High‐Performance Perovskite Solar Cells via Synergistic Grating Microstructures and Dynamic‐Bonded Ion‐Conductive Elastomers

Abstract Perovskite solar cells (PSCs) have emerged as a prominent focus in energy research owing to their remarkable power conversion efficiency (PCE). However, the realization, maintenance, and even repair of the high efficiency of perovskite solar cells are still difficult research issues. Herein, a synergistic strategy of grating microstructures and ion‐conducting elastomers (ICE) based on dynamic hindered urea‐carbamate bonds is proposed to realize high‐efficiency and long‐term stable PSCs. The grating microstructured PbI₂ (G‐PbI₂) can initially optimize the crystallization behavior of perovskite, based on the fact that the introduction of ICE in PbI₂ achieves 25.61% efficient PSCs. The ICE featuring graded hindered urea‐carbamate dynamic bonds demonstrates triple‐functionality: i) Abundant carbonyl (‐C(O)‐) coordination sites within the ICE strongly interact with PbI₂, enhancing perovskite crystallization kinetics; ii) The ICE intrinsic conductivity facilitates efficient charge carrier transport and extraction at grain boundaries and interfaces; iii) The moisture‐responsive behavior of hindered urea bonds coupled with dynamic bond reorganization endows the device with exceptional hydrothermal stability (T₈₀>1500 h), and even more interestingly, ICE‐containing devices can be simply heat‐treated to recover photovoltaic performance. A synergistic strategy of ICE based on hierarchical dynamic covalent networks and microstructures opens new insights into the field of constructing, maintaining, and restoring high‐efficiency PSCs.