Uncovering the Effect of Lattice Strain and Oxygen Deficiency on Electrocatalytic Activity of Perovskite Cobaltite Thin Films
Abstract
Developing cost effective electrocatalysts with high oxygen evolution reaction (OER) activity is essential for large-scale application of many electrochemical energy systems. Although the impacts of either lattice strain or oxygen defects on the OER performance of oxide catalysts have been extensively investigated, the effects of both factors are normally treated separately. In this work, the coupled effects of both strain and oxygen deficiency on the electrocatalytic activity of La0.7Sr0.3CoO3-δ (LSC) thin films grown on single crystal substrates (LaAlO3 (LAO) and SrTiO3 (STO)) are investigated. Electrochemical tests show that the OER activities of LSC films are higher under compression than under tension, and are diminished as oxygen vacancies are introduced by vacuum annealing. Both experimental and computational results indicate that the LSC films under tension (e.g., LSC/STO) have larger oxygen deficiency than the films under compression (e.g., LSC/LAO), which attribute to smaller oxygen vacancy formation energy. Such strain-induced excessive oxygen vacancies in the LSC/STO increases the eg state occupancy and enlarges the energy gap between the O 2p and Co 3d band, resulting in lower OER activity. Understanding the critical role of strain–defect coupling is important for achieving the rational design of highly active and durable catalysts for energy devices.
- Authors:
-
- Guangzhou Key Laboratory for Surface Chemistry of Energy MaterialsGuangdong Engineering and Technology and Research Center for Surface Chemistry of Energy MaterialsState Key Laboratory of Pulp and Paper EngineeringSchool of Environment and EnergySouth China University of Technology Guangzhou Guangdong 510006 China
- Materials Science and EngineeringGeorgia Institute of Technology Atlanta GA USA
- Institute of Nuclear and New Energy TechnologyTsinghua University Beijing China
- School of Advanced MaterialsShenzhen Graduate SchoolPeking University Shenzhen China
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1493070
- Alternate Identifier(s):
- OSTI ID: 1493071; OSTI ID: 1530194
- Grant/Contract Number:
- AC02‐05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Advanced Science
- Additional Journal Information:
- Journal Name: Advanced Science Journal Volume: 6 Journal Issue: 6; Journal ID: ISSN 2198-3844
- Publisher:
- Wiley
- Country of Publication:
- Germany
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 30 DIRECT ENERGY CONVERSION
Citation Formats
Liu, Xi, Zhang, Lei, Zheng, Yun, Guo, Zheng, Zhu, Yunmin, Chen, Huijun, Li, Fei, Liu, Peipei, Yu, Bo, Wang, Xinwei, Liu, Jiang, Chen, Yan, and Liu, Meilin. Uncovering the Effect of Lattice Strain and Oxygen Deficiency on Electrocatalytic Activity of Perovskite Cobaltite Thin Films. Germany: N. p., 2019.
Web. doi:10.1002/advs.201801898.
Liu, Xi, Zhang, Lei, Zheng, Yun, Guo, Zheng, Zhu, Yunmin, Chen, Huijun, Li, Fei, Liu, Peipei, Yu, Bo, Wang, Xinwei, Liu, Jiang, Chen, Yan, & Liu, Meilin. Uncovering the Effect of Lattice Strain and Oxygen Deficiency on Electrocatalytic Activity of Perovskite Cobaltite Thin Films. Germany. https://doi.org/10.1002/advs.201801898
Liu, Xi, Zhang, Lei, Zheng, Yun, Guo, Zheng, Zhu, Yunmin, Chen, Huijun, Li, Fei, Liu, Peipei, Yu, Bo, Wang, Xinwei, Liu, Jiang, Chen, Yan, and Liu, Meilin. Wed .
"Uncovering the Effect of Lattice Strain and Oxygen Deficiency on Electrocatalytic Activity of Perovskite Cobaltite Thin Films". Germany. https://doi.org/10.1002/advs.201801898.
