Bio‐Mimetic Frozen Soil: Physical Water Confinement and Triple‐Phase Interface for Aqueous Cryogenic Quasi‐Solid Batteries

The freezing of aqueous electrolytes at subzero temperatures remains a fundamental challenge that severely limits the low‐temperature operation of rechargeable batteries. Here, we propose a biomimetic frozen soil quasi‐solid‐state electrolyte, which can regulate the state of water and inhibit ice formation by altering the physical environment of water. By constructing a biomimetic capillary network via colloidal assembly, it facilitates the formation of freezing‐resistant capillary and adsorbed water, enabling continuous ion transport pathways even under extreme conditions. Furthermore, a robust triple‐phase interfacial architecture‐composed of a colloidal skeleton, an inorganic robust phase, and an organic flexible phase is exquisitely designed, which synergistically suppresses dendrite growth, mitigates parasitic reactions, and enhances interfacial ion transport. As a result, the symmetric Zn//Zn cells achieve exceptional cycling stability over 9300 cycles at −40°C, and full cells paired with V 2 O 3 cathode retain 92% capacity after 1500 cycles under low‐temperature conditions. This work establishes a physical paradigm for designing anti‐freezing electrolytes and opens a generalized pathway toward high‐performance aqueous batteries capable of operating in harsh environments.