Engineering doping-vacancy double defects and insights into the conversion mechanisms of an Mn–O–F ultrafine nanowire anode for enhanced Li/Na-ion storage and hybrid capacitors

The behavior of Li/Na-ion capacitors (LICs/NICs) is largely limited by the low number of electroactive sites in conventional insertion-type anodes. In this work, we demonstrated a novel doping-vacancy double-defective and conversion-type Mn-O-F ultrafine nanowire (denoted as MnF2-E) anode to boost the number of electroactive sites for enhanced LICs/NICs. Owing to the unique hetero oxygen-doping and intrinsic fluorine-vacancy double defects, the Mn-O-F nanowires exhibited superior electroactive sites and thus dramatically enhanced Li/Na-ion storage capability than pristine MnF2 micro/nano-crystals. Both the optimal MnF2 screened by orthogonal experiments and derived Mn-O-F anodes and commercial activated carbon (AC) cathode were used to construct MnF2//AC and MnF2-E//AC LICs/NICs, which were optimized by tuning the active mass ratios of the cathode/anode and the working voltage windows of the hybrid capacitors. The LICs/NICs based on the Mn-O-F anode demonstrated a considerably superior performance than the devices based on the MnF2 anode under the optimal voltages of 0-4 V and 0-4.3 V. The Mn-O-F anode exhibited dominant diffusion/surface-controlled kinetics for Li/Na-ion storage, respectively, showing a major conversion mechanism for the charge storage processes. This work provides a new concept of double-defective and conversion-type electrode materials to improve the Li/Na-ion storage capability and will have a significant impact on the relevant fields.