Breaking the Electronic Conductivity Bottleneck of Manganese Oxide Family for High‐Power Fluorinated Graphite Composite Cathode by Ligand‐Field High‐Dimensional Constraining Strategy

Abstract Primary lithium fluorinated graphite (Li/CF_x) batteries with superior energy density are an indispensable energy supply for multiple fields but suffer from sluggish reaction kinetics of the CF_x cathode. Designing composite cathodes emerges as a solution to this problem. Despite the optimal composite component for CF_x, the manganese oxide family represented by MnO₂ is still faced with an intrinsic electronic conductivity bottleneck, which severely limits the power density of the composite cathode. Here, a cation‐induced high‐dimensional constraining strategy from the perspective of ligand‐field stacking structure topological design, which breaks the molecular orbital hybridization of pristine semiconductive oxides to transform them into the high‐conductivity metallic state while competitively maintaining structural stability, is proposed. Through first‐principles phase diagram calculations, mixed‐valent Mn₅O₈ () is explored as an ideal high‐dimensional constraining material with satisfied conductivity and large‐scale production feasibility. Experiments demonstrate that the as‐proposed CF_x @ Mn₅O₈ composite cathode achieves 2.36 times the power density (11399 W kg⁻¹) of pristine CF_x and a higher CF_x conversion ratio (86%). Such a high‐dimensional field‐constraining strategy is rooted in the established four‐quadrant electronic structure tuning framework, which fundamentally changes the orbital symmetry under the ligand field to overcome the common conductivity challenge of wide transition metal oxide materials.