High content anion (S/Se/P) doping assisted by defect engineering with fast charge transfer kinetics for high-performance sodium ion capacitors.

ABSTRACT

The rate-determining process for sodium storage in TiO2 is greatly depending on charge transfer happening in the electrode materials owing to its inferior diffusion coefficient and electronic conductivity. Apart from reducing the diffusion distance of ion/electron, the increasement of ionic/electronic mobility in the crystal lattice is also very important for charge transport. Here, an oxygen vacancy (OV) engineering assisted in high-content anion (S/Se/P) doping strategy to enhance charge transfer kinetics for ultrafast sodium-storage performance is proposed. Theoretical calculations indicate that OV-engineering evokes spontaneous S doping into the TiO2 phase and achieves high dopant concentration to bring about impurity state electron donor and electronic delocalization over S occupied sites, which can largely reduce the migration barrier of Na+. To realize the speculation, high-content anion doped anatase TiO2/C composites (9.82 at% for S in A-TiO2-x-S/C) are elaborately designed. The optimized A-TiO2-x-S/C anode exhibits extraordinarily high-rate capability with 209.6 mAh g-1 at 5000 mA g-1. The assembled sodium ion capacitors deliver an ultrahigh energy density of 150.1 Wh kg-1 at a power density of 150 W kg-1 when applied as anode materials. This work provides a new strategy to realize high content anion doping concentration, and enhances the charge transfer kinetics for TiO2, which delivers an efficient approach for the design of electrode materials with fast kinetic.