Dynamic Reversible Oxidation-Reduction of Iodide Ions for Operationally Stable Perovskite Solar Cells under ISOS-L-3 Protocol

Despite rapid advancements in the photovoltaic efficiencies of perovskite solar cells (PSCs), their operational stability remains a significant challenge for commercialization. This instability mainly arises from light-induced halide ion migration and subsequent oxidation into iodine (I₂). The situation is exacerbated when considering the heat effects at elevated temperatures, leading to the volatilization of I₂ and resulting in irreversible device degradation. Mercaptoethylammonium iodide (ESAI) is thus incorporated into perovskite as an additive to inhibit the oxidation of iodide anion (I⁻) and the light-induced degradation pathway of FAPbI₃→FAI+PbI₂. Additionally, the formation of a thiol-disulfide/I⁻-I₂ redox pair within the perovskite film provides a dynamic mechanism for the continuous reduction of I₂ under light and thermal stresses, facilitating the healing of iodine-induced degradations. This approach significantly enhances the operational stability of PSCs. Under the ISOS-L-3 testing protocol (maximum power point (MPP) tracking in an environment with relative humidity of ≈50% at ≈65 °C), the treated PSCs maintain 97% of their original power conversion efficieney (PCE) after 300 h of aging. In contrast, control devices exhibit almost complete degradation, primarily due to rapid thermal-induced I₂ volatilization. These results demonstrate a promising strategy to overcome critical stability challenges in PSCs, particularly in scenarios involving thermal effects.