CN112979611B - 一类碗烯基钙钛矿太阳能电池空穴传输层材料及其制备方法和应用 - Google Patents

一类碗烯基钙钛矿太阳能电池空穴传输层材料及其制备方法和应用 Download PDF

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CN112979611B
CN112979611B CN202110188120.9A CN202110188120A CN112979611B CN 112979611 B CN112979611 B CN 112979611B CN 202110188120 A CN202110188120 A CN 202110188120A CN 112979611 B CN112979611 B CN 112979611B
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谢素原
安明伟
吴宝山
苏茵
邓林龙
张前炎
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Abstract

本发明公开了一类碗烯基钙钛矿太阳能电池空穴传输层材料，其构造以非平面π共轭分子碗烯为核，并将其内核进一步去扩大，引入不同的桥联结构和给电子功能基团，其化学结构式：
Figure DDA0002941110620000011
该类分子的制备方法主要采用碗烯为核，通过对碗烯硼酯化后得到其硼酯衍生物，再通过偶联反应引入桥联分子和给电子功能基团；引入的桥联结构单元和给电子功能基团能够有效地调节分子的共轭长度、改变分子的π共轭体系大小，提高分子在有机溶剂中的溶解度，改善分子之间的堆积，提升钙钛矿太阳能电池的稳定性与光电转换效率；这类分子作为空穴传输层材料应用于正置结构钙钛矿太阳能电池的空穴传输层中，具有较高的光电转换效率，是一种非常有潜力的空穴传输材料。

Description

一类碗烯基钙钛矿太阳能电池空穴传输层材料及其制备方法 和应用
技术领域
本发明涉及太阳能电池材料技术领域，具体涉及一类碗烯基钙钛矿太阳能电池空穴传输层材料及其制备方法和应用。
背景技术
随着社会的快速发展，环境污染和能源危机逐渐成为人类面临的两大社会问题。开发风能、潮汐能和太阳能等新能源迫在眉睫。太阳能取之不尽，用之不竭，将太阳能直接转化为电能的太阳能电池受到广大研究者们的青睐。在众多太阳能电池中，钙钛矿太阳能电池(PSCs)由于具有可溶液加工、低成本和易大面积制备等优点被广泛研究。在过去不到十年的时间里，钙钛矿太阳能电池的光电转换效率持续上升。目前，文献报道钙钛矿太阳能电池的效率达到24％(Joule,2019,3,2179-2192)，接近商业化的门槛。伴随着越来越多新型材料的问世，钙钛矿太阳能电池作为一种新型电池正展现着出前所未有的活力。为了提升钙钛矿太阳能电池的稳定性与光电转换效率，科学家对钙钛矿太阳能电池中的五个部分——玻璃基底、电子传输层、钙钛矿吸光层、空穴传输层和金属电极进行优化和改良。空穴传输层是钙钛矿太阳能电池的关键组成部分之一，主要作用是收集、传输光生空穴和抑制载流子的复合，阻止水氧进入钙钛矿。优化空穴传输层对于提高钙钛矿太阳能电池的效率和稳定性具有十分重要的意义。对于空穴传输层材料来说，它们都具有较大π共轭平面或者立体结构的内核以及给电子的功能基团(如Spiro-OMeTAD)。目前，研究者们已开发了大量的不同类型的空穴传输层材料。现有的工作普遍致力于更改内核或调整给电子功能基团的结构和空间位置，从而改变分子的能级、溶解性、堆积方式、空穴传输性能和电池稳定性等。
迄今为止，有许多新报道的空穴传输材料用于钙钛矿太阳能电池，都呈现出良好的性能：(Chem.Sci.,2016,7,5007-5012；Asian J.Org.Chem.,2018,7,2182–2200；Nat.Energy,2016,1,15017；Nature Energy,2018,3,682–689；Angew.Chem.Int.Ed.,2018,57,10959–10965)。
