Enhancing Na-Ion Storage at Subzero Temperature via Interlayer Confinement of Sn²⁺

Sluggish kinetics and limited reversible capacity present two major challenges for layered titanates to achieve satisfactory sodium-ion storage performance at subzero-temperatures (subzero-T). To facilitate sodiation dynamics and improve reversible capacity, we proposed an additive-free anode with Sn­(II) located between layers. Sn-5s in interlayer-confining Sn­(II), which has a larger negative charge, will hybridize with O-2p to trigger charge redistribution, thereby enhancing electronic conductivity. H-titanates with an open framework are designed to stabilize Sn­(II) and restrain subsequent volume expansion, which could potentially surpass the capacity limitation of titanate-based materials via a joint alloying–intercalation reaction with high reversibility. Moreover, the generation of conductive Na₁₄Sn₄ and the expansion of interlayer spacing resulting from the interlayered alloying reaction are beneficial for charge transfer. These effects synergistically endow the modified sample with a considerably lower activation energy and a 3-fold increase in diffusion. Consequently, the designed anode delivers excellent subzero-T adaptability when compared to the unmodified sample, maintaining capacity retention of 91% after 1200 cycles at −20 °C and 90% after 850 cycles at −30 °C.