Density-Functional-Theory Modeling of Cation Diffusion in Bulk La1-xSrxMnO3±δ ( x=0.0–0.25 ) for Solid-Oxide Fuel-Cell Cathodes

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan C.; Abernathy, Harry; Hackett, Gregory

doi:10.1103/PhysRevApplied.8.044001

Title: Density-Functional-Theory Modeling of Cation Diffusion in Bulk ${La}_{1 - x} {Sr}_{x} {MnO}_{3 \pm δ}$ ( $x = 0.0 - 0.25$ ) for Solid-Oxide Fuel-Cell Cathodes

Journal Article · 03 October 2017 · Physical Review Applied

DOI: https://doi.org/10.1103/PhysRevApplied.8.044001 · OSTI ID:1406264

Lee, Yueh-Lin ^[1]; Duan, Yuhua ^[1]; Morgan, Dane ^[2]; Sorescu, Dan C. ^[1]; Abernathy, Harry ^[3]; Hackett, Gregory ^[4]

National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering
National Energy Technology Lab. (NETL), Morgantown, WV (United States); AECOM, Morgantown, WV (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); National Energy Technology Lab. (NETL), Morgantown, WV (United States)

In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La_1-xSr_xMnO_3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., La$$x\atop{A}$$) V_A"' of a V_A"' -V_B"' cluster, where La$$x\atop{A}$$, V_A"' and V_B"' are La³⁺, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V_A"' -V_B"' is the first nearest-neighbor V_A"' and V_B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\atop{A}$$ hop into a V_A"'. This decrease in the cation migration barrier is attributed to the presence of the V_B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

OSTI ID:: 1406264

Alternate ID(s):: OSTI ID: 1398160

Report Number(s):: NETL-PUB--21077; {"","Journal ID: ISSN 2331-7019","Journal ID: ISSN PRAHB2"}

Journal Information:: Physical Review Applied, Journal Name: Physical Review Applied Journal Issue: 4 Vol. 8; ISSN 2331-7019; ISSN PRAHB2

