Galvanic Interfacial Reconstruction Enables Ultralong‐Life Low‐Temperature Organic Zinc‐Ion Batteries

ABSTRACT Rechargeable zinc‐ion batteries are promising for large‐scale energy storage; however, hydrogen evolution, corrosion, and freezing in aqueous electrolytes, coupled with high polarization and insufficient interfacial regulation in organic electrolytes, severely restrict their long‐life operation over a wide temperature range. Here, we report a galvanic interfacial reconstruction strategy in a DMF‐based organic electrolyte through the introduction of InCl 3 . The spontaneous galvanic displacement reaction between Zn and In 3+ forms an In‐rich heterometallic interphase (In‐HMI) on the Zn surface without substantially perturbing the DMF‐dominated Zn 2+ solvation structure. This zincophilic interphase provides uniformly distributed heterogeneous nucleation sites, effectively lowers the Zn nucleation barrier, homogenizes Zn 2+ deposition, and suppresses dendrite growth, thereby endowing the DMF‐In electrolyte with excellent low‐temperature Zn plating/stripping reversibility. Consequently, Zn||Zn symmetric cells operate stably for over 15 000 h at −40°C under 1.0 mA cm −2 /1.0 mAh cm −2 with low polarization. Moreover, Zn||VO 2 full cells retain a stable capacity of 90 mAh g −1 after 1000 cycles at −40°C and 0.5 C. The corresponding Zn||NH 4 V 4 O 10 pouch cell also maintains stable cycling under a high total active‐material loading of 186.5 mg, highlighting the viability of galvanic interfacial reconstruction for durable low‐temperature organic zinc‐ion batteries.