Boosting the Electrochemical Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, Mn_yFe_1-yF₃@CF_x was generated by the all-fluoride strategy, converting most of the carbon in Mn_yFe_1-yF₃@C into electrochemical active CF_x through a controllable NF₃ gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite. The loading mass of the active substance had been increased to 86%. The theoretical and actual discharge capacity of Mn_yFe_1-yF₃@CF_x composite was up to 765 mAh g^-1 (pure FeF₃ is 712 mAh g^-1) and 728 mAh g^-1, respectively. The discharge capacity at the high-voltage (3.0 V) platform was more than three times higher than that of the non-Mn-doped composite (FeF₃@CF_x).