Extensible‐Aligned Liquid Crystalline Interphase Enabling Ordering‐Induced Deposition for Ultra‐Stable Zinc Metal Batteries

Zinc metal anodes for aqueous zinc metal batteries (AZMBs) are famous for their high theoretical capacity and environmental kindliness, but their practical deployment is prevented by dendrite growth triggered by chaotic ionic flows and rampant side reactions due to active H 2 O within the solvation structure. Herein, an extended‐range ordered liquid crystalline hydroxyapatite (OHA) nanorods with rich polar groups are initially designed as an orderly modulation interphase to regulate the behavior of ion transport and break down ion‐dipole interactions between Zn 2+ and H 2 O. As evidenced by experimentally and theoretically analyses, the abundant functional groups disrupt the hydrogen‐bond network and the zincophilic phosphate groups act as favorable nucleation sites, collaboratively reshaping the solvation shell and suppressing the activity of water. Simultaneously, the extended‐range ordered nanostructure of OHA can provide continuous and uniform Zn 2+ transport channel, suppressing ionic vortices and promoting homogeneous deposition. Furthermore, a derived organic–inorganic interphase gradually becomes visible as the cycle progresses, indicating enhanced reaction kinetics and interface stability. Therefore, the as‐fabricated symmetric cell maintains reversible stability of 2080 h cycling at 1 mA cm −2 . Full cells pairing with V 2 O 5‐x cathodes deliver 333 mAh g −1 after 3600 cycles at 5 A g −1 , showcasing promising potentials of extended‐range ordered liquid crystal for practical AZMBs.