Pulsed Laser Deposition and Characterization of Heteroepitaxial LiMn2O4/La0.5Sr0.5CoO3 Bilayer Thin Films as Model Lithium Ion Battery Cathodes

Yu, Xiankai; Chen, Xiao; Buchholz, D. Bruce; Li, Qianqian; Wu, Jinsong; Fenter, Paul A.; Bedzyk, Michael J.; Dravid, Vinayak P.; Barnett, Scott A.

doi:10.1021/acsanm.7b00133

Pulsed Laser Deposition and Characterization of Heteroepitaxial LiMn₂O₄/La_0.5Sr_0.5CoO₃ Bilayer Thin Films as Model Lithium Ion Battery Cathodes

Journal Article · Mon Jan 01 23:00:00 EST 2018 · ACS Applied Nano Materials

DOI:https://doi.org/10.1021/acsanm.7b00133· OSTI ID:1483643

^[1]; Chen, Xiao ^[1]; Buchholz, D. Bruce ^[1]; Li, Qianqian ^[1]; ^[1]; ^[2]; ^[1]; ^[1]; Barnett, Scott A. ^[1]

Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Epitaxial LiMn₂O₄ (LMO)/La_0.5Sr_0.5CoO₃ (LSCO) bilayer thin films were grown on single crystalline SrTiO₃ (STO) (111) substrates as model lithium ion battery cathodes. The LSCO layer was used as an electrically conducting buffer layer for electrochemical testing. The LMO and LSCO layers were both epitaxial, with sub-nano flat LMO/LSCO interfaces as seen by X-ray diffraction, synchrotron X-ray scattering, and high-resolution transmission electron microscopy (HRTEM), but with a large LMO surface roughness due to the relatively large lattice mismatch with LSCO. Three-dimensional islands and depressions were formed on the strain-relaxed LMO layer, and misfit dislocations at the LMO/LSCO interface were discerned through HRTEM imaging, suggesting a Stranski–Krastanov (SK) mode thin-film growth. A crystalline structural change from cubic spinel at the LMO surface and interior to tetragonal oxygen-deficient LMO at the LMO/LSCO interface was examined. Furthermore, electrochemical tests along with in situ synchrotron X-ray scattering measurements on the epitaxial LMO/LSCO bilayers showed a significant loss of capacity after the first cycle, which was attributed to an electrical conductivity loss of the LSCO buffer layer due to irreversible lattice oxygen loss.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1483643

Journal Information:: ACS Applied Nano Materials, Journal Name: ACS Applied Nano Materials Journal Issue: 2 Vol. 1; ISSN 2574-0970

