Defect-Tolerant Diffusion Channels for Mg2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO4 and Mgx Fe2–xB2O5
Abstract
The reversible room temperature intercalation of Mg2+ ions is difficult to achieve, but may offer substantial advantages in the design of next-generation batteries if this electrochemical process can be successfully realized. Two types of quadruple ribbon-type transition metal borates (MgxFe2-xB2O5 and MgVBO4) with high theoretical capacities (186 mAh/g and 360 mAh/g) have been synthesized and structurally characterized through the combined Rietveld refinement of synchrotron and time-of-flight neutron diffraction data. Neither MgVBO4 nor MgxFe2-xB2O5 can be chemically oxidized at room temperature, though Mg can be dynamically removed from the latter phase at elevated temperatures (approximately 200 - 500 °C). Findings show that Mg diffusion in the MgxFe2-xB2O5 structure is more facile for the inner two octahedral sites than for the two outer octahedral sites in the ribbons, a result supported by both the refined site occupancies after Mg removal and by bond valence sum difference map calculations of diffusion paths in the pristine material. Mg diffusion in this pyroborate MgxFe2-xB2O5 framework is also found to be tolerant to the presence of Mg/Fe disorder since Mg ions can diffuse through interstitial channels which bypass Fe-containing sites.
- Authors:
-
- Stony Brook Univ., NY (United States). Dept. of Chemistry
- Stony Brook Univ., NY (United States). Dept. of Chemistry; Univ. of Cambridge (United Kingdom)
- Stony Brook Univ., NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1239784
- Report Number(s):
- BNL-111676-2015-JA
Journal ID: ISSN 0897-4756; R&D Project: CO009; KC0302010
- Grant/Contract Number:
- SC0012583; AC02-98CH10086; AC05-00OR22725; AC02-06CH11357; SC0001294
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 27; Journal Issue: 13; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Bo, Shou-Hang, Grey, Clare P., and Khalifah, Peter G. Defect-Tolerant Diffusion Channels for Mg2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO4 and Mgx Fe2–xB2O5. United States: N. p., 2015.
Web. doi:10.1021/acs.chemmater.5b01040.
Bo, Shou-Hang, Grey, Clare P., & Khalifah, Peter G. Defect-Tolerant Diffusion Channels for Mg2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO4 and Mgx Fe2–xB2O5. United States. https://doi.org/10.1021/acs.chemmater.5b01040
Bo, Shou-Hang, Grey, Clare P., and Khalifah, Peter G. Wed .
"Defect-Tolerant Diffusion Channels for Mg2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO4 and Mgx Fe2–xB2O5". United States. https://doi.org/10.1021/acs.chemmater.5b01040. https://www.osti.gov/servlets/purl/1239784.
@article{osti_1239784,
title = {Defect-Tolerant Diffusion Channels for Mg2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO4 and Mgx Fe2–xB2O5},
author = {Bo, Shou-Hang and Grey, Clare P. and Khalifah, Peter G.},
abstractNote = {The reversible room temperature intercalation of Mg2+ ions is difficult to achieve, but may offer substantial advantages in the design of next-generation batteries if this electrochemical process can be successfully realized. Two types of quadruple ribbon-type transition metal borates (MgxFe2-xB2O5 and MgVBO4) with high theoretical capacities (186 mAh/g and 360 mAh/g) have been synthesized and structurally characterized through the combined Rietveld refinement of synchrotron and time-of-flight neutron diffraction data. Neither MgVBO4 nor MgxFe2-xB2O5 can be chemically oxidized at room temperature, though Mg can be dynamically removed from the latter phase at elevated temperatures (approximately 200 - 500 °C). Findings show that Mg diffusion in the MgxFe2-xB2O5 structure is more facile for the inner two octahedral sites than for the two outer octahedral sites in the ribbons, a result supported by both the refined site occupancies after Mg removal and by bond valence sum difference map calculations of diffusion paths in the pristine material. Mg diffusion in this pyroborate MgxFe2-xB2O5 framework is also found to be tolerant to the presence of Mg/Fe disorder since Mg ions can diffuse through interstitial channels which bypass Fe-containing sites.},
doi = {10.1021/acs.chemmater.5b01040},
journal = {Chemistry of Materials},
number = 13,
volume = 27,
place = {United States},
year = {Wed Jun 10 00:00:00 EDT 2015},
month = {Wed Jun 10 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 33 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Mg rechargeable batteries: an on-going challenge
journal, January 2013
- Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef
- Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279
MgFePO 4 F as a feasible cathode material for magnesium batteries
journal, January 2014
- Huang, Zhen-Dong; Masese, Titus; Orikasa, Yuki
- J. Mater. Chem. A, Vol. 2, Issue 30
A high energy-density tin anode for rechargeable magnesium-ion batteries
journal, January 2013
- Singh, Nikhilendra; Arthur, Timothy S.; Ling, Chen
- Chem. Commun., Vol. 49, Issue 2
Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries
journal, August 2012
- Guo, Yong-sheng; Zhang, Fan; Yang, Jun
- Energy & Environmental Science, Vol. 5, Issue 10, p. 9100-9106
α-MnO2 as a cathode material for rechargeable Mg batteries
journal, September 2012
- Zhang, Ruigang; Yu, Xiqian; Nam, Kyung-Wan
- Electrochemistry Communications, Vol. 23
Magnesium insertion electrodes for rechargeable nonaqueous batteries — a competitive alternative to lithium?
