Abstract
The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm−2) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li3N SSE. This vacancy-rich β-Li3N SSE shows a high ionic conductivity of 2.14 × 10−3 S cm−1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li3N achieve breakthroughs in high critical current densities up to 45 mA cm−2 and high capacities up to 7.5 mAh cm−2, and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li3N is unveiled as intrinsic stability to lithium metal. In addition, β-Li3N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li3N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi0.83Co0.11Mn0.06O2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g−1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g−1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li3N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm−2 for the compact pellet-type cells and around 2.2 mAh cm−2 for the all-solid-state lithium metal pouch cells.
| Original language | English |
|---|---|
| Journal | Nature Nanotechnology |
| DOIs | |
| State | Accepted/In press - 2024 |
Funding
This work was funded by the Natural Sciences and Engineering Research Council of Canada (NSERC), the Canada Research Chair Program, the Canada Foundation for Innovation (CFI), the Ontario Research Fund, the Canadian Light Source (CLS) at the University of Saskatchewan and the University of Western Ontario. CLS was supported by CFI, NSERC, NRC, CHIR and the University of Saskatchewan. W.L. and M.L. acknowledge the receipt of support from the CLSI Graduate and Post-Doctoral Student Travel Support Program. W.L. appreciates the funding support from Mitacs Accelerate Fellowships. We also appreciate the help of the beamline scientists of SGM and SXRMB beamlines at the Canadian Light Source: T. Regier, J. Dynes, Z. Arthur, M. Shakouri, Q. Xiao and A. Paterson. Y.M. acknowledges the funding support from National Science Foundation award number 1940166 and the computational facilities from the University of Maryland supercomputing resources and the Maryland Advanced Research Computing Center (MARCC). Part of this work was conducted at the NOMAD beamlines at ORNL\u2019s Spallation Neutron Source, which was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, US Department of Energy. J. Liu would like to thank the partial financial support from ORNL LDRD number 10761.