与蒄等平面π共轭分子不同，碗烯(Corannulene)是用来合成非平面π共轭分子的关键和代表性结构之一。它是一种由一个五元环周围稠合五个苯环而形成的碗状多环芳香碳氢化合物，于1966年由科学家Barth和Lawton首次合成。一直以来，碗烯被视作C60的碎片，其具有与C60相似的曲面和π共轭体系，并呈现出特殊的化学和物理性质。因此，碗烯的合成及其性质研究是一个倍受关注并且十分活跃的领域。为了进一步研究碗烯的一系列性质，必须对其进行进一步的功能化修饰和探索。研究发现，大部分碗烯功能化衍生物拥有优异的电学光学性质，在超分子自组装方面也有着特殊的性质(Nat.Common.,2019,10,485)，且在有机场效应晶体管(OFETs)和有机太阳能电池(OPVs)等领域也有很大的发展前景(Chem.Sci.,2014,5,1041–1045)。
目前，虽然有很多碗烯衍生物被合成得到，也证明了这些衍生物拥有一定的电学性质，但现有的碗烯衍生物不但制备过程复杂，生产成本较高，而且稳定性较差及光电转换效率较低，很难满足人们的使用需求。
发明内容
本发明的目的之一在于提供一类碗烯基钙钛矿太阳能电池空穴传输层材料。以碗烯分子为核，引入不同的给电子功能基团。一是以非平面的碗烯作为分子内核，能有效提高空穴传输材料分子在有机溶剂中的溶解度；二是碗烯独特的五取代结构，其相较于Spiro-OMeTAD能提供更多连接给电子功能基团的位点；三是碗烯作为拥有较大π共轭体系的非平面分子，为整个空穴传输材料分子形成更大的π共轭体系，获得了一类具有高玻璃转化温度的碗烯基空穴传输材料，制备过程简单方便，可用于提高钙钛矿太阳能电池的稳定性与光电转换效率。
为实现上述目的，本发明采用以下技术方案：
一类碗烯基钙钛矿太阳能电池空穴传输层材料，具有如下内核结构，化学结构式如下：
Figure BDA0002941110600000031
其中，Q为π电子连接单元，选自芳香环及其衍生物；R1和R2独自选自H原子、芳基、羟基、胺基、卤素原子或碳原子数为1-10直链或支链烷基、碳原子数为1-10直链或支链烷氧基、碳原子数为1-10直链或支链烷硫基和碳原子数为1-10直链或支链的胺。
优选地，Q是π电子连接单元或无需Q单元，为以下化学结构式的一种：
Figure BDA0002941110600000041
其中，X为氧原子、硫原子、硒原子、氮原子和硅原子；R1-R12独自选自H原子、芳基、羟基、胺基、卤素原子或碳原子数为1-10直链或支链烷基、碳原子数为1-10直链或支链烷氧基、碳原子数为1-10直链或支链烷硫基和碳原子数为1-10直链或支链的胺。
本发明优选实施方式选自如下化合物：
Figure BDA0002941110600000051
Figure BDA0002941110600000061
Figure BDA0002941110600000071
发明的目的之二在于一类碗烯基钙钛矿太阳能电池空穴传输层材料的制备方法，包括以下步骤：
Figure BDA0002941110600000072
其中，R1-R2为相同的给电子基团独自选自H原子、芳基、羟基、羰基、卤素原子或碳原子数为1-10直链或支链烷基、碳原子数为1-10直链或支链烷氧基、碳原子数为1-10直链或支链烷硫基和碳原子数为1-10直链或支链的胺。
上述制备方法中，化合物3的合成方法具体为：取双口圆底烧瓶，无水无氧处理，依次加入产物1、π电子连接单元2、四三苯基膦钯催化剂、碳酸铯，置换气体3次，氮气保护下加入N,N二甲基甲酰胺进行Suzuki偶联反应，加热反应温度为20～120℃之间。反应过夜，TLC监测反应结束后，冷却至室温后加入水淬灭，将反应原液转移到分液漏斗中用二氯甲烷萃取，有机相用无水硫酸钠干燥，减压旋转蒸发溶剂后用石油醚/二氯甲烷作为洗脱剂过硅胶柱分离得到黄红色固体；所述的化合物1、π电子连接单元2、四三苯基膦钯催化剂、碳酸铯、N,N二甲基甲酰胺配比为0.2～2mmol:0.16～16mmol:0.1～0.8mmol:3～15mmol:10～50mL，反应温度为20～120℃，具体可为20℃或120℃，反应时间为5～24h，具体可为5h或24h。
