜太阳能电池，在高海拔部队巡防、野外作战、探险、航天空间飞行器、室内低照度应用场景及小型化轻柔便携式能源供给等领域应用前景广阔。叠层电池的结构，可以在有限空间内更优的组合模块，单个更高电压的模块组合，能够形成更可靠的电池模组，使得能源密度最大化。
需要强调的是：对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。

Claims (10)

1.一种柔性钙钛矿薄膜太阳能电池，其特征在于：包括框架（1）、含溴薄膜层（2）、超薄氧化锡层（3）、吸收层（4）、柔性衬底层（5）、钙钛矿薄膜层（6）、钾铯离子层（7）、电荷复合层（8）和柔性玻璃层（9），所述含溴薄膜层（2）设置在框架（1）最下部，所述含溴薄膜层（2）上部设置超薄氧化锡层（3），所述柔性衬底层（5）设置在超薄氧化锡层（3）上，所述柔性衬底层（5）与超薄氧化锡层（3）之间形成加强区域，所述加强区域内设置吸收层（4），所述柔性衬底层（5）设置为规则的起伏式结构，所述钾铯离子层（7）间隔设置在柔性衬底层（5）的凸起上，所述钙钛矿薄膜层（6）扣合设置在柔性衬底层（5）上，所述电荷复合层（8）设置在钙钛矿薄膜层（6）上，所述电荷复合层（8）呈凹陷结构线性阵列设置有全无机空穴传输层（81），所述柔性柔性玻璃层（9）密封固定设置在电荷复合层（8）顶部。
2.根据权利要求1所述的柔性钙钛矿薄膜太阳能电池，其特征在于：所述电荷复合层（8）由超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO复合组成。
3.根据权利要求1所述的柔性钙钛矿薄膜太阳能电池，其特征在于：所述柔性衬底层（5）波峰与波谷的差值为5m～6.3mm。
4.根据权利要求1所述的柔性钙钛矿薄膜太阳能电池，其特征在于：所述全无机空穴传输层（81）的表面均匀设置有直径为0.5mm～0.8mm的凸起点。
5.根据权利要求1所述的柔性钙钛矿薄膜太阳能电池，其特征在于：两个全无机空穴传输层（81）之间的间隔为3cm～5cm。
6.根据权利要求1-5任意一项所述的柔性钙钛矿薄膜太阳能电池的制备方法，其特征在于：包括以下步骤，
A：含溴薄膜层封装设置在框架下部作为基底，将基底输送至集电器腔中，采用磁控溅射将弱取向的多晶膜进行沉积；
B、将金属吸收层采用红外激光加热，并在真空环境下退火后分块封装设置在含溴薄膜层上，各个金属吸收层之间的间隙为2mm～3mm；
C、将柔性衬底层冷却到-20℃～-25℃后粘结设置在各个金属吸收层上；
D、将厚度为3mm～5mm的钾铯离子层在折弯机上折弯为与柔性衬底层、钙钛矿薄膜层相配合的凹陷状结构后，采用分隔式分布的方式固定粘结扣合在柔性衬底层，钙钛矿薄膜层密封设置在柔性衬底层，并且柔性衬底层上设置有与钾铯离子层相配合的凹槽，钾铯离子层顶部粘结在柔性衬底层上的凹槽内，然后进行60℃～80℃加热；
E、电荷复合层中的超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO通过粘合的方式在60℃～80℃的条件下粘结复合组成，所述超薄氧化锡SnO2电子传输层位于最上层，所述铝掺杂氧化锌AZO位于中层，所述氧化铟锡ITO位于最下层；
F、柔性玻璃层在外表面印刷完成后粘合设置在超薄氧化锡SnO2电子传输层上，所述柔性玻璃层与框架之间粘结密封符合。
7.根据权利要求6所述的柔性钙钛矿薄膜太阳能电池的制备方法，其特征在于：所述步骤C中将柔性衬底层的冷却温度设置为-22℃。
8.根据权利要求6所述的柔性钙钛矿薄膜太阳能电池的制备方法，其特征在于：所述步骤D中钾铯离子层顶部粘结在柔性衬底层上的凹槽内后进行加热的温度设置68℃。
9.根据权利要求6所述的柔性钙钛矿薄膜太阳能电池的制备方法，其特征在于：所述步骤D中钾铯离子层顶部粘结在柔性衬底层上的凹槽内后进行60℃～80℃加热的时间为8～10min。
10.根据权利要求6所述的柔性钙钛矿薄膜太阳能电池的制备方法，其特征在于：所述超薄氧化锡SnO2电子传输层、铝掺杂氧化锌AZO和氧化铟锡ITO通过粘合的方式在65℃的条件下粘结复合组成。
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