Chemical durability and degradation mechanisms of CsPbI3 as a potential host phase for cesium and iodine sequestration

Abstract

Effective nuclear waste management of radioactive cesium and off-gas iodine from complex waste streams of used fuels is essential for the sustainable development of advanced nuclear fuel cycles. Once cesium and iodine are separated from their respective waste streams, host phases are required to immobilize them into a durable waste form matrix for long-term disposition. The inorganic metal halide perovskite, CsPbI₃, has a unique crystal structure capable of incorporating both cesium and iodine simultaneously. Exposure to groundwater in geological repositories is a long-term concern for waste forms, as this may cause corrosion and decrease the waste form's ability to retain radionuclides. In this study, we explore the potential of CsPbI₃ perovskite as a promising host phase to incorporate Cs and I, and investigate its chemical durability and degradation mechanisms in an aqueous environment. CsPbI₃ was synthesized through a solution-based method and was consolidated into dense pellets by spark plasma sintering. The chemical durability of the CsPbI₃ pellets was evaluated by static leaching tests in deionized water at different temperatures of 25, 58, and 90 °C. The elemental release mechanisms and surface alteration of the monolithic CsPbI₃ pellets were investigated. Both I and Cs displayed a non-congruent leaching behavior and faster release rates as compared to Pb, particularly at longer leaching durations and higher temperatures. At the initial leaching stage, a PbI₂ alteration layer formed on the surface of the pellet due to the rapid release of Cs and I, followed by the formation of a PbI(OH) alteration layer. The activation energies for both dissolution and diffusion controlled mechanisms were determined to be 44.90 kJ mol⁻¹ and 45.40 kJ mol⁻¹ for Pb, 27.10 kJ mol⁻¹ and 40.82 kJ mol⁻¹ for I and 24.27 kJ mol⁻¹ and 23.86 kJ mol⁻¹ for Cs, respectively. These results show a clear decrease in activation energies from Pb to I and Cs, suggesting a preferential release of I and Cs. The solution-based synthesis of CsPbI₃ as a host phase for Cs and I and the fundamental understanding of the chemical durability and degradation behavior will be useful for further exploring its application for immobilizing iodine and cesium into final durable waste forms for long-term geological disposition.