Three-Dimensionally Printed Ionogel-Coated Ceramic Electrolytes for Solid-State Lithium Batteries.

Wei, Liying; Feng, Yan; Ge, Shuhui; Liu, Shujie; Ma, Yanyan; Yan, Jianhua · ACS Nano · 2025

basic_science · Level V

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Abstract

Stereolithography three-dimensional (3D) printing technology enables the customization of ceramic-based solid electrolyte structures with desired electrochemical properties; however, formulating slurries that both are highly ceramic-loaded and have low viscosity for printing poses a challenge. Here, we propose an ionogel-coated ceramic approach to prepare a shear-thinning fast-ion conductor ceramic (Li<sub>6.5</sub>La<sub>3</sub>Zr<sub>1.5</sub>Ta<sub>0.5</sub>O<sub>12</sub>) slurry, which possesses both a high ceramic content of 50 wt % and a low viscosity of 1.53 Pa·s. Utilizing this slurry, 3D symmetric honeycomb briquette-like electrolyte films are printed, and solid-state lithium batteries are easily fabricated by filling the cathode and anode slurries into the respective symmetric honeycombs. The atomic-level interaction between ceramic/ionogel interfaces and the integrated electrode/electrolyte interface facilitates rapid Li<sup>+</sup> transport across multiscale interphases in batteries. Additionally, the interactions of ceramic nanoparticles and ionic liquids with Li salt substantially increase the concentration of free Li<sup>+</sup>, both of which enhance the ionic conductivity and ensure stable Li<sup>+</sup> transport efficiency. Solid-state lithium batteries can cycle stably 500 times without obvious degradation at 0.5 C and 50 °C. The strategy offers a feasible solution for printing customized solid-state ceramic-based electrolytes.