The rational design of anode materials is a challenge in developing sodium ion batteries. Alloy anodes provide high gravimetric and volumetric capacities but suffer the short cycle life as a result of the continuous and accumulated pulverization, resulting from a large volume change during the cycling process. Herein, using pure Sn, an irreversible conversion reaction combined with an alloy reaction (SnO), and a reversible conversion reaction combined with an alloy reaction (Sn4P3) as samples, we demonstrate that the pulverization and aggregation of the alloy anode can be partially recovered and the accumulation of pulverization and aggregation during charge/discharge cycles can be terminated using a reversible conversion reaction combined with an alloy reaction. The cycling stability of three Sn-based anodes increases in order of Sn4P3 > SnO > Sn. The enhancement in Sn4P3 can be attributed to a reversible reaction of Sn4P3 + 9Na ↔ 4Sn + 3Na3P, which repairs the cracks, damage, and aggregation of Sn particles that occurred in the alloy process of 4Sn + 15Na ↔ Na15Sn4 during cycling and, hence, terminates the pulverization. The repair mechanism looks like the self-healing feature in nature, where the damage can be healed by itself. Therefore, the suggested mechanism can be called self-healing, while the repaired anode can be termed as the self-healing anode. The use of self-healing strategies to build an electrode architecture is new and highly desirable because it can increase the cycle life and provide a general approach toward stable electrode materials.
Keywords: alloy anode; cycling stability; self-healing; sodium-ion batteries; tin anode.