TY - JOUR
T1 - Highly Sensitive Detection and Mapping of Incipient and Steady-State Oxygen Evolution from Operating Li-Ion Battery Cathodes via Scanning Electrochemical Microscopy
AU - Mishra, Abhiroop
AU - Sarbapalli, Dipobrato
AU - Hossain, Md Sazzad
AU - Gossage, Zachary T.
AU - Li, Zheng
AU - Urban, Alexander
AU - Rodríguez-López, Joaquín
N1 - The authors gratefully acknowledge financial support from Alfred P. Sloan Foundation under grant numbers G-2020-12649, G-2020-12650, and G-2020-12651. Sample preparation and characterization were carried out in part in the Materials Research Laboratory at the University of Illinois. The authors thank Dr. Richard T. Haasch for XPS data collection. A.M. thanks Kenneth Madsen, Xinhao Li, and Kendrich Hatfield for helpful discussions.
PY - 2022/8
Y1 - 2022/8
N2 - Lattice oxygen loss during cathode charging significantly limits the charge storage capacity of lithium-ion batteries (LiBs). Therefore, elucidating the oxygen loss and subsequent surface reconstruction phenomena remains an ongoing pursuit with practical implications. In this article, we report an in situ oxygen detection strategy using scanning electrochemical microscopy (SECM) that reveals an unprecedented two-stage oxygen evolution behavior from commercial cathodes. This highly sensitive SECM method captured an unreported transient oxygen release at less than 3.3 V vs Li+/Li during the first charge cycle of LiCoO2, LiNi0.33Mn0.33Co0.33O2 and LiNi0.8Mn0.1Co0.1O2. At the main oxygen loss process above 3.3 V vs Li+/Li, SECM mapping highlighted spatial and temporal heterogeneities. Finite element simulations were used to quantify the rate of instantaneous oxygen release, with rates of ∼30 pmol cm−2s for the steady-state oxygen evolution. This SECM approach revealed incipient degradation processes and created new quantitative and spatially resolved opportunities for investigating degradation in operating LiB cathodes.
AB - Lattice oxygen loss during cathode charging significantly limits the charge storage capacity of lithium-ion batteries (LiBs). Therefore, elucidating the oxygen loss and subsequent surface reconstruction phenomena remains an ongoing pursuit with practical implications. In this article, we report an in situ oxygen detection strategy using scanning electrochemical microscopy (SECM) that reveals an unprecedented two-stage oxygen evolution behavior from commercial cathodes. This highly sensitive SECM method captured an unreported transient oxygen release at less than 3.3 V vs Li+/Li during the first charge cycle of LiCoO2, LiNi0.33Mn0.33Co0.33O2 and LiNi0.8Mn0.1Co0.1O2. At the main oxygen loss process above 3.3 V vs Li+/Li, SECM mapping highlighted spatial and temporal heterogeneities. Finite element simulations were used to quantify the rate of instantaneous oxygen release, with rates of ∼30 pmol cm−2s for the steady-state oxygen evolution. This SECM approach revealed incipient degradation processes and created new quantitative and spatially resolved opportunities for investigating degradation in operating LiB cathodes.
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U2 - 10.1149/1945-7111/ac857e
DO - 10.1149/1945-7111/ac857e
M3 - Article
AN - SCOPUS:85135996875
SN - 0013-4651
VL - 169
JO - Journal of the Electrochemical Society
JF - Journal of the Electrochemical Society
IS - 8
M1 - 086501
ER -