Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO4

Parajuli, Prakash; Park, Haesun; Kwon, Bob Jin; Guo, Jinglong; Key, Baris; Vaughey, John T.; Zapol, Peter; Klie, Robert F.

doi:10.1021/acs.chemmater.0c03121

Title: Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO₄

Journal Article · Mon Nov 30 00:00:00 EST 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c03121· OSTI ID:1780646

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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). Joint Center for Energy Storage Research (JCESR)
Univ. of Illinois, Chicago, IL (United States)

Irreversible structural transformation in intercalation-type cathode materials, which has been frequently observed, has been perceived as a principal cause of capacity fading and voltage decay in (uni) multivalent batteries. Herein, we explored the electron beam-induced spinel to defective rocksalt phase transitions in MgCrMnO₄, a potential multivalent cation intercalation cathode, using atomic-resolution imaging and spectroscopy in an aberration-corrected scanning transmission electron microscope. This dynamic electron beam irradiation study of specific structural transformations provides an atomistic understanding of the structural evolution observed in transition-metal oxide spinels during electrochemical cycling using multivalent cations, such as Mg²⁺. By combining an imaging study with first-principles modeling, we demonstrate that the mechanism of the spinel to defective rocksalt transformation in MgCrMnO₄ nanostructures is enabled by the presence of oxygen vacancies and is, therefore, very similar to that observed in transition-metal oxide spinels upon Li intercalation.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1780646

