High-Energy-Density Sodium-Ion Hybrid Capacitors Enabled by Interface-Engineered Hierarchical TiO₂ Nanosheet Anodes

Sodium-ion hybrid capacitors are known for their high power densities and superior cycle life compared to Na-ion batteries. However, low energy densities (<100 Wh kg–1) due to the lack of high-capacity (>150 mAh g–1) anodes capable of fast charging are delaying their practical implementation. Herein, we report a high-performance Na-ion hybrid capacitor based on an interface-engineered hierarchical TiO2 nanosheet anode consisting of bronze (∼15%) and anatase (∼85%) crystallites (∼10 nm). This pseudocapacitive dual-phase anode demonstrated exceptional specific capacity of 289 mAh g–1 at 0.025 A g–1 and excellent rate capability (110 mAh g–1 at 1.0 A g–1). The Na-ion hybrid capacitor integrating a dual-phase hierarchical TiO2 nanosheet anode and an activated carbon cathode exhibited a high energy density of 200 Wh kg–1 (based on the total mass of active materials in both electrodes) and power density of 6191 W kg–1. These values are in the energy and power density range of Li-ion batteries (100–300 Wh kg–1) and supercapacitors (5000–15 000 W kg–1), respectively. Furthermore, exceptional capacity retention of 80% is observed after 5000 charge–discharge cycles. Outstanding electrochemical performance of the demonstrated Na-ion hybrid capacitor is credited to the enhanced pseudocapacitive Na-ion intercalation of the two-dimensional TiO2 anode resulting from nanointerfaces between bronze and anatase crystallites. Mechanistic investigations evidenced Na-ion storage through intercalation pseudocapacitance with minimal structural changes. This approach of nanointerface-induced pseudocapacitance presents great opportunities toward developing advanced electrode materials for next-generation Na-ion hybrid capacitors.