Abstract
Understanding the decaying mechanism in lithium-ion batteries (LIBs) is critical to establishing a stable electrolyte system. Despite the advent of various novel electrolyte solvents designated for high-voltage LIBs, their working principles are not fully understood. Currently, oxidative decomposition of electrolytes is believed to be the major cause of capacity fade, and tremendous effort has been devoted to discovering a new electrolyte with enhanced anodic stability. However, the oxidative decomposition process cannot solely explain the rapid decay of some electrolyte systems with intrinsic high anodic stability when used with a high-nickel layered oxide cathode such as LiNi0.6Mn0.2Co0.2O2 (NMC622). In this report, a study of the quantitative structure-activity relationship was conducted to deepen the mechanistic understanding of the decay in high-voltage LIBs. The results obtained from the newly introduced molecular pair analysis and linear free-energy relationship (LFER) studies were highly consistent with the solvation-involved decaying mechanism in a high-nickel layered oxide cathode cycling at high voltage (> 4.5 V vs. Li/Li+). There was no evidence correlating the solvation ability of electrolyte solvents with the decay of a high-nickel layered oxide cathode cycling at a relatively low voltage (< 4.3 V vs. Li/Li+), nor with the high-voltage spinel cathode LiNi0.5Mn1.5O4 (LNMO). Undoubtedly, the unveiled mechanistic insight provides a critical guideline for the development of an appropriate electrolyte system targeting different high-voltage cathode materials.
Original language | English |
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Article number | 105843 |
Journal | Nano Energy |
Volume | 83 |
DOIs | |
State | Published - May 2021 |
Externally published | Yes |
Funding
The authors gratefully acknowledge support from the U.S. Department of Energy (DOE), Vehicle Technologies Office (VTO). Argonne National Laboratory is operated by DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357 . The NMC and LNMO electrodes were manufactured at the DOE’s CAMP Facility, at Argonne National Laboratory. The CAMP Facility is fully supported by the DOE VTO within the core funding of the Applied Battery Research for Transportation Program . The authors also thank K. Pupek and G. Krumdick from Argonne’s Materials Engineering Research Facility for providing FEMC. We also acknowledge the computing resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. The authors gratefully acknowledge support from the U.S. Department of Energy (DOE), Vehicle Technologies Office (VTO). Argonne National Laboratory is operated by DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. The NMC and LNMO electrodes were manufactured at the DOE's CAMP Facility, at Argonne National Laboratory. The CAMP Facility is fully supported by the DOE VTO within the core funding of the Applied Battery Research for Transportation Program. The authors also thank K. Pupek and G. Krumdick from Argonne's Materials Engineering Research Facility for providing FEMC. We also acknowledge the computing resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory.
Keywords
- Decaying mechanism
- Electrolyte solvation
- Lithium-ion batteries
- Quantitative structure-activity relationship
- Relative solvating power