Understanding the Low-Voltage Hysteresis of Anionic Redox in Na2 Mn 3 O 7
Abstract
he large voltage hysteresis remains one of the biggest barriers to optimizing Li/Na-ion cathodes using lattice anionic redox reaction, despite their very high energy density and relative low-cost. Very recently, a layered sodium cathode Na2Mn3O7 (or Na4/7Mn6/71/7O2, is vacancy) was reported to have reversible lattice oxygen redox with much suppressed voltage hysteresis. However, the structural and electronic structural origin of this small voltage hysteresis has not been well understood. In this article, through systematic studies using ex situ/in situ electron paramagnetic resonance and X-ray diffraction, we demonstrate that the exceptional small voltage hysteresis (< 50mV) between charge and discharge curves is rooted in the well-maintained oxygen stacking sequence in the absence of irreversible gliding of oxygen layers and cation migration from the transition metal (TM) layers. In addition, we further identify that the 4.2 V charge/discharge plateau is associated with a zero-strain (de)intercalation process of Na+ ions from distorted octahedral sites, while the 4.5 V plateau is linked to a reversible shrink/expansion process of the manganese-site vacancy during (de)intercalation of Na+ ions at distorted prismatic sites. As a result, it is expected these findings will inspire further exploration of new cathode materials that can achieve both high energy density andmore »
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Center for High Pressure Science and Technology Advanced Research, Beijing (China)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1523738
- Alternate Identifier(s):
- OSTI ID: 1512261; OSTI ID: 1558108
- Report Number(s):
- BNL-211621-2019-JAAM
Journal ID: ISSN 0897-4756
- Grant/Contract Number:
- AC05-00OR22725; SC0012704; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 10; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Song, Bohang, Tang, Mingxue, Hu, Enyuan, Borkiewicz, Olaf J., Wiaderek, Kamila M., Zhang, Yiman, Phillip, Nathan D., Liu, Xiaoming, Shadike, Zulipiya, Li, Cheng, Song, Likai, Hu, Yan-Yan, Chi, Miaofang, Veith, Gabriel M., Yang, Xiao-Qing, Liu, Jue, Nanda, Jagjit, Page, Katharine, and Huq, Ashfia. Understanding the Low-Voltage Hysteresis of Anionic Redox in Na2 Mn 3 O 7. United States: N. p., 2019.
Web. doi:10.1021/acs.chemmater.9b00772.
Song, Bohang, Tang, Mingxue, Hu, Enyuan, Borkiewicz, Olaf J., Wiaderek, Kamila M., Zhang, Yiman, Phillip, Nathan D., Liu, Xiaoming, Shadike, Zulipiya, Li, Cheng, Song, Likai, Hu, Yan-Yan, Chi, Miaofang, Veith, Gabriel M., Yang, Xiao-Qing, Liu, Jue, Nanda, Jagjit, Page, Katharine, & Huq, Ashfia. Understanding the Low-Voltage Hysteresis of Anionic Redox in Na2 Mn 3 O 7. United States. https://doi.org/10.1021/acs.chemmater.9b00772
Song, Bohang, Tang, Mingxue, Hu, Enyuan, Borkiewicz, Olaf J., Wiaderek, Kamila M., Zhang, Yiman, Phillip, Nathan D., Liu, Xiaoming, Shadike, Zulipiya, Li, Cheng, Song, Likai, Hu, Yan-Yan, Chi, Miaofang, Veith, Gabriel M., Yang, Xiao-Qing, Liu, Jue, Nanda, Jagjit, Page, Katharine, and Huq, Ashfia. Wed .
"Understanding the Low-Voltage Hysteresis of Anionic Redox in Na2 Mn 3 O 7". United States. https://doi.org/10.1021/acs.chemmater.9b00772. https://www.osti.gov/servlets/purl/1523738.
@article{osti_1523738,
title = {Understanding the Low-Voltage Hysteresis of Anionic Redox in Na2 Mn 3 O 7},
author = {Song, Bohang and Tang, Mingxue and Hu, Enyuan and Borkiewicz, Olaf J. and Wiaderek, Kamila M. and Zhang, Yiman and Phillip, Nathan D. and Liu, Xiaoming and Shadike, Zulipiya and Li, Cheng and Song, Likai and Hu, Yan-Yan and Chi, Miaofang and Veith, Gabriel M. and Yang, Xiao-Qing and Liu, Jue and Nanda, Jagjit and Page, Katharine and Huq, Ashfia},
abstractNote = {he large voltage hysteresis remains one of the biggest barriers to optimizing Li/Na-ion cathodes using lattice anionic redox reaction, despite their very high energy density and relative low-cost. Very recently, a layered sodium cathode Na2Mn3O7 (or Na4/7Mn6/71/7O2, is vacancy) was reported to have reversible lattice oxygen redox with much suppressed voltage hysteresis. However, the structural and electronic structural origin of this small voltage hysteresis has not been well understood. In this article, through systematic studies using ex situ/in situ electron paramagnetic resonance and X-ray diffraction, we demonstrate that the exceptional small voltage hysteresis (< 50mV) between charge and discharge curves is rooted in the well-maintained oxygen stacking sequence in the absence of irreversible gliding of oxygen layers and cation migration from the transition metal (TM) layers. In addition, we further identify that the 4.2 V charge/discharge plateau is associated with a zero-strain (de)intercalation process of Na+ ions from distorted octahedral sites, while the 4.5 V plateau is linked to a reversible shrink/expansion process of the manganese-site vacancy during (de)intercalation of Na+ ions at distorted prismatic sites. As a result, it is expected these findings will inspire further exploration of new cathode materials that can achieve both high energy density and efficiency by using lattice anionic redox.},
doi = {10.1021/acs.chemmater.9b00772},
journal = {Chemistry of Materials},
number = 10,
volume = 31,
place = {United States},
year = {Wed May 01 00:00:00 EDT 2019},
month = {Wed May 01 00:00:00 EDT 2019}
}
Web of Science