Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling
Abstract
Capacity fading during long-term cycling (>1500×) is still a critical challenge for Li-ion batteries that use Ni-rich layered oxides, e.g. LiNi0.8Co0.15Al0.05O2 (NCA), as the cathode. Microcracks have been previously recognized as one of the primary reasons for the observed capacity fade. Although there exists a generally developed mechanical understanding of microcracks, the role of the electrolyte has not been clearly understood, especially after extended cycling and at the atomic scale. Here, we unveil the microstructural evolution of spherical NCA secondary particles after long-term cycling using scanning transmission electron microscopy accompanied with electron energy loss spectroscopy. In this work, we found that the microcracks initiated and grew through grain boundaries, which then serve as the pathway for electrolyte penetration into secondary NCA particles. Additionally, the rock-salt phase reconstruction is prone to occur at the (003) surfaces of the primary particles or the crack surfaces, largely due to electrolyte (LiPF6 EC/EMC) corrosion. Crack propagation within the NCA grains is primarily a joint consequence from electrolyte corrosion and mechanical strain during lithiation/delithiation. During extended cycling, due to the distinctive surface facets, the primary grains located in the center of the secondary particles experience more intensive electrolyte corrosion, leading to a reduced contact withmore »
- Authors:
-
[1];
[2];
[3];
[4];
[5];
[4];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Univ. of Kentucky, Lexington, KY (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of Texas, Austin, TX (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1809085
- Alternate Identifier(s):
- OSTI ID: 1762512; OSTI ID: 1775207
- Grant/Contract Number:
- AC05-00OR22725; EE0007762; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Liu, Xiaoming, Zhan, Xiaowen, Hood, Zachary D., Li, Wangda, Leonard, Donovan N., Manthiram, Arumugam, and Chi, Miaofang. Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling. United States: N. p., 2021.
Web. doi:10.1039/d0ta07814j.
Liu, Xiaoming, Zhan, Xiaowen, Hood, Zachary D., Li, Wangda, Leonard, Donovan N., Manthiram, Arumugam, & Chi, Miaofang. Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling. United States. https://doi.org/10.1039/d0ta07814j
Liu, Xiaoming, Zhan, Xiaowen, Hood, Zachary D., Li, Wangda, Leonard, Donovan N., Manthiram, Arumugam, and Chi, Miaofang. Mon .
"Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling". United States. https://doi.org/10.1039/d0ta07814j. https://www.osti.gov/servlets/purl/1809085.
@article{osti_1809085,
title = {Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling},
author = {Liu, Xiaoming and Zhan, Xiaowen and Hood, Zachary D. and Li, Wangda and Leonard, Donovan N. and Manthiram, Arumugam and Chi, Miaofang},
abstractNote = {Capacity fading during long-term cycling (>1500×) is still a critical challenge for Li-ion batteries that use Ni-rich layered oxides, e.g. LiNi0.8Co0.15Al0.05O2 (NCA), as the cathode. Microcracks have been previously recognized as one of the primary reasons for the observed capacity fade. Although there exists a generally developed mechanical understanding of microcracks, the role of the electrolyte has not been clearly understood, especially after extended cycling and at the atomic scale. Here, we unveil the microstructural evolution of spherical NCA secondary particles after long-term cycling using scanning transmission electron microscopy accompanied with electron energy loss spectroscopy. In this work, we found that the microcracks initiated and grew through grain boundaries, which then serve as the pathway for electrolyte penetration into secondary NCA particles. Additionally, the rock-salt phase reconstruction is prone to occur at the (003) surfaces of the primary particles or the crack surfaces, largely due to electrolyte (LiPF6 EC/EMC) corrosion. Crack propagation within the NCA grains is primarily a joint consequence from electrolyte corrosion and mechanical strain during lithiation/delithiation. During extended cycling, due to the distinctive surface facets, the primary grains located in the center of the secondary particles experience more intensive electrolyte corrosion, leading to a reduced contact with nearby particles, impairing the overall capacity. These results establish the initiation and growth mechanism of microcracks and voids in NCA-based cathodes during cycling and point out the role of the electrolyte in affecting the degradation of NCA-based cathodes.},
doi = {10.1039/d0ta07814j},
journal = {Journal of Materials Chemistry. A},
number = 4,
volume = 9,
place = {United States},
year = {Mon Jan 25 00:00:00 EST 2021},
month = {Mon Jan 25 00:00:00 EST 2021}
}
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