Atomic-Level Understanding of Surface Reconstruction Based on Li[NixMnyCo1–x–y]O2 Single-Crystal Studies
Abstract
The stability of cathode particle surfaces that are directly exposed to the electrolyte is one of the most crucial and determining factors for cathode performance at high operating voltages. Theory has predicted a strong dependence of surface stability on chemical compositions as well as surface facets of layered oxides, yet conflicting results on the correlations exist as most experimental studies focus on cycled secondary particles recovered from composite electrodes. Here, we synthesize well-formed Li[NixMnyCo1–x–y]O2 (NMC) single-crystal samples, carefully define pristine surface properties, and then monitor their evolution with cycling. Atomic-resolution scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELS) analysis show the formation of a surface reconstruction layer (SRL) as well as an extended surface reduction layer on pristine, Li-permeable non-(001) surfaces, even before cycling. We reveal a transition region with chemical gradient, in which the layered structure gradually densifies and eventually transforms into the SRL on the top surface. Contrary to these observations, no SRL is observed on pristine, Li-impermeable (001) surfaces, revealing the facet-dependent nature of surface reconstructions during particle synthesis. Upon electrochemical cycling, significant composition-and facet-dependent SRL growth is observed. The driving force and mechanism for surface reconstruction are further discussed. The present studymore »
- Authors:
-
[2];
[3];
[3];
[3];
[2];
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Illinois, Chicago, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC)
- OSTI Identifier:
- 1660390
- Grant/Contract Number:
- AC02-06CH11357; AC02-76SF00515; AC02-05CH11231; CBET-1805938
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Energy Materials
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 5; Journal ID: ISSN 2574-0962
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Li-ion battery cathodes; Li[NixMnyCo1-x-y]O2 (NMC); composition-dependent; single crystals; surface reconstruction; surface-face dependent
Citation Formats
Zhu, Jian, Sharifi-Asl, Soroosh, Garcia, Juan C., Iddir, Hakim H., Croy, Jason R., Shahbazian-Yassar, Reza, and Chen, Guoying. Atomic-Level Understanding of Surface Reconstruction Based on Li[NixMnyCo1–x–y]O2 Single-Crystal Studies. United States: N. p., 2020.
Web. doi:10.1021/acsaem.0c00411.
Zhu, Jian, Sharifi-Asl, Soroosh, Garcia, Juan C., Iddir, Hakim H., Croy, Jason R., Shahbazian-Yassar, Reza, & Chen, Guoying. Atomic-Level Understanding of Surface Reconstruction Based on Li[NixMnyCo1–x–y]O2 Single-Crystal Studies. United States. https://doi.org/10.1021/acsaem.0c00411
Zhu, Jian, Sharifi-Asl, Soroosh, Garcia, Juan C., Iddir, Hakim H., Croy, Jason R., Shahbazian-Yassar, Reza, and Chen, Guoying. Thu .
"Atomic-Level Understanding of Surface Reconstruction Based on Li[NixMnyCo1–x–y]O2 Single-Crystal Studies". United States. https://doi.org/10.1021/acsaem.0c00411. https://www.osti.gov/servlets/purl/1660390.
@article{osti_1660390,
title = {Atomic-Level Understanding of Surface Reconstruction Based on Li[NixMnyCo1–x–y]O2 Single-Crystal Studies},
author = {Zhu, Jian and Sharifi-Asl, Soroosh and Garcia, Juan C. and Iddir, Hakim H. and Croy, Jason R. and Shahbazian-Yassar, Reza and Chen, Guoying},
abstractNote = {The stability of cathode particle surfaces that are directly exposed to the electrolyte is one of the most crucial and determining factors for cathode performance at high operating voltages. Theory has predicted a strong dependence of surface stability on chemical compositions as well as surface facets of layered oxides, yet conflicting results on the correlations exist as most experimental studies focus on cycled secondary particles recovered from composite electrodes. Here, we synthesize well-formed Li[NixMnyCo1–x–y]O2 (NMC) single-crystal samples, carefully define pristine surface properties, and then monitor their evolution with cycling. Atomic-resolution scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELS) analysis show the formation of a surface reconstruction layer (SRL) as well as an extended surface reduction layer on pristine, Li-permeable non-(001) surfaces, even before cycling. We reveal a transition region with chemical gradient, in which the layered structure gradually densifies and eventually transforms into the SRL on the top surface. Contrary to these observations, no SRL is observed on pristine, Li-impermeable (001) surfaces, revealing the facet-dependent nature of surface reconstructions during particle synthesis. Upon electrochemical cycling, significant composition-and facet-dependent SRL growth is observed. The driving force and mechanism for surface reconstruction are further discussed. The present study provides insights into the origin as well as the nature of SRLs, highlighting the significance of surface engineering in cathode material optimization.},
doi = {10.1021/acsaem.0c00411},
journal = {ACS Applied Energy Materials},
number = 5,
volume = 3,
place = {United States},
year = {Thu Apr 30 00:00:00 EDT 2020},
month = {Thu Apr 30 00:00:00 EDT 2020}
}
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