Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration
Abstract
In this work, we present findings on the mechanisms of hysteresis in lithium-rich cathode oxides. It is generally reported that the energy inefficiency, observed during electrochemical cycling of Li-rich electrodes, is a direct result of anion redox processes. Similarly, the coupled phenomenon of cation migration has been cited as being a mere consequence of that process with no essential ramification to hysteresis. Such works, however, have only shown correlations and not causation. Specifically, studies that clearly preclude the complete absence of either anion redox or cation migration (down to defect-level concentrations) are not reported yet. Herein, we present first principles calculations and experimental data on a bespoke Li-rich system that is indubitably immune to oxygen activity but yet exhibits significant energy inefficiency. Additionally, the results directly implicate transition metal migration as the fundamental, sole process responsible for hysteresis in this material. This study is of particular importance to the design and development of new Li-rich materials aimed at eliminating the role of oxygen and enhancing the effective cationic redox contribution to the capacity and points out the essential need to develop materials devoid of transition metal migration to interstitial sites in both layered and disordered oxides alike.
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; Canadian Light Source, Inc.
- OSTI Identifier:
- 1659430
- Alternate Identifier(s):
- OSTI ID: 1693540
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Power Sources
- Additional Journal Information:
- Journal Volume: 471; Journal ID: ISSN 0378-7753
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; anion redox; DFT; disordered rock salt; hysteresis; lithium rich; oxygen redox; XAFS; XANES; XAS
Citation Formats
Croy, Jason R., Garcia, Juan C., Iddir, Hakim, Trask, Stephen E., and Balasubramanian, Mahalingam. Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration. United States: N. p., 2020.
Web. doi:10.1016/j.jpowsour.2020.228335.
Croy, Jason R., Garcia, Juan C., Iddir, Hakim, Trask, Stephen E., & Balasubramanian, Mahalingam. Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration. United States. https://doi.org/10.1016/j.jpowsour.2020.228335
Croy, Jason R., Garcia, Juan C., Iddir, Hakim, Trask, Stephen E., and Balasubramanian, Mahalingam. Wed .
"Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration". United States. https://doi.org/10.1016/j.jpowsour.2020.228335. https://www.osti.gov/servlets/purl/1659430.
@article{osti_1659430,
title = {Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration},
author = {Croy, Jason R. and Garcia, Juan C. and Iddir, Hakim and Trask, Stephen E. and Balasubramanian, Mahalingam},
abstractNote = {In this work, we present findings on the mechanisms of hysteresis in lithium-rich cathode oxides. It is generally reported that the energy inefficiency, observed during electrochemical cycling of Li-rich electrodes, is a direct result of anion redox processes. Similarly, the coupled phenomenon of cation migration has been cited as being a mere consequence of that process with no essential ramification to hysteresis. Such works, however, have only shown correlations and not causation. Specifically, studies that clearly preclude the complete absence of either anion redox or cation migration (down to defect-level concentrations) are not reported yet. Herein, we present first principles calculations and experimental data on a bespoke Li-rich system that is indubitably immune to oxygen activity but yet exhibits significant energy inefficiency. Additionally, the results directly implicate transition metal migration as the fundamental, sole process responsible for hysteresis in this material. This study is of particular importance to the design and development of new Li-rich materials aimed at eliminating the role of oxygen and enhancing the effective cationic redox contribution to the capacity and points out the essential need to develop materials devoid of transition metal migration to interstitial sites in both layered and disordered oxides alike.},
doi = {10.1016/j.jpowsour.2020.228335},
journal = {Journal of Power Sources},
number = ,
volume = 471,
place = {United States},
year = {Wed Jun 24 00:00:00 EDT 2020},
month = {Wed Jun 24 00:00:00 EDT 2020}
}
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