Polyethylene oxide-Based solid electrolytes with fast Li-ion transport channels constructed from 2D montmorillonite for solid-state lithium-metal batteries

Schematic illustration for the architecture of SSLMB with a magnification showing CSSE and the structures of LiIL@LiMNT. The [EMIM]+ and [TFSI]− in space-filling model are randomly displayed in the layer of LiMNT. [Display omitted] •Li-containing ionic liquid was inserted into a 2D LiMNT structure (LiIL@LiMNT).•LiIL@LiMNT provides a fast 2D Li-ion transport channel in PEO-based Electrolytes.•This CSSE has a high ionic conductivity and Li-ion transference number (0.38).•SSLMBs deliver impressive cycling performance with LFP and NMC111 cathodes. Polyethylene oxide (PEO)-based solid-state electrolytes (SSEs) typically struggle with poor ionic conductivity, low lithium (Li)-ion transference number, and narrow electrochemical window. For overcoming these drawbacks, we designed a promising composite SSE (CSSE), i.e., a Li-containing ionic liquid (LiIL) was inserted into the Li-montmorillonite (LiMNT) layered structure to form an active filler (LiIL@LiMNT), involving two-dimensional (2D) fast transport channels of Li-ion inside PEO electrolyte. Benefitting from an enhancement of the 2D Li-ion transport channels, the obtained CSSE exhibited an excellent ion conductivity of 1.38 × 10−4 S cm−1 at 30 °C as well as a satisfactory Li-ion transference number (0.38). A Li symmetric battery with the CSSE exhibited a steady cycle for 3000 h with 0.2 mA cm−2 at 60 °C. Under the rate of 0.5C at 60 °C, the solid-state Li-metal batteries (SSLMBs) assembled with LiFePO4 and LiNi0.33Co0.33Mn0.33O2 cathodes maintained a considerable reversible capacity after 400 and 100 cycles, respectively. The assembled SSLMB also achieved a satisfactory performance at 40 °C. The 2D active filler prepared in this work forms efficient 2D Li-ion transport channels inside the CSSE while maintaining a tight interfacial contact with electrodes, which is crucial to achieve a superior performance for CSSEs. This strategy of constructing 2D ion transport channels in polymer electrolytes also provides another way for the design of other CSSEs.