Flexible composite solid electrolyte with high stable interphase for dendrite-free and durable all-solid-state lithium metal batteries

Composite solid-state electrolytes (CSEs) that integrate the merits of different components are considered to be promising candidate for the next-generation high-energy density lithium metal batteries. Herein, we have successfully designed a flexible CSE membrane consisting of ceramic conductor Li1.3Al0.3Ti1.7(PO4)3 (LATP) fillers, polyethylene oxide (PEO) matrix, and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) ionic liquid. In particular, the addition of ionic liquid (BMP-TFSI) can not only decrease the interface impendence between the polymer and LATP ceramic fillers and improve the ionic conductivity, but also prevent the adverse reaction between Ti4+ in LATP and Li metal and further enhance the interface stability. Benefitted by the synergistic effect of organic-inorganic hybrids, the obtained composite electrolyte membrane achieves an excellent ionic conductivity of 2.42×10−4 S cm−1 at 30 oC and a wide electrochemical stability window of 5 V (vs Li+/Li). Moreover, the CSE membrane exhibits outstanding Li dendrite suppression capability, which is proved by galvanostatic Li plating/stripping tests for 1000 h. Assembled with this solid electrolyte membrane and commercial LiFePO4 cathode, all-solid-state lithium metal batteries demonstrate superior rate capability and extremely cycling stability at both 30 and 45 oC. These results demonstrate such flexible composite electrolyte is a promising alternative electrolyte for practical high-energy density all-solid-state batteries.