Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries
Abstract
Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na0.66CoxMn0.66–xTi0.34O2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66CoxMn0.66–xTi0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g-1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g-1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.
- Authors:
-
- Department of Materials Science, Fudan University, Shanghai 200433 P. R. China
- Chemistry Division, Brookhaven National Laboratory, Upton NY 11973 USA
- Department of Chemistry & Laser Chemistry Institute, Fudan University, Shanghai 200433 P. R. China
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1368103
- Alternate Identifier(s):
- OSTI ID: 1368104; OSTI ID: 1376159
- Report Number(s):
- BNL-114116-2017-JA
Journal ID: ISSN 2198-3844; 1700219
- Grant/Contract Number:
- AC02-06CH11357; SC0012704
- Resource Type:
- Published Article
- Journal Name:
- Advanced Science
- Additional Journal Information:
- Journal Name: Advanced Science; Journal ID: ISSN 2198-3844
- Publisher:
- Wiley
- Country of Publication:
- Germany
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; National Synchrotron Light Source
Citation Formats
Wang, Qin-Chao, Hu, Enyuan, Pan, Yang, Xiao, Na, Hong, Fan, Fu, Zheng-Wen, Wu, Xiao-Jing, Bak, Seong-Min, Yang, Xiao-Qing, and Zhou, Yong-Ning. Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries. Germany: N. p., 2017.
Web. doi:10.1002/advs.201700219.
Wang, Qin-Chao, Hu, Enyuan, Pan, Yang, Xiao, Na, Hong, Fan, Fu, Zheng-Wen, Wu, Xiao-Jing, Bak, Seong-Min, Yang, Xiao-Qing, & Zhou, Yong-Ning. Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries. Germany. https://doi.org/10.1002/advs.201700219
Wang, Qin-Chao, Hu, Enyuan, Pan, Yang, Xiao, Na, Hong, Fan, Fu, Zheng-Wen, Wu, Xiao-Jing, Bak, Seong-Min, Yang, Xiao-Qing, and Zhou, Yong-Ning. Thu .
"Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries". Germany. https://doi.org/10.1002/advs.201700219.
@article{osti_1368103,
title = {Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries},
author = {Wang, Qin-Chao and Hu, Enyuan and Pan, Yang and Xiao, Na and Hong, Fan and Fu, Zheng-Wen and Wu, Xiao-Jing and Bak, Seong-Min and Yang, Xiao-Qing and Zhou, Yong-Ning},
abstractNote = {Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na0.66CoxMn0.66–xTi0.34O2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66CoxMn0.66–xTi0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g-1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g-1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.},
doi = {10.1002/advs.201700219},
journal = {Advanced Science},
number = ,
volume = ,
place = {Germany},
year = {Thu Jul 06 00:00:00 EDT 2017},
month = {Thu Jul 06 00:00:00 EDT 2017}
}
https://doi.org/10.1002/advs.201700219
Web of Science
Works referenced in this record:
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries
journal, January 2015
- Han, Man Huon; Gonzalo, Elena; Singh, Gurpreet
- Energy & Environmental Science, Vol. 8, Issue 1
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015
- Kundu, Dipan; Talaie, Elahe; Duffort, Victor
- Angewandte Chemie International Edition, Vol. 54, Issue 11
Dissolution of Spinel Oxides and Capacity Losses in 4V Li / LixMn2O4 Cells
journal, January 1996
- Jang, Dong H.; Shin, Young J.; Oh, Seung M.
