有机无机杂化钙钛矿太阳能电池的制备与稳定性研究
发布时间：2019-02-23 14:53
【摘要】：近几年来,基于有机无机杂化钙钛矿材料CH3NH3PbI3的第三代太阳电池——钙钛矿太阳能电池(Perovskite solar cells)备受人们关注,被《Science》评选为2013年十大科学突破之一。得益于其制备成本低,光谱吸收效率高和载流子扩散长度长(1?m)等特点,这类电池得到了快速的发展。其光电转换性能(Power conversion efficiency)在短短6年时间内已经达到了22.1%的NREL认证效率。尽管钙钛矿太阳能电池的光电转换性能不断被刷新,钙钛矿薄膜在潮湿空气中制备时易分解和器件不稳定的问题仍旧限制着钙钛矿太阳能电池的发展。本文从提高钙钛矿薄膜和器件的稳定性入手,通过加入过量甲基碘化胺(CH3NH3I,MAI)到钙钛矿前驱体溶液中,抑制薄膜在空气中分解,降低钙钛矿薄膜缺陷;通过使用具有自组装功能的富勒烯材料(PCBDAN)修饰TiO2电子传输层,提高了平面结构的钙钛矿太阳能电池性能,同时抑制器件光电转换效率在持续光照下的衰减;最后,通过使用喷雾热解法制备的NiO取代3,4-乙烯二氧噻吩聚合制备聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)作为空穴传输层,制备反型结构钙钛矿太阳能电池,并研究了器件的稳定性。取得的研究结果如下:(1)提出了一种在常规湿度空气条件下(湿度~50%RH)制备高质量的钙钛矿薄膜的办法:通过优化钙钛矿前驱体中甲基碘化胺MAI过量的比例,控制钙钛矿薄膜在空气中加热的时间,得到由均匀晶粒组成且无孔洞的钙钛矿薄膜。通过XRD分析,钙钛矿薄膜在潮湿空气中加热分解的问题得到解决。通过XPS分析,过量MAI可以抑制钙钛矿薄膜中金属铅(Pb0)的出现,同时钙钛矿晶体中的碘铅比(I/Pb)从2.51提高到2.91,更加接近单个钙钛矿晶体中I/Pb成分的比例。通过荧光光谱(PL)和时间分辨荧光光谱(TRPL)测试表明,钙钛矿薄膜的PL强度提升了1倍,载流子寿命(?)从25.4 ns提高到101.8 ns。最终,在空气中制备结构为FTO/Compact TiO2/Mesoscopic TiO2/MAPbI3/Spiro-oMeTAD/Au的正向支架钙钛矿太阳能电池的性能从14.06%提升到18.23%。(2)以自组装的富勒烯电子传输材料PCBDAN修饰二氧化钛界面,制备结构为FTO/Compact TiO2/PCBDNAN/Perovskite/Spiro-oMeTAD/Au的平面钙钛矿太阳能电池。通过修饰,提高了钙钛矿薄膜的晶粒大小,加快了界面的电子传输,抑制了界面的缺陷对钙钛矿薄膜的催化分解。最终,修饰后的平面钙钛矿太阳能电池的性能从13.64%提高到了16.78%。同时,未封装的器件在7日持续光照后器件性能从低于20%提升到大于70%。(3)用热喷雾制备NiO取代3,4-乙烯二氧噻吩聚合制备聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)作为空穴传输层,结合第二章钙钛矿制备的改进方法,组装结构为FTO/NiO/Perovskite/PCBM/Ag的反型结构钙钛矿太阳能电池。最终电池的光电转化效率PCE高达16.34%,并且器件的稳定性大幅度提高。
[Abstract]:In recent years, (Perovskite solar cells), the third generation solar cell based on organic-inorganic hybrid perovskite material CH3NH3PbI3, has attracted much attention, and has been selected as one of the top ten scientific breakthroughs in 2013 by < Science >. Due to its low preparation cost, high spectral absorption efficiency and long carrier diffusion length (1m), this kind of cell has been developed rapidly. Its photoelectric conversion performance (Power conversion efficiency) has reached 22.1% NREL authentication efficiency in just 6 years. Although the photoconversion performance of perovskite solar cells is constantly being refreshed, the problems of perovskite thin films being easily decomposed and device instability in wet air still limit the development of perovskite solar cells. In order to improve the stability of perovskite films and devices, by adding excessive methyliodiamine (CH3NH3I,MAI) into perovskite precursor solution, the decomposition of perovskite films in air is inhibited and the defects of perovskite films are reduced. The self-assembled fullerene material (PCBDAN) was used to modify the TiO2 electron transport layer to improve the performance of planar perovskite solar cells and to restrain the decay of photovoltaic conversion efficiency under continuous illumination. Finally, the inverse perovskite solar cells were prepared by using the spray pyrolysis method to prepare polystyrene sulfonic acid (PEDOT:PSS) as the hole transport layer by the polymerization of NiO instead of 3N 4- ethylenedioxythiophene. The stability of the device is also studied. The results obtained are as follows: (1) A method of preparing high quality perovskite films under conventional humidity and air conditions (humidity ~ 50%RH) is proposed: by optimizing the ratio of MAI excess in perovskite precursor, By controlling the heating time of perovskite film in air, the porous perovskite thin film composed of uniform grains was obtained. By XRD analysis, the decomposition of perovskite films in humid air was solved. By XPS analysis, excessive MAI can inhibit the appearance of lead (Pb0) in perovskite films, and the ratio of iodine to lead (I/Pb) in perovskite crystals is increased from 2.51 to 2.91. It is closer to the ratio of I/Pb in a single perovskite crystal. The results of fluorescence (PL) and time-resolved fluorescence spectroscopy (TRPL) show that the PL intensity of perovskite thin films is twice as high as that of perovskite films, and the carrier lifetime (?) Increase from 25.4 ns to 101.8 ns. Eventually, The performance of perovskite solar cells with FTO/Compact TiO2/Mesoscopic TiO2/MAPbI3/Spiro-oMeTAD/Au structure in air was improved from 14.06% to 18.23%. (2) Self-assembled fullerene electron transport materials PCBDAN modified titanium dioxide interface, A planar perovskite solar cell with FTO/Compact TiO2/PCBDNAN/Perovskite/Spiro-oMeTAD/Au structure was prepared. By modification, the grain size of perovskite film is increased, the electron transport at the interface is accelerated, and the catalytic decomposition of perovskite film is restrained by the defects of the interface. Finally, the performance of the modified planar perovskite solar cells increased from 13.64% to 16.78%. meanwhile, The performance of unencapsulated devices was improved from less than 20% to more than 70% after 7 days of continuous illumination. (3) Polymerization of (3) 4-ethylenedioxythiophene (NiO) -polyphenylene (3) was prepared by thermal spray. Sulfonic acid (PEDOT:PSS) acts as a hole transport layer, Combined with the improved method of preparation of perovskite in chapter 2, the anti-perovskite solar cells with FTO/NiO/Perovskite/PCBM/Ag structure were assembled. Finally, the photoelectric conversion efficiency (PCE) of the battery is up to 16.34%, and the stability of the device is greatly improved.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM914.4