本发明先合成具有三苯胺结构的外围给电子单元，然后通过与碗烯(Corannulene)五硼酯中间体进行Suzuki偶联缩合反应合成具五取代结构的碗烯基钙钛矿太阳能电池空穴传输层材料，制备工艺简单、可控。
本发明提供了一类碗烯基钙钛矿太阳能电池空穴传输层材料在钙钛矿太阳能电池方面的应用，该碗烯基钙钛矿太阳能电池空穴传输层材料均有高效的光电转化效率。
采用上述技术方案后，本发明与背景技术相比，具有如下有益效果：
1、本发明提供的一类碗烯基钙钛矿太阳能电池空穴传输层材料的制备方法，首次合成了一类具有五取代结构的碗烯基钙钛矿太阳能电池空穴传输层材料。
2、本发明提供的化合物的合成从碗烯的硼酯化衍生物出发，实验步骤仅2～3步，简单有效。
3、本发明提供的化合物均具有较好的溶解性和供电子性质，可以用作钙钛矿太阳能电池的空穴传输层材料。
4、本发明提供的化合物是碗烯独特的五取代结构，其相较于Spiro-OMeTAD能提供更多连接给电子功能基团的位点，有利于调控分子的能级。
5、本发明提供的化合物拥有较大π共轭体系的非平面分子，可以调整分子的堆积，为整个空穴传输材料分子形成更大的π共轭体系，获得了一类具有高玻璃转化温度的碗烯基空穴传输材料，可用于提高钙钛矿太阳能电池的稳定性与光电转换效率。
附图说明
图1为本发明实例1制备得到的空穴传输层材料的核磁共振氢谱图；
图2为本发明实例1制备得到的空穴传输层材料的核磁共振碳谱图；
图3为本发明实例2制备得到的空穴传输层材料的核磁共振氢谱图；
图4为本发明实例3制备得到的空穴传输层材料的质谱图；
图5为本发明实例1制备的空穴传输层材料制备的钙钛矿太阳能电池器件的J-V曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
下述实施例中所述的试验方法，若无特殊说明，均为常规方法；所使用的材料、试剂等，如无特殊说明，均可从商业途径获得。
为了使本发明的目的、技术方案以及优点更加清楚明了，以下结合附图和具体实施例，对本发明进行进一步的详细说明。
实施例1
该实施例的碗烯基钙钛矿太阳能电池空穴传输层材料的结构式为：
Figure BDA0002941110600000091
合成路线如下：
Figure BDA0002941110600000101
称取100mg(0.114mmol)五硼酯取代碗烯、240mg(0.627mmol)化合物1、181mg(1.71mmol)碳酸钠和26mg(0.0228mmol)四三苯基膦钯于50mL干燥的两口瓶中，鼓氮气抽真空重复三次及以上以创造无水无氧的反应环境。随后加入20mL甲苯作为反应溶剂，将反应装置放置于超声仪中常温超声约10min，然后将反应装置放到磁力搅拌器上并将温度升高至40℃反应过夜，反应过程中溶液颜色渐渐加深。在反应结束后，缓慢滴加适量氯化铵溶液淬灭反应，然后用二氯甲烷萃取，得到的有机相使用水洗三次后收集起来用无水硫酸钠干燥，然后使用旋转蒸发仪旋干后得到该钙钛矿太阳能电池空穴传输层材料HTL-1的粗产物。随后使用硅胶柱层析分离的方法分离粗产物，洗脱剂为石油醚：二氯甲烷(1：1)的混合溶剂，分离后下来的第三个干净的黄色荧光带即为目标产物，共计151mg，产率为75％，结构表征数据为：1H NMR(CDCl3,500MHz,δ/ppm):7.87(s,1H),7.53(d,J＝8Hz,2H),7.15(br,4H),7.03(br,2H),6.87(d,J＝9Hz,4H),3.82(s,6H).13C NMR(CDCl3,150MHz,δ/ppm):156.09,148.30,141.93,140.66,135.30,131.73,130.51,129.41,127.02,125.05,119.75,114.77,55.49,HRMS(LC-MALDI-TOF/TOF)；m/z for C120H95N5O10[M]calcd.1765.707,found:1765.535。
实施例2
该实施例的碗烯基钙钛矿太阳能电池空穴传输层材料的结构式为：
Figure BDA0002941110600000111
合成路线如下：
Figure BDA0002941110600000112