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Polymorphic forms and defect structure formation within homogeneity domain of LaMnO3 phase Horyń, R.; Sikora, A.; Bukowska, E. Journal of Alloys and Compounds, Vol. 353, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)01312-9	journal	April 2003
Towards Comprehensive Description of Stack Durability/Reliability Behavior Yokokawa, H. Fuel Cells, Vol. 15, Issue 5 https://doi.org/10.1002/fuce.201400182	journal	February 2015
Defect chemistry modelling of oxygen-stoichiometry, vacancy concentrations, and conductivity of (La1−xSrx)yMnO3±δ Poulsen, F. Solid State Ionics, Vol. 129, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00322-7	journal	April 2000
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Characterization of Lanthanum Zirconate Formation at the A-Site-Deficient Strontium-Doped Lanthanum Manganite Cathode/Yttrium-Stabilized Zirconia Electrolyte Interface of Solid Oxide Fuel Cells Chen, Aijie; Bourne, Gerald; Siebein, Kerry Journal of the American Ceramic Society, Vol. 91, Issue 8 https://doi.org/10.1111/j.1551-2916.2008.02524.x	journal	August 2008
Diffusion of La and Mn in Ba _0.5 Sr _0.5 Co _0.8 Fe _0.2 O _3−δ polycrystalline ceramics Harvey, Steven P.; De Souza, Roger A.; Martin, Manfred Energy Environ. Sci., Vol. 5, Issue 2 https://doi.org/10.1039/C1EE02740A	journal	January 2012
Probing the Electronic Structures of Ternary Perovskite and Pyrochlore Oxides Containing Sn ⁴⁺ or Sb ⁵⁺ Mizoguchi, Hiroshi; Eng, Hank W.; Woodward, Patrick M. Inorganic Chemistry, Vol. 43, Issue 5 https://doi.org/10.1021/ic034551c	journal	March 2004
Reaction Kinetics and Mechanisms between La _0.65 Sr _0.3 MnO ₃ and 8 mol% Yttria-Stabilized Zirconia Yang, Chih-Chung T.; Wei, Wen-Cheng J.; Roosen, Andreas Journal of the American Ceramic Society, Vol. 87, Issue 6 https://doi.org/10.1111/j.1551-2916.2004.01110.x	journal	June 2004
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
The defect chemistry of La1−ΔMnO3+δ Nakamura, Keikichi Journal of Solid State Chemistry, Vol. 173, Issue 2 https://doi.org/10.1016/S0022-4596(03)00091-4	journal	July 2003
Structural transitions and transport-half-metallic ferromagnetism in LaMnO 3 at elevated pressure He, Jiangang; Chen, Ming-Xing; Chen, Xing-Qiu Physical Review B, Vol. 85, Issue 19 https://doi.org/10.1103/PhysRevB.85.195135	journal	May 2012
In situ study of activation and de-activation of LSM fuel cell cathodes – Electrochemistry and surface analysis of thin-film electrodes Huber, Anne-Katrin; Falk, Mareike; Rohnke, Marcus Journal of Catalysis, Vol. 294 https://doi.org/10.1016/j.jcat.2012.07.010	journal	October 2012
First-principles thermodynamic modeling of lanthanum chromate perovskites Dalach, P.; Ellis, D. E.; van de Walle, A. Physical Review B, Vol. 85, Issue 1 https://doi.org/10.1103/PhysRevB.85.014108	journal	January 2012
Diffusion in Solids: Fundamentals, Methods, Materials, Diffusion-Controlled Processes Mehrer, Helmut Springer Series in Solid-State Sciences https://doi.org/10.1007/978-3-540-71488-0	book	January 2007
Structural phase diagram of La 1 − x Sr x Mn O 3 + δ : Relationship to magnetic and transport properties Mitchell, J. F.; Argyriou, D. N.; Potter, C. D. Physical Review B, Vol. 54, Issue 9 https://doi.org/10.1103/PhysRevB.54.6172	journal	September 1996
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
Oxygen tracer diffusion in undoped lanthanum manganites Berenov, A. Solid State Ionics, Vol. 122, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00077-6	journal	July 1999
The Principles Determining the Structure of Complex Ionic Crystals Pauling, Linus Journal of the American Chemical Society, Vol. 51, Issue 4 https://doi.org/10.1021/ja01379a006	journal	April 1929
Cation tracer diffusion of ¹³⁸ La, ⁸⁴ Sr and ²⁵ Mg in polycrystalline La _0.9 Sr _0.1 Ga _0.9 Mg _0.1 O _2.9 Schulz, Olaf; Martin, Manfred; Argirusis, Christos Phys. Chem. Chem. Phys., Vol. 5, Issue 11 https://doi.org/10.1039/B301882M	journal	January 2003
Collective and Tracer Diffusion via a Defect Cluster in LSGM Belova, Irina V.; Murch, Graeme E.; Samuelis, D. Defect and Diffusion Forum, Vol. 263 https://doi.org/10.4028/www.scientific.net/DDF.263.81	journal	March 2007
Formation and migration of cation defects in the perovskite oxide LaMnO3 De Souza, Roger A.; Islam, M. Saiful; Ivers-Tiffée, Ellen Journal of Materials Chemistry, Vol. 9, Issue 7 https://doi.org/10.1039/a901512d	journal	January 1999
Band theory and Mott insulators: Hubbard U instead of Stoner I Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K. Physical Review B, Vol. 44, Issue 3, p. 943-954 https://doi.org/10.1103/PhysRevB.44.943	journal	July 1991
High-temperature deformation and defect chemistry of (La1−xSrx)1−yMnO3+δ Cook, R. E.; Goretta, K. C.; Wolfenstine, J. Acta Materialia, Vol. 47, Issue 10 https://doi.org/10.1016/S1359-6454(99)00160-3	journal	August 1999
A-Site Diffusion in La _{1 − x} Sr _x MnO ₃ : Ab Initio and Kinetic Monte Carlo Calculations Puchala, B.; Lee, Y. -L.; Morgan, D. Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.077308jes	journal	January 2013
LaMnO perovskites modelled with and without antisite defects using the CALPHAD approach Grundy, A.; Hallstedt, B.; Gauckler, L. Solid State Ionics, Vol. 173, Issue 1-4 https://doi.org/10.1016/j.ssi.2004.07.046	journal	September 2004
Oxidation energies of transition metal oxides within the GGA + U framework Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.195107	journal	May 2006
Sintering Behavior of Doped Lanthanum and Yttrium Manganite Stevenson, Jeffry W.; Hallman, Paul F.; Armstrong, Timothy R. Journal of the American Ceramic Society, Vol. 78, Issue 3 https://doi.org/10.1111/j.1151-2916.1995.tb08207.x	journal	March 1995
Cation Self-Diffusion and Nonstoichiometry of Lanthanum Manganite Studied by Diffusion Couple Measurements Palcut, Marián; Wiik, Kjell; Grande, Tor The Journal of Physical Chemistry C, Vol. 111, Issue 2 https://doi.org/10.1021/jp0642746	journal	January 2007
Sintering and grain growth of (La,Sr)MnO electrodes of solid oxide fuel cells under polarization Jiang, S.; Wang, W. Solid State Ionics, Vol. 176, Issue 13-14 https://doi.org/10.1016/j.ssi.2005.02.013	journal	April 2005
