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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 (NNSFC); 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. 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, and Chen, Zhongwei. Wed . "Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries". United States. doi: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 = {2018},
month = {1}
}

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Works referenced in this record:

Encapsulation and Ostwald Ripening of Au and Au–Cl Complex Nanostructures in Silica Shells
journal, September 2006

  • Lou, X. W.; Yuan, C.; Rhoades, E.
  • Advanced Functional Materials, Vol. 16, Issue 13
  • DOI: 10.1002/adfm.200500909

Metal-Air Batteries with High Energy Density: Li-Air versus Zn-Air
journal, December 2010

  • Lee, Jang-Soo; Tai Kim, Sun; Cao, Ruiguo
  • Advanced Energy Materials, Vol. 1, Issue 1, p. 34-50
  • DOI: 10.1002/aenm.201000010

Electrochemical performance of annealed cobalt–benzotriazole/CNTs catalysts towards the oxygen reduction reaction
journal, January 2011

  • Morozan, Adina; Jégou, Pascale; Jousselme, Bruno
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 48
  • DOI: 10.1039/c1cp23199e

Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries
journal, July 2017


A metal–organic framework-derived bifunctional oxygen electrocatalyst
journal, January 2016


Metal-Organic-Framework-Based Materials as Platforms for Renewable Energy and Environmental Applications
journal, September 2017


Single crystalline pyrochlore nanoparticles with metallic conduction as efficient bi-functional oxygen electrocatalysts for Zn–air batteries
journal, January 2017

  • Park, Joohyuk; Risch, Marcel; Nam, Gyutae
  • Energy & Environmental Science, Vol. 10, Issue 1
  • DOI: 10.1039/C6EE03046G

Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal–air batteries
journal, January 2016

  • Lee, Dong Un; Xu, Pan; Cano, Zachary P.
  • Journal of Materials Chemistry A, Vol. 4, Issue 19
  • DOI: 10.1039/C6TA00173D

Hierarchical Zn/Ni-MOF-2 Nanosheet-Assembled Hollow Nanocubes for Multicomponent Catalytic Reactions
journal, July 2014


Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts
journal, December 2010

  • Cheng, Fangyi; Shen, Jian; Peng, Bo
  • Nature Chemistry, Vol. 3, Issue 1
  • DOI: 10.1038/nchem.931

Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis
journal, June 2015

  • Li, Chun; Han, Xiaopeng; Cheng, Fangyi
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8345

Rapid synthesis of ultrathin, defect-free ZIF-8 membranes via chemical vapour modification of a polymeric support
journal, January 2015

  • Shamsaei, Ezzatollah; Low, Ze-Xian; Lin, Xiaocheng
  • Chemical Communications, Vol. 51, Issue 57
  • DOI: 10.1039/C5CC03537F

Strongly Coupled Inorganic/Nanocarbon Hybrid Materials for Advanced Electrocatalysis
journal, January 2013

  • Liang, Yongye; Li, Yanguang; Wang, Hailiang
  • Journal of the American Chemical Society, Vol. 135, Issue 6
  • DOI: 10.1021/ja3089923

Co@Co 3 O 4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode
journal, February 2016

  • Aijaz, Arshad; Masa, Justus; Rösler, Christoph
  • Angewandte Chemie International Edition, Vol. 55, Issue 12
  • DOI: 10.1002/anie.201509382

Chemistry of Multitudinous Active Sites for Oxygen Reduction Reaction in Transition Metal–Nitrogen–Carbon Electrocatalysts
journal, November 2015

  • Artyushkova, Kateryna; Serov, Alexey; Rojas-Carbonell, Santiago
  • The Journal of Physical Chemistry C, Vol. 119, Issue 46
  • DOI: 10.1021/acs.jpcc.5b07653

Pomegranate-Inspired Design of Highly Active and Durable Bifunctional Electrocatalysts for Rechargeable Metal-Air Batteries
journal, March 2016

  • Li, Ge; Wang, Xiaolei; Fu, Jing
  • Angewandte Chemie International Edition, Vol. 55, Issue 16
  • DOI: 10.1002/anie.201600750

Interface Engineered W x C@WS 2 Nanostructure for Enhanced Hydrogen Evolution Catalysis
journal, January 2017

  • Wang, Fengmei; He, Peng; Li, Yuanchang
  • Advanced Functional Materials, Vol. 27, Issue 7
  • DOI: 10.1002/adfm.201605802

Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?
journal, April 2013

  • Hansen, Thomas W.; DeLaRiva, Andrew T.; Challa, Sivakumar R.
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar3002427

Advanced zinc-air batteries based on high-performance hybrid electrocatalysts
journal, May 2013

  • Li, Yanguang; Gong, Ming; Liang, Yongye
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2812

Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra
journal, July 2005


Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice?
journal, May 2017


Covalent Hybrid of Spinel Manganese–Cobalt Oxide and Graphene as Advanced Oxygen Reduction Electrocatalysts
journal, February 2012

  • Liang, Yongye; Wang, Hailiang; Zhou, Jigang
  • Journal of the American Chemical Society, Vol. 134, Issue 7
  • DOI: 10.1021/ja210924t

Nickel–cobalt oxides supported on Co/N decorated graphene as an excellent bifunctional oxygen catalyst
journal, January 2017

  • Hao, Yongchao; Xu, Yuqi; Liu, Junfeng
  • Journal of Materials Chemistry A, Vol. 5, Issue 11
  • DOI: 10.1039/C7TA00299H

Oxygen electrocatalysts in metal–air batteries: from aqueous to nonaqueous electrolytes
journal, January 2014

  • Wang, Zhong-Li; Xu, Dan; Xu, Ji-Jing
  • Chem. Soc. Rev., Vol. 43, Issue 22
  • DOI: 10.1039/C3CS60248F

Metal-Free Catalysts for Oxygen Reduction Reaction
journal, May 2015

  • Dai, Liming; Xue, Yuhua; Qu, Liangti
  • Chemical Reviews, Vol. 115, Issue 11
  • DOI: 10.1021/cr5003563

In Situ Coupling of Strung Co 4 N and Intertwined N–C Fibers toward Free-Standing Bifunctional Cathode for Robust, Efficient, and Flexible Zn–Air Batteries
journal, August 2016

  • Meng, Fanlu; Zhong, Haixia; Bao, Di
  • Journal of the American Chemical Society, Vol. 138, Issue 32
  • DOI: 10.1021/jacs.6b05046

Metal–organic-framework-engaged formation of Co nanoparticle-embedded carbon@Co 9 S 8 double-shelled nanocages for efficient oxygen reduction
journal, January 2016

  • Hu, Han; Han, Lei; Yu, Mengzhou
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE02903A

General Oriented Formation of Carbon Nanotubes from Metal–Organic Frameworks
journal, June 2017

  • Meng, Jiashen; Niu, Chaojiang; Xu, Linhan
  • Journal of the American Chemical Society, Vol. 139, Issue 24
  • DOI: 10.1021/jacs.7b01942

Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications
journal, April 2012

  • Wang, Haibo; Maiyalagan, Thandavarayan; Wang, Xin
  • ACS Catalysis, Vol. 2, Issue 5
  • DOI: 10.1021/cs200652y

3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries
journal, April 2016


Highly Active and Durable Core–Corona Structured Bifunctional Catalyst for Rechargeable Metal–Air Battery Application
journal, January 2012

  • Chen, Zhu; Yu, Aiping; Higgins, Drew
  • Nano Letters, Vol. 12, Issue 4
  • DOI: 10.1021/nl2044327

A general and scalable synthesis approach to porous graphene
journal, September 2014

  • Zhou, Ding; Cui, Yi; Xiao, Pei-Wen
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5716

Recent advances in zinc–air batteries
journal, January 2014


Highly Active and Durable Nanocrystal-Decorated Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries
journal, August 2015


Recent Advances in Metal Oxide-based Electrode Architecture Design for Electrochemical Energy Storage
journal, August 2012


Oxygen Reduction Characteristics of Heat-Treated Catalysts Based on Cobalt-Porphyrin Ion Complexes
journal, January 1998

  • Okada, Tatsuhiro
  • Journal of The Electrochemical Society, Vol. 145, Issue 3
  • DOI: 10.1149/1.1838350

Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction
journal, August 2011

  • Liang, Yongye; Li, Yanguang; Wang, Hailiang
  • Nature Materials, Vol. 10, Issue 10, p. 780-786
  • DOI: 10.1038/nmat3087

Recent Progress in Non-Precious Catalysts for Metal-Air Batteries
journal, June 2012

  • Cao, Ruiguo; Lee, Jang-Soo; Liu, Meilin
  • Advanced Energy Materials, Vol. 2, Issue 7
  • DOI: 10.1002/aenm.201200013

