Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide
Abstract
Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li2MnO3, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. In this paper, we originally design a Na-rich layered oxide prototype, namely Na3RuO4 (Ru5+), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Finally, our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.
- Authors:
-
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.; Univ. of Tsukuba (Japan). Graduate School of System and Information Engineering
- Nanjing Univ. (China). Center of Energy Storage Materials & Technology. College of Engineering and Applied Sciences. National Lab. of Solid State Microstructures. Collaborative Innovation Center of Advanced Microstructures
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.
- Shanghai Jiao Tong Univ. (China). State Key Lab. of Metal Matrix Composites. School of Material Science and Engineering
- Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
- Nanjing Univ. (China). Center of Energy Storage Materials & Technology. College of Engineering and Applied Sciences. National Lab. of Solid State Microstructures. Collaborative Innovation Center of Advanced Microstructures; National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.; Univ. of Tsukuba (Japan). Graduate School of System and Information Engineering
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Nanjing Univ. (China); Shanghai Jiao Tong Univ. (China)
- Sponsoring Org.:
- USDOE Office of Science (SC); Japan Science and Technology Agency (JST); National Basic Research Program of China; National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jiangsu Province (China); China Scholarship Council (CSC)
- OSTI Identifier:
- 1471523
- Grant/Contract Number:
- AC02-06CH11357; 2014CB932300; 21373111; 21633003; 51602144; BK20170630
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, and Zhou, Haoshen. Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide. United States: N. p., 2018.
Web. doi:10.1039/C7EE03554C.
Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, & Zhou, Haoshen. Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide. United States. https://doi.org/10.1039/C7EE03554C
Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, and Zhou, Haoshen. Fri .
"Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide". United States. https://doi.org/10.1039/C7EE03554C. https://www.osti.gov/servlets/purl/1471523.
@article{osti_1471523,
title = {Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide},
author = {Qiao, Yu and Guo, Shaohua and Zhu, Kai and Liu, Pan and Li, Xiang and Jiang, Kezhu and Sun, Cheng-Jun and Chen, Mingwei and Zhou, Haoshen},
abstractNote = {Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li2MnO3, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. In this paper, we originally design a Na-rich layered oxide prototype, namely Na3RuO4 (Ru5+), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Finally, our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.},
doi = {10.1039/C7EE03554C},
journal = {Energy & Environmental Science},
number = 2,
volume = 11,
place = {United States},
year = {2018},
month = {1}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013
- Sathiya, M.; Rousse, G.; Ramesha, K.
- Nature Materials, Vol. 12, Issue 9
Study of the nanosized Li2MnO3: Electrochemical behavior, structure, magnetic properties, and vibrational modes
journal, May 2013
- Amalraj, S. Francis; Sharon, Daniel; Talianker, Michael
- Electrochimica Acta, Vol. 97
Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3
journal, February 2017
- Pearce, Paul E.; Perez, Arnaud J.; Rousse, Gwenaelle
- Nature Materials, Vol. 16, Issue 5
Anionic Redox in Rechargeable Lithium Batteries
journal, June 2017
- Li, Biao; Xia, Dingguo
- Advanced Materials, Vol. 29, Issue 48
Understanding and Controlling Anionic Electrochemical Activity in High-Capacity Oxides for Next Generation Li-Ion Batteries
journal, January 2017
- Qiu, Bao; Zhang, Minghao; Xia, Yonggao
- Chemistry of Materials, Vol. 29, Issue 3
Redox Potential Paradox in Na x MO 2 for Sodium-Ion Battery Cathodes
journal, February 2016
- Nanba, Yusuke; Iwao, Tatsumi; Boisse, Benoit Mortemard de
- Chemistry of Materials, Vol. 28, Issue 4
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016
- Luo, Kun; Roberts, Matthew R.; Hao, Rong
- Nature Chemistry, Vol. 8, Issue 7
Review—Li-Rich Layered Oxide Cathodes for Next-Generation Li-Ion Batteries: Chances and Challenges
journal, January 2015
- Rozier, Patrick; Tarascon, Jean Marie
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries
journal, March 2010
- Baddour-Hadjean, Rita; Pereira-Ramos, Jean-Pierre
- Chemical Reviews, Vol. 110, Issue 3
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016
- Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
- Nature Chemistry, Vol. 8, Issue 7
Lattice vibrations of materials for lithium rechargeable batteries III. Lithium manganese oxides
journal, June 2003
- Julien, C. M.; Massot, M.
