Ultrafast and Highly Efficient Sodium Ion Storage in Manganese‐Based Tunnel‐Structured Cathode

Na0.44MnO2 with tunnel structure is considered a promising low‐cost cathode material for sodium‐ion batteries. However, the sluggish Na+ transport kinetics and low initial Coulombic efficiency restrict its practical applications in rechargeable sodium‐ion batteries. Herein, a manganese‐based tunnel‐structured cathode with high rate capability and high initial Coulombic efficiency is prepared by niobium doping and sodium compensation. Via materials characterizations and theoretical calculations, it is demonstrated that a proper amount of niobium doping in tunnel structure can effectively improve its structural stability and charge transport kinetics, resulting in outstanding rate capability (76.6% capacity retained from 0.5 to 30 C) and superior cycling performance (82.3% capacity retention after 800 cycles at 5 C) for the optimized Nb‐doped Na0.44MnO2 cathode (Na0.44Mn0.98Nb0.02O2). Furthermore, NaCrO2 is added into the Na0.44Mn0.98Nb0.02O2 cathode as a self‐sacrificing sodium compensation additive, and a high initial Coulombic efficiency close to 100% is achieved for the composite cathode. This work establishes a facile strategy to design advanced manganese‐based cathode materials for large‐scale energy storage applications. The introduction of Nb in tunnel Na0.44MnO2 can simultaneously reinforce the tunnel structure and enable fast electron and Na+ transport, thus resulting in greatly improved cycle life and rate capability. Using NaCrO2 for Na compensation, a high initial coulombic efficiency can be obtained for the tunnel type cathode, and the assembled pouch type full cell achieves a high energy density.