A Novel Plastic‐Crystal Electrolyte with Fast Ion‐Transport Channels for Solid Zinc‐Ion Batteries

Abstract Miniaturized solid zinc‐ion batteries that are safe, environmentally friendly, and low‐cost are ideal candidates for powering emerging microelectronics. However, sluggish Zn 2+ mobility in solid phases hampers the viability of solid Zn 2+ electrolytes and hence their practicability. Here, nanoscale Zn 2+ channels are successfully engineered in a plastic‐crystal electrolyte, thus activating fast Zn 2+ solid‐state transport. The ion‐dipole interaction exerted by water molecules orients amphiphilic anions in bilayers, further forming a layered architecture backed by long‐range van der Waals attractive forces. In the interlayer, the heteroleptic coordination contributed by the water molecule and anion frees the Zn 2+ from anionic traps, leading to a high Zn 2+ conductivity of 2.2 × 10 −3 S cm −1 . This elaborately tailored texture confers a combination of robust mechanical characteristics and outstanding electrochemical performance upon the resultant electrolyte. The applicability is demonstrated by the high Zn 2+ platting/stripping efficiency (99.6%), durable longevity of symmetric Zn‐Zn and Zn‐MnO 2 cells, as well as the engineering of versatile micro batteries (MBs). This work provides new perspectives for developing super multivalent ion conductors through the innovative design of ion‐conducting nanochannels.