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

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 Mn₅ O₈ ( Mn 2 2 + Mn 3 4 + O 8 ${\rm{Mn}}_2^{2 + }{\rm{Mn}}_3^{4 + }{{\rm{O}}_8}$ ) 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 @ Mn₅ O₈ 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.