Abstract The low ion transport is a major obstacle for low‐temperature (LT) sodium‐ion batteries (SIBs). Herein, a core‐shell structure of bismuth (Bi) nanospheres coated with carbon (Bi@C) is constructed by utilizing a novel Bi‐based complex (1,4,5,8‐naphthalenetetracarboxylic dianhydride as the ligand) as the precursor, which provides an effective template to fabricate Bi‐based anodes. At −40°C, the Bi@C anode achieves a high capacity, which is equivalent to 96% of that at 25°C, benefitting from the core‐shell nanostructured engineering and Na+‐ether‐solvent cointercalation process. The special Na+‐diglyme cointercalation behavior may effectively reduce the activation energy and accelerate the Na+ diffusion kinetics, enabling the excellent low‐temperature performance of the Bi@C electrode. As expected, the fabricated Na3V2(PO4)3//Bi@C full‐cell delivers impressive rechargeability in the ether‐based electrolyte at −40°C. Density functional theory calculations and electrochemical tests also reveal the fast reaction kinetic mechanism at LT, thanks to a much lower diffusion energy barrier (167 meV) and a lower reaction activation energy (32.2 kJ mol−1) of Bi@C anode in comparison with that of bulk Bi. This work provides a rational design of Bi‐based electrodes for rechargeable SIBs under extreme conditions.