- Journal of The Electrochemical Society, Vol. 143, Issue 7, p. 2204-2211
Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O3-Layered Metal Oxide Cathode
journal, October 2015
- Mu, Linqin; Xu, Shuyin; Li, Yunming
- Advanced Materials, Vol. 27, Issue 43
High-Performance P2-Phase Na 2/3 Mn 0.8 Fe 0.1 Ti 0.1 O 2 Cathode Material for Ambient-Temperature Sodium-Ion Batteries
journal, December 2015
- Han, Man Huon; Gonzalo, Elena; Sharma, Neeraj
- Chemistry of Materials, Vol. 28, Issue 1
New-type K0.7Fe0.5Mn0.5O2 cathode with an expanded and stabilized interlayer structure for high-capacity sodium-ion batteries
journal, May 2017
- Wang, Xuanpeng; Hu, Ping; Niu, Chaojiang
- Nano Energy, Vol. 35
Synthesis and electrochemical behaviors of layered Na0.67[Mn0.65Co0.2Ni0.15]O2 microflakes as a stable cathode material for sodium-ion batteries
journal, January 2013
- Yuan, Dingding; He, Wei; Pei, Feng
- Journal of Materials Chemistry A, Vol. 1, Issue 12
A new electrode material for rechargeable sodium batteries: P2-type Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 with anomalously high reversible capacity
journal, January 2014
- Yabuuchi, Naoaki; Hara, Ryo; Kubota, Kei
- J. Mater. Chem. A, Vol. 2, Issue 40
The P2-Na2/3Co2/3Mn1/3O2 phase: structure, physical properties and electrochemical behavior as positive electrode in sodium battery
journal, January 2011
- Carlier, D.; Cheng, J. H.; Berthelot, R.
- Dalton Transactions, Vol. 40, Issue 36
Microscopy Study of Structural Evolution in Epitaxial LiCoO 2 Positive Electrode Films during Electrochemical Cycling
journal, March 2016
- Tan, Haiyan; Takeuchi, Saya; Bharathi, K. Kamala
- ACS Applied Materials & Interfaces, Vol. 8, Issue 10
Electrochemical intercalation of sodium in NaxCoO2 bronzes
journal, August 1981
- Delmas, C.; Braconnier, J.; Fouassier, C.
- Solid State Ionics, Vol. 3-4
Phase transition behavior of NaCrO2 during sodium extraction studied by synchrotron-based X-ray diffraction and absorption spectroscopy
journal, January 2013
- Zhou, Yong-Ning; Ding, Jing-Jing; Nam, Kyung-Wan
- Journal of Materials Chemistry A, Vol. 1, Issue 37
P2-Na0.6[Cr0.6Ti0.4]O2 cation-disordered electrode for high-rate symmetric rechargeable sodium-ion batteries
journal, April 2015
- Wang, Yuesheng; Xiao, Ruijuan; Hu, Yong-Sheng
- Nature Communications, Vol. 6, Issue 1
Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries
journal, January 2017
- Cao, Ming-Hui; Wang, Yong; Shadike, Zulipiya
- Journal of Materials Chemistry A, Vol. 5, 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
Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries
journal, December 2016
- Wang, Xuanpeng; Xu, Xiaoming; Niu, Chaojiang
- Nano Letters, Vol. 17, Issue 1
Synthesis and characterization of high-temperature hexagonal P2-Na0.6 MnO2 and its electrochemical behaviour as cathode in sodium cells
journal, February 2002
- Caballero, A.; Hernán, L.; Morales, J.
- Journal of Materials Chemistry, Vol. 12, Issue 4
A Novel High Capacity Positive Electrode Material with Tunnel-Type Structure for Aqueous Sodium-Ion Batteries
journal, August 2015
- Wang, Yuesheng; Mu, Linqin; Liu, Jue
- Advanced Energy Materials, Vol. 5, Issue 22
Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries
journal, April 2015
- Han, Jung-Gu; Lee, Sung Jun; Lee, Jaegi
- ACS Applied Materials & Interfaces, Vol. 7, Issue 15
Na-ion batteries, recent advances and present challenges to become low cost energy storage systems
journal, January 2012
- Palomares, Verónica; Serras, Paula; Villaluenga, Irune
- Energy & Environmental Science, Vol. 5, Issue 3
Unveiling the Role of Co in Improving the High-Rate Capability and Cycling Performance of Layered Na 0.7 Mn 0.7 Ni 0.3– x Co x O 2 Cathode Materials for Sodium-Ion Batteries
journal, June 2016
- Li, Zheng-Yao; Zhang, Jicheng; Gao, Rui
- ACS Applied Materials & Interfaces, Vol. 8, Issue 24
Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries
journal, November 2014
- Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan
- Nature Communications, Vol. 5, Issue 1
Building better batteries
journal, February 2008
- Armand, M.; Tarascon, J.-M.
