β-NaVOPO4 obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries
Abstract
Vanadyl phosphates (VOPO4) represent a class of attractive cathodes in lithium-ion batteries. However, the exploration of this type of materials in sodium-ion batteries is rare. Here, we report for the first time the synthesis of orthorhombic β-NaVOPO4 by first chemically extracting lithium from beta-LiVOPO4 and then inserting sodium into the obtained β-VOPO4 by a microwave-assisted solvothermal process with NaI, which serves both as a reducing agent and sodium source. Intermediate NaxVOPO4 compositions with x = 0.3, 0.5, and 0.8 have also been obtained by controlling the amount of NaI in the reaction mixture. Joint Rietveld refinement of synchrotron X-ray diffraction (XRD) and neutron diffraction confirms that the fully sodiated β-NaVOPO4 is isostructural with the lithium counterpart β-LiVOPO4. Bond valence sum maps suggest that sodium ions possibly diffuse along the [010] direction in the lattice, similar to the ionic conduction pathway in β-LiVOPO4. Although the initial discharge capacity is low due to the protons in the structure, it steadily increases with cycling with a long plateau at 3.3 V. As a result, ex situ XRD data of cycled β-VOPO4 and β-NaVOPO4 electrodes confirm the reversible reaction in sodium cells involving the V4+/V5+ redox couple.
- Authors:
-
- Univ. of Texas, Austin, TX (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1261529
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 28; Journal Issue: 5; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
He, Guang, Huq, Ashfia, Manthiram, Arumugam, and Kan, Wang Hay. β-NaVOPO4 obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries. United States: N. p., 2016.
Web. doi:10.1021/acs.chemmater.5b04992.
He, Guang, Huq, Ashfia, Manthiram, Arumugam, & Kan, Wang Hay. β-NaVOPO4 obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries. United States. https://doi.org/10.1021/acs.chemmater.5b04992
He, Guang, Huq, Ashfia, Manthiram, Arumugam, and Kan, Wang Hay. Tue .
"β-NaVOPO4 obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries". United States. https://doi.org/10.1021/acs.chemmater.5b04992. https://www.osti.gov/servlets/purl/1261529.
@article{osti_1261529,
title = {β-NaVOPO4 obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries},
author = {He, Guang and Huq, Ashfia and Manthiram, Arumugam and Kan, Wang Hay},
abstractNote = {Vanadyl phosphates (VOPO4) represent a class of attractive cathodes in lithium-ion batteries. However, the exploration of this type of materials in sodium-ion batteries is rare. Here, we report for the first time the synthesis of orthorhombic β-NaVOPO4 by first chemically extracting lithium from beta-LiVOPO4 and then inserting sodium into the obtained β-VOPO4 by a microwave-assisted solvothermal process with NaI, which serves both as a reducing agent and sodium source. Intermediate NaxVOPO4 compositions with x = 0.3, 0.5, and 0.8 have also been obtained by controlling the amount of NaI in the reaction mixture. Joint Rietveld refinement of synchrotron X-ray diffraction (XRD) and neutron diffraction confirms that the fully sodiated β-NaVOPO4 is isostructural with the lithium counterpart β-LiVOPO4. Bond valence sum maps suggest that sodium ions possibly diffuse along the [010] direction in the lattice, similar to the ionic conduction pathway in β-LiVOPO4. Although the initial discharge capacity is low due to the protons in the structure, it steadily increases with cycling with a long plateau at 3.3 V. As a result, ex situ XRD data of cycled β-VOPO4 and β-NaVOPO4 electrodes confirm the reversible reaction in sodium cells involving the V4+/V5+ redox couple.},
doi = {10.1021/acs.chemmater.5b04992},
journal = {Chemistry of Materials},
number = 5,
volume = 28,
place = {United States},
year = {Tue Feb 02 00:00:00 EST 2016},
month = {Tue Feb 02 00:00:00 EST 2016}
}
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Works referenced in this record:
Soft Chemistry Synthesis and Characterization of Layered Li1-xNi1-yCoyO2-δ (0 ≤ x ≤ 1 and 0 ≤ y ≤ 1)
journal, September 2001
- Chebiam, R. V.; Prado, F.; Manthiram, A.
- Chemistry of Materials, Vol. 13, Issue 9, p. 2951-2957
Synthesis and Characterization of P3-Type CoO 2 - δ
journal, September 2002
- Venkatraman, S.; Manthiram, A.