Journal Information:: Chemistry of Materials, Vol. 32, Issue 24; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Magnesium-Ion Storage Capability of MXenes Zhao, Meng-Qiang; Ren, Chang E.; Alhabeb, Mohamed ACS Applied Energy Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsaem.8b02253	journal	January 2019
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Chemically sensitive structure-imaging with a scanning transmission electron microscope Pennycook, S. J.; Boatner, L. A. Nature, Vol. 336, Issue 6199 https://doi.org/10.1038/336565a0	journal	December 1988
High Voltage Mg-Ion Battery Cathode via a Solid Solution Cr–Mn Spinel Oxide Kwon, Bob Jin; Yin, Liang; Park, Haesun Chemistry of Materials, Vol. 32, Issue 15 https://doi.org/10.1021/acs.chemmater.0c01988	journal	July 2020
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn3O4 nanoparticles Laffont, L.; Gibot, P. Materials Characterization, Vol. 61, Issue 11 https://doi.org/10.1016/j.matchar.2010.09.001	journal	November 2010
In situ tracking the reversible spinel-rocksalt structural transformation between Mn3O4 and MnO San, Xingyuan; Zhang, Bo; Wang, Jing Micron, Vol. 92 https://doi.org/10.1016/j.micron.2016.09.008	journal	January 2017
A high capacity thiospinel cathode for Mg batteries Sun, Xiaoqi; Bonnick, Patrick; Duffort, Victor Energy & Environmental Science, Vol. 9, Issue 7 https://doi.org/10.1039/C6EE00724D	journal	January 2016
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C. Chemical Reviews, Vol. 117, Issue 5 https://doi.org/10.1021/acs.chemrev.6b00614	journal	February 2017
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations Liu, Miao; Rong, Ziqin; Malik, Rahul Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03389B	journal	January 2015
Direct observation of the structural and electronic changes of Li2MnO3 during electron irradiation Phillips, Patrick J.; Iddir, Hakim; Abraham, Daniel P. Applied Physics Letters, Vol. 105, Issue 11 https://doi.org/10.1063/1.4896264	journal	September 2014
Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides Qian, Danna; Xu, Bo; Chi, Miaofang Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01799D	journal	January 2014
Atomic scale dynamics of a solid state chemical reaction directly determined by annular dark-field electron microscopy Pennycook, Timothy J.; Jones, Lewys; Pettersson, Henrik Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep07555	journal	December 2014
Influence of Inversion on Mg Mobility and Electrochemistry in Spinels Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Urban, Alexander Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b02820	journal	September 2017
EELS analysis of cation valence states and oxygen vacancies in magnetic oxides Wang, Z. L.; Yin, J. S.; Jiang, Y. D. Micron, Vol. 31, Issue 5 https://doi.org/10.1016/S0968-4328(99)00139-0	journal	October 2000
Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy Zhang, S.; Livi, K. J. T.; Gaillot, A. -C. American Mineralogist, Vol. 95, Issue 11-12 https://doi.org/10.2138/am.2010.3468	journal	November 2010
Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P. Chemistry of Materials, Vol. 26, Issue 21 https://doi.org/10.1021/cm5031415	journal	October 2014
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Insight into the Atomic Structure of High-Voltage Spinel LiNi _0.5 Mn _1.5 O ₄ Cathode Material in the First Cycle Lin, Mingxiang; Ben, Liubin; Sun, Yang Chemistry of Materials, Vol. 27, Issue 1 https://doi.org/10.1021/cm503972a	journal	December 2014
Modelling the inelastic scattering of fast electrons Allen, L. J.; D׳Alfonso, A. J.; Findlay, S. D. Ultramicroscopy, Vol. 151 https://doi.org/10.1016/j.ultramic.2014.10.011	journal	April 2015
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Engineering nano-composite Li4Ti5O12 anodes via scanning electron-probe fabrication Su, Dong; Wang, Feng; Ma, Chao Nano Energy, Vol. 2, Issue 3 https://doi.org/10.1016/j.nanoen.2012.10.009	journal	May 2013
Atomic scale study of the life cycle of a dislocation in graphene from birth to annihilation Lehtinen, O.; Kurasch, S.; Krasheninnikov, A. V. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3098	journal	June 2013
Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2 Lin, Yung-Chang; Dumcenco, Dumitru O.; Huang, Ying-Sheng Nature Nanotechnology, Vol. 9, Issue 5 https://doi.org/10.1038/nnano.2014.64	journal	April 2014
Controlled-valence properties of ${La}_{1 - x}$ ${Sr}_{x}$ ${FeO}_{3}$ and ${La}_{1 - x}$ ${Sr}_{x}$ ${MnO}_{3}$ studied by soft-x-ray absorption spectroscopy Abbate, M.; de Groot, F. M. F.; Fuggle, J. C. Physical Review B, Vol. 46, Issue 8 https://doi.org/10.1103/PhysRevB.46.4511	journal	August 1992
Effect of temperature on the structure of manganites Irani, K. S.; Sinha, A. P. B.; Biswas, A. B. Journal of Physics and Chemistry of Solids, Vol. 23, Issue 6 https://doi.org/10.1016/0022-3697(62)90530-9	journal	June 1962
Electron beam damage in oxides: a review Jiang, Nan Reports on Progress in Physics, Vol. 79, Issue 1 https://doi.org/10.1088/0034-4885/79/1/016501	journal	December 2015
Observation of Electron-Beam-Induced Phase Evolution Mimicking the Effect of the Charge–Discharge Cycle in Li-Rich Layered Cathode Materials Used for Li Ion Batteries Lu, Ping; Yan, Pengfei; Romero, Eric Chemistry of Materials, Vol. 27, Issue 4 https://doi.org/10.1021/cm5045573	journal	February 2015
Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides Gilbert, B.; Frazer, B. H.; Belz, A. The Journal of Physical Chemistry A, Vol. 107, Issue 16 https://doi.org/10.1021/jp021493s	journal	April 2003
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Oxidation state and chemical shift investigation in transition metal oxides by EELS Tan, Haiyan; Verbeeck, Jo; Abakumov, Artem Ultramicroscopy, Vol. 116 https://doi.org/10.1016/j.ultramic.2012.03.002	journal	May 2012
Oxygen $K$ near-edge fine structure: An electron-energy-loss investigation with comparisons to new theory for selected $3 d$ Transition-metal oxides Grunes, L. A.; Leapman, R. D.; Wilker, C. N. Physical Review B, Vol. 25, Issue 12 https://doi.org/10.1103/PhysRevB.25.7157	journal	June 1982
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
Atomic-Scale Tracking of a Phase Transition from Spinel to Rocksalt in Lithium Manganese Oxide Gao, Peng; Ishikawa, Ryo; Tochigi, Eita Chemistry of Materials, Vol. 29, Issue 3 https://doi.org/10.1021/acs.chemmater.6b03659	journal	January 2017
Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study Xu, Bo; Fell, Christopher R.; Chi, Miaofang Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c1ee01131f	journal	January 2011
The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes Urban, Alexander; Lee, Jinhyuk; Ceder, Gerbrand Advanced Energy Materials, Vol. 4, Issue 13 https://doi.org/10.1002/aenm.201400478	journal	May 2014
Layered-to-Spinel Phase Transition in Li[sub x]MnO[sub 2] Reed, J.; Ceder, G.; Van Der Ven, A. Electrochemical and Solid-State Letters, Vol. 4, Issue 6 https://doi.org/10.1149/1.1368896	journal	January 2001
Structural and Transport Properties of Mg1−xMnxMn2O4±δ Spinels Malavasi, Lorenzo; Ghigna, Paolo; Chiodelli, Gaetano Journal of Solid State Chemistry, Vol. 166, Issue 1 https://doi.org/10.1006/jssc.2002.9577	journal	June 2002
Atomic-resolution imaging of oxidation states in manganites Varela, M.; Oxley, M. P.; Luo, W. Physical Review B, Vol. 79, Issue 8 https://doi.org/10.1103/PhysRevB.79.085117	journal	February 2009
Direct Observation of Dopant Atom Diffusion in a Bulk Semiconductor Crystal Enhanced by a Large Size Mismatch Ishikawa, Ryo; Mishra, Rohan; Lupini, Andrew R. Physical Review Letters, Vol. 113, Issue 15 https://doi.org/10.1103/PhysRevLett.113.155501	journal	October 2014
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Oxidation states of Mn and Fe in various compound oxide systems Schmid, H. K.; Mader, W. Micron, Vol. 37, Issue 5 https://doi.org/10.1016/j.micron.2005.12.004	journal	July 2006
Dislocation-Driven Deformations in Graphene Warner, J. H.; Margine, E. R.; Mukai, M. Science, Vol. 337, Issue 6091 https://doi.org/10.1126/science.1217529	journal	July 2012
Specimen temperature increases during transmission electron microscopy Thornburg, D. D.; Wayman, C. M. Physica Status Solidi (a), Vol. 15, Issue 2 https://doi.org/10.1002/pssa.2210150209	journal	February 1973
Feasible transformation of MgCo2O4 from spinel to defect rocksalt structure under electron irradiation Okamoto, Norihiko L.; Shimokawa, Kohei; Tanimura, Hiroshi Scripta Materialia, Vol. 167 https://doi.org/10.1016/j.scriptamat.2019.03.034	journal	July 2019
A neutron diffraction study of the cation migration in MgMn2O4 Radhakrishnan, N. K.; Biswas, A. B. Physica Status Solidi (a), Vol. 37, Issue 2 https://doi.org/10.1002/pssa.2210370245	journal	October 1976

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Title: Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO₄