Introducing Ce Into CuFePBA@CuCo‐ldh to Construct Mott–Schottky Heterojunctions with Optimized Electron Redistribution for High‐Performance Supercapacitors

Abstract Designing Schottky heterojunctions with tunable interfacial electronic structures can effectively optimize charge transport dynamics. In this work, a novel strategy to modulate the electronic structure of CuColdh is proposed by introducing cerium (Ce d ) into CuFe PBA@CuCo‐ldh composites (CFP@ldh) to construct Mott–Schottky (M–S) heterojunctions and obtaining two different junction types (double Schottky heterojunction). The synthesized CFP@Ce d ldh exhibits a distinctive microsphere structure comprising numerous nanoneedles, enhancing the formation of electroactive sites and inducing a built‐in electric field. In addition, the introduction of Ce in CuCo‐ldh together with the close contact between CuCo‐ldh and CFP forms a double Schottky heterostructure, which leads to strong interfacial interactions and facilitates the diffusion of the electrolyte ions by decreasing the energy barrier at the interface. Furthermore, Density‐functional theory (DFT) calculations further confirm that the formation of the “double Schottky heterojunction” increases the electron density near the Fermi energy level of CFP@Ce d ldh, which promotes ion diffusion and charge transport. The electrochemical performance of CFP@Ce d ldh is markedly improved, with specific capacity increasing from 690 to 992 C g −1 . The hybrid supercapacitor (CFP@Ce d ldh//AC) achieved 86.52% capacitance retention after 10 000 cycles. This study presents a promising avenue for designing high‐performance electrode materials with Mott–Schottky heterojunctions.