Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs
Pinar Karayaylali
1
,
S. Nowak
2
,
Livia Giordano
3
,
Magali Gauthier
4
,
Wesley Hong
5
,
Ronghui Kou
6
,
Qinghao Li
7
,
John W. Vinson
8
,
Thomas Kroll
2
,
Dimosthenis Sokaras
2
,
Chengjun Sun
6
,
Nenian Charles
4
,
Filippo Maglia
9
,
Roland Jung
9
,
9
BMW Group, Petuelring 130, Munich 80788, Germany
|
Publication type: Journal Article
Publication date: 2019-09-11
scimago Q1
wos Q1
SJR: 2.065
CiteScore: 12.0
Impact factor: 7.0
ISSN: 08974756, 15205002
PubMed ID:
32210521
Materials Chemistry
General Chemistry
General Chemical Engineering
Abstract
Anion redox in lithium transition metal oxides such as Li2RuO3 and Li2MnO3, has catalyzed intensive research efforts to find transition metal oxides with anion redox that may boost the energy density of lithium-ion batteries. The physical origin of observed anion redox remains debated, and more direct experimental evidence is needed. In this work, we have shown electronic signatures of oxygen-oxygen coupling, direct evidence central to lattice oxygen redox (O2-/(O2)n-), in charged Li2-xRuO3 after Ru oxidation (Ru4+/Ru5+) upon first-electron removal with lithium de-intercalation. Experimental Ru L3-edge high-energy-resolution fluorescence detected X-ray absorption spectra (HERFD-XAS), supported by ab-initio simulations, revealed that the increased intensity in the high-energy shoulder upon lithium de-intercalation resulted from increased O-O coupling, inducing (O-O) σ*-like states with π overlap with Ru d-manifolds, in agreement with O K-edge XAS spectra. Experimental and simulated O K-edge X-ray emission spectra (XES) further supported this observation with the broadening of the oxygen non-bonding feature upon charging, also originated from (O-O) σ* states. This lattice oxygen redox of Li2-xRuO3 was accompanied by a small amount of O2 evolution in the first charge from differential electrochemistry mass spectrometry (DEMS) but diminished in the subsequent cycles, in agreement with the more reduced states of Ru in later cycles from Ru L3-edge HERFD-XAS. These observations indicated that Ru redox contributed more to discharge capacities after the first cycle. This study has pinpointed the key spectral fingerprints related to lattice oxygen redox from a molecular level and constructed a transferrable framework to rationally interpret the spectroscopic features by combining advanced experiments and theoretical calculations to design materials for Li-ion batteries and electrocatalysis applications.
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Total citations:
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Citations from 2024:
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(18%)
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GOST
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Karayaylali P. et al. Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs // Chemistry of Materials. 2019. Vol. 31. No. 19. pp. 7864-7876.
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Karayaylali P., Nowak S., Giordano L., Gauthier M., Hong W., Kou R., Li Q., Vinson J. W., Kroll T., Sokaras D., Sun C., Charles N., Maglia F., Jung R., Shao-Horn Y. Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs // Chemistry of Materials. 2019. Vol. 31. No. 19. pp. 7864-7876.
Cite this
RIS
Copy
TY - JOUR
DO - 10.1021/acs.chemmater.9b01821
UR - https://doi.org/10.1021/acs.chemmater.9b01821
TI - Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs
T2 - Chemistry of Materials
AU - Karayaylali, Pinar
AU - Nowak, S.
AU - Giordano, Livia
AU - Gauthier, Magali
AU - Hong, Wesley
AU - Kou, Ronghui
AU - Li, Qinghao
AU - Vinson, John W.
AU - Kroll, Thomas
AU - Sokaras, Dimosthenis
AU - Sun, Chengjun
AU - Charles, Nenian
AU - Maglia, Filippo
AU - Jung, Roland
AU - Shao-Horn, Yang
PY - 2019
DA - 2019/09/11
PB - American Chemical Society (ACS)
SP - 7864-7876
IS - 19
VL - 31
PMID - 32210521
SN - 0897-4756
SN - 1520-5002
ER -
Cite this
BibTex (up to 50 authors)
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@article{2019_Karayaylali,
author = {Pinar Karayaylali and S. Nowak and Livia Giordano and Magali Gauthier and Wesley Hong and Ronghui Kou and Qinghao Li and John W. Vinson and Thomas Kroll and Dimosthenis Sokaras and Chengjun Sun and Nenian Charles and Filippo Maglia and Roland Jung and Yang Shao-Horn},
title = {Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs},
journal = {Chemistry of Materials},
year = {2019},
volume = {31},
publisher = {American Chemical Society (ACS)},
month = {sep},
url = {https://doi.org/10.1021/acs.chemmater.9b01821},
number = {19},
pages = {7864--7876},
doi = {10.1021/acs.chemmater.9b01821}
}
Cite this
MLA
Copy
Karayaylali, Pinar, et al. “Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs.” Chemistry of Materials, vol. 31, no. 19, Sep. 2019, pp. 7864-7876. https://doi.org/10.1021/acs.chemmater.9b01821.