Oriented Crystal Growth of Li_0.33La_0.557TiO₃ Nanowire Induced by One-Dimensional Polymer Sheath toward Rapid Lithium-Ion Transfer

Superionic conductor-based solid-state electrolytes with preferred crystal structures hold great promise for realizing ultrafast lithium-ion (Li⁺) transfer, which is urgently desired for all-solid-state lithium batteries. However, the precise control of crystal growth of superionic conductors is still challenging since the crystals always spontaneously grow to disordered structures with the lowest internal energy to ensure thermodynamic stability. Herein, a coaxial nanowire with a polyvinylpyrrolidone (PVP) sheath and a Li_0.33La_0.557TiO₃ (LLTO) precursor core (PVP/LLTO-caNW) is prepared through coaxial electrospinning, followed by sintering into LLTO nanowire with an oriented crystal structure (LLTO-caNW). We demonstrate that the one-dimensional PVP sheath as a sacrificial layer generates uniform and the strongest adsorption ability on the (110) phase among different LLTO crystal planes, which induces the crystal to preferentially grow along the <i>c</i>-axis (the fastest Li⁺ transfer direction) during the nucleation and growth processes. As a result, the prepared LLTO-caNW displays an ultrahigh bulk ionic conductivity of 3.13 × 10^-3 S cm^-1, exceeding most LLTO crystals and approaching the theoretical conductivity. Meanwhile, the oriented crystal growth imparts to LLTO-caNW significantly reduced grain boundary resistance, and the grain-boundary conductivity reaches up to 1.09 × 10^-3 S cm^-1. This endows the composite solid electrolyte with high ionic conduction performance and superior cycle stability in the assembled all-solid-state lithium battery.