Probing Mg Migration in Spinel Oxides
Abstract
Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. In this paper, we present a combined experimental and theoretical study of Mg migration within three spinel oxides, which reveal critical features that influence it. Experimental activation energies for a Mg2+ hop to an adjacent vacancy, as low as ~0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of Mg2+. Subsequent electrochemical experiments demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chemical stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high density of energy storage.
- Authors:
-
- Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Oxford (United Kingdom)
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
- Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Univ. of Illinois, Chicago, IL (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- ISIS Pulsed Neutron and Muon Source, Rutherford Appleton Laboratory, Didcot OX11 0QX, U.K.
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Science and Technology Facilities Council (STFC); Ramsay Memorial Trust
- OSTI Identifier:
- 1606525
- Alternate Identifier(s):
- OSTI ID: 1597692; OSTI ID: 1766478
- Report Number(s):
- PNNL-SA-129154
Journal ID: ISSN 0897-4756; 137865
- Grant/Contract Number:
- AC05-76RL01830; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 2; 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; Spinel; Oxides; Genetics; Electrodes; Transition metals
Citation Formats
Bayliss, Ryan D., Key, Baris, Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Kwon, Bob Jin, Lapidus, Saul H., Dogan, Fulya, Adil, Abdullah A., Lipton, Andrew S., Baker, Peter J., Ceder, Gerbrand, Vaughey, John T., and Cabana, Jordi. Probing Mg Migration in Spinel Oxides. United States: N. p., 2019.
Web. doi:10.1021/acs.chemmater.9b02450.
Bayliss, Ryan D., Key, Baris, Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Kwon, Bob Jin, Lapidus, Saul H., Dogan, Fulya, Adil, Abdullah A., Lipton, Andrew S., Baker, Peter J., Ceder, Gerbrand, Vaughey, John T., & Cabana, Jordi. Probing Mg Migration in Spinel Oxides. United States. https://doi.org/10.1021/acs.chemmater.9b02450
Bayliss, Ryan D., Key, Baris, Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Kwon, Bob Jin, Lapidus, Saul H., Dogan, Fulya, Adil, Abdullah A., Lipton, Andrew S., Baker, Peter J., Ceder, Gerbrand, Vaughey, John T., and Cabana, Jordi. Thu .
"Probing Mg Migration in Spinel Oxides". United States. https://doi.org/10.1021/acs.chemmater.9b02450. https://www.osti.gov/servlets/purl/1606525.
@article{osti_1606525,
title = {Probing Mg Migration in Spinel Oxides},
author = {Bayliss, Ryan D. and Key, Baris and Sai Gautam, Gopalakrishnan and Canepa, Pieremanuele and Kwon, Bob Jin and Lapidus, Saul H. and Dogan, Fulya and Adil, Abdullah A. and Lipton, Andrew S. and Baker, Peter J. and Ceder, Gerbrand and Vaughey, John T. and Cabana, Jordi},
abstractNote = {Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. In this paper, we present a combined experimental and theoretical study of Mg migration within three spinel oxides, which reveal critical features that influence it. Experimental activation energies for a Mg2+ hop to an adjacent vacancy, as low as ~0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of Mg2+. Subsequent electrochemical experiments demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chemical stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high density of energy storage.},
doi = {10.1021/acs.chemmater.9b02450},
journal = {Chemistry of Materials},
number = 2,
volume = 32,
place = {United States},
year = {2019},
month = {12}
}
Web of Science
Works referenced in this record:
Prototype systems for rechargeable magnesium batteries
journal, October 2000
- Aurbach, D.; Lu, Z.; Schechter, A.
- Nature, Vol. 407, Issue 6805, p. 724-727
Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond
journal, October 2014
- Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas
- Chemical Reviews, Vol. 114, Issue 23
Practical Stability Limits of Magnesium Electrolytes
journal, January 2016
- Lipson, Albert L.; Han, Sang-Don; Pan, Baofei
- Journal of The Electrochemical Society, Vol. 163, Issue 10
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges
journal, February 2017
- Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C.
- Chemical Reviews, Vol. 117, Issue 5
A high capacity thiospinel cathode for Mg batteries
journal, January 2016
- Sun, Xiaoqi; Bonnick, Patrick; Duffort, Victor
- Energy & Environmental Science, Vol. 9, Issue 7
Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host
journal, April 2015
- Kim, Chunjoong; Phillips, Patrick J.; Key, Baris
- Advanced Materials, Vol. 27, Issue 22
Role of Structural H 2 O in Intercalation Electrodes: The Case of Mg in Nanocrystalline Xerogel-V 2 O 5
journal, March 2016
- Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Richards, William Davidson
- Nano Letters, Vol. 16, Issue 4
A dedicated powder diffraction beamline at the Advanced Photon Source: Commissioning and early operational results
journal, August 2008
- Wang, Jun; Toby, Brian H.; Lee, Peter L.
- Review of Scientific Instruments, Vol. 79, Issue 8
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
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012
- Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
Optimising a muon spectrometer for measurements at the ISIS pulsed muon source
journal, July 2014
- Giblin, S. R.; Cottrell, S. P.; King, P. J. C.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 751
Spin-polarized muons in condensed matter physics
journal, May 1999
- Blundell, S. J.
