Dynamic Covalent Chemistry Enabled Self-Healing and Antifreezing Eutectogel Electrolyte for Long-Life Zinc-Ion Batteries

Zinc-ion batteries (ZIBs) are regarded as promising candidates for flexible wearable electronics due to their high safety, environmental friendliness, and low cost. However, the uncontrollable dendrite growth and side reactions at the zinc anode hinder their practical application. Here, we report a multinetwork antifreeze eutectogel (SB eutectogel) electrolyte that demonstrates superior self-healing efficiency (70%) with Schiff base. The synergistic effects of the dynamic imine bonds and metal-coordination interactions endow the SB eutectogel with antifreezing capability (Tg = -95.1 °C), robust environmental adaptability, a strong binding energy of -35.68 eV, high conductivity (1.71 mS·cm⁻¹), and a wide electrochemical stability window, which collectively suppress zinc dendrite growth and parasitic reactions throughout cycling. The Zn//Zn symmetric cell with this electrolyte demonstrates an extended cycling life of 1800 h (0.2 mA·cm⁻²/ 0.2 mAh·cm⁻²), and the Zn//PANI full cell exhibits 80.15% retention of its original specific capacity after 2850 cycles, with an average Coulombic efficiency of 99.88%. Furthermore, the Zn//Zn cell exhibits prolonged cycling stability, with a duration of 800 h at -20 °C (0.1 mA·cm⁻²/0.1 mAh·cm⁻²). Additionally, flexible batteries based on SB eutectogel electrolytes can power light bulb at low temperatures. This Schiff-based eutectogel electrolyte with excellent self-healing efficiency, freezing resistance, and high electrochemical stability is expected to pave the way for the development of high-performance flexible energy storage and wearable devices.