- Nature, Vol. 451, Issue 7179, p. 652-657
Superior Electrochemical Performance and Storage Mechanism of Na 3 V 2 (PO 4 ) 3 Cathode for Room-Temperature Sodium-Ion Batteries
journal, October 2012
- Jian, Zelang; Han, Wenze; Lu, Xia
- Advanced Energy Materials, Vol. 3, Issue 2
Conjugated polymer–inorganic semiconductor hybrid solar cells
journal, January 2011
- Xu, Tingting; Qiao, Qiquan
- Energy & Environmental Science, Vol. 4, Issue 8
P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries
journal, April 2012
- Yabuuchi, Naoaki; Kajiyama, Masataka; Iwatate, Junichi
- Nature Materials, Vol. 11, Issue 6
A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries
journal, February 2013
- Suo, Liumin; Hu, Yong-Sheng; Li, Hong
- Nature Communications, Vol. 4, Issue 1
P2-type Na0.67Mn0.65Fe0.2Ni0.15O2 Cathode Material with High-capacity for Sodium-ion Battery
journal, January 2014
- Yuan, Dingding; Hu, Xiaohong; Qian, Jiangfeng
- Electrochimica Acta, Vol. 116
Fe-Based Tunnel-Type Na 0.61 [Mn 0.27 Fe 0.34 Ti 0.39 ]O 2 Designed by a New Strategy as a Cathode Material for Sodium-Ion Batteries
journal, August 2015
- Xu, Shuyin; Wang, Yuesheng; Ben, Liubin
- Advanced Energy Materials, Vol. 5, Issue 22
The T # 2-Li 2/3 Co 2/3 Mn 1/3 O 2 System. 1. Its Structural Characterization
journal, April 2004
- Tournadre, F.; Croguennec, L.; Saadoune, I.
- Chemistry of Materials, Vol. 16, Issue 8
The Stability of Orthorhombic and Monoclinic-Layered LiMnO[sub 2]
journal, January 1999
- Ceder, G.
- Electrochemical and Solid-State Letters, Vol. 2, Issue 11
Layered oxides as positive electrode materials for Na-ion batteries
journal, May 2014
- Kubota, Kei; Yabuuchi, Naoaki; Yoshida, Hiroaki
- MRS Bulletin, Vol. 39, Issue 5
IFEFFIT : interactive XAFS analysis and FEFF fitting
journal, March 2001
- Newville, Matthew
- Journal of Synchrotron Radiation, Vol. 8, Issue 2
FeO 0.7 F 1.3 /C Nanocomposite as a High-Capacity Cathode Material for Sodium-Ion Batteries
journal, November 2014
- Zhou, Yong-Ning; Sina, Mahsa; Pereira, Nathalie
- Advanced Functional Materials, Vol. 25, Issue 5
Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries
journal, May 2012
- Kim, Sung-Wook; Seo, Dong-Hwa; Ma, Xiaohua
- Advanced Energy Materials, Vol. 2, Issue 7, p. 710-721
A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries
journal, August 2013
- Wang, Yuesheng; Yu, Xiqian; Xu, Shuyin
- Nature Communications, Vol. 4, Issue 1
Structural classification and properties of the layered oxides
journal, January 1980
- Delmas, C.; Fouassier, C.; Hagenmuller, P.
- Physica B+C, Vol. 99, Issue 1-4
Air-Stable Copper-Based P2-Na 7/9 Cu 2/9 Fe 1/9 Mn 2/3 O 2 as a New Positive Electrode Material for Sodium-Ion Batteries
journal, May 2015
- Li, Yunming; Yang, Zhenzhong; Xu, Shuyin
- Advanced Science, Vol. 2, Issue 6
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
Computational and Experimental Investigation of Ti Substitution in Li 1 (Ni x Mn x Co 1–2 x – y Ti y )O 2 for Lithium Ion Batteries
journal, October 2014
- Markus, Isaac M.; Lin, Feng; Kam, Kinson C.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 21
Research Development on Sodium-Ion Batteries
journal, October 2014
- Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
- Chemical Reviews, Vol. 114, Issue 23
Disodium Terephthalate (Na2C8H4O4) as High Performance Anode Material for Low-Cost Room-Temperature Sodium-Ion Battery
journal, May 2012
- Zhao, Liang; Zhao, Junmei; Hu, Yong-Sheng
- Advanced Energy Materials, Vol. 2, Issue 8
Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes
journal, October 2015
- Croy, Jason R.; Balasubramanian, Mahalingam; Gallagher, Kevin G.
- Accounts of Chemical Research, Vol. 48, Issue 11