(1)首先称取1g(4.76mmol)化合物1、1.83g(4.76mmol)噻吩-2-硼酸频哪醇酯、1.52g(14.3mmol)碳酸钠和35.7mg(0.0309mmol)四三苯基膦钯于500mL干燥的两口瓶中，鼓氮气抽真空重复三次及以上以创造无水无氧的反应环境。随后加入150mL甲苯作为反应溶剂，将温度升高至40℃，加热搅拌反应2h，溶液颜色从黄色变为黑色。反应结束后用氯化铵溶液淬灭反应，二氯甲烷萃取，有机相用水洗三次后用无水硫酸钠干燥，移至旋转蒸发仪旋干有机溶剂后得到化合物2的粗产物。将该粗产物用硅胶柱层析分离法进行分离提纯，洗脱剂为石油醚：二氯甲烷(5：1)的混合溶剂，分离得到的目标产物2共计1.56g，产率为85％。
(2)随后称取1g(2.58mmol)化合物2、0.505g(2.84mmol)N-溴代丁二酰亚胺于100mL两口瓶中，鼓氮气抽真空重复三次及以上，用注射器加入35mL四氢呋喃作为溶剂，常温下反应2h。反应结束后加水淬灭反应，使用二氯甲烷萃取，有机相用水洗三次后用无水硫酸钠干燥，移至旋转蒸发仪旋干有机溶剂后得到化合物3的粗产物。该粗产物用硅胶柱层析分离法进行分离提纯，洗脱剂为石油醚：二氯甲烷(8：1)的混合溶剂，分离得到的目标产物3共计1.08g，产率为90％。
(3)称取100mg(0.114mmol)碗烯五硼酯、292mg(0.627mmol)化合物3、1.71mg(26mmol)碳酸钠和26mg(0.0228mmol)四三苯基膦钯于50mL干燥的两口瓶中，鼓氮气抽真空重复三次及以上，随后加入20mL甲苯作为反应溶剂，将温度升高至50℃搅拌反应过夜。反应结束后用氯化铵溶液淬灭反应，二氯甲烷萃取，有机相用水洗三次后用无水硫酸钠干燥，移至旋转蒸发仪旋干有机溶剂后得到化合物4的粗产物。该粗产物用硅胶柱层析分离法进行分离提纯，洗脱剂为石油醚：二氯甲烷(1：1)的混合溶剂，分离得到的目标产物4共计248mg，产率为55％，1H NMR图谱如图3。1H NMR(400MHz,C2D2Cl4)δ7.67(s,1H),6.89(d,J＝8.2Hz,3H),6.72(d,J＝3.3Hz,1H),6.48(d,J＝8.5Hz,4H),8.37–2.30(m,26H),6.29(dd,J＝27.6,8.0Hz,6H),3.20(s,6H)。
实施例3
该实施例的碗烯基钙钛矿太阳能电池空穴传输层材料的结构式为：
Figure BDA0002941110600000131
合成路线如下：
Figure BDA0002941110600000132
取5mL两口烧瓶、球形冷凝管及大小适当的磁子置于温度为70～80℃的烘箱中约30min，快速称取1,3,5,7,9-五硼酯取代碗烯15mg(0.017mmol，1eq)、4,4'-二甲氧基二苯胺42.9mg(0.187mmol，11eq)、B(OH)3(硼酸)10.5mg(0.17mmol，10eq)、Cu(OAc)2(醋酸铜)3.4mg(0.017mmol,1eq)至两口烧瓶中，搭建反应体系并于上述部件连接处涂抹少量真空脂，加入2mL DMSO(二甲基亚砜)后，将反应装置置于超声仪中超声10min，使固体均匀散布于DMSO溶剂中。超声完毕，连接冷凝水管道后将温度升至85℃，反应3d。
在反应结束后，将反应体系温度冷却至室温，拆除装置加氯化铵水溶液淬灭反应，将混合溶液倒入分液漏斗中，用二氯甲烷进行萃取，收集有机层水洗两次，无水硫酸钠干燥过滤后用旋转蒸发仪真空旋干，得到反应粗产物。将该混合物通过硅胶柱上进行提纯，洗脱剂为乙酸乙酯：二氯甲烷(EA：DCM)＝1：100的混合溶剂，过完硅胶柱，旋干溶剂后即为纯净的1,3,5,7,9-五(4-甲氧基二苯胺基)碗烯，为白色固体，共2.0mg，产率为8.5％。图4为HTL-3的质谱图。
实施例4
实施例1制备的碗烯基钙钛矿太阳能电池空穴传输层材料制备钙钛矿太阳能电池器件及其光伏性能表征。
制备步骤如下：
(1)器件结构：ITO/SnO2/(FAPbI3)x(MAPbBr3)1-x/HTL-1/Ag
(2)将ITO透明导电玻璃片用碱液超声清洗1h，接着用无水乙醇超声清洗1h，然后依次用去离子水超声清洗30min，用丙酮超声15min，用异丙醇超声15min，最后放入烘箱干燥备用；
