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Title: Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries

Abstract

A critical bottleneck limiting the performance of rechargeable zinc-air batteries lies in the inefficient bifunctional electrocatalysts for the oxygen reduction and evolution reactions at the air electrodes. Hybridizing transition-metal oxides with functional graphene materials has shown great advantages due to their catalytic synergism. However, both the mediocre catalytic activity of metal oxides and the restricted 2D mass/charge transfer of graphene render these hybrid catalysts inefficient. Here, an effective strategy combining anion substitution, defect engineering, and the dopant effect to address the above two critical issues is shown. This strategy is demonstrated on a hybrid catalyst consisting of sulfur-deficient cobalt oxysulfide single crystals and nitrogen-doped graphene nanomeshes (CoO 0.87S 0.13/GN). The defect chemistries of both oxygen-vacancy-rich, nonstoichiometric cobalt oxysulfides and edge-nitrogen-rich graphene nanomeshes lead to a remarkable improvement in electrocatalytic performance, where CoO 0.87S 0.13/GN exhibits strongly comparable catalytic activity to and much better stability than the best-known benchmark noble-metal catalysts. In application to quasi-solid-state zinc-air batteries, CoO 0.87S 0.13/GN as a freestanding catalyst assembly benefits from both structural integrity and enhanced charge transfer to achieve efficient and very stable cycling operation over 300 cycles with a low discharge-charge voltage gap of 0.77 V at 20 mA cm(-2) under ambient conditions.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1]; ORCiD logo [1]
  1. Department of Chemical Engineering, Waterloo Institute for Nanotechnology, Waterloo Institute for Sustainable Energy, University of Waterloo, Waterloo Ontario N2L 3G1 Canada
  2. Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of Education), Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300072 China
  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology
OSTI Identifier:
1462489
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 35; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
bifunctional electrocatalysts; graphene nanomeshes; oxygen evolution reaction; oxygen reduction reaction; zinc-air batteries

Citation Formats

Fu, Jing, Hassan, Fathy M., Zhong, Cheng, Lu, Jun, Liu, Han, Yu, Aiping, and Chen, Zhongwei. Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries. United States: N. p., 2017. Web. doi:10.1002/adma.201702526.
Fu, Jing, Hassan, Fathy M., Zhong, Cheng, Lu, Jun, Liu, Han, Yu, Aiping, & Chen, Zhongwei. Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries. United States. doi:10.1002/adma.201702526.
Fu, Jing, Hassan, Fathy M., Zhong, Cheng, Lu, Jun, Liu, Han, Yu, Aiping, and Chen, Zhongwei. Mon . "Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries". United States. doi:10.1002/adma.201702526.
@article{osti_1462489,
title = {Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries},
author = {Fu, Jing and Hassan, Fathy M. and Zhong, Cheng and Lu, Jun and Liu, Han and Yu, Aiping and Chen, Zhongwei},
abstractNote = {A critical bottleneck limiting the performance of rechargeable zinc-air batteries lies in the inefficient bifunctional electrocatalysts for the oxygen reduction and evolution reactions at the air electrodes. Hybridizing transition-metal oxides with functional graphene materials has shown great advantages due to their catalytic synergism. However, both the mediocre catalytic activity of metal oxides and the restricted 2D mass/charge transfer of graphene render these hybrid catalysts inefficient. Here, an effective strategy combining anion substitution, defect engineering, and the dopant effect to address the above two critical issues is shown. This strategy is demonstrated on a hybrid catalyst consisting of sulfur-deficient cobalt oxysulfide single crystals and nitrogen-doped graphene nanomeshes (CoO0.87S0.13/GN). The defect chemistries of both oxygen-vacancy-rich, nonstoichiometric cobalt oxysulfides and edge-nitrogen-rich graphene nanomeshes lead to a remarkable improvement in electrocatalytic performance, where CoO0.87S0.13/GN exhibits strongly comparable catalytic activity to and much better stability than the best-known benchmark noble-metal catalysts. In application to quasi-solid-state zinc-air batteries, CoO0.87S0.13/GN as a freestanding catalyst assembly benefits from both structural integrity and enhanced charge transfer to achieve efficient and very stable cycling operation over 300 cycles with a low discharge-charge voltage gap of 0.77 V at 20 mA cm(-2) under ambient conditions.},
doi = {10.1002/adma.201702526},
journal = {Advanced Materials},
issn = {0935-9648},
number = 35,
volume = 29,
place = {United States},
year = {2017},
month = {7}
}

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