Self-organized hetero-nanodomains actuating super Li(+) conduction in glass ceramics

Easy-to-manufacture Li(2)S-P(2)S(5) 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(−1) are prepared. The high Li(+) conductivity ensures stable operation of a 220 μm thick LiNi(0.6)Mn(0.2)Co(0.2)O(2) composite cathode (8 mAh cm(−2)), with which the all-solid-state lithium battery reaches a high energy density of 420 Wh kg(−1) by cell mass and 834 Wh L(−1) by cell volume at room temperature. These findings bring about powerful new degrees of freedom for engineering super ionic conductors.