Lattice creation and annihilation of LaMnO3+δ caused by nonstoichiometry change Miyoshi, S. Solid State Ionics, Vol. 154-155 https://doi.org/10.1016/S0167-2738(02)00441-1	journal	December 2002
Nonstoichiometric behavior and phase stability of rare earth manganites at 1200°C: (1). LaMnO3 Kamata, Kiichiro; Nakajima, Tadashi; Hayashi, Tsuyoshi Materials Research Bulletin, Vol. 13, Issue 1 https://doi.org/10.1016/0025-5408(78)90026-0	journal	January 1978
Modeling of cation diffusion in oxygen ion conductors using molecular dynamics Kilo, M. Solid State Ionics, Vol. 175, Issue 1-4 https://doi.org/10.1016/j.ssi.2004.09.059	journal	November 2004
Reactions between Strontium-Substituted Lanthanum Manganite and Yttria-Stabilized Zirconia: II, Diffusion Couples Kleveland, Kjersti; Einarsrud, Mari-Ann; Schmidt, Christian R. Journal of the American Ceramic Society, Vol. 82, Issue 3 https://doi.org/10.1111/j.1151-2916.1999.tb01824.x	journal	March 1999
Refinement of the bulk defect model for LaxSr1−xMnO3±δ☆ Mebane, D. Solid State Ionics, Vol. 178, Issue 39-40 https://doi.org/10.1016/j.ssi.2008.01.016	journal	March 2008
Oxidation-reduction behavior of undoped and Sr-doped LaMnO3 nonstoichiometry and defect structure Kuo, J. H.; Anderson, H. U.; Sparlin, D. M. Journal of Solid State Chemistry, Vol. 83, Issue 1 https://doi.org/10.1016/0022-4596(89)90053-4	journal	November 1989
Ab initio and empirical defect modeling of LaMnO _3±δ for solid oxidefuel cell cathodes Lee, Yueh-Lin; Morgan, Dane Phys. Chem. Chem. Phys., Vol. 14, Issue 1 https://doi.org/10.1039/C1CP22380A	journal	January 2012
In-situ study of operating SOFC LSM/YSZ cathodes under polarization by photoelectron microscopy Backhaus-Ricoult, M.; Adib, K.; St. Clair, T. Solid State Ionics, Vol. 179, Issue 21-26 https://doi.org/10.1016/j.ssi.2008.02.033	journal	September 2008
First-Principles Study of Lanthanum Strontium Manganite: Insights into Electronic Structure and Oxygen Vacancy Formation Pavone, Michele; Muñoz-García, Ana B.; Ritzmann, Andrew M. The Journal of Physical Chemistry C, Vol. 118, Issue 25 https://doi.org/10.1021/jp500352h	journal	June 2014
Impurity diffusion of 141Pr in LaMnO3, LaCoO3 and LaFeO3 materials Palcut, Marián; Christensen, Jens S.; Wiik, Kjell Physical Chemistry Chemical Physics, Vol. 10, Issue 43 https://doi.org/10.1039/b808789j	journal	January 2008
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Effects of cation vacancy distribution in doped LaMnO3+δ perovskites Malavasi, Lorenzo; Ritter, Clemens; Cristina Mozzati, Maria Journal of Solid State Chemistry, Vol. 178, Issue 6 https://doi.org/10.1016/j.jssc.2005.04.019	journal	June 2005
Cation inter-diffusion between LaMnO3 and LaCoO3 materials Palcut, Marián; Knibbe, Ruth; Wiik, Kjell Solid State Ionics, Vol. 202, Issue 1 https://doi.org/10.1016/j.ssi.2011.09.003	journal	November 2011
A computational study of yttria-stabilized zirconia: II. Cation diffusion Dong, Yanhao; Qi, Liang; Li, Ju Acta Materialia, Vol. 126 https://doi.org/10.1016/j.actamat.2017.01.008	journal	March 2017
Interdiffusion across solid electrolyte-electrode interface Hu, Jia-Mian; Liang, Linyun; Ji, Yanzhou Applied Physics Letters, Vol. 104, Issue 21 https://doi.org/10.1063/1.4879835	journal	May 2014
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
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Development of lanthanum strontium manganite perovskite cathode materials of solid oxide fuel cells: a review Jiang, San Ping Journal of Materials Science, Vol. 43, Issue 21 https://doi.org/10.1007/s10853-008-2966-6	journal	November 2008
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
Sintering and mechanical characteristics of lanthanum strontium manganite Meixner, D. Solid State Ionics, Vol. 146, Issue 3-4 https://doi.org/10.1016/S0167-2738(01)01027-X	journal	February 2002
B-Site cation diffusivity of Mn and Cr in perovskite-type LaMnO3 with cation-deficit nonstoichiometry Miyoshi, Shogo; Martin, Manfred Physical Chemistry Chemical Physics, Vol. 11, Issue 17 https://doi.org/10.1039/b901208g	journal	January 2009
Periodic boundary conditions in ab initio calculations Makov, G.; Payne, M. C. Physical Review B, Vol. 51, Issue 7 https://doi.org/10.1103/PhysRevB.51.4014	journal	February 1995
Structural defects in LaMnO3 phase studied by neutron diffraction Wołcyrz, M.; Horyń, R.; Bourée, F. Journal of Alloys and Compounds, Vol. 353, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)01313-0	journal	April 2003
Dielectric anomaly at T N in La Mn O 3 as a signature of coupling between spin and orbital degrees of freedom Mondal, Parthasarathi; Bhattacharya, Dipten; Choudhury, Pranab Physical Review B, Vol. 76, Issue 17 https://doi.org/10.1103/PhysRevB.76.172403	journal	November 2007
Oxygen nonstoichiometry and defect equilibrium in the perovskite-type oxides La1−xSrxMnO3+d Mizusaki, J. Solid State Ionics, Vol. 129, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00323-9	journal	April 2000
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Use of diffusional creep to investigate mass transport in (La, Sr)MnO3 Wolfenstine, J. Solid State Ionics, Vol. 92, Issue 1-2 https://doi.org/10.1016/S0167-2738(96)00461-4	journal	November 1996
A computational study of cation defects in LaGaO3 De Souza, Roger A.; Maier, Joachim Physical Chemistry Chemical Physics, Vol. 5, Issue 4 https://doi.org/10.1039/b209062g	journal	January 2003
Ab initio energetics of La B O 3 ( 001 ) ( B = Mn , Fe, Co, and Ni) for solid oxide fuel cell cathodes Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan Physical Review B, Vol. 80, Issue 22 https://doi.org/10.1103/PhysRevB.80.224101	journal	December 2009
Examination of the mechanism for the reversible aging behavior at open circuit when changing the operating temperature of (La0.8Sr0.2)0.95MnO3 electrodes Abernathy, Harry; Finklea, Harry O.; Mebane, David S. Solid State Ionics, Vol. 272 https://doi.org/10.1016/j.ssi.2015.01.013	journal	April 2015
Thermodynamic analysis on interface between perovskite electrode and YSZ electrolyte Yokokawa, H. Solid State Ionics, Vol. 40-41 https://doi.org/10.1016/0167-2738(90)90366-Y	journal	August 1990