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Structural Distortion and Compositional Gradients Adjacent to Epitaxial LiMn ₂ O ₄ Thin Film Interfaces Gao, Xiang; Ikuhara, Yumi H.; Fisher, Craig A. J. Advanced Materials Interfaces, Vol. 1, Issue 8 https://doi.org/10.1002/admi.201400143	journal	June 2014
Lithium Intercalation Behavior in Multilayer Silicon Electrodes Fister, Tim T.; Esbenshade, Jennifer; Chen, Xiao Advanced Energy Materials, Vol. 4, Issue 7 https://doi.org/10.1002/aenm.201301494	journal	January 2014
Oxygen-Vacancy Ordering at Surfaces of Lithium Manganese(III,IV) Oxide Spinel Nanoparticles Huang, Rong; Ikuhara, Yumi H.; Mizoguchi, Teruyasu Angewandte Chemie International Edition, Vol. 50, Issue 13 https://doi.org/10.1002/anie.201004638	journal	February 2011
Structural, electrical, and surface characteristics of La 0.5 Sr 0.5 CoO 3 thin films prepared by pulsed-laser deposition Gunasekaran, R. A.; Pedarnig, J. D.; Dinescu, M. Applied Physics A: Materials Science & Processing, Vol. 69, Issue 6 https://doi.org/10.1007/s003390051042	journal	December 1999
Defects in epitaxial multilayers: II. Dislocation pile-ups, threading dislocations, slip lines and cracks Matthews, J. W.; Blakeslee, A. E. Journal of Crystal Growth, Vol. 29, Issue 3, p. 273-280 https://doi.org/10.1016/0022-0248(75)90171-2	journal	July 1975
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells Gummow, R. J.; de Kock, A.; Thackeray, M. M. Solid State Ionics, Vol. 69, Issue 1, p. 59-67 https://doi.org/10.1016/0167-2738(94)90450-2	journal	April 1994
Surface characterization and catalytic properties of La1 − xAxMO3 perovskite oxides. Part II. Studies on La1 − xBaxMnO3 (0 ⩽ x ⩽ 0.2) oxides Gunasekaran, N.; Rajadurai, S.; Carberry, J. Solid State Ionics, Vol. 81, Issue 3-4 https://doi.org/10.1016/0167-2738(95)00189-D	journal	November 1995
Influences of substrates and substrate temperatures on characteristics of epitaxial La0.5Sr0.5CoO3 thin films Li, Meiya; Wang, Zhong-Lie; Fan, Shoushan Thin Solid Films, Vol. 323, Issue 1-2 https://doi.org/10.1016/S0040-6090(97)01033-X	journal	June 1998
High-temperature electrical conductivity and thermopower in nonstoichiometric La1−xSrxCoO3−δ (x=0.6) Mitberg, E. Solid State Ionics, Vol. 130, Issue 3-4 https://doi.org/10.1016/S0167-2738(00)00670-6	journal	May 2000
Surface roughness of thin layers—a comparison of XRR and SFM measurements Filies, O.; Böling, O.; Grewer, K. Applied Surface Science, Vol. 141, Issue 3-4 https://doi.org/10.1016/S0169-4332(98)00524-8	journal	March 1999
The relationships between phases and structures of lithium manganese spinels Kanno, Ryoji; Kondo, Atsuro; Yonemura, Masao Journal of Power Sources, Vol. 81-82 https://doi.org/10.1016/S0378-7753(99)00103-2	journal	September 1999
Effects of oxygen defects on structure and properties of Sm0.5Sr0.5CoO3-δ annealed in different atmospheres Lu, Yi; Chen, Le; Lu, Chunhua Journal of Rare Earths, Vol. 31, Issue 12 https://doi.org/10.1016/S1002-0721(12)60424-4	journal	December 2013
Progress and prospective of solid-state lithium batteries Takada, Kazunori Acta Materialia, Vol. 61, Issue 3, p. 759-770 https://doi.org/10.1016/j.actamat.2012.10.034	journal	February 2013
Cyclic voltammetry and galvanostatic cycling characteristics of LiNiVO4 thin films during lithium insertion and re/de-insertion Reddy, M. V.; Pecquenard, B.; Vinatier, P. Electrochemistry Communications, Vol. 9, Issue 3 https://doi.org/10.1016/j.elecom.2006.10.011	journal	March 2007
Effective enhancement of electrochemical performance for spherical spinel LiMn2O4 via Li ion conductive Li2ZrO3 coating Yi, Xin; Wang, Xianyou; Ju, Bowei Electrochimica Acta, Vol. 134 https://doi.org/10.1016/j.electacta.2014.04.148	journal	July 2014
