Аннотация:A novel approach is proposed to design high-quality NASICON–type solid-state electrolytes (SSEs) based on Li1.3Al0.3Ti1.7(PO4)3 (LATP) by incorporating nanoparticles into a matrix of microparticles, which could efficiently improve densification of LATP SSEs by sintering. Moreover, LATP SSEs with bimodal microstructures are obtained by tuning mass ratio of 60 nm and 600 nm ceramic particles, which are fabricated by sol-polymer and molten quenching methods, respectively. The LATP SSE containing 60 nm and 600 nm particles with the mass ratio of 10%/90% displays a high ionic conductivity of (5.93 ± 0.24)× 10−4 S/cm at room temperature and relative density of 95.5 ± 1.1% after sintering at 900 °C for 6 h. Besides, the Li||LATP||Li symmetric cell with the mass ratio of 10%/90% exhibits better cyclic stability with a steady polarization voltage of 121.2 mV than that of other ratios. Therefore, SSEs with multimodal microstructures pave a promising venue for practical application of high-energy-density and safe solid-state Li metal battery.