- Chemistry of Materials, Vol. 14, Issue 9
Lithium insertion into Fe2(MO4)3 frameworks: Comparison of M = W with M = Mo
journal, December 1987
- Manthiram, A.; Goodenough, J. B.
- Journal of Solid State Chemistry, Vol. 71, Issue 2
Lithium insertion into Fe2(SO4)3 frameworks
journal, May 1989
- Manthiram, A.; Goodenough, J. B.
- Journal of Power Sources, Vol. 26, Issue 3-4
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997
- Padhi, A. K.
- Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
Microwave-Solvothermal Synthesis of Nanostructured Li 2 MSiO 4 /C (M = Mn and Fe) Cathodes for Lithium-Ion Batteries
journal, October 2010
- Muraliganth, T.; Stroukoff, K. R.; Manthiram, A.
- Chemistry of Materials, Vol. 22, Issue 20
Polyanionic (Phosphates, Silicates, Sulfates) Frameworks as Electrode Materials for Rechargeable Li (or Na) Batteries
journal, June 2013
- Masquelier, Christian; Croguennec, Laurence
- Chemical Reviews, Vol. 113, Issue 8
Research Development on Sodium-Ion Batteries
journal, October 2014
- Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
- Chemical Reviews, Vol. 114, Issue 23
The First Report on Excellent Cycling Stability and Superior Rate Capability of Na 3 V 2 (PO 4 ) 3 for Sodium Ion Batteries
journal, November 2012
- Saravanan, Kuppan; Mason, Chad W.; Rudola, Ashish
- Advanced Energy Materials, Vol. 3, Issue 4
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
Effect of Carbon Matrix Dimensions on the Electrochemical Properties of Na 3 V 2 (PO 4 ) 3 Nanograins for High-Performance Symmetric Sodium-Ion Batteries
journal, March 2014
- Li, Shuo; Dong, Yifan; Xu, Lin
- Advanced Materials, Vol. 26, Issue 21
Carbon-Coated Na 3 V 2 (PO 4 ) 3 Embedded in Porous Carbon Matrix: An Ultrafast Na-Storage Cathode with the Potential of Outperforming Li Cathodes
journal, March 2014
- Zhu, Changbao; Song, Kepeng; van Aken, Peter A.
- Nano Letters, Vol. 14, Issue 4
Nanoconfined Carbon-Coated Na 3 V 2 (PO 4 ) 3 Particles in Mesoporous Carbon Enabling Ultralong Cycle Life for Sodium-Ion Batteries
journal, February 2015
- Jiang, Yu; Yang, Zhenzhong; Li, Weihan
- Advanced Energy Materials, Vol. 5, Issue 10
High rate performance of a Na3V2(PO4)3/C cathode prepared by pyro-synthesis for sodium-ion batteries
journal, January 2012
- Kang, Jungwon; Baek, Sora; Mathew, Vinod
- Journal of Materials Chemistry, Vol. 22, Issue 39
Electrochemical and Thermal Properties of NASICON Structured Na 3 V 2 (PO 4 ) 3 as a Sodium Rechargeable Battery Cathode: A Combined Experimental and Theoretical Study
journal, January 2012
- Lim, Soo Yeon; Kim, Heejin; Shakoor, R. A.
- Journal of The Electrochemical Society, Vol. 159, Issue 9
Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries
journal, January 2012
- Jian, Zelang; Zhao, Liang; Pan, Huilin
- Electrochemistry Communications, Vol. 14, Issue 1
A 3.4 V Layered VOPO 4 Cathode for Na-Ion Batteries
journal, January 2016
- He, Guang; Kan, Wang Hay; Manthiram, Arumugam
- Chemistry of Materials, Vol. 28, Issue 2
Electrochemical performance of different Li-VOPO4 systems
journal, July 2001
- Dupré, N.; Gaubicher, J.; Angenault, J.
- Journal of Power Sources, Vol. 97-98
Vanadyl phosphates of VOPO4 as a cathode of Li-ion rechargeable batteries
journal, June 2003
- Azmi, Bustam M.; Ishihara, Tatsumi; Nishiguchi, Hiroyasu
- Journal of Power Sources, Vol. 119-121
Chemical and Electrochemical Lithiation of LiVOPO 4 Cathodes for Lithium-Ion Batteries
journal, June 2014
- Harrison, Katharine L.; Bridges, Craig A.; Segre, Carlo U.
- Chemistry of Materials, Vol. 26, Issue 12
Interfacial Effects in ε-Li x VOPO 4 and Evolution of the Electronic Structure
journal, December 2015
- Quackenbush, N. F.; Wangoh, L.; Scanlon, D. O.
