LAUSR

Primary lithium fluorinated graphite (Li/CFx) batteries with superior energy density are an indispensable energy supply for multiple fields but suffer from sluggish reaction kinetics of the CFx cathode. Designing composite cathodes emerges as a solution to this problem. Despite the optimal composite component for CFx, 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 ( Mn22+Mn34+O8${\rm{Mn}}_2^{2 + }{\rm{Mn}}_3^{4 + }{{\rm{O}}_8}$ ) is explored as an ideal high‐dimensional constraining material with satisfied conductivity and large‐scale production feasibility. Experiments demonstrate that the as‐proposed CFx @ Mn5O8 composite cathode achieves 2.36 times the power density (11399 W kg−1) of pristine CFx and a higher CFx 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.