Sr content on the structure and magnetic properties of La1−xSrxCoO3 Xie, Q. Y.; Wu, Z. P.; Wu, X. S. Journal of Alloys and Compounds, Vol. 474, Issue 1-2 https://doi.org/10.1016/j.jallcom.2008.06.045	journal	April 2009
Electrochemistry of LiMn2O4 epitaxial films deposited on various single crystal substrates Sonoyama, Noriyuki; Iwase, Kosuke; Takatsuka, Hironori Journal of Power Sources, Vol. 189, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.10.037	journal	April 2009
Recent developments in cathode materials for lithium ion batteries Fergus, Jeffrey W. Journal of Power Sources, Vol. 195, Issue 4, p. 939-954 https://doi.org/10.1016/j.jpowsour.2009.08.089	journal	February 2010
Lithium batteries: Status, prospects and future Scrosati, Bruno; Garche, Jürgen Journal of Power Sources, Vol. 195, Issue 9 https://doi.org/10.1016/j.jpowsour.2009.11.048	journal	May 2010
Fabrication and electrochemical properties of LiMn2O4/SrRuO3 multi-layer epitaxial thin film electrodes Suzuki, Kota; Kim, Kyungsu; Taminato, Sou Journal of Power Sources, Vol. 226 https://doi.org/10.1016/j.jpowsour.2012.11.008	journal	March 2013
Fabrication of all-solid-state battery using epitaxial LiCoO2 thin films Shiraki, Susumu; Oki, Hideki; Takagi, Yoshitaka Journal of Power Sources, Vol. 267 https://doi.org/10.1016/j.jpowsour.2014.05.133	journal	December 2014
In situ methods for Li-ion battery research: A review of recent developments Harks, P. P. R. M. L.; Mulder, F. M.; Notten, P. H. L. Journal of Power Sources, Vol. 288 https://doi.org/10.1016/j.jpowsour.2015.04.084	journal	August 2015
Magnetic properties of the chemically delithiated LixMn2O4 with 0.07≤x≤1 Mukai, Kazuhiko; Sugiyama, Jun; Kamazawa, Kazuya Journal of Solid State Chemistry, Vol. 184, Issue 5 https://doi.org/10.1016/j.jssc.2011.03.019	journal	May 2011
Synthesis and characterization of the lithium-deficient Fe-substituted Li–Mn oxide spinel phases Piszora, P.; Nowicki, W.; Darul, J. Materials Letters, Vol. 58, Issue 7-8 https://doi.org/10.1016/j.matlet.2003.09.047	journal	March 2004
Hetero-epitaxial growth of Li0.17La0.61TiO3 solid electrolyte on LiMn2O4 electrode for all solid-state batteries Kim, Sangryun; Hirayama, Masaaki; Suzuki, Kota Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.040	journal	September 2014
Preparation and in-situ characterization of well-defined solid electrolyte/electrode interfaces in thin-film lithium batteries Haruta, Masakazu; Shiraki, Susumu; Ohsawa, Takeo Solid State Ionics, Vol. 285 https://doi.org/10.1016/j.ssi.2015.06.007	journal	February 2016
Epitaxial growth of Cu(100) and Pt(100) thin films on perovskite substrates Francis, Andrew J.; Cao, Yan; Salvador, Paul A. Thin Solid Films, Vol. 496, Issue 2 https://doi.org/10.1016/j.tsf.2005.08.367	journal	February 2006
Orientation control of LiCoO2 epitaxial thin films on metal substrates Shiraki, Susumu; Takagi, Yoshitaka; Shimizu, Ryota Thin Solid Films, Vol. 600 https://doi.org/10.1016/j.tsf.2016.01.032	journal	February 2016
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights Gauthier, Magali; Carney, Thomas J.; Grimaud, Alexis The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b01727	journal	October 2015
High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn ₂ O ₄ Thin Films Put, Brecht; Vereecken, Philippe M.; Labyedh, Nouha ACS Applied Materials & Interfaces, Vol. 7, Issue 40 https://doi.org/10.1021/acsami.5b06386	journal	September 2015
