Perovskite solar cells (PSCs) represent a promising next‐generation photovoltaic technology considering their high efficiency and low cost. At the current stage, resolving the stability bottleneck is extremely urgent to realize PSCs’ commercialization since the efficiencies of these cells are improved to a level comparable to that of crystalline silicon solar cells. Similar to other functional layers, a proper choice of the rear electrode atop the perovskite layer is equally important for achieving the device's long‐term stability. This topic has not been comprehensively reviewed before. Here, recent progress in the development of rear electrodes based on metals, carbon‐based materials, transparent conductive oxides, and conductive polymers is summarized, especially focusing on their different impacts on the device's long‐term stability and associated degradation mechanisms. In the context of practical applications, the impacts of rear electrode materials on the device's overall efficiency and cost‐effectiveness are also discussed.

It is widely believed that excess/residual lead iodide (PbI2) can affect the performance of perovskite solar cells . Moderate PbI2 can enhance efficiency by passivating defects, while extremely active PbI2 leads to non‐negligible hysteresis effects and reduces device stability. Although several efforts are made to investigate the role of excess PbI2, its impact is still underestimated. Recent advances further demonstrate the extraordinary potential of modifying excess PbI2; however, a comprehensive study is required to obtain a deeper understanding. Herein, the important breakthroughs regarding excess PbI2 are reviewed and the mechanism of excess PbI2 in terms of efficiency and stability is rethought. In addition, the origins, verification, and regulation of residual PbI2 are summarized.

In perovskite solar cells, the formation of residual/excess lead iodide (PbI2) in the perovskite film is detrimental to device stability. However, the understanding of the effect of residual/excess PbI2 and...