Regulating Multi‐Metal Ion Orbital Interactions to Enhance Kinetics and Structural Stability in Lithium Manganese Iron Phosphate Cathodes

ABSTRACT Lithium manganese iron phosphate (LMFP) offers high safety and high energy density for lithium‐ion batteries, yet its commercialization is bottlenecked by poor conductivity and severe Jahn–Teller (J–T) distortion. Here, we report a multi‐metal ion (Ni, Cu, Ti) orbital engineering strategy to simultaneously decouple these twin challenges in a customized LiMn 0.475 Fe 0.475 Ni 0.03 Cu 0.01 Ti 0.01 PO 4 (LMFP‐NCT) cathode. Mechanistically, enhanced orbital hybridization between heteroatoms and the host lattice optimizes localized electronic distribution and narrows the bandgap, boosting intrinsic conductivity and ionic diffusivity by an order of magnitude. Importantly, the tailored orbital occupation effectively suppresses e g orbital degeneracy, transitioning the MnO 6 octahedra into a structurally robust, controlled‐distortion state. Supported by the d ‐band center theory, this strategy enhances metal‐oxygen σ ‐bonds, leading to minimal volume variation (4.29%) and suppressed Mn dissolution (reduced by 48.4%). Consequently, the LMFP‐NCT delivers doubled capacity at 6C compared with LMFP and an exceptional 92.3% capacity retention after 1000 cycles at 1C. When paired in full cells, it maintains 96.4% of its capacity over 500 cycles. This work provides profound insights for designing high‐performance LMFP cathodes by fundamentally conquering J–T distortion and kinetic limitations.