Crystalline Electrolyte Boosts High Performance of All-Solid-State Lithium-Ion Batteries

The rigid solid–solid contact at the interface between the solid electrolyte and electrodes in full-solid-state lithium-ion batteries (ASSBs) presents a considerable challenge to lithium ion transport. To address this, we propose using Li-concentrated succinonitrile (Li-SN45) as an efficient bilateral interface modifier in ASSBs. This material boasts exceptional ionic conductivity of 3.38 mS cm^–1 and excellent corrosion resistance to the Li metal anode. The assembled ASSBs using layered cathodes and Li metal demonstrate outstanding discharge capacity (170 mAh g^–1 @ 20 mA g^–1) and superior long-term cycling performance (97% capacity retention after 100 cycles). MALDI-TOF results suggest the formation of a crystalline structure in Li-SN45, which facilitates smooth “anion-free” Li⁺ hopping paths assisted by the oxygen atoms, as revealed by the solved crystal structure. Our findings enriched the understanding of Li transport dynamics in electrolytes of ASSBs, paving the way to designing superior next-generation ASSBs with fast Li transport.