Epitaxial Strain-Controlled Ionic Conductivity in Li-Ion Solid Electrolyte Li _0.33 La _0.56 TiO ₃ Thin Films Wei, Jie; Ogawa, Daisuke; Fukumura, Tomoteru Crystal Growth & Design, Vol. 15, Issue 5 https://doi.org/10.1021/cg501834s	journal	March 2015
Dynamic Structural Changes at LiMn ₂ O ₄ /Electrolyte Interface during Lithium Battery Reaction Hirayama, Masaaki; Ido, Hedekazu; Kim, KyungSu Journal of the American Chemical Society, Vol. 132, Issue 43 https://doi.org/10.1021/ja105389t	journal	November 2010
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Simulation of Aqueous Dissolution of Lithium Manganate Spinel from First Principles Benedek, R.; Thackeray, M. M.; Low, J. The Journal of Physical Chemistry C, Vol. 116, Issue 6 https://doi.org/10.1021/jp208793k	journal	February 2012
Preparation, Comparative Energy Storage Properties, and Impedance Spectroscopy Studies of Environmentally Friendly Cathode, Li(MMn _11/6 )O ₄ (M = Mn _1/6 , Co _1/6 , (Co _1/12 Cr _1/12 )) Reddy, M. V.; Sakunthala, A.; SelvashekaraPandian, S. The Journal of Physical Chemistry C, Vol. 117, Issue 18 https://doi.org/10.1021/jp309180k	journal	April 2013
In Situ TEM Observation of Local Phase Transformation in a Rechargeable LiMn ₂ O ₄ Nanowire Battery Lee, Soyeon; Oshima, Yoshifumi; Hosono, Eiji The Journal of Physical Chemistry C, Vol. 117, Issue 46 https://doi.org/10.1021/jp409032r	journal	November 2013
Atomic Layer Deposition of Spinel Lithium Manganese Oxide by Film-Body-Controlled Lithium Incorporation for Thin-Film Lithium-Ion Batteries Miikkulainen, Ville; Ruud, Amund; Østreng, Erik The Journal of Physical Chemistry C, Vol. 118, Issue 2 https://doi.org/10.1021/jp409399y	journal	December 2013
Epitaxial Growth of LiMn ₂ O ₄ Thin Films by Chemical Solution Deposition for Multilayer Lithium-Ion Batteries Ikuhara, Yumi H.; Gao, Xiang; Huang, Rong The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp504305q	journal	August 2014
Materials Challenges and Opportunities of Lithium Ion Batteries Manthiram, Arumugam The Journal of Physical Chemistry Letters, Vol. 2, Issue 3 https://doi.org/10.1021/jz1015422	journal	January 2011
A Truncated Manganese Spinel Cathode for Excellent Power and Lifetime in Lithium-Ion Batteries Kim, Joo-Seong; Kim, KyungSu; Cho, Woosuk Nano Letters, Vol. 12, Issue 12 https://doi.org/10.1021/nl303619s	journal	February 2012
Visualization of Electrode–Electrolyte Interfaces in LiPF ₆ /EC/DEC Electrolyte for Lithium Ion Batteries via in Situ TEM Zeng, Zhiyuan; Liang, Wen-I; Liao, Hong-Gang Nano Letters, Vol. 14, Issue 4 https://doi.org/10.1021/nl403922u	journal	March 2014
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach Lu, Jun; Zhan, Chun; Wu, Tianpin Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6693	journal	December 2014
Relation between oxygen stoichiometry and thermodynamic properties and the electronic structure of nonstoichiometric perovskite La _0.6 Sr _0.4 CoO _3−δ Bychkov, S. F.; Sokolov, A. G.; Popov, M. P. Physical Chemistry Chemical Physics, Vol. 18, Issue 42 https://doi.org/10.1039/C6CP05435H	journal	January 2016
Enhanced electrocatalytic activity of three-dimensionally-ordered macroporous La _0.6 Sr _0.4 CoO _3−δ perovskite oxide for Li–O ₂ battery application Oh, Mi Young; Lee, Jong Ju; Zahoor, Awan RSC Advances, Vol. 6, Issue 38 https://doi.org/10.1039/C6RA02459A	journal	January 2016
Epitaxial growth and lithium ion conductivity of lithium-oxide garnet for an all solid-state battery electrolyte Kim, Sangryun; Hirayama, Masaaki; Taminato, Sou Dalton Transactions, Vol. 42, Issue 36 https://doi.org/10.1039/c3dt51795k	journal	January 2013
