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On the nature of the thermal decomposition of methylammonium lead iodide perovskite, CH3NH3PbI3: an attempt to rationalise contradictory experimental results

Abstract

The nature of the gas phase released during the thermal decomposition of CH3NH3PbI3 (methylammonium lead iodide) to PbI2 (lead diiodide) under vacuum is discussed on the basis of thermodynamic predictions, recently published experimental results, and new experiments presented here. From the scanty data currently available the nature of the main decomposition path is not clear, because both the process releasing HI(g) + CH3NH2(g) (1) and that leading to NH3(g) + CH3I(g) (2) were observed under different conditions. Our thermodynamic analysis show that process (2) is largely favoured for all the CH3NH3PbX3 (X = Cl, Br, I) compounds. However, Knudsen Effusion Mass Spectrometric experiments presented here (temperature range 140 °C – 240 °C) show that HI(g) and CH3NH2(g) are the largely prevailing species in the vapor, with process (2) occurring to a much smaller extent than suggested from thermodynamic driving force, thus remaining of minor importance under effusion conditions. We also found that this process is comparatively enhanced by high temperatures and low effusion rates (high impedance orifice). Our experimental evidence suggests that the thermodynamically favoured process(2) is affected by a significant kinetic hindrance. In the overall, the prevailing decomposition path is likely to depend markedly on the actual operative conditions

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Publication details

The article was received on 26 Feb 2017, accepted on 04 May 2017 and first published on 08 May 2017


Article type: Paper
DOI: 10.1039/C7SE00114B
Citation: Sustainable Energy Fuels, 2017, Accepted Manuscript
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    On the nature of the thermal decomposition of methylammonium lead iodide perovskite, CH3NH3PbI3: an attempt to rationalise contradictory experimental results

    A. Latini, G. Gigli and A. CICCIOLI, Sustainable Energy Fuels, 2017, Accepted Manuscript , DOI: 10.1039/C7SE00114B

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