- Materials Science and Engineering: B, Vol. 100, Issue 1
Improving Energy Density and Structural Stability of Manganese Oxide Cathodes for Na-Ion Batteries by Structural Lithium Substitution
journal, December 2016
- de la Llave, Ezequiel; Talaie, Elahe; Levi, Elena
- Chemistry of Materials, Vol. 28, Issue 24
Mechanistic Insight into the Superoxide Induced Ring Opening in Propylene Carbonate Based Electrolytes using in Situ Surface-Enhanced Infrared Spectroscopy
journal, March 2016
- Vivek, J. Padmanabhan; Berry, Neil; Papageorgiou, Georgios
- Journal of the American Chemical Society, Vol. 138, Issue 11
A 3.8-V earth-abundant sodium battery electrode
journal, July 2014
- Barpanda, Prabeer; Oyama, Gosuke; Nishimura, Shin-ichi
- Nature Communications, Vol. 5, Issue 1
Reactions in the Rechargeable Lithium–O 2 Battery with Alkyl Carbonate Electrolytes
journal, May 2011
- Freunberger, Stefan A.; Chen, Yuhui; Peng, Zhangquan
- Journal of the American Chemical Society, Vol. 133, Issue 20
Isolated spin 3/2 plaquettes in Na3RuO4
journal, June 2005
- Regan, K. A.; Huang, Q.; Cava, R. J.
- Journal of Solid State Chemistry, Vol. 178, Issue 6
Anionic redox processes for electrochemical devices
journal, January 2016
- Grimaud, A.; Hong, W. T.; Shao-Horn, Y.
- Nature Materials, Vol. 15, Issue 2
X-ray Photoemission Spectroscopy Study of Cationic and Anionic Redox Processes in High-Capacity Li-Ion Battery Layered-Oxide Electrodes
journal, January 2016
- Foix, Dominique; Sathiya, Mariyappan; McCalla, Eric
- The Journal of Physical Chemistry C, Vol. 120, Issue 2
Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2
journal, February 2015
- Oishi, Masatsugu; Yogi, Chihiro; Watanabe, Iwao
- Journal of Power Sources, Vol. 276
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2
journal, August 2016
- Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló
- Journal of the American Chemical Society, Vol. 138, Issue 35
Lithium Extraction Mechanism in Li-Rich Li 2 MnO 3 Involving Oxygen Hole Formation and Dimerization
journal, September 2016
- Chen, Hungru; Islam, M. Saiful
- Chemistry of Materials, Vol. 28, Issue 18
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries
journal, January 2016
- Saubanère, M.; McCalla, E.; Tarascon, J. -M.
- Energy & Environmental Science, Vol. 9, Issue 3
New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries
journal, May 2014
- Yabuuchi, Naoaki; Hara, Ryo; Kajiyama, Masataka
- Advanced Energy Materials, Vol. 4, Issue 13
Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries
journal, January 2016
- Assat, Gaurav; Delacourt, Charles; Corte, Daniel Alves Dalla
- Journal of The Electrochemical Society, Vol. 163, Issue 14
Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2
journal, March 2011
- Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek
- Journal of the American Chemical Society, Vol. 133, Issue 12
Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode
journal, January 2018
- Rong, Xiaohui; Liu, Jue; Hu, Enyuan
- Joule, Vol. 2, Issue 1
Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
journal, April 2016
- Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao
- Nature Communications, Vol. 7, Issue 1
Shell-isolated nanoparticle-enhanced Raman spectroscopy
journal, March 2010
- Li, Jian Feng; Huang, Yi Fan; Ding, Yong
- Nature, Vol. 464, Issue 7287, p. 392-395
A New High-Energy Cathode for a Na-Ion Battery with Ultrahigh Stability
journal, September 2013
- Park, Young-Uk; Seo, Dong-Hwa; Kwon, Hyung-Soon
- Journal of the American Chemical Society, Vol. 135, Issue 37
Layered Na2RuO3 as a cathode material for Na-ion batteries
journal, August 2013
- Tamaru, Mao; Wang, Xianfen; Okubo, Masashi
- Electrochemistry Communications, Vol. 33
Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes
journal, November 2015
- Qiao, Ruimin; Wray, L. Andrew; Kim, Jung-Hyun
- The Journal of Physical Chemistry C, Vol. 119, Issue 49
Insights into the stable layered structure of a Li-rich cathode material for lithium-ion batteries
journal, January 2017
- An, Juan; Shi, Liyi; Chen, Guorong
- Journal of Materials Chemistry A, Vol. 5, Issue 37
Direct In situ Observation of Li 2 O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni x Li (1–2 x )/3 Mn (2– x )/3 ]O 2 (0 ≤ x ≤0.5)
journal, January 2014
- Hy, Sunny; Felix, Felix; Rick, John
- Journal of the American Chemical Society, Vol. 136, Issue 3
Anionic redox chemistry in Na-rich Na 2 Ru 1−y Sn y O 3 positive electrode material for Na-ion batteries
journal, April 2015
- Rozier, Patrick; Sathiya, Mariyappan; Paulraj, Alagar-Raj
- Electrochemistry Communications, Vol. 53
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries
journal, December 2016
- Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue
- Nature Communications, Vol. 7, Issue 1
Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li 2 MnO 3 , studied by soft X-ray absorption spectroscopy
journal, January 2016
- Oishi, Masatsugu; Yamanaka, Keisuke; Watanabe, Iwao
- Journal of Materials Chemistry A, Vol. 4, Issue 23
Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: x Li 2 MnO 3 ·(1 − x )LiMn 0.333 Ni 0.333 Co 0.333 O 2 (0 ≤ x ≤ 0.7)
journal, October 2008
- Johnson, Christopher S.; Li, Naichao; Lefief, Christina
- Chemistry of Materials, Vol. 20, Issue 19
Exploring reversible oxidation of oxygen in a manganese oxide
journal, January 2016
- Du, Ke; Zhu, Jinyou; Hu, Guorong
- Energy & Environmental Science, Vol. 9, Issue 8
High Performance Li 2 Ru 1– y Mn y O 3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding
journal, March 2013
- Sathiya, M.; Ramesha, K.; Rousse, G.