@article{osti_1493070,
title = {Uncovering the Effect of Lattice Strain and Oxygen Deficiency on Electrocatalytic Activity of Perovskite Cobaltite Thin Films},
author = {Liu, Xi and Zhang, Lei and Zheng, Yun and Guo, Zheng and Zhu, Yunmin and Chen, Huijun and Li, Fei and Liu, Peipei and Yu, Bo and Wang, Xinwei and Liu, Jiang and Chen, Yan and Liu, Meilin},
abstractNote = {Developing cost effective electrocatalysts with high oxygen evolution reaction (OER) activity is essential for large-scale application of many electrochemical energy systems. Although the impacts of either lattice strain or oxygen defects on the OER performance of oxide catalysts have been extensively investigated, the effects of both factors are normally treated separately. In this work, the coupled effects of both strain and oxygen deficiency on the electrocatalytic activity of La0.7Sr0.3CoO3-δ (LSC) thin films grown on single crystal substrates (LaAlO3 (LAO) and SrTiO3 (STO)) are investigated. Electrochemical tests show that the OER activities of LSC films are higher under compression than under tension, and are diminished as oxygen vacancies are introduced by vacuum annealing. Both experimental and computational results indicate that the LSC films under tension (e.g., LSC/STO) have larger oxygen deficiency than the films under compression (e.g., LSC/LAO), which attribute to smaller oxygen vacancy formation energy. Such strain-induced excessive oxygen vacancies in the LSC/STO increases the eg state occupancy and enlarges the energy gap between the O 2p and Co 3d band, resulting in lower OER activity. Understanding the critical role of strain–defect coupling is important for achieving the rational design of highly active and durable catalysts for energy devices.},
doi = {10.1002/advs.201801898},
journal = {Advanced Science},
number = 6,
volume = 6,
place = {Germany},
year = {Wed Jan 30 00:00:00 EST 2019},
month = {Wed Jan 30 00:00:00 EST 2019}
}
https://doi.org/10.1002/advs.201801898
Web of Science
Figures / Tables:
Works referenced in this record:
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
X-ray photoelectron spectrum of low-spin Co(III) in LiCoO2
journal, January 1978
- Oku, Masaoki
- Journal of Solid State Chemistry, Vol. 23, Issue 1-2
Oxygen Evolution Reaction on La 1– x Sr x CoO 3 Perovskites: A Combined Experimental and Theoretical Study of Their Structural, Electronic, and Electrochemical Properties
journal, November 2015
- Cheng, Xi; Fabbri, Emiliana; Nachtegaal, Maarten
- Chemistry of Materials, Vol. 27, Issue 22
Spin-State Regulation of Perovskite Cobaltite to Realize Enhanced Oxygen Evolution Activity
journal, November 2017
- Tong, Yun; Guo, Yuqiao; Chen, Pengzuo
- Chem, Vol. 3, Issue 5
Descriptors of Oxygen-Evolution Activity for Oxides: A Statistical Evaluation
journal, December 2015
- Hong, Wesley T.; Welsch, Roy E.; Shao-Horn, Yang
- The Journal of Physical Chemistry C, Vol. 120, Issue 1
A robust and active hybrid catalyst for facile oxygen reduction in solid oxide fuel cells
journal, January 2017
- Chen, Yu; Chen, Yan; Ding, Dong
- Energy & Environmental Science, Vol. 10, Issue 4
Plasma-Engraved Co 3 O 4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction
journal, March 2016
- Xu, Lei; Jiang, Qianqian; Xiao, Zhaohui
- Angewandte Chemie International Edition, Vol. 55, Issue 17
Reducibility of Co at the La 0.8 Sr 0.2 CoO 3 /(La 0.5 Sr 0.5 ) 2 CoO 4 hetero-interface at elevated temperatures
journal, January 2014
- Tsvetkov, Nikolai; Chen, Yan; Yildiz, Bilge
- Journal of Materials Chemistry A, Vol. 2, Issue 35
A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation
journal, October 2010
- Gorlin, Yelena; Jaramillo, Thomas F.
- Journal of the American Chemical Society, Vol. 132, Issue 39, p. 13612-13614
Engineering the Electronic State of a Perovskite Electrocatalyst for Synergistically Enhanced Oxygen Evolution Reaction
journal, August 2015
- Guo, Yuqiao; Tong, Yun; Chen, Pengzuo
- Advanced Materials, Vol. 27, Issue 39
Impact of Sr segregation on the electronic structure and oxygen reduction activity of SrTi1−xFexO3 surfaces
journal, January 2012
- Chen, Yan; Jung, WooChul; Cai, Zhuhua
- Energy & Environmental Science, Vol. 5, Issue 7
Density functional theory + U analysis of the electronic structure and defect chemistry of LSCF (La 0.5 Sr 0.5 Co 0.25 Fe 0.75 O 3−δ )
journal, January 2016
- Ritzmann, Andrew M.; Dieterich, Johannes M.; Carter, Emily A.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 17
In situ examination of oxygen non-stoichiometry in La 0.80 Sr 0.20 CoO 3−δ thin films at intermediate and low temperatures by x-ray diffraction
journal, April 2014
- Biegalski, M. D.; Crumlin, E.; Belianinov, A.
