Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale
Abstract
Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. However, their application is limited by the voltage decay upon cycling, and the origin of such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 to 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. Thus, this discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.
- Authors:
-
- General Motors Global R&D Center, Warren, MI (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Washington, Seattle, WA (United States)
- Optimal, Inc., Plymouth, MI (United States)
- Optimal, Inc. Plymouth, MI (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1214471
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Wu, Yan, Ma, Cheng, Yang, Jihui, Li, Zicheng, Allard, Jr., Lawrence Frederick, Liang, Chengdu, and Chi, Miaofang. Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale. United States: N. p., 2015.
Web. doi:10.1039/C4TA06856D.
Wu, Yan, Ma, Cheng, Yang, Jihui, Li, Zicheng, Allard, Jr., Lawrence Frederick, Liang, Chengdu, & Chi, Miaofang. Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale. United States. https://doi.org/10.1039/C4TA06856D
Wu, Yan, Ma, Cheng, Yang, Jihui, Li, Zicheng, Allard, Jr., Lawrence Frederick, Liang, Chengdu, and Chi, Miaofang. Wed .
"Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale". United States. https://doi.org/10.1039/C4TA06856D. https://www.osti.gov/servlets/purl/1214471.
@article{osti_1214471,
title = {Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale},
author = {Wu, Yan and Ma, Cheng and Yang, Jihui and Li, Zicheng and Allard, Jr., Lawrence Frederick and Liang, Chengdu and Chi, Miaofang},
abstractNote = {Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. However, their application is limited by the voltage decay upon cycling, and the origin of such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 to 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. Thus, this discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.},
doi = {10.1039/C4TA06856D},
journal = {Journal of Materials Chemistry. A},
number = 10,
volume = 3,
place = {United States},
year = {Wed Jan 21 00:00:00 EST 2015},
month = {Wed Jan 21 00:00:00 EST 2015}
}
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