有機(jī)無機(jī)雜化鈣鈦礦太陽能電池的制備與穩(wěn)定性研究
發(fā)布時(shí)間：2019-02-23 14:53
【摘要】：近幾年來,基于有機(jī)無機(jī)雜化鈣鈦礦材料CH3NH3PbI3的第三代太陽電池——鈣鈦礦太陽能電池(Perovskite solar cells)備受人們關(guān)注,被《Science》評選為2013年十大科學(xué)突破之一。得益于其制備成本低,光譜吸收效率高和載流子擴(kuò)散長度長(1?m)等特點(diǎn),這類電池得到了快速的發(fā)展。其光電轉(zhuǎn)換性能(Power conversion efficiency)在短短6年時(shí)間內(nèi)已經(jīng)達(dá)到了22.1%的NREL認(rèn)證效率。盡管鈣鈦礦太陽能電池的光電轉(zhuǎn)換性能不斷被刷新,鈣鈦礦薄膜在潮濕空氣中制備時(shí)易分解和器件不穩(wěn)定的問題仍舊限制著鈣鈦礦太陽能電池的發(fā)展。本文從提高鈣鈦礦薄膜和器件的穩(wěn)定性入手,通過加入過量甲基碘化胺(CH3NH3I,MAI)到鈣鈦礦前驅(qū)體溶液中,抑制薄膜在空氣中分解,降低鈣鈦礦薄膜缺陷;通過使用具有自組裝功能的富勒烯材料(PCBDAN)修飾TiO2電子傳輸層,提高了平面結(jié)構(gòu)的鈣鈦礦太陽能電池性能,同時(shí)抑制器件光電轉(zhuǎn)換效率在持續(xù)光照下的衰減;最后,通過使用噴霧熱解法制備的NiO取代3,4-乙烯二氧噻吩聚合制備聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)作為空穴傳輸層,制備反型結(jié)構(gòu)鈣鈦礦太陽能電池,并研究了器件的穩(wěn)定性。取得的研究結(jié)果如下:(1)提出了一種在常規(guī)濕度空氣條件下(濕度~50%RH)制備高質(zhì)量的鈣鈦礦薄膜的辦法:通過優(yōu)化鈣鈦礦前驅(qū)體中甲基碘化胺MAI過量的比例,控制鈣鈦礦薄膜在空氣中加熱的時(shí)間,得到由均勻晶粒組成且無孔洞的鈣鈦礦薄膜。通過XRD分析,鈣鈦礦薄膜在潮濕空氣中加熱分解的問題得到解決。通過XPS分析,過量MAI可以抑制鈣鈦礦薄膜中金屬鉛(Pb0)的出現(xiàn),同時(shí)鈣鈦礦晶體中的碘鉛比(I/Pb)從2.51提高到2.91,更加接近單個(gè)鈣鈦礦晶體中I/Pb成分的比例。通過熒光光譜(PL)和時(shí)間分辨熒光光譜(TRPL)測試表明,鈣鈦礦薄膜的PL強(qiáng)度提升了1倍,載流子壽命(?)從25.4 ns提高到101.8 ns。最終,在空氣中制備結(jié)構(gòu)為FTO/Compact TiO2/Mesoscopic TiO2/MAPbI3/Spiro-oMeTAD/Au的正向支架鈣鈦礦太陽能電池的性能從14.06%提升到18.23%。(2)以自組裝的富勒烯電子傳輸材料PCBDAN修飾二氧化鈦界面,制備結(jié)構(gòu)為FTO/Compact TiO2/PCBDNAN/Perovskite/Spiro-oMeTAD/Au的平面鈣鈦礦太陽能電池。通過修飾,提高了鈣鈦礦薄膜的晶粒大小,加快了界面的電子傳輸,抑制了界面的缺陷對鈣鈦礦薄膜的催化分解。最終,修飾后的平面鈣鈦礦太陽能電池的性能從13.64%提高到了16.78%。同時(shí),未封裝的器件在7日持續(xù)光照后器件性能從低于20%提升到大于70%。(3)用熱噴霧制備NiO取代3,4-乙烯二氧噻吩聚合制備聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)作為空穴傳輸層,結(jié)合第二章鈣鈦礦制備的改進(jìn)方法,組裝結(jié)構(gòu)為FTO/NiO/Perovskite/PCBM/Ag的反型結(jié)構(gòu)鈣鈦礦太陽能電池。最終電池的光電轉(zhuǎn)化效率PCE高達(dá)16.34%,并且器件的穩(wěn)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.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM914.4
本文編號：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.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM914.4
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 郭旭東;牛廣達(dá);王立鐸;;高效率鈣鈦礦型太陽能電池的化學(xué)穩(wěn)定性及其研究進(jìn)展[J];化學(xué)學(xué)報(bào);2015年03期
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