本文编号：2428933
[Abstract]:In recent years, (Perovskite solar cells), the third generation solar cell based on organic-inorganic hybrid perovskite material CH3NH3PbI3, has attracted much attention, and has been selected as one of the top ten scientific breakthroughs in 2013 by < Science >. Due to its low preparation cost, high spectral absorption efficiency and long carrier diffusion length (1m), this kind of cell has been developed rapidly. Its photoelectric conversion performance (Power conversion efficiency) has reached 22.1% NREL authentication efficiency in just 6 years. Although the photoconversion performance of perovskite solar cells is constantly being refreshed, the problems of perovskite thin films being easily decomposed and device instability in wet air still limit the development of perovskite solar cells. In order to improve the stability of perovskite films and devices, by adding excessive methyliodiamine (CH3NH3I,MAI) into perovskite precursor solution, the decomposition of perovskite films in air is inhibited and the defects of perovskite films are reduced. The self-assembled fullerene material (PCBDAN) was used to modify the TiO2 electron transport layer to improve the performance of planar perovskite solar cells and to restrain the decay of photovoltaic conversion efficiency under continuous illumination. Finally, the inverse perovskite solar cells were prepared by using the spray pyrolysis method to prepare polystyrene sulfonic acid (PEDOT:PSS) as the hole transport layer by the polymerization of NiO instead of 3N 4- ethylenedioxythiophene. The stability of the device is also studied. The results obtained are as follows: (1) A method of preparing high quality perovskite films under conventional humidity and air conditions (humidity ~ 50%RH) is proposed: by optimizing the ratio of MAI excess in perovskite precursor, By controlling the heating time of perovskite film in air, the porous perovskite thin film composed of uniform grains was obtained. By XRD analysis, the decomposition of perovskite films in humid air was solved. By XPS analysis, excessive MAI can inhibit the appearance of lead (Pb0) in perovskite films, and the ratio of iodine to lead (I/Pb) in perovskite crystals is increased from 2.51 to 2.91. It is closer to the ratio of I/Pb in a single perovskite crystal. The results of fluorescence (PL) and time-resolved fluorescence spectroscopy (TRPL) show that the PL intensity of perovskite thin films is twice as high as that of perovskite films, and the carrier lifetime (?) Increase from 25.4 ns to 101.8 ns. Eventually, The performance of perovskite solar cells with FTO/Compact TiO2/Mesoscopic TiO2/MAPbI3/Spiro-oMeTAD/Au structure in air was improved from 14.06% to 18.23%. (2) Self-assembled fullerene electron transport materials PCBDAN modified titanium dioxide interface, A planar perovskite solar cell with FTO/Compact TiO2/PCBDNAN/Perovskite/Spiro-oMeTAD/Au structure was prepared. By modification, the grain size of perovskite film is increased, the electron transport at the interface is accelerated, and the catalytic decomposition of perovskite film is restrained by the defects of the interface. Finally, the performance of the modified planar perovskite solar cells increased from 13.64% to 16.78%. meanwhile, The performance of unencapsulated devices was improved from less than 20% to more than 70% after 7 days of continuous illumination. (3) Polymerization of (3) 4-ethylenedioxythiophene (NiO) -polyphenylene (3) was prepared by thermal spray. Sulfonic acid (PEDOT:PSS) acts as a hole transport layer, Combined with the improved method of preparation of perovskite in chapter 2, the anti-perovskite solar cells with FTO/NiO/Perovskite/PCBM/Ag structure were assembled. Finally, the photoelectric conversion efficiency (PCE) of the battery is up to 16.34%, and the stability of the device is greatly improved.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM914.4
【参考文献】
相关期刊论文 前1条
1 郭旭东;牛广达;王立铎;;高效率钙钛矿型太阳能电池的化学稳定性及其研究进展[J];化学学报;2015年03期
，本文编号：2428933
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