Although organometal halide perovskites (OHPs) have desirable photovoltaic properties, their photoelectrochemical (PEC) water‐splitting application for hydrogen production is limited by the instability originating from their intrinsic ionic defects and hygroscopic vulnerability. Herein, a highly efficient and stable OHP‐based photocathode achieved by a new zwitterion (L‐proline) passivation and a eutectic gallium indium alloy (EGaIn) encapsulation method is described. The zwitterion, which has both cations and anions, can simultaneously passivate both positively and negatively charged defects in OHPs. The resulting OHP photovoltaic cells with passivated shows an over 20% power conversion efficiency with an open‐circuit voltage of 1.13 V and a short‐circuit current of 22.13 mA cm−2. The EGaIn‐incorporated Ti foil provides complete encapsulation from the external environment while maintaining good transport of photogenerated charges from OHPs. Thus, these photocathodes exhibit a remarkable average photocurrent density of 21.2 mA cm−2 which has less than 5% current loss between PV cells and PEC cells. More admirably, the photocathode has the highest stability over 54 hours under continuous full sunlight illumination in a sulfuric acid electrolyte.

A long-term operational stability over 1000 hours in the inverted type perovskite solar cells based on the MAPbI3 layer is demonstrated under ionic defect-free conditions.

Ionic defects (e.g., organic cations and halide anions), preferably residing along grain boundaries (GBs) and on perovskite film surfaces, are known to be a major source of the notorious environmental instability of perovskite solar cells (PeSCs). Although passivating ionic defects is desirable, previous approaches using Lewis base or acid molecules as additives suppress only the negatively or positively charged defects, thus leaving oppositely charged defects. In this work, both the cationic and anionic defects inside methyl ammonium lead tri‐iodide (MAPbI3) are simultaneously passivated by introducing a zwitterionic form of the amino acid, L‐alanine, into the precursor solution as an additive. L‐alanine has both positive (NH3+) and negative (COO−) functional groups at a specific solvent pH, thereby passivating both the cation and anion defects in MAPbI3. The addition of L‐alanine increases the grain size of the perovskite crystals and lengthens the charge carrier lifetime (τ > 1 µs), leading to improved power conversion efficiencies (PCEs) of 20.3% (from 18.3% without an additive) for small‐area (4.64 mm2) devices and 15.6% (from 13.5%) for large‐area submodules (9.06 cm2). More importantly, the authors’ approach also significantly enhances the shelf storage and photoirradiation stabilities of PeSCs.