Self-organized hetero-nanodomains actuating super Li conduction in glass ceramics.

Easy-to-manufacture LiS-PS glass ceramics are the key to large-scale all-solid-state lithium batteries from an industrial point of view, while their commercialization is greatly hampered by the low room temperature Li conductivity, especially due to the lack of solutions. Herein, we propose a nanocrystallization strategy to fabricate super Li-conductive glass ceramics. Through regulating the nucleation energy, the crystallites within glass ceramics can self-organize into hetero-nanodomains during the solid-state reaction. Cryogenic transmission electron microscope and electron holography directly demonstrate the numerous closely spaced grain boundaries with enriched charge carriers, which actuate superior Li-conduction as confirmed by variable-temperature solid-state nuclear magnetic resonance. Glass ceramics with a record Li conductivity of 13.2 mS cm are prepared. The high Li conductivity ensures stable operation of a 220 μm thick LiNiMnCoO composite cathode (8 mAh cm), with which the all-solid-state lithium battery reaches a high energy density of 420 Wh kg by cell mass and 834 Wh L by cell volume at room temperature. These findings bring about powerful new degrees of freedom for engineering super ionic conductors.