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Title: Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

Abstract

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co3O4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co3O4@PGS) is synthesized via ionic exchange and redox between Co2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells provides an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co3O4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm-2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm-2 is achieved by Zn–air batteries with Co/Co3O4@PGS within the rechargeable air electrode.

Authors:
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [3];  [4];  [3];  [4];  [5]; ORCiD logo [2]
  1. National Center for Nanoscience and Technology, Beijing (China). CAS Key Lab. for Nanosystem and Hierarchical Fabrication. CAS Center for Excellence in Nanoscience; Univ. of Chinese Academy of Sciences, Beijing (China); Univ. of Waterloo, ON (Canada). Dept. of Chemical Engineering. Waterloo Inst. for Nanotechnology. Waterloo Inst. for Sustainable Energy
  2. Univ. of Waterloo, ON (Canada). Dept. of Chemical Engineering. Waterloo Inst. for Nanotechnology. Waterloo Inst. for Sustainable Energy
  3. Henan Normal Univ., Xinxiang (China). School of Chemistry and Chemical Engineering
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  5. National Center for Nanoscience and Technology, Beijing (China). CAS Key Lab. for Nanosystem and Hierarchical Fabrication. CAS Center for Excellence in Nanoscience; Univ. of Chinese Academy of Sciences, Beijing (China)
Publication Date:
Research Org.:
Univ. of Waterloo, ON (Canada); National Center for Nanoscience and Technology, Beijing (China); Henan Normal Univ., Xinxiang (China); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE; Natural Sciences and Engineering Research Council of Canada (NSERC); National Natural Science Foundation of China (NSFC); 111 Project (China); Chinese Academy of Sciences (CAS)
OSTI Identifier:
1425093
Report Number(s):
BNL-203305-2018-JAAM
Journal ID: ISSN 1614-6832; TRN: US1802042
Grant/Contract Number:  
SC0012704; 21573083; D17007; XDA09040101
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 15; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; interpenetrating phases; metal-organic frameworks; bifunctional electrocatalysts; Zn-air batteries

Citation Formats

Jiang, Yi, Deng, Ya-Ping, Fu, Jing, Lee, Dong Un, Liang, Ruilin, Cano, Zachary Paul, Liu, Yangshuai, Bai, Zhengyu, Hwang, Sooyeon, Yang, Lin, Su, Dong, Chu, Weiguo, and Chen, Zhongwei. Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries. United States: N. p., 2018. Web. doi:10.1002/aenm.201702900.
Jiang, Yi, Deng, Ya-Ping, Fu, Jing, Lee, Dong Un, Liang, Ruilin, Cano, Zachary Paul, Liu, Yangshuai, Bai, Zhengyu, Hwang, Sooyeon, Yang, Lin, Su, Dong, Chu, Weiguo, & Chen, Zhongwei. Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries. United States. https://doi.org/10.1002/aenm.201702900
Jiang, Yi, Deng, Ya-Ping, Fu, Jing, Lee, Dong Un, Liang, Ruilin, Cano, Zachary Paul, Liu, Yangshuai, Bai, Zhengyu, Hwang, Sooyeon, Yang, Lin, Su, Dong, Chu, Weiguo, and Chen, Zhongwei. Wed . "Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries". United States. https://doi.org/10.1002/aenm.201702900. https://www.osti.gov/servlets/purl/1425093.
@article{osti_1425093,
title = {Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries},
author = {Jiang, Yi and Deng, Ya-Ping and Fu, Jing and Lee, Dong Un and Liang, Ruilin and Cano, Zachary Paul and Liu, Yangshuai and Bai, Zhengyu and Hwang, Sooyeon and Yang, Lin and Su, Dong and Chu, Weiguo and Chen, Zhongwei},
abstractNote = {Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co3O4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co3O4@PGS) is synthesized via ionic exchange and redox between Co2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells provides an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co3O4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm-2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm-2 is achieved by Zn–air batteries with Co/Co3O4@PGS within the rechargeable air electrode.},
doi = {10.1002/aenm.201702900},
journal = {Advanced Energy Materials},
number = 15,
volume = 8,
place = {United States},
year = {Wed Jan 31 00:00:00 EST 2018},
month = {Wed Jan 31 00:00:00 EST 2018}
}

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Hierarchical tri-functional electrocatalysts derived from bimetallic–imidazolate framework for overall water splitting and rechargeable zinc–air batteries
journal, January 2019

  • Ahn, Sung Hoon; Manthiram, Arumugam
  • Journal of Materials Chemistry A, Vol. 7, Issue 14
  • DOI: 10.1039/c9ta01340g

Cu and Co nanoparticle-Co-decorated N-doped graphene nanosheets: a high efficiency bifunctional electrocatalyst for rechargeable Zn–air batteries
journal, January 2019

  • Liu, Peitao; Hu, Yating; Liu, Xiaokai
  • Journal of Materials Chemistry A, Vol. 7, Issue 20
  • DOI: 10.1039/c9ta02894c

Toward a new generation of low cost, efficient, and durable metal–air flow batteries
journal, January 2019

  • Yu, Wentao; Shang, Wenxu; Tan, Peng
  • Journal of Materials Chemistry A, Vol. 7, Issue 47
  • DOI: 10.1039/c9ta10658h

Metal-organic framework-derived structures for next-generation rechargeable batteries
journal, December 2018


Tuning Interfacial Structures for Better Catalysis of Water Electrolysis
journal, May 2019

  • Xiang, Rui; Peng, Lishan; Wei, Zidong
  • Chemistry – A European Journal, Vol. 25, Issue 42
  • DOI: 10.1002/chem.201901168