- Contemporary Physics, Vol. 40, Issue 3
Zero-and low-field spin relaxation studied by positive muons
journal, August 1979
- Hayano, R. S.; Uemura, Y. J.; Imazato, J.
- Physical Review B, Vol. 20, Issue 3
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Ab initio molecular dynamics for liquid metals
journal, December 1995
- Kresse, G.
- Journal of Non-Crystalline Solids, Vol. 192-193
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Role of the crystal-field theory in determining the structures of spinels
journal, January 1982
- Burdett, Jeremy K.; Price, Geoffrey D.; Price, Sarah L.
- Journal of the American Chemical Society, Vol. 104, Issue 1
Electrical Properties and Cation Migration in MgMn2O4
journal, January 1964
- Rosenberg, M.; Nicolau, P.
- physica status solidi (b), Vol. 6, Issue 1
Diagrammatic Separation of Different Crystal Structures of A2BX4 Compounds Without Energy Minimization: A Pseudopotential Orbital Radii Approach
journal, May 2010
- Zhang, Xiuwen; Zunger, Alex
- Advanced Functional Materials, Vol. 20, Issue 12
Influence of Inversion on Mg Mobility and Electrochemistry in Spinels
journal, September 2017
- Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Urban, Alexander
- Chemistry of Materials, Vol. 29, Issue 18
NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries
journal, October 2004
- Grey, Clare P.; Dupré, Nicolas
- Chemical Reviews, Vol. 104, Issue 10
A systematic study of 25 Mg NMR in paramagnetic transition metal oxides: applications to Mg-ion battery materials
journal, January 2017
- Lee, Jeongjae; Seymour, Ieuan D.; Pell, Andrew J.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 1
Ultraslow Li diffusion in spinel-type structured Li 4 Ti 5 O 12 —A comparison of results from solid state NMR and impedance spectroscopy
journal, January 2007
- Wilkening, Martin; Amade, Roger; Iwaniak, Wojciech
- Phys. Chem. Chem. Phys., Vol. 9, Issue 10
Tetragonal Li10GeP2S12 and Li7GePS8 – exploring the Li ion dynamics in LGPS Li electrolytes
journal, January 2013
- Kuhn, Alexander; Duppel, Viola; Lotsch, Bettina V.
- Energy & Environmental Science, Vol. 6, Issue 12
Li self-diffusion in garnet-type Li La Zr O as probed directly by diffusion-induced spin-lattice relaxation NMR spectroscopy
journal, March 2011
- Kuhn, A.; Narayanan, S.; Spencer, L.
- Physical Review B, Vol. 83, Issue 9
Tracer diffusion measurements in solid lithium: a test case for the comparison between NMR in static and pulsed magnetic field gradients after upgrading a standard solid state NMR spectrometer
journal, September 2004
- Marion Fischer, D.; Duwe, Peter; Indris, Sylvio
- Solid State Nuclear Magnetic Resonance, Vol. 26, Issue 2
Variable-Temperature 7 Li Solid-State NMR Investigation of Li-Ion Mobility and Its Correlation with Conductivity in Pore-Filling Polymer Electrolytes for Secondary Batteries
journal, November 2006
- Jeon, Jae-Deok; Kwak, Seung-Yeop
- Macromolecules, Vol. 39, Issue 23
Formation of MgO during Chemical Magnesiation of Mg-Ion Battery Materials
journal, January 2015
- Wang, H.; Senguttuvan, P.; Proffit, D. L.
- ECS Electrochemistry Letters, Vol. 4, Issue 8
6 Li and 7 Li MAS NMR Studies of Lithium Manganate Cathode Materials
journal, December 1998
- Lee, Young Joo; Wang, Francis; Grey, Clare P.
- Journal of the American Chemical Society, Vol. 120, Issue 48
Relaxation Effects in Nuclear Magnetic Resonance Absorption
journal, April 1948
- Bloembergen, N.; Purcell, E. M.; Pound, R. V.
- Physical Review, Vol. 73, Issue 7
Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations
journal, January 2015
- Liu, Miao; Rong, Ziqin; Malik, Rahul
- Energy & Environmental Science, Vol. 8, Issue 3
Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures
journal, August 2015
- Rong, Ziqin; Malik, Rahul; Canepa, Pieremanuele
- Chemistry of Materials, Vol. 27, Issue 17
First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel
journal, December 2017
- Chen, Tina; Sai Gautam, Gopalakrishnan; Huang, Wenxuan
- Chemistry of Materials, Vol. 30, Issue 1
Real-Time Monitoring of Cation Dissolution/Deintercalation Kinetics from Transition-Metal Oxides in Organic Environments
journal, July 2018
- Lopes, Pietro P.; Zorko, Milena; Hawthorne, Krista L.
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 17
Synthesis and characterization of chromium spinels as potential electrode support materials for intermediate temperature solid oxide fuel cells
journal, November 2011
- Stefan, E.; Irvine, J. T. S.
- Journal of Materials Science, Vol. 46, Issue 22
Characterization of Electronic and Ionic Transport in Li 1- x Ni 0 . 8 Co 0.15 Al 0.05 O 2 (NCA)
journal, January 2015
- Amin, Ruhul; Ravnsbæk, Dorthe Bomholdt; Chiang, Yet-Ming
- Journal of The Electrochemical Society, Vol. 162, Issue 7