Control of Halogen Atom in Inorganic Metal‐Halide Perovskites Enables Large Piezoelectricity for Electromechanical Energy Generation

Abstract Regulating the strain of inorganic perovskites has emerged as a critical approach to control their electronic and optical properties. Here, an alternative strategy to further control the piezoelectric properties by substituting the halogen atom (I/Br) in the CsPbX 3 perovskite (X = Cl, Br) structure is adopted. A series of piezoelectric materials with excellent piezoelectric coefficients ( d 33 ) are unveiled. Iodine‐incorporated CsPbBr 2 I demonstrates the record intrinsic piezoelectric response ( d 33 ≈47 pC N −1 ) among all inorganic metal halide perovskites. This leads to an excellent electrical output power of ≈ 0.375 mW (24.8 µW cm −2 N −1 ) in the piezoelectric energy generator (PEG) which is higher than those of the pristine/mixed perovskite references with CsPbX 3 (X = I, Br, Cl). With its structural phase remaining unchanged, the strained CsPbBr 2 I retains its superior piezoelectricity in both thin film and nanocrystal powder forms, further demonstrating its repeatability and versatility of applications. The origin of high piezoelectricity is found to be due to halogen‐induced anisotropic lattice strain in the unit‐cell along the c ‐axis, and octahedral distortion. This study reveals an avenue to design new piezoelectric materials by modifying their halide constituents and paves the way to design efficient PEGs for improved electromechanical energy conversion.