Comparative Investigation of the Critical Role of Mn, Zn, and Mn/Zn Co‐Doping in Modulating Local Coordination Environment, Magnetic Behavior, and Supercapacitor Performance of α‐Cu ₂ V ₂ O ₇

Mn‐, Zn‐, and Mn/Zn‐doped α‐Cu 2 V 2 O 7 (CVO) samples are synthesized to investigate the interplay between local structural distortion, magnetic behavior, and electrochemical performance. Structural analysis via X‐ray diffraction, X‐ray absorption near edge structure, and extended X‐ray absorption fine structure, along with vibrational studies using Raman spectroscopy, confirms the substitutional incorporation of Mn and Zn at Cu sites. Doping introduces increased asymmetry in CuO bond lengths and bond angles, disrupting super‐exchange pathways. Temperature‐dependent magnetization measurements reveal a marginal decrease in the Néel temperature (T N ) with Zn and Mn/Zn co‐doping, while field‐dependent studies indicate enhanced magnetic hysteresis and a notable zero‐field‐cooled exchange bias. Electrochemical characterization highlights the strong influence of local structure: the Mn/Zn‐doped CVO exhibits the highest Debye–Waller factors (σ 2 ) for both first and second coordination shells, reduced Cu coordination number, and pronounced CuO1 and CuO2 bond length variations. These distortions promote enhanced charge storage, resulting in superior specific capacitance compared to singly doped analogs. This study underscores the critical role of the local coordination environment in simultaneously tailoring the magnetic and electrochemical properties of CVO‐based electrode materials.