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Title: 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:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [1];  [1];  [1];  [1];  [3];  [4];  [1]; ORCiD logo [1]; ORCiD logo [2]
  1. 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
  2. Materials Science and EngineeringGeorgia Institute of Technology Atlanta GA USA
  3. Institute of Nuclear and New Energy TechnologyTsinghua University Beijing China
  4. 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/advs.201801898

Citation Metrics:
Cited by: 125 works
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Figures / Tables:

Figure 1 Figure 1: a) Illustration of sample preparation process for LSC thin film electrode. A gold pattern was embedded into the thin film to serve as the current collector for electrochemical measurement; b) illustration of the OER measurement sets up with the film as the WE. c,d) AFM images of LSCmore » model thin films grown on LAO (c) and STO (b) substrates. The surface roughness is less than 1 nm.« less

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