- Applied Physics Letters, Vol. 104, Issue 16
X-ray photoelectron spectroscopy study of the ionic configuration of the spinel CuMnCoO 4
journal, September 1983
- Brabers, V. A. M.; Setten, F. van
- Journal of Physics D: Applied Physics, Vol. 16, Issue 9
Tensile Lattice Strain Accelerates Oxygen Surface Exchange and Diffusion in La 1– x Sr x CoO 3−δ Thin Films
journal, April 2013
- Kubicek, Markus; Cai, Zhuhua; Ma, Wen
- ACS Nano, Vol. 7, Issue 4
Nonstoichiometric Oxides as Low-Cost and Highly-Efficient Oxygen Reduction/Evolution Catalysts for Low-Temperature Electrochemical Devices
journal, August 2015
- Chen, Dengjie; Chen, Chi; Baiyee, Zarah Medina
- Chemical Reviews, Vol. 115, Issue 18
Impact of Strain-Induced Changes in Defect Chemistry on Catalytic Activity of Nd 2 NiO 4+δ Electrodes
journal, October 2018
- Li, Fei; Li, Yifeng; Chen, Huijun
- ACS Applied Materials & Interfaces, Vol. 10, Issue 43
Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts
journal, March 2016
- Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.
- Nature Communications, Vol. 7, Issue 1
A highly active and stable IrO x /SrIrO 3 catalyst for the oxygen evolution reaction
journal, September 2016
- Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori
- Science, Vol. 353, Issue 6303
Dislocations Accelerate Oxygen Ion Diffusion in La 0.8 Sr 0.2 MnO 3 Epitaxial Thin Films
journal, September 2017
- Navickas, Edvinas; Chen, Yan; Lu, Qiyang
- ACS Nano, Vol. 11, Issue 11
Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution
journal, January 2017
- Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong
- Nature Chemistry, Vol. 9, Issue 5
Strain-Enhanced Oxygen Dynamics and Redox Reversibility in Topotactic SrCoO 3-δ (0 < δ ≤ 0.5)
journal, January 2017
- Hu, Songbai; Wang, Yu; Cazorla, Claudio
- Chemistry of Materials, Vol. 29, Issue 2
Defect Engineering in Single-Layer MoS 2 Using Heavy Ion Irradiation
journal, November 2018
- He, Zuyun; Zhao, Ran; Chen, Xiaofei
- ACS Applied Materials & Interfaces, Vol. 10, Issue 49
Identification of Hydroperoxy Species as Reaction Intermediates in the Electrochemical Evolution of Oxygen on Gold
journal, May 2010
- Yeo, Boon Siang; Klaus, Shannon L.; Ross, Philip N.
- ChemPhysChem
High-Performance Li-O 2 Batteries with Trilayered Pd/MnO x /Pd Nanomembranes
journal, May 2015
- Lu, Xueyi; Deng, Junwen; Si, Wenping
- Advanced Science, Vol. 2, Issue 9
Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain
journal, May 2017
- Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul
- Nature Communications, Vol. 8, Issue 1
Chemomechanics of ionically conductive ceramics for electrical energy conversion and storage
journal, January 2014
- Swallow, J. G.; Woodford, W. H.; Chen, Y.
- Journal of Electroceramics, Vol. 32, Issue 1
Synthesis and Activities of Rutile IrO 2 and RuO 2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions
journal, January 2012
- Lee, Youngmin; Suntivich, Jin; May, Kevin J.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 3
Nonstoichiometry of the perovskite-type oxides La1−xSrxCoO3−δ
journal, May 1989
- Mizusaki, Junichiro; Mima, Yasuo; Yamauchi, Shigeru
- Journal of Solid State Chemistry, Vol. 80, Issue 1
Electronic structure, x-ray spectra, and magnetic properties of the LiCoO2−δ and NaxCoO2 nonstoichiometric oxides
journal, February 2002
- Galakhov, V. R.; Karelina, V. V.; Kellerman, D. G.
- Physics of the Solid State, Vol. 44, Issue 2
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Thermal and Chemical Expansion of Sr-Doped Lanthanum Cobalt Oxide (La 1 - x Sr x CoO 3 - δ )
journal, August 2005
- Chen, ; Adler, Stuart B.