journal, September 1999
- Novák, Petr; Imhof, Roman; Haas, Otto
- Electrochimica Acta, Vol. 45, Issue 1-2, p. 351-367
Prototype systems for rechargeable magnesium batteries
journal, October 2000
- Aurbach, D.; Lu, Z.; Schechter, A.
- Nature, Vol. 407, Issue 6805, p. 724-727
Electrochemical intercalation of Mg2+ in 3D hierarchically porous magnesium cobalt silicate and its application as an advanced cathode material in rechargeable magnesium batteries
journal, January 2011
- NuLi, Yanna; Zheng, Yupei; Wang, Ying
- Journal of Materials Chemistry, Vol. 21, Issue 33
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries
journal, February 2006
- Kang, Kisuk; Shirley Meng, Ying; Breger, Julien
- Science, Vol. 311, Issue 5763, p. 977-980
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
The Spinel Phase of LiMn[sub 2]O[sub 4] as a Cathode in Secondary Lithium Cells
journal, January 1991
- Tarascon, J. M.
- Journal of The Electrochemical Society, Vol. 138, Issue 10
Lithium Iron Borates as High-Capacity Battery Electrodes
journal, June 2010
- Yamada, Atsuo; Iwane, Nobuyuki; Harada, Yu
- Advanced Materials, Vol. 22, Issue 32
Degradation and (de)lithiation processes in the high capacity battery material LiFeBO3
journal, January 2012
- Bo, Shou-Hang; Wang, Feng; Janssen, Yuri
- Journal of Materials Chemistry, Vol. 22, Issue 18
Titanium-III warwickites: A family of one-dimensional disordered magnetic systems
journal, December 1994
- Fernandes, J. C.; Guimarães, R. B.; Continentino, M. A.
- Physical Review B, Vol. 50, Issue 22
Crystal structure and chemistry of yuanfuliite and its relationships with warwickite [Crystal structure and chemistry of yuanfuliite and its relationships with warwickite]
journal, May 1999
- Appel, Peter W. Uitterdijk; Bigi, Simona; Brigatti, Maria Franca
- European Journal of Mineralogy, Vol. 11, Issue 3
Incommensurate Charge Order Phase in due to Geometrical Frustration
journal, December 2007
- Angst, M.; Hermann, R. P.; Schweika, W.
- Physical Review Letters, Vol. 99, Issue 25
Charge Order Superstructure with Integer Iron Valence in
journal, August 2007
- Angst, M.; Khalifah, P.; Hermann, R. P.
- Physical Review Letters, Vol. 99, Issue 8
Refinement of the crystal structure of triclinic magnesium pyroborate
journal, March 1959
- Block, S.; Burley, G.; Perloff, A.
- Journal of Research of the National Bureau of Standards, Vol. 62, Issue 3
Triclinic Mg2B2O5
journal, March 1995
- Guo, G. C.; Cheng, W. D.; Chen, J. T.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 51, Issue 3
The crystal structure of magnesium pyroborate
journal, September 1952
- Takéuchi, Y.
- Acta Crystallographica, Vol. 5, Issue 5
Corrigendum to “Synthesis, crystal structure and characterization of iron pyroborate (Fe2B2O5) single crystals” [J. Solid State Chem. 182 (2009) 2004–2009]
journal, October 2009
- Kawano, Tetsuya; Morito, Haruhiko; Yamada, Takahiro
- Journal of Solid State Chemistry, Vol. 182, Issue 10
Study of the Insertion/Deinsertion Mechanism of Sodium into Na 0.44 MnO 2
journal, April 2007
- Sauvage, F.; Laffont, L.; Tarascon, J. -M.
- Inorganic Chemistry, Vol. 46, Issue 8
Preparation, crystal structure and photoluminescence of Mn2+-doped magnesium pyroborates solid solutions, (Mg1–xMnx)2B2O5
journal, November 2010
- Kawano, Tetsuya; Suehiro, Takayuki; Sato, Tsugio
- Journal of Luminescence, Vol. 130, Issue 11
Strongly disordered Heisenberg spin-1 chains: Vanadium warwickites
journal, April 1996
- Continentino, M. A.; Fernandes, J. C.; Guimaräes, R. B.