- Chemistry of Materials, Vol. 25, Issue 7
Research Development on Sodium-Ion Batteries
journal, October 2014
- Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
- Chemical Reviews, Vol. 114, Issue 23
Works referencing / citing this record:
Exposing {010} Active Facets by Multiple-Layer Oriented Stacking Nanosheets for High-Performance Capacitive Sodium-Ion Oxide Cathode
journal, August 2018
- Xiao, Yao; Wang, Peng-Fei; Yin, Ya-Xia
- Advanced Materials, Vol. 30, Issue 40
Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries
journal, May 2019
- Zhang, Xiaoyu; Qiao, Yu; Guo, Shaohua
- Advanced Materials, Vol. 31, Issue 27
A New Type of Li‐Rich Rock‐Salt Oxide Li 2 Ni 1/3 Ru 2/3 O 3 with Reversible Anionic Redox Chemistry
journal, January 2019
- Li, Xiang; Qiao, Yu; Guo, Shaohua
- Advanced Materials, Vol. 31, Issue 11
Synthesis and characterization of Ru doped NaNi0.5Mn0.3Ti0.2O2 cathode material with improved electrochemical performance for sodium-ion batteries
journal, January 2019
- Leng, Mingzhe; Bi, Jianqiang; Wang, Weili
- Ionics, Vol. 25, Issue 3
Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S
journal, October 2019
- Wang, Tian; Ren, Guo-Xi; Shadike, Zulipiya
- Nature Communications, Vol. 10, Issue 1
Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials
journal, July 2019
- Radin, Maxwell D.; Vinckeviciute, Julija; Seshadri, Ram
- Nature Energy, Vol. 4, Issue 8
Na 2 Ru 1−x Mn x O 3 as the cathode for sodium-ion batteries
journal, January 2019
- Li, Xiang; Guo, Shaohua; Qiu, Feilong
- Journal of Materials Chemistry A, Vol. 7, Issue 9
Correlation between Ru–O hybridization and the oxygen evolution reaction in ruthenate epitaxial thin films
journal, January 2019
- Lee, Sang A.; Lee, Jegon; Oh, Seokjae
- Sustainable Energy & Fuels, Vol. 3, Issue 10
Simultaneously tuning cationic and anionic redox in a P2-Na 0.67 Mn 0.75 Ni 0.25 O 2 cathode material through synergic Cu/Mg co-doping
journal, January 2019
- Kong, Weijin; Gao, Rui; Li, Qingyuan
- Journal of Materials Chemistry A, Vol. 7, Issue 15
Review on anionic redox in sodium-ion batteries
journal, January 2019
- Xu, Hang; Guo, Shaohua; Zhou, Haoshen
- Journal of Materials Chemistry A, Vol. 7, Issue 41
Na 2 SeO 3 : A Na-Ion Battery Positive Electrode Material with High Capacity
journal, November 2018
- Su, Bizhe; Zhang, Jiaolong; Fujita, Manabu
- Journal of The Electrochemical Society, Vol. 166, Issue 3
Understanding Oxygen Redox in Cu-Doped P2-Na 0.67 Mn 0.8 Fe 0.1 Co 0.1 O 2 Cathode Materials for Na-Ion Batteries
journal, January 2018
- Li, Ling; Wang, Huibo; Han, Wenze
- Journal of The Electrochemical Society, Vol. 165, Issue 16
Air-Stable NaxTMO2 Cathodes for Sodium Storage
journal, May 2019
- Zhang, Yi; Zhang, Renyuan; Huang, Yunhui
- Frontiers in Chemistry, Vol. 7
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