- Chemistry of Materials, Vol. 17, Issue 17
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Tuning Electronic Structure of Single Layer MoS 2 through Defect and Interface Engineering
journal, February 2018
- Chen, Yan; Huang, Shengxi; Ji, Xiang
- ACS Nano, Vol. 12, Issue 3
In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction
journal, May 2014
- Sanchez Casalongue, Hernan G.; Ng, May Ling; Kaya, Sarp
- Angewandte Chemie International Edition, Vol. 53, Issue 28
Anisotropic Chemical Expansion of La 1– x Sr x CoO 3−δ
journal, March 2013
- Chen, Xinzhi; Grande, Tor
- Chemistry of Materials, Vol. 25, Issue 6
Interpretation of the x-ray photoemission spectra of cobalt oxides and cobalt oxide surfaces
journal, October 1976
- Chuang, T. J.; Brundle, C. R.; Rice, D. W.
- Surface Science, Vol. 59, Issue 2
Role of Strain and Conductivity in Oxygen Electrocatalysis on LaCoO 3 Thin Films
journal, January 2015
- Stoerzinger, Kelsey A.; Choi, Woo Seok; Jeen, Hyoungjeen
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 3
Modified Oxygen Defect Chemistry at Transition Metal Oxide Heterostructures Probed by Hard X-ray Photoelectron Spectroscopy and X-ray Diffraction
journal, April 2018
- Chen, Yan; Fong, Dillon D.; Herbert, F. William
- Chemistry of Materials, Vol. 30, Issue 10
Effect of oxygenation on electrocatalysis of La0.6Ca0.4CoO3−x in bifunctional air electrode
journal, May 2003
- Wu, Nae-Lih; Liu, Wei-Ren; Su, Sern-Jei
- Electrochimica Acta, Vol. 48, Issue 11
Electrochemical topotactic oxidation of nonstoichiometric perovskites at ambient temperature
journal, April 2002
- Nemudry, A.; Goldberg, E. L.; Aguirre, M.
- Solid State Sciences, Vol. 4, Issue 5
Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides
journal, January 2017
- Hong, Wesley T.; Stoerzinger, Kelsey A.; Lee, Yueh-Lin
- Energy & Environmental Science, Vol. 10, Issue 10
Strain coupling of oxygen non-stoichiometry in perovskite thin films
journal, December 2017
- Herklotz, Andreas; Lee, Dongkyu; Guo, Er-Jia
- Journal of Physics: Condensed Matter, Vol. 29, Issue 49
Electronic Activation of Cathode Superlattices at Elevated Temperatures - Source of Markedly Accelerated Oxygen Reduction Kinetics
journal, May 2013
- Chen, Yan; Cai, Zhuhua; Kuru, Yener
- Advanced Energy Materials, Vol. 3, Issue 9
Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO 3 Perovskites
journal, February 2016
- Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.
- Journal of the American Chemical Society, Vol. 138, Issue 8
Surface Electronic Structure Transitions at High Temperature on Perovskite Oxides: The Case of Strained La 0.8 Sr 0.2 CoO 3 Thin Films
journal, November 2011
- Cai, Zhuhua; Kuru, Yener; Han, Jeong Woo
- Journal of the American Chemical Society, Vol. 133, Issue 44
Nonstoichiometric Perovskite CaMnO 3−δ for Oxygen Electrocatalysis with High Activity
journal, August 2014
- Du, Jing; Zhang, Tianran; Cheng, Fangyi
- Inorganic Chemistry, Vol. 53, Issue 17
Segregated Chemistry and Structure on (001) and (100) Surfaces of (La 1– x Sr x ) 2 CoO 4 Override the Crystal Anisotropy in Oxygen Exchange Kinetics
journal, July 2015
- Chen, Yan; Téllez, Helena; Burriel, Mónica
- Chemistry of Materials, Vol. 27, Issue 15
Prediction of solid oxide fuel cell cathode activity with first-principles descriptors
journal, January 2011
- Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan
- Energy & Environmental Science, Vol. 4, Issue 10
Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability
journal, January 2017
- Li, Yifeng; Zhang, Wenqiang; Zheng, Yun
- Chemical Society Reviews, Vol. 46, Issue 20
Filling the oxygen vacancies in Co 3 O 4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting
journal, January 2017
- Xiao, Zhaohui; Wang, Yu; Huang, Yu-Cheng
- Energy & Environmental Science, Vol. 10, Issue 12
Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes
journal, June 2014
- Mefford, J. Tyler; Hardin, William G.; Dai, Sheng
- Nature Materials, Vol. 13, Issue 7
Improving the Electrocatalytic Activity and Durability of the La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ Cathode by Surface Modification
journal, October 2018
- Chen, Huijun; Guo, Zheng; Zhang, Lei A.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 46
Figures / Tables found in this record: