Comprehensively Strengthened Metal‐Oxygen Bonds for Reversible Anionic Redox Reaction
Abstract
Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O2 and O2 release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na0.71Li0.22Al0.05Mn0.73O2 (NLAM) cathode material is developed by introducing Al3+ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al3+ radius, the TMO2 skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g—1 at 20 mA g—1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g—1. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. Importantly, this finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.
- Authors:
-
- Wuhan Univ. of Technology (China). State Key Lab. of Advanced Technology for Materials Synthesis and Processing
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Wuhan Univ. of Technology (China). State Key Lab. of Advanced Technology for Materials Synthesis and Processing; Wuhan Univ. of Technology (China). Hubei Longzhong Lab.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- OSTI Identifier:
- 2310288
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Functional Materials
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 24; Journal ID: ISSN 1616-301X
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Al substitutions; anionic redox reactions; layered oxides; O2 releases; sodium-ion batteries
Citation Formats
Cai, Congcong, Li, Xinyuan, Hu, Ping, Zhu, Ting, Li, Jiantao, Fan, Hao, Yu, Ruohan, Zhang, Tianyi, Lee, Sungsik, Zhou, Liang, and Mai, Liqiang. Comprehensively Strengthened Metal‐Oxygen Bonds for Reversible Anionic Redox Reaction. United States: N. p., 2023.
Web. doi:10.1002/adfm.202215155.
Cai, Congcong, Li, Xinyuan, Hu, Ping, Zhu, Ting, Li, Jiantao, Fan, Hao, Yu, Ruohan, Zhang, Tianyi, Lee, Sungsik, Zhou, Liang, & Mai, Liqiang. Comprehensively Strengthened Metal‐Oxygen Bonds for Reversible Anionic Redox Reaction. United States. https://doi.org/10.1002/adfm.202215155
Cai, Congcong, Li, Xinyuan, Hu, Ping, Zhu, Ting, Li, Jiantao, Fan, Hao, Yu, Ruohan, Zhang, Tianyi, Lee, Sungsik, Zhou, Liang, and Mai, Liqiang. Mon .
"Comprehensively Strengthened Metal‐Oxygen Bonds for Reversible Anionic Redox Reaction". United States. https://doi.org/10.1002/adfm.202215155. https://www.osti.gov/servlets/purl/2310288.
@article{osti_2310288,
title = {Comprehensively Strengthened Metal‐Oxygen Bonds for Reversible Anionic Redox Reaction},
author = {Cai, Congcong and Li, Xinyuan and Hu, Ping and Zhu, Ting and Li, Jiantao and Fan, Hao and Yu, Ruohan and Zhang, Tianyi and Lee, Sungsik and Zhou, Liang and Mai, Liqiang},
abstractNote = {Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O2 and O2 release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na0.71Li0.22Al0.05Mn0.73O2 (NLAM) cathode material is developed by introducing Al3+ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al3+ radius, the TMO2 skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g—1 at 20 mA g—1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g—1. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. Importantly, this finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.},
doi = {10.1002/adfm.202215155},
journal = {Advanced Functional Materials},
number = 24,
volume = 33,
place = {United States},
year = {Mon Mar 06 00:00:00 EST 2023},
month = {Mon Mar 06 00:00:00 EST 2023}
}
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