Ionic liquid modified graphene nanosheets anchoring manganese oxide nanoparticles as efficient electrocatalysts for Zn–air batteries
journal, January 2011

  • Lee, Jang-Soo; Lee, Taemin; Song, Hyun-Kon
  • Energy & Environmental Science, Vol. 4, Issue 10
  • DOI: 10.1039/c1ee01942b

Monoclinic ZIF-8 Nanosheet-Derived 2D Carbon Nanosheets as Sulfur Immobilizer for High-Performance Lithium Sulfur Batteries
journal, July 2017

  • Jiang, Yi; Liu, Haiqiang; Tan, Xinghua
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 30
  • DOI: 10.1021/acsami.7b04432

A dual-metal–organic-framework derived electrocatalyst for oxygen reduction
journal, January 2016

  • Guan, Bu Yuan; Yu, Le; (David) Lou, Xiong Wen
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE02171A

Flexible Rechargeable Zinc-Air Batteries through Morphological Emulation of Human Hair Array
journal, May 2016

  • Fu, Jing; Hassan, Fathy Mohamed; Li, Jingde
  • Advanced Materials, Vol. 28, Issue 30
  • DOI: 10.1002/adma.201600762

Electrically Rechargeable Zinc-Air Batteries: Progress, Challenges, and Perspectives
journal, November 2016

  • Fu, Jing; Cano, Zachary Paul; Park, Moon Gyu
  • Advanced Materials, Vol. 29, Issue 7
  • DOI: 10.1002/adma.201604685

Thermal Conversion of Core–Shell Metal–Organic Frameworks: A New Method for Selectively Functionalized Nanoporous Hybrid Carbon
journal, January 2015

  • Tang, Jing; Salunkhe, Rahul R.; Liu, Jian
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja511539a

Cobalt Oxide and Cobalt-Graphitic Carbon Core-Shell Based Catalysts with Remarkably High Oxygen Reduction Reaction Activity
journal, April 2016


Hierarchical Tubular Structures Composed of Co 3 O 4 Hollow Nanoparticles and Carbon Nanotubes for Lithium Storage
journal, April 2016

  • Chen, Yu Ming; Yu, Le; Lou, Xiong Wen David
  • Angewandte Chemie International Edition, Vol. 55, Issue 20
  • DOI: 10.1002/anie.201600133

Mn x O y /NC and Co x O y /NC Nanoparticles Embedded in a Nitrogen-Doped Carbon Matrix for High-Performance Bifunctional Oxygen Electrodes
journal, June 2014

  • Masa, Justus; Xia, Wei; Sinev, Ilya
  • Angewandte Chemie International Edition, Vol. 53, Issue 32
  • DOI: 10.1002/anie.201402710

Metal–organic framework derived carbon-confined Ni 2 P nanocrystals supported on graphene for an efficient oxygen evolution reaction
journal, January 2017

  • Wang, Manman; Lin, Mengting; Li, Jiantao
  • Chemical Communications, Vol. 53, Issue 59
  • DOI: 10.1039/C7CC03558F

Optimizing nanoparticle perovskite for bifunctional oxygen electrocatalysis
journal, January 2016

  • Jung, Jae-Il; Risch, Marcel; Park, Seungkyu
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE03124A

Strongly Coupled NiCo 2 O 4 -rGO Hybrid Nanosheets as a Methanol-Tolerant Electrocatalyst for the Oxygen Reduction Reaction
journal, December 2013


Active Site Structures in Nitrogen-Doped Carbon-Supported Cobalt Catalysts for the Oxygen Reduction Reaction
journal, November 2016

  • Qian, Yingdan; Liu, Zheng; Zhang, Hui
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 48
  • DOI: 10.1021/acsami.6b11927

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016

  • Yin, Peiqun; Yao, Tao; Wu, Yuen
  • Angewandte Chemie International Edition, Vol. 55, Issue 36
  • DOI: 10.1002/anie.201604802

Nitrogen-Doped Co 3 O 4 Mesoporous Nanowire Arrays as an Additive-Free Air-Cathode for Flexible Solid-State Zinc-Air Batteries
journal, February 2017


Holey graphene frameworks for highly efficient capacitive energy storage
journal, August 2014

  • Xu, Yuxi; Lin, Zhaoyang; Zhong, Xing
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5554