Cited By (1)

Controlling surface cation segregation in a nanostructured double perovskite GdBaCo ₂ O _5+δ electrode for solid oxide fuel cells Anjum, Uzma; Agarwal, Manish; Khan, Tuhin Suvra Nanoscale, Vol. 11, Issue 44 https://doi.org/10.1039/c9nr04734d	journal	January 2019

Similar Records

Ferromagnetism and superconductivity in CeFeAs

_{1 - x}

P_{x}

O (

0 \leq x \leq 40 %

)

Journal Article · 2012 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1052061

Jesche, A.; Förster, T.; Spehling, J.; +10 more

Electrical transport properties of Ti-doped Fe

_{2}

O_{3}

(0001) epitaxial films

Journal Article · 2011 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1034586

Zhao, B.; Kaspar, T. C.; Droubay, T. C.; +5 more

{}^{77}{Se}

NMR investigation of the

K_{x}

_{2 - y}

_{2}

high-

T_{c}

superconductor (

T_{c} = 33

Journal Article · 2011 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1385538

Torchetti, D. A.; Fu, M.; Christensen, D. C.; +4 more

Related Subjects

03
20
32
25
30
36
54
60
Solid Oxide Fuel Cell
Cation Diffusion
La(1-x)Sr(x)MnO3 (x=0
0.25)
Density functional Theory

Title: Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

Citation Formats

References (61)

Cited By (1)

Similar Records

Related Subjects

Title: Density-Functional-Theory Modeling of Cation Diffusion in Bulk ${La}_{1 - x} {Sr}_{x} {MnO}_{3 \pm δ}$ ( $x = 0.0 - 0.25$ ) for Solid-Oxide Fuel-Cell Cathodes