biostudies-literatureWang YDutch Research Council (NWO)669https://www.ebi.ac.uk/biostudies/studies/S-EPMC9905078biostudies-literatureUnknown14(1)Easy-to-manufacture Li₂S-P₂S₅ 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_0.6Mn_0.2Co_0.2O₂ 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.Nature communicationsSelf-organized hetero-nanodomains actuating super Li⁺ conduction in glass ceramics.PMC9905078184.035.002Li JLi CSheu HSHu ZCui LJiang FChen LChang CKQu HZhang SLi XJu Jvan Eck ERHCui GLiu BMa JWang YKentgens APMfalseSelf-organized hetero-nanodomains actuating super Li⁺ conduction in glass ceramics.Easy-to-manufacture Li₂S-P₂S₅ 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_0.6Mn_0.2Co_0.2O₂ 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.2023-01-01T00:00:00Z2023 Feb2026-03-15T16:07:54.624Z2025-04-05T17:07:36.478ZS-EPMC99050783675057310.1038/s41467-023-35982-7