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Title: Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

Abstract

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here in this paper, we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Furthermore, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

Authors:
 [1];  [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Energy Frontier Research Center - Center for Electrochemical Energy Science (CEES)
OSTI Identifier:
1459884
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 2; Journal Issue: 12; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Zhan, Chun, Yao, Zhenpeng, Lu, Jun, Ma, Lu, Maroni, Victor A., Li, Liang, Lee, Eungje, Alp, Esen E., Wu, Tianpin, Wen, Jianguo, Ren, Yang, Johnson, Christopher, Thackeray, Michael M., Chan, Maria K. Y., Wolverton, Chris, and Amine, Khalil. Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox. United States: N. p., 2017. Web. doi:10.1038/s41560-017-0043-6.
Zhan, Chun, Yao, Zhenpeng, Lu, Jun, Ma, Lu, Maroni, Victor A., Li, Liang, Lee, Eungje, Alp, Esen E., Wu, Tianpin, Wen, Jianguo, Ren, Yang, Johnson, Christopher, Thackeray, Michael M., Chan, Maria K. Y., Wolverton, Chris, & Amine, Khalil. Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox. United States. doi:10.1038/s41560-017-0043-6.
Zhan, Chun, Yao, Zhenpeng, Lu, Jun, Ma, Lu, Maroni, Victor A., Li, Liang, Lee, Eungje, Alp, Esen E., Wu, Tianpin, Wen, Jianguo, Ren, Yang, Johnson, Christopher, Thackeray, Michael M., Chan, Maria K. Y., Wolverton, Chris, and Amine, Khalil. Fri . "Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox". United States. doi:10.1038/s41560-017-0043-6. https://www.osti.gov/servlets/purl/1459884.
@article{osti_1459884,
title = {Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox},
author = {Zhan, Chun and Yao, Zhenpeng and Lu, Jun and Ma, Lu and Maroni, Victor A. and Li, Liang and Lee, Eungje and Alp, Esen E. and Wu, Tianpin and Wen, Jianguo and Ren, Yang and Johnson, Christopher and Thackeray, Michael M. and Chan, Maria K. Y. and Wolverton, Chris and Amine, Khalil},
abstractNote = {Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here in this paper, we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Furthermore, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.},
doi = {10.1038/s41560-017-0043-6},
journal = {Nature Energy},
number = 12,
volume = 2,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Phase conversion of LFO during electrochemical cycling. a, Structure of a 2×2×2 Li2O supercell and a Li5FeO4 unit cell both with the [100] view. b, The charge-discharge behaviour of LFO in the first 6 cycles between 4.7 V and 1 V (first cycle in red line and themore » following 5 cycles in blue). (c) The ex-situ Raman spectra obtained with 633 nm laser and ex-situ high energy XRD patterns (d) collected at different states of charge and discharge corresponding to the points in a (labelled as appoint i-viii) . The pristine LFO power and the cathode collected at point “i” and “ii” show typical features of the anti-fluorite Li5FeO4, with the prominent band at about 660 cm-1 and multiple bands at lower frequency according to ref 25. The fitting of Raman spectra at point “iii” and refinement of XRD patterns are given in Supplementary Figure 1. e, 2D contour of in-situ XRD patterns collected in the first charge, illustrating the continuous evolution of XRD patterns from “i” to “viii” in panel d. The vertical dash lines in d and e label the diffraction peaks indexed to the (200), (220) and (222) planes of the disordered rocksalt phase.« less

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    Works referencing / citing this record:

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    An oxalate cathode for lithium ion batteries with combined cationic and polyanionic redox
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