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Title: Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs

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 the observed anion redox remains debatable, 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-/(O-2)(n-)), in charged Li2-xRuO3 after Ru oxidation (Ru-4(+)/Ru5+) upon first electron removal with lithium deintercalation. Experimental Ru L-3-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 deintercalation resulted from increased O-O coupling, inducing (O-O) sigma*-like states with pi overlap with Ru d-manifolds, in agreement with O K-edge XAS spectra. Experimental and simulated O K-edge X-ray emission spectra further supported this observation with the broadening of the oxygen nonbonding feature upon charging, also originated from (O-O) sigma* states. This lattice oxygen redox of Li2-xRuO3 was accompanied by a small amount of O-2 evolution in the first charge from differential electrochemistry mass spectrometry but diminished in the subsequent cycles, in agreement with the more reduced states of Ru in later cyclesmore » from Ru L-3-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.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [1];  [4];  [5]; ORCiD logo [6];  [2];  [2];  [4];  [3];  [7];  [7]; ORCiD logo [8]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Research Lab. of Electronics
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  6. National Institute of Standards and Technology, Gaithersburg 20899, Maryland, United States
  7. BMW Group, Petuelring 130, Munich 80788, Germany
  8. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering, Research Lab. of Electronics, Dept. of Mechanical Engineering
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1576798
Alternate Identifier(s):
OSTI ID: 1615148
Grant/Contract Number:  
AC02-76SF00515; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 19; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Yu, Yang, Karayaylali, Pinar, Nowak, Stanisław H., Giordano, Livia, Gauthier, Magali, Hong, Wesley, Kou, Ronghui, Li, Qinghao, Vinson, John, Kroll, Thomas, Sokaras, Dimosthenis, Sun, Cheng-Jun, Charles, Nenian, Maglia, Filippo, Jung, Roland, and Shao-Horn, Yang. Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.9b01821.
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Yu, Yang, Karayaylali, Pinar, Nowak, Stanisław H., Giordano, Livia, Gauthier, Magali, Hong, Wesley, Kou, Ronghui, Li, Qinghao, Vinson, John, Kroll, Thomas, Sokaras, Dimosthenis, Sun, Cheng-Jun, Charles, Nenian, Maglia, Filippo, Jung, Roland, & Shao-Horn, Yang. Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs. United States. https://doi.org/10.1021/acs.chemmater.9b01821
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Yu, Yang, Karayaylali, Pinar, Nowak, Stanisław H., Giordano, Livia, Gauthier, Magali, Hong, Wesley, Kou, Ronghui, Li, Qinghao, Vinson, John, Kroll, Thomas, Sokaras, Dimosthenis, Sun, Cheng-Jun, Charles, Nenian, Maglia, Filippo, Jung, Roland, and Shao-Horn, Yang. Mon . "Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs". United States. https://doi.org/10.1021/acs.chemmater.9b01821. https://www.osti.gov/servlets/purl/1576798.
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@article{osti_1576798,
title = {Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs},
author = {Yu, Yang and Karayaylali, Pinar and Nowak, Stanisław H. and Giordano, Livia and Gauthier, Magali and Hong, Wesley and Kou, Ronghui and Li, Qinghao and Vinson, John and Kroll, Thomas and Sokaras, Dimosthenis and Sun, Cheng-Jun and Charles, Nenian and Maglia, Filippo and Jung, Roland and Shao-Horn, Yang},
abstractNote = {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 the observed anion redox remains debatable, 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-/(O-2)(n-)), in charged Li2-xRuO3 after Ru oxidation (Ru-4(+)/Ru5+) upon first electron removal with lithium deintercalation. Experimental Ru L-3-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 deintercalation resulted from increased O-O coupling, inducing (O-O) sigma*-like states with pi overlap with Ru d-manifolds, in agreement with O K-edge XAS spectra. Experimental and simulated O K-edge X-ray emission spectra further supported this observation with the broadening of the oxygen nonbonding feature upon charging, also originated from (O-O) sigma* states. This lattice oxygen redox of Li2-xRuO3 was accompanied by a small amount of O-2 evolution in the first charge from differential electrochemistry mass spectrometry but diminished in the subsequent cycles, in agreement with the more reduced states of Ru in later cycles from Ru L-3-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.},
doi = {10.1021/acs.chemmater.9b01821},
journal = {Chemistry of Materials},
number = 19,
volume = 31,
place = {United States},
year = {Mon Sep 09 00:00:00 EDT 2019},
month = {Mon Sep 09 00:00:00 EDT 2019}
}
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