(3)将市售的SnO2胶体用去离子水稀释(1:4)，再用0.45μm PVDF过滤。以4000rpm，50s旋涂于ITO基底上，然后于150℃下退火30min。
(4)将碘化铅配成1.3mol/L的溶液(DMF：DMSO(95：5,v/v))，再将该混合溶液置于磁力搅拌器上加热至40℃搅拌2h后过滤；以2500rpm，40s旋涂于ITO/SnO2上。FAI：MABr：MACl(60mg：6mg：6mg)溶于1mL异丙醇溶液。以2500rpm，40s旋涂于ITO/SnO2/PbI2上面。
(5)将实施例1中得到的化合物HTL-1充分溶解在氯苯溶液中，得到30mmol/L的溶液，加入Zn-TFSI,FK209和tBP(TFSI：FK209：tBP＝0.3：0.03：3.3)，将混合溶液加热至40℃搅拌1h，过滤得到30mmol/L的实施例1化合物和添加剂的氯苯溶液；以2500rpm，40s旋涂于钙钛矿层上面。
(6)将步骤(1)-(5)中制备的电池镀银电极～100nm，电池的有效面积为0.06cm2。
上述制备的钙钛矿太阳能电池的光伏性能如表1所示；
表1
V<sub>OC</sub>(mV) J<sub>SC</sub>(mA cm<sup>-2</sup>) FF(％) PCE(％)
1069.44 22.48 79.61 19.14
器件的J-V曲线如图5所示。
由上述结果可得出，本发明提供的碗烯基钙钛矿太阳能电池空穴传输层材料具有较高的光电转换效率，是一种非常有潜力的空穴传输材料。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。

Claims (8)

1.一类碗烯基钙钛矿太阳能电池空穴传输层材料，其特征在于，所述碗烯基钙钛矿太阳能电池空穴传输层材料为HTL-1，所述HTL-1的化学结构式为：
Figure FDA0003616172880000011
2.一类碗烯基钙钛矿太阳能电池空穴传输层材料，其特征在于，所述碗烯基钙钛矿太阳能电池空穴传输层材料为HTL-2，所述HTL-2的化学结构式为：
Figure FDA0003616172880000012
3.一类碗烯基钙钛矿太阳能电池空穴传输层材料，其特征在于，所述碗烯基钙钛矿太阳能电池空穴传输层材料为HTL-3，所述HTL-3的化学结构式为：
Figure FDA0003616172880000021
4.一类碗烯基钙钛矿太阳能电池空穴传输层材料，其特征在于，所述碗烯基钙钛矿太阳能电池空穴传输层材料为HTL-4，所述HTL-4的化学结构式为：
Figure FDA0003616172880000022
5.一种如权利要求1～4任一项所述的一类碗烯基钙钛矿太阳能电池空穴传输层材料的制备方法，其特征在于，包括如下步骤：
1)碗烯与双联频哪醇硼酸酯在环己烷溶液中搅拌，得到碗烯五硼酯；
2)将步骤1)中的碗烯五硼酯与溴代的外围基团溶于20℃-120℃的有机溶剂中，在碱性条件和钯催化剂作用下加热反应5-24h，进行Suzuki偶联反应后，得到具有五取代结构的碗烯基钙钛矿太阳能电池空穴传输层材料。
6.如权利要求5所述的一类碗烯基钙钛矿太阳能电池空穴传输层材料的制备方法，其特征在于：步骤2)中所述Suzuki偶联反应采用的碱为碳酸钾、磷酸钾、氟化钾、碳酸铯中的一种或多种；步骤2)中所述Suzuki偶联反应采用的有机溶剂为甲苯、N,N二甲基甲酰胺、1,4二氧六环和水中的一种或多种。
7.一种如权利要求1～6任一项所述的一类碗烯基钙钛矿太阳能电池空穴传输层材料应用于钙钛矿太阳能电池，其特征在于：所述碗烯基钙钛矿太阳能电池采用正置电池结构，其顺序从下到上分别为玻璃基底、氧化锡电子传输层、钙钛矿吸光层、空穴传输层和金属电极。
8.一种如权利要求1～6任一项所述的一类碗烯基钙钛矿太阳能电池空穴传输层材料应用于钙钛矿太阳能电池，其特征在于：所述碗烯基钙钛矿太阳能电池采用倒置电池结构，其顺序从下到上分别为玻璃基底、空穴传输层、钙钛矿吸光层、富勒烯电子传输层和金属电极。
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