- Philosophical Magazine B, Vol. 73, Issue 4
Synthesis of Magnesium Borate (Mg 2 B 2 O 5 ) Nanowires by Chemical Vapor Deposition Method
journal, June 2004
- Li, Yan; Fan, Zhiyong; Lu, Jia G.
- Chemistry of Materials, Vol. 16, Issue 13
Catalyst-Free Synthesis, Structural, and Mechanical Characterization of Twinned Mg 2 B 2 O 5 Nanowires
journal, February 2008
- Tao, Xinyong; Li, Xiaodong
- Nano Letters, Vol. 8, Issue 2
Relationship between bond valence and bond softness of alkali halides and chalcogenides
journal, May 2001
- Adams, Stefan
- Acta Crystallographica Section B Structural Science, Vol. 57, Issue 3
Chemical and steric constraints in inorganic solids
journal, October 1992
- Brown, I. D.
- Acta Crystallographica Section B Structural Science, Vol. 48, Issue 5
Influence of Chemical and Spatial Constraints on the Structures of Inorganic Compounds
journal, June 1997
- Brown, I. D.
- Acta Crystallographica Section B Structural Science, Vol. 53, Issue 3
Proton ordering in the Peierls-distorted hydrogen molybdenum bronze H 0.33 MoO 3 : structure and physical properties
journal, December 1993
- Adams, S.; Ehses, K. -H.; Spilker, J.
- Acta Crystallographica Section B Structural Science, Vol. 49, Issue 6
Determining Ionic Conductivity from Structural Models of Fast Ionic Conductors
journal, May 2000
- Adams, St.; Swenson, J.
- Physical Review Letters, Vol. 84, Issue 18
Application of the bond valence method to reverse Monte Carlo produced structural models of superionic glasses
journal, June 2001
- Swenson, Jan; Adams, Stefan
- Physical Review B, Vol. 64, Issue 2
Structural Modulation in the High Capacity Battery Cathode Material LiFeBO 3
journal, July 2012
- Janssen, Yuri; Middlemiss, Derek S.; Bo, Shou-Hang
- Journal of the American Chemical Society, Vol. 134, Issue 30
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Some transition metal (oxy)phosphates and vanadium oxides for lithium batteries
journal, January 2005
- Whittingham, M. Stanley; Song, Yanning; Lutta, Samuel
- Journal of Materials Chemistry, Vol. 15, Issue 33
Electrochemical Property: Structure Relationships in Monoclinic Li 3 - y V 2 (PO 4 ) 3
journal, August 2003
- Yin, S. -C.; Grondey, H.; Strobel, P.
- Journal of the American Chemical Society, Vol. 125, Issue 34
Phase Diagram of Li[sub x]FePO[sub 4]
journal, January 2006
- Dodd, J. L.; Yazami, R.; Fultz, B.
- Electrochemical and Solid-State Letters, Vol. 9, Issue 3
First-principles study of the magnesiation of olivines: redox reaction mechanism, electrochemical and thermodynamic properties
journal, January 2012
- Ling, Chen; Banerjee, Debasish; Song, Wei
- Journal of Materials Chemistry, Vol. 22, Issue 27
Experimental visualization of lithium diffusion in LixFePO4
journal, August 2008
- Nishimura, Shin-ichi; Kobayashi, Genki; Ohoyama, Kenji
- Nature Materials, Vol. 7, Issue 9
High-temperature order-disorder in (Fe0.5Mn0.5)2SiO4 and (Mg0.5Mn0.5)2SiO4 olivines: an in situ neutron diffraction study [High-temperature order-disorder in (Fe0.5Mn0.5)2SiO4 and (Mg0.5Mn0.5)2SiO4 olivines: an in situ neutron diffraction study]
journal, June 1997
- Redfern, Simon A. T.; Henderson, C. Michael B.; Knight, Kevin S.
- European Journal of Mineralogy, Vol. 9, Issue 2
Particle Size Dependence of the Ionic Diffusivity
journal, October 2010
- Malik, Rahul; Burch, Damian; Bazant, Martin
- Nano Letters, Vol. 10, Issue 10
Works referencing / citing this record:
Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries
journal, September 2015
- Massé, Robert C.; Uchaker, Evan; Cao, Guozhong
- Science China Materials, Vol. 58, Issue 9
Controlled hydroxy-fluorination reaction of anatase to promote Mg 2+ mobility in rechargeable magnesium batteries
journal, January 2018
- Ma, Jiwei; Koketsu, Toshinari; Morgan, Benjamin. J.
- Chemical Communications, Vol. 54, Issue 72