Rational design of hybrid electrolyte for all-solid-state lithium battery based on investigation of lithium-ion transport mechanism

[Display omitted] •HPE with 10 wt% LATP exhibits an ionic conductivity of 7.23 × 10−4 S cm−1.•The mechanism of Li-ion migration in the polymer-LATP mixture is investigated through DFT calculations.•Unique Li-ion transport in HPEs distinct from LATP’s intrinsic conductivity.•The addition of LATP particles improves the mechanical strength and effectively inhibits dendrite growth.•High performance HPEs advance all-solid-state lithium batteries (ASSBs). Lithium all-solid-state batteries (ASSBs) are a promising technology for achieving high energy density, long cycle life, and safe rechargeable battery systems. Among these, Li ASSBs using solid polymer electrolytes (SPEs) have gained attention owing to their processability, lightweight nature, flexibility, and favorable electrode contacts. However, SPEs have low ionic conductivity, low Li+ transference number, and lack mechanical strength, limiting cell performance. Therefore, the present study focuses on the development of hybrid polymer electrolytes (HPEs) by incorporating Li1+xAlxTi2-x(PO4)3 (LATP) of Li/Na superionic conductor-type materials into SPEs. The HPEs with LATP 10 wt% exhibited significant improvements with an ionic conductivity of 7.23 × 10−4 S cm−1 at 45 °C and a Li+ transference number of 0.61. Density functional theory calculations supported the enhanced Li-ion migration through the polymer-LATP interface achieved by the optimized LATP content. The addition of LATP particles enhanced the mechanical strength of the electrolytes, effectively suppressing dendrite growth, resulting in a 66.65 % capacity retention after 320 cycles, highlighting the crucial role of high-performance HPEs in advanced ASSBs. By addressing the limitations of SPEs, HPEs offer promising opportunities to unlock the full potential of solid-state battery technologies for various energy storage systems.