Regulating Na content and Mn defects in birnessite for high-voltage aqueous sodium-ion batteries

Na-birnessite is a promising low-cost positive electrode material for aqueous sodium-ion batteries. However, its sodium storage capability is limited by narrow potential window and low redox activity in aqueous electrolytes. Herein, a Na-rich birnessite (NaMnO2•0.1H2O) with a highly ordered layered structure is reported as an advanced positive electrode for aqueous sodium-ion batteries, greatly suppressing Mn migration and its accompanying domino degradation effect, which enables a promoted upper charging cut-off potential up to 1.4 V (vs. Ag/AgCl), an enhanced specific capacity of 199.9 mAh g−1 at a specific current of 0.2 A g−1 based on the mass of active material for positive electrode, and greatly improved structural stability. In particular, a 3.0 V NaxH2–xTi2O5||NaMnO2•0.1H2O aqueous full cell prototype is validated, exhibiting a large specific energy of 117.1 Wh kg−1 based on the total mass of active materials in both positive and negative electrodes as well as a long cycle life. This work elucidates how interlayer chemistry and structural defects influence sodium ion storage in layered structures and provides opportunities for developing high-voltage aqueous batteries with large specific energy. Instability is a key challenge in aqueous sodium-ion batteries. Here, authors propose a Na-rich birnessite with high Na content and minimal Mn defects, suppressing Mn migration and its accompanying domino degradation effect, which enables a wide potential window and improved structural stability.