Stability and Compressibility of Cation-Doped High-Entropy Oxide MgCoNiCuZnO 5

Chen, Jian; Liu, Weixin; Liu, Junxiu; Zhang, Xiaoliang; Yuan, Mingzhi; Zhao, Yunlei; Yan, Jiejuan; Hou, Mingqiang; Yan, Jinyuan; Kunz, Martin; Tamura, Nobumichi; Zhang, Hengzhong; Yin, Zhoulan

doi:10.1021/acs.jpcc.9b04992

Title: Stability and Compressibility of Cation-Doped High-Entropy Oxide MgCoNiCuZnO ₅

Journal Article · 02 July 2019 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.9b04992 · OSTI ID:1580895

Chen, Jian ^[1]; Liu, Weixin ^[2]; Liu, Junxiu ^[2]; Zhang, Xiaoliang ^[2]; Yuan, Mingzhi ^[2]; Zhao, Yunlei ^[2]; Yan, Jiejuan ^[3]; Hou, Mingqiang ^[3]; Yan, Jinyuan ^[4]; Kunz, Martin ^[4]; Tamura, Nobumichi ^[4];

^[2]; Yin, Zhoulan ^[5]

Central South Univ., Hunan (China); Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Central South Univ., Hunan (China)

High-entropy oxides (HEOx) are multicomponent (≥5) complex oxides that possess material properties and functions unexpected from their constituent simple oxides. Previous studies demonstrated that a cation-doped HEOx, MgCoNiCuZnO₅, shows good catalytic activity, excellent ionic conductivity, and high energy storage. The structural and mechanical stabilities of materials are pivotal to their applications. However, how temperature and pressure influence the structural stability of cation-doped HEOx and how doping affects the mechanical properties are yet to be understood. In this work, we investigated the structural stabilities of undoped and Li/Mn-doped MgCoNiCuZnO₅ in heating or under compression using in situ synchrotron X-ray diffraction (XRD), and determined their elastic moduli using high-pressure XRD. Our results show that the HEOx compounds are structurally stable at temperatures up to ~450 °C or at pressures up to ~50 GPa, and that Li/Mn doping makes the HEOx more compressible. Our molecular static (MS) calculations predicted that the formation reaction of a HEOx is endothermic, consistent with the fact that a single-phase HEOx can only be produced at high temperatures. The MS calculations also revealed that the observed doping-induced elastic softening stems from the introduction of the Li-O/Mn-O ionic bonds in the HEOx compound, which are weaker than other cation-oxygen ionic bonds in the undoped HEOx. These findings will be indispensable to engineer HEOx materials for use in ion batteries, catalysis, and other fields.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: AC02-05CH11231; 21875005

OSTI ID:: 1580895

Journal Information:: Journal of Physical Chemistry. C, Vol. 123, Issue 29; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 39 works

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References (36)

Entropy-stabilized oxides Rost, Christina M.; Sachet, Edward; Borman, Trent Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9485	journal	September 2015
Colossal dielectric constant in high entropy oxides Bérardan, David; Franger, Sylvain; Dragoe, Diana physica status solidi (RRL) - Rapid Research Letters, Vol. 10, Issue 4 https://doi.org/10.1002/pssr.201600043	journal	March 2016
High-entropy fluorite oxides Gild, Joshua; Samiee, Mojtaba; Braun, Jeffrey L. Journal of the European Ceramic Society, Vol. 38, Issue 10 https://doi.org/10.1016/j.jeurceramsoc.2018.04.010	journal	August 2018
GULP: Capabilities and prospects Gale, Julian D. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6 https://doi.org/10.1524/zkri.220.5.552.65070	journal	January 2005
The elastic properties of lithium oxide and their variation with temperature Hull, S.; Farley, T. W. D.; Hayes, W. Journal of Nuclear Materials, Vol. 160, Issue 2-3 https://doi.org/10.1016/0022-3115(88)90039-6	journal	December 1988
Multicomponent equiatomic rare earth oxides Djenadic, Ruzica; Sarkar, Abhishek; Clemens, Oliver Materials Research Letters, Vol. 5, Issue 2 https://doi.org/10.1080/21663831.2016.1220433	journal	August 2016
Synthesis and microstructure of the (Co,Cr,Fe,Mn,Ni) 3 O 4 high entropy oxide characterized by spinel structure Dąbrowa, Juliusz; Stygar, Mirosław; Mikuła, Andrzej Materials Letters, Vol. 216 https://doi.org/10.1016/j.matlet.2017.12.148	journal	April 2018
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Rare earth and transition metal based entropy stabilised perovskite type oxides Sarkar, Abhishek; Djenadic, Ruzica; Wang, Di Journal of the European Ceramic Society, Vol. 38, Issue 5 https://doi.org/10.1016/j.jeurceramsoc.2017.12.058	journal	May 2018
Entropy-stabilized metal oxide solid solutions as CO oxidation catalysts with high-temperature stability Chen, Hao; Fu, Jie; Zhang, Pengfei Journal of Materials Chemistry A, Vol. 6, Issue 24 https://doi.org/10.1039/C8TA01772G	journal	January 2018
Pressure and temperature dependence of the elastic properties of synthetic MnO Pacalo, R. E.; Graham, E. K. Physics and Chemistry of Minerals, Vol. 18, Issue 1 https://doi.org/10.1007/BF00199046	journal	July 1991
A new class of high-entropy perovskite oxides Jiang, Sicong; Hu, Tao; Gild, Joshua Scripta Materialia, Vol. 142 https://doi.org/10.1016/j.scriptamat.2017.08.040	journal	January 2018
Room temperature lithium superionic conductivity in high entropy oxides Bérardan, D.; Franger, S.; Meena, A. K. Journal of Materials Chemistry A, Vol. 4, Issue 24 https://doi.org/10.1039/C6TA03249D	journal	January 2016
Charge compensation and electrostatic transferability in three entropy-stabilized oxides: Results from density functional theory calculations Rak, Zs.; Rost, C. M.; Lim, M. Journal of Applied Physics, Vol. 120, Issue 9 https://doi.org/10.1063/1.4962135	journal	September 2016
Compressibility and structural stability of nanoparticulate goethite Fernando, Sandra; Baynes, Meredith; Chen, Bin RSC Advances, Vol. 2, Issue 17 https://doi.org/10.1039/c2ra20217d	journal	January 2012
Hydrostatic limits of 11 pressure transmitting media Klotz, S.; Chervin, J-C.; Munsch, P. Journal of Physics D: Applied Physics, Vol. 42, Issue 7, Article No. 075413 https://doi.org/10.1088/0022-3727/42/7/075413	journal	March 2009
Potential models for ionic oxides Lewis, G. V.; Catlow, C. R. A. Journal of Physics C: Solid State Physics, Vol. 18, Issue 6 https://doi.org/10.1088/0022-3719/18/6/010	journal	February 1985
Elastic Constants and Thermodynamic Properties of Cu, Cu₂O and CuO from First-Principles Calculations Liu, Na Na; Sun, Jian Lin; Wu, Di Advanced Materials Research, Vol. 335-336 https://doi.org/10.4028/www.scientific.net/AMR.335-336.328	journal	September 2011
Chemical expansion affected oxygen vacancy stability in different oxide structures from first principles calculations Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen Computational Materials Science, Vol. 99 https://doi.org/10.1016/j.commatsci.2014.12.030	journal	March 2015
High pressure study of transition metal monoxides MnO and CoO: Structure and electrical resistance Ito, E.; Yamazaki, D.; Yoshino, T. Physics of the Earth and Planetary Interiors, Vol. 228 https://doi.org/10.1016/j.pepi.2013.12.009	journal	March 2014
High entropy oxides for reversible energy storage Sarkar, Abhishek; Velasco, Leonardo; Wang, Di Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05774-5	journal	August 2018
Theory of the Dielectric Constants of Alkali Halide Crystals Dick, B. G.; Overhauser, A. W. Physical Review, Vol. 112, Issue 1 https://doi.org/10.1103/PhysRev.112.90	journal	October 1958
The High-Pressure Phase of Zincite Gerward, L.; Olsen, J. S. Journal of Synchrotron Radiation, Vol. 2, Issue 5 https://doi.org/10.1107/S0909049595009447	journal	September 1995
Crystallography Open Database (COD): an open-access collection of crystal structures and platform for world-wide collaboration Gražulis, Saulius; Daškevič, Adriana; Merkys, Andrius Nucleic Acids Research, Vol. 40, Issue D1 https://doi.org/10.1093/nar/gkr900	journal	November 2011
Reciprocating Compression of ZnO Probed by X-ray Diffraction: The Size Effect on Structural Properties under High Pressure Wang, Qiming; Li, Shourui; He, Qiang Inorganic Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/acs.inorgchem.8b00357	journal	April 2018
Finite strain isotherm and velocities for single-crystal and polycrystalline NaCl at high pressures and 300°K Birch, Francis Journal of Geophysical Research, Vol. 83, Issue B3, p. 1257-1268 https://doi.org/10.1029/JB083iB03p01257	journal	January 1978
Effect of Mn-doping on performance of Li3V2(PO4)3/C cathode material for lithium ion batteries Zhai, Ting; Zhao, Min-shou; Wang, Dan-dan Transactions of Nonferrous Metals Society of China, Vol. 21, Issue 3 https://doi.org/10.1016/S1003-6326(11)60746-2	journal	March 2011
A profile refinement method for nuclear and magnetic structures Rietveld, H. M. Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71 https://doi.org/10.1107/S0021889869006558	journal	June 1969
Multicomponent equiatomic rare earth oxides with a narrow band gap and associated praseodymium multivalency Sarkar, Abhishek; Loho, Christoph; Velasco, Leonardo Dalton Transactions, Vol. 46, Issue 36 https://doi.org/10.1039/C7DT02077E	journal	January 2017
A beamline for high-pressure studies at the Advanced Light Source with a superconducting bending magnet as the source Kunz, Martin; MacDowell, Alastair A.; Caldwell, Wendel A. Journal of Synchrotron Radiation, Vol. 12, Issue 5 https://doi.org/10.1107/S0909049505020959	journal	August 2005
Lattice dynamics and hyperfine interactions in ZnO and ZnSe at high external pressures Karzel, H.; Potzel, W.; Köfferlein, M. Physical Review B, Vol. 53, Issue 17 https://doi.org/10.1103/PhysRevB.53.11425	journal	May 1996
The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE00050F	journal	January 2018
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
High pressure studies up to 50GPa of CuO Ȧrsbrink, S.; Gerward, L.; Olsen, J. Staun High Pressure Research, Vol. 10, Issue 3 https://doi.org/10.1080/08957959208201470	journal	July 1992
Ab Initio Calculations of Elastic Constants of Li ₂ O under Pressure Xiao-Feng, Li; Xiang-Rong, Chen; Guang-Fu, Ji Chinese Physics Letters, Vol. 23, Issue 4 https://doi.org/10.1088/0256-307X/23/4/045	journal	March 2006

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Solid‐state synthesis of multicomponent equiatomic rare‐earth oxides Pianassola, Matheus; Loveday, Madeline; McMurray, Jake W. Journal of the American Ceramic Society, Vol. 103, Issue 4 https://doi.org/10.1111/jace.16971	journal	December 2019