- Chemistry of Materials, Vol. 27, Issue 24
Redox transformations of simple vanadium phosphates: the synthesis of ε-VOPO4
journal, April 1996
- Lim, S.
- Solid State Ionics, Vol. 84, Issue 3-4
Positive electrode materials for lithium batteries based on VOPO4
journal, April 2001
- Dupré, N.
- Solid State Ionics, Vol. 140, Issue 3-4
Phase transition induced by lithium insertion in αI- and αII-VOPO4
journal, August 2004
- Dupré, N.; Wallez, G.; Gaubicher, J.
- Journal of Solid State Chemistry, Vol. 177, Issue 8
The crystal structure of ε-VOPO4
journal, July 2006
- Girgsdies, F.; Dong, W. -S.; Bartley, J. K.
- Solid State Sciences, Vol. 8, Issue 7
Crystallochemistry of VPO phases and application to catalysis
journal, January 1987
- Bordes, E.
- Catalysis Today, Vol. 1, Issue 5
The crystal structure of δ-VOPO4 and its relationship to ω-VOPO4
journal, July 2009
- Girgsdies, Frank; Schneider, Matthias; Brückner, Angelika
- Solid State Sciences, Vol. 11, Issue 7
Crystal structure of a new polytype in the V–P–O system: is ω-VOPO4 a dynamically stabilised metastable network?
journal, August 2001
- Amorós, Pedro; Marcos, M. Dolores; Roca, Manuel
- Journal of Physics and Chemistry of Solids, Vol. 62, Issue 8
Highly Reversible Li Insertion at 4 V in ɛ-VOPO[sub 4]/α-LiVOPO[sub 4] Cathodes
journal, January 1999
- Kerr, T. A.
- Electrochemical and Solid-State Letters, Vol. 3, Issue 10
Li/β-VOPO[sub 4]: A New 4 V System for Lithium Batteries
journal, January 1999
- Gaubicher, J.
- Journal of The Electrochemical Society, Vol. 146, Issue 12
Synthesis and electrochemical studies of layer-structured metastable αI-LiVOPO4
journal, January 2012
- Shahul Hameed, A.; Nagarathinam, Mangayarkarasi; Reddy, M. V.
- Journal of Materials Chemistry, Vol. 22, Issue 15
Exploration of NaVOPO4 as a cathode for a Na-ion battery
journal, January 2013
- Song, Jie; Xu, Maowen; Wang, Long
- Chemical Communications, Vol. 49, Issue 46
LiVOPO4: A cathode material for 4V lithium ion batteries
journal, April 2009
- Ren, M. M.; Zhou, Z.; Su, L. W.
- Journal of Power Sources, Vol. 189, Issue 1
Towards the understanding of poor electrochemical activity of triclinic LiVOPO4: Experimental characterization and theoretical investigations
journal, October 2008
- Yang, Yong; Fang, Haisheng; Zheng, Jing
- Solid State Sciences, Vol. 10, Issue 10
Powgen: A third-generation highresolution high-throughput powder diffraction instrument at the Spallation Neutron Source
book, December 2011
- Huq, A.; Hodges, J. P.; Gourdon, O.
- European Powder Diffraction Conference; August 2010, Darmstadt, Germany
A profile refinement method for nuclear and magnetic structures
journal, June 1969
- Rietveld, H. M.
- Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71
EXPGUI , a graphical user interface for GSAS
journal, April 2001
- Toby, Brian H.
- Journal of Applied Crystallography, Vol. 34, Issue 2
Phase stability and its impact on the electrochemical performance of VOPO 4 and LiVOPO 4
journal, January 2014
- Ling, Chen; Zhang, Ruigang; Mizuno, Fuminori
- Journal of Materials Chemistry A, Vol. 2, Issue 31
Microwave-Assisted Solvothermal Synthesis and Characterization of Various Polymorphs of LiVOPO 4
journal, April 2013
- Harrison, Katharine L.; Manthiram, Arumugam
- Chemistry of Materials, Vol. 25, Issue 9
Synthesis and Crystal Structure of a New Layered Phosphate, Li2VPO6
journal, July 1993
- Korthuis, V. C.; Hoffmann, R. -D.; Huang, Jinfan
- Journal of Solid State Chemistry, Vol. 105, Issue 1
Crystal structure of βVPO5
journal, November 1972
- Gopal, R.; Calvo, C.