Electrical and magnetic properties of La0.5Sr0.5CoO3 thin films Luo, G. P.; Wang, Y. S.; Chen, S. Y. Applied Physics Letters, Vol. 76, Issue 14 https://doi.org/10.1063/1.126208	journal	April 2000
Mechanisms of Stranski-Krastanov growth Baskaran, Arvind; Smereka, Peter Journal of Applied Physics, Vol. 111, Issue 4 https://doi.org/10.1063/1.3679068	journal	February 2012
Epitaxial and highly electrical conductive La0.5Sr0.5TiO3 films grown by pulsed laser deposition in vacuum Wu, Wenbin; Lu, Fei; Wong, K. H. Journal of Applied Physics, Vol. 88, Issue 2 https://doi.org/10.1063/1.373724	journal	July 2000
Preparation and characterization of epitaxial films and of an all a -axis oriented heterostructure on (001) by pulsed laser deposition Chan, P. W.; Wu, Wenbin; Wong, K. H. Journal of Physics D: Applied Physics, Vol. 30, Issue 6 https://doi.org/10.1088/0022-3727/30/6/008	journal	March 1997
SiGe heterostructures for FET applications Whall, T. E.; Parker, E. H. C. Journal of Physics D: Applied Physics, Vol. 31, Issue 12 https://doi.org/10.1088/0022-3727/31/12/003	journal	June 1998
Interaction between surface morphology and misfit dislocations as strain relaxation modes in lattice-mismatched heteroepitaxy Hull, R.; Gray, J.; Wu, C. C. Journal of Physics: Condensed Matter, Vol. 14, Issue 48 https://doi.org/10.1088/0953-8984/14/48/323	journal	November 2002
Elegant design of electrode and electrode/electrolyte interface in lithium-ion batteries by atomic layer deposition Liu, Jian; Sun, Xueliang Nanotechnology, Vol. 26, Issue 2 https://doi.org/10.1088/0957-4484/26/2/024001	journal	December 2014
Surface phase diagram and stability of (001) and (111) LiM n 2 O 4 spinel oxides Kim, Soo; Aykol, Muratahan; Wolverton, C. Physical Review B, Vol. 92, Issue 11 https://doi.org/10.1103/PhysRevB.92.115411	journal	September 2015
Solvated Li-Ion Transfer at Interface Between Graphite and Electrolyte Abe, Takeshi; Fukuda, Hideo; Iriyama, Yasutoshi Journal of The Electrochemical Society, Vol. 151, Issue 8 https://doi.org/10.1149/1.1763141	journal	January 2004
Cyclic Voltammetry of Pulsed Laser Deposited Li x Mn2 O 4 Thin Films Rougier, A.; Striebel, K. A.; Wen, S. J. Journal of The Electrochemical Society, Vol. 145, Issue 9 https://doi.org/10.1149/1.1838750	journal	September 1998
Characterization of Electrode/Electrolyte Interface with X-Ray Reflectometry and Epitaxial-Film LiMn[sub 2]O[sub 4] Electrode Hirayama, Masaaki; Sonoyama, Noriyuki; Ito, Masumi Journal of The Electrochemical Society, Vol. 154, Issue 11 https://doi.org/10.1149/1.2778853	journal	January 2007
Synthesis, Characterization, and Electrochemical Cycling Behavior of the Ru-Doped Spinel, Li[Mn[sub 2−x]Ru[sub x]]O[sub 4] (x=0, 0.1, and 0.25) Reddy, M. V.; Manoharan, S. Sundar; John, Jimmy Journal of The Electrochemical Society, Vol. 156, Issue 8 https://doi.org/10.1149/1.3139013	journal	January 2009
Preparation of Li1.03Mn1.97O4 and Li1.06Mn1.94O4 by the Polymer Precursor Method and X-ray, Neutron Diffraction and Electrochemical Studies Reddy, M. V.; Raju, M. J. Silvister; Sharma, N. Journal of The Electrochemical Society, Vol. 158, Issue 11 https://doi.org/10.1149/2.074111jes	journal	January 2011
Interfaces between solution-derived LiMn ₂ O ₄ thin films and MgO and Au/MgO substrates Ikuhara, Yumi H.; Ma, Xiuliang; Iwamoto, Yuji Journal of Materials Research, Vol. 17, Issue 2 https://doi.org/10.1557/JMR.2002.0051	journal	February 2002
Epitaxial growth of Li ₄ Ti ₅ O ₁₂ thin films using RF magnetron sputtering Kumatani, Akichika; Shiraki, Susumu; Takagi, Yoshitaka Japanese Journal of Applied Physics, Vol. 53, Issue 5 https://doi.org/10.7567/JJAP.53.058001	journal	April 2014

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