Construction and Operating Mechanism of High‐Rate Mo‐Doped Na 3 V 2 (PO 4 ) 3 @C Nanowires toward Practicable Wide‐Temperature‐Tolerance Na‐Ion and Hybrid Li/Na‐Ion Batteries

The growing demand for cost‐efficiency and safe energy storage systems has stimulated enormous interest worldwide in advanced cathodes for practicle “beyond‐Li‐ion” batteries. Herein, a feasible electrospinning/annealing avenue for the construction of 1D Mo‐doped Na 3 V 2 (PO 4 ) 3 nanowires in situ coated with carbon nanoshell (MNVP@C NWs) toward next‐generation Na‐ion batteries (NIBs) and hybrid Li/Na‐ion batteries (HLNIBs) as a high‐rate cathode material, is reported. Particularly, the intrinsic hybrid Li/Na‐ion storage mechanism of the MNVP@C NWs is unveiled for the HLNIBs with comprehensive characterizations. The resultant MNVP@C NWs demonstrate rapid electronic/ionic transport and rigid structural tolerance within operating temperatures from ‐25 to 55 °C, benefiting from its unique structural/compositional merits. More competitively, the MNVP@C NWs assembled pouch‐type NIBs (‐15 to 25 °C) and HLNIBs (‐25 to 55 °C) both exhibit remarkable wide‐temperature‐tolerance electrochemical properties in terms of high‐rate capabilities and long‐duration cycling lifespan, along with material‐level energy densities of ≈262.4 and ≈186.1 Wh kg ‐1 at 25 °C, respectively. The contribution here is expected to exert a stimulative impact upon the future design of versatile cathodes for advanced high energy/power rechargeable batteries.