skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [6]; ORCiD logo [7];  [8]; ORCiD logo [9]; ORCiD logo [10];  [4]; ORCiD logo [2]; ORCiD logo [8]
  1. Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Oxford (United Kingdom)
  2. 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
  3. 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
  4. 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
  5. 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
  6. Argonne National Lab. (ANL), Argonne, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  8. Univ. of Illinois, Chicago, IL (United States)
  9. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  10. 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. 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., & 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

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
  • DOI: 10.1038/35037553

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
  • DOI: 10.1021/cr500049y

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
  • DOI: 10.1149/2.0451610jes

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
  • DOI: 10.1021/acs.chemrev.6b00614

A high capacity thiospinel cathode for Mg batteries
journal, January 2016

  • Sun, Xiaoqi; Bonnick, Patrick; Duffort, Victor
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/c6ee00724d

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
  • DOI: 10.1002/adma.201500083

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
  • DOI: 10.1021/acs.nanolett.5b05273

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
  • DOI: 10.1063/1.2969260

A profile refinement method for nuclear and magnetic structures
journal, June 1969


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
  • DOI: 10.1016/j.nimb.2012.05.037

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
  • DOI: 10.1016/j.nima.2014.03.010

Spin-polarized muons in condensed matter physics
journal, May 1999


Zero-and low-field spin relaxation studied by positive muons
journal, August 1979


Inhomogeneous Electron Gas
journal, November 1964


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Ab initio molecular dynamics for liquid metals
journal, December 1995


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


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
  • DOI: 10.1103/physrevlett.77.3865

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
  • DOI: 10.1021/ja00365a019

Electrical Properties and Cation Migration in MgMn2O4
journal, January 1964


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
  • DOI: 10.1021/acs.chemmater.7b02820

NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries
journal, October 2004

  • Grey, Clare P.; Dupré, Nicolas
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020734p

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
  • DOI: 10.1039/c6cp06338a

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
  • DOI: 10.1039/b616269j

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
  • DOI: 10.1039/c3ee41728j

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
  • DOI: 10.1149/2.0051508eel

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
  • DOI: 10.1021/ja9817794

Relaxation Effects in Nuclear Magnetic Resonance Absorption
journal, April 1948


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
  • DOI: 10.1039/c4ee03389b

Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures
journal, August 2015


First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel
journal, December 2017


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
  • DOI: 10.1021/acs.jpclett.8b01936

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
  • DOI: 10.1149/2.0171507jes