Intrinsic thermal decomposition pathways of lead halide perovskites APbX3
Intrinsic thermal decomposition pathways of lead halide perovskites APbX3
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DOI：
10.1016/j.solmat.2020.110559
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发表时间：
2020-08-15
影响因子：
6.9
通讯作者：
Troshin, Pavel A.
中科院分区：
文献类型：
--
作者：
Akbulatov, Azat F.;Martynenko, Vyacheslav M.;Troshin, Pavel A.
本文系统地研究了一系列复合卤化铅APbX(3)作为钙钛矿型太阳能电池吸收材料的本征热稳定性。在力学上，钙钛矿APbX(3)在热应力条件下首先分解形成PbX2和AX盐。后者的热分解产生多个挥发性产物，并用质谱仪进行分析。我们重新确认了MAPbI(3)的CH3I+NH3分解路线，并首次观察到CH4、乙烯和HI(由CH3I形成)。在FAPbI(3)中，与NH4I和HCN一起形成了2-氨基丙二腈(而不是最近报道的1，3，5-三氮)。重要的是，卤化铅钙钛矿的稳定性与其结构中包含的一价阳离子卤化物(或其分解产物)的挥发性有很好的相关性。特别是，MAPbX(3)的稳定性最低，因为它们包含了最易挥发(或容易分解)的甲基卤化铵MAX。相反，全无机CsPbX3在太阳能电池运行条件下不挥发，因此具有显著的组成稳定性。所建立的关系和材料分解途径为合理设计适用于地面和空间应用的具有更高热稳定性的新型钙钛矿型太阳能电池吸波材料提供了重要的指导。
We present a systematic study on intrinsic thermal stability of a series of complex lead halides APbX(3), used as absorber materials in perovskite solar cells. Mechanistically, the perovskites APbX(3) were shown to decompose under thermal stress conditions initially to form PbX2 and AX salts. Thermolysis of the latter yields multiple volatile products, which were analyzed by mass spectrometry. We reconfirmed the CH3I + NH3 decomposition route for MAPbI(3) and observed for the first time CH4, ethylene and HI (formed from CH3I). In case of FAPbI(3), the formation of 2-aminomalononitrile (not 1,3,5-triazine as reported recently) was revealed along with NH4I and HCN. Importantly, the stability of the lead halide perovskites shows a good correlation with the volatility of univalent cation halides (or their decomposition products) incorporated in their structure. In particular, MAPbX(3) have the lowest stability since they incorporate the most volatile (or easy to decompose) methylammonium halides MAX. On the contrary, all-inorganic CsPbX3 show remarkable compositional stability since CsBr and CsI are non-volatile under the solar cell operation conditions. The established relationship and material decomposition pathways provide important guidelines for rational design of novel absorber materials for perovskite solar cells with improved thermal stability suitable for terrestrial and space applications.