- Journal of Solid State Chemistry, Vol. 5, Issue 3
Crystal Chemistry of Electrochemically and Chemically Lithiated Layered α I -LiVOPO 4
journal, September 2015
- He, Guang; Bridges, Craig A.; Manthiram, Arumugam
- Chemistry of Materials, Vol. 27, Issue 19
Phenomenological model of anisotropic peak broadening in powder diffraction
journal, April 1999
- Stephens, Peter W.
- Journal of Applied Crystallography, Vol. 32, Issue 2
Calculations of Li-Ion Diffusion in Olivine Phosphates
journal, September 2011
- Dathar, Gopi Krishna Phani; Sheppard, Daniel; Stevenson, Keith J.
- Chemistry of Materials, Vol. 23, Issue 17
High-Voltage Pyrophosphate Cathode: Insights into Local Structure and Lithium-Diffusion Pathways
journal, November 2012
- Clark, John M.; Nishimura, Shin-ichi; Yamada, Atsuo
- Angewandte Chemie International Edition, Vol. 51, Issue 52
3DBVSMAPPER : a program for automatically generating bond-valence sum landscapes
journal, August 2012
- Sale, Matthew; Avdeev, Maxim
- Journal of Applied Crystallography, Vol. 45, Issue 5
ε-VOPO[sub 4]: Electrochemical Synthesis and Enhanced Cathode Behavior
journal, January 2005
- Song, Yanning; Zavalij, Peter Y.; Whittingham, M. Stanley
- Journal of The Electrochemical Society, Vol. 152, Issue 4
Intercalation Pseudocapacitance in Ultrathin VOPO 4 Nanosheets: Toward High-Rate Alkali-Ion-Based Electrochemical Energy Storage
journal, December 2015
- Zhu, Yue; Peng, Lele; Chen, Dahong
- Nano Letters, Vol. 16, Issue 1
Works referencing / citing this record:
Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries
journal, October 2018
- Liu, Rui; Liang, Ziteng; Gong, Zhengliang
- Small Methods, Vol. 3, Issue 4
Preparation, structure and properties of Na 2 Mn 3 (SO 4 ) 4 : a new potential candidate with high voltage for Na-ion batteries
journal, January 2016
- Gao, Jianhua; Sha, Xunshan; Liu, Xi
- Journal of Materials Chemistry A, Vol. 4, Issue 30
Advanced sodium-ion pseudocapacitor performance of oxygen-implanted hard carbon derived from carbon spheres
journal, November 2018
- Yin, Li; Feng, Junlan; Zhang, Xuehua
- Journal of Materials Science, Vol. 54, Issue 5
Structural and electrochemical studies of novel Na 7 V 3 Al(P 2 O 7 ) 4 (PO 4 ) and Na 7 V 2 Al 2 (P 2 O 7 ) 4 (PO 4 ) high-voltage cathode materials for Na-ion batteries
journal, January 2017
- Kovrugin, Vadim M.; Chotard, Jean-Noël; Fauth, François
- Journal of Materials Chemistry A, Vol. 5, Issue 27
Research progress on vanadium-based cathode materials for sodium ion batteries
journal, January 2018
- Wang, Qinghong; Xu, Jiantie; Zhang, Wenchao
- Journal of Materials Chemistry A, Vol. 6, Issue 19
Vanadium‐Based Nanomaterials: A Promising Family for Emerging Metal‐Ion Batteries
journal, January 2020
- Xu, Xiaoming; Xiong, Fangyu; Meng, Jiashen
- Advanced Functional Materials, Vol. 30, Issue 10
Advanced Cathode Materials for Sodium-Ion Batteries: What Determines Our Choices?
journal, April 2017
- Dai, Zhengfei; Mani, Ulaganathan; Tan, Hui Teng
- Small Methods, Vol. 1, Issue 5
Recent Advances in Sodium-Ion Battery Materials
journal, June 2018
- Fang, Yongjin; Xiao, Lifen; Chen, Zhongxue
- Electrochemical Energy Reviews, Vol. 1, Issue 3
Diffusion mechanism of Na ion–polaron complex in potential cathode materials NaVOPO 4 and VOPO 4 for rechargeable sodium-ion batteries
journal, January 2018
- Luong, Huu Duc; Pham, Thi Dung; Morikawa, Yoshitada
- Physical Chemistry Chemical Physics, Vol. 20, Issue 36
KVOPO 4 : A New High Capacity Multielectron Na-Ion Battery Cathode
journal, May 2018
- Ding, Jia; Lin, Yuh-Chieh; Liu, Jue
- Advanced Energy Materials, Vol. 8, Issue 21