Abstract
LiNiO2 (LNO) is a promising cathode material for next-generation Li-ion batteries due to its exceptionally high capacity and cobalt-free composition that enables more sustainable and ethical large-scale manufacturing. However, its poor cycle life at high operating voltages over 4.1 V impedes its practical use, thus motivating efforts to elucidate and mitigate LiNiO2 degradation mechanisms at high states of charge. Here, a multiscale exploration of high-voltage degradation cascades associated with oxygen stacking chemistry in cobalt-free LiNiO2, is presented. Lattice oxygen loss is found to play a critical role in the local O3–O1 stacking transition at high states of charge, which subsequently leads to Ni-ion migration and irreversible stacking faults during cycling. This undesirable atomic-scale structural evolution accelerates microscale electrochemical creep, cracking, and even bending of layers, ultimately resulting in macroscopic mechanical degradation of LNO particles. By employing a graphene-based hermetic surface coating, oxygen loss is attenuated in LNO at high states of charge, which suppresses the initiation of the degradation cascade and thus substantially improves the high-voltage capacity retention of LNO. Overall, this study provides mechanistic insight into the high-voltage degradation of LNO, which will inform ongoing efforts to employ cobalt-free cathodes in Li-ion battery technology.
| Original language | English (US) |
|---|---|
| Article number | 2106402 |
| Journal | Advanced Materials |
| Volume | 34 |
| Issue number | 3 |
| DOIs | |
| State | Published - Jan 20 2022 |
Funding
This work was primarily supported by the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award # DE-AC02-06CH11357. This research was also supported by the Basic Science Research Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Education (Grant No. 2020R1A6A3A03038630). Graphene powder production was supported by the National Science Foundation Scalable Nanomanufacturing Program (Grant Nos. NSF CMMI-1727846 and NSF CMMI-2039268) and the National Science Foundation Future Manufacturing Program (Grant No. NSF CMMI-2037026). This work made use of the EPIC facility of the Northwestern University NUANCE Center, which is supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (Grant No. NSF ECCS-1542205), the Materials Research Science and Engineering Center (Grant No. NSF DMR-1720139), the State of Illinois, and Northwestern University. Synchrotron Powder X-ray Diffraction was performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT was supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. Baseline material synthesis was conducted at the Argonne National Laboratory (ANL) Materials Engineering Research Facility (MERF). MERF was supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, and the Vehicle Technologies Office. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors thank Beam Scientist Mike Guise for his valuable assistance in the beamline during the COVID-19 pandemic. Also, the authors thank DND-CAT Director Denis T. Keane for his support and helpful discussions. This work was primarily supported by the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award # DE‐AC02‐06CH11357. This research was also supported by the Basic Science Research Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Education (Grant No. 2020R1A6A3A03038630). Graphene powder production was supported by the National Science Foundation Scalable Nanomanufacturing Program (Grant Nos. NSF CMMI‐1727846 and NSF CMMI‐2039268) and the National Science Foundation Future Manufacturing Program (Grant No. NSF CMMI‐2037026). This work made use of the EPIC facility of the Northwestern University NUANCE Center, which is supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (Grant No. NSF ECCS‐1542205), the Materials Research Science and Engineering Center (Grant No. NSF DMR‐1720139), the State of Illinois, and Northwestern University. Synchrotron Powder X‐ray Diffraction was performed at the DuPont‐Northwestern‐Dow Collaborative Access Team (DND‐CAT) located at Sector 5 of the Advanced Photon Source (APS). DND‐CAT was supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. Baseline material synthesis was conducted at the Argonne National Laboratory (ANL) Materials Engineering Research Facility (MERF). MERF was supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, and the Vehicle Technologies Office. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. The authors thank Beam Scientist Mike Guise for his valuable assistance in the beamline during the COVID‐19 pandemic. Also, the authors thank DND‐CAT Director Denis T. Keane for his support and helpful discussions.
ASJC Scopus subject areas
- Mechanics of Materials
- Mechanical Engineering
- General Materials Science
