Recently, the attention to sodium-ion batteries has been refocused on large-scale energy storage applications, due to sodium's low cost and infinite abundance. Sodium is one of the most abundant elements on earth and exhibits chemical properties similar to lithium. Owing to their superior sodium storage capability especially for excellent safety and stability, Ti-based compounds have been extensively investigated as both cathode and anode materials. Herein we outline the current cathodes and anodes, and emphasize the critical roles of titanium in developing advanced electrodes for sodium-ion batteries. The latest advances and progress in the exploration of Ti-based compounds with various different frameworks such as NASICON, tunnel, MXenes, spinel, and layered structures are systematically reviewed. The straightforward linking of the structure–function–property relationship for Ti-based compounds, especially for layered Na/Ti-containing oxides, is summarized and analyzed. The titanium element plays a critical role in both positive and negative electrodes, i.e., supplying the charge transfer and high safety for anodes and greatly enhancing the structural and cycling stability for cathodes. Based on the bi-functional roles of titanium, a new concept of symmetric Na-ion cells employing layered Na/Ti-containing oxides as bipolar electrodes is proposed and realized. Symmetric Na-ion cells already offered a high voltage and withstood long time charge–discharge processes, demonstrating the practicality beyond the proof of concept. The participation of titanium in sodium-based electrode materials will greatly promote the development of room-temperature sodium-ion batteries towards stationary energy storage.
