DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long‐Life Rechargeable Zinc–Air Batteries

Abstract

Abstract Metal phosphides and heteroatom‐doped carbons have been regarded as promising candidates as bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, both have suffered from stability issues during repeated ORR and OER operations in zinc–air batteries (ZABs). Herein, this study reports a versatile cobalt‐based hybrid catalyst with a 1D structure by integrating the metal‐organic framework‐derived conversion approach and an in situ crosslinking method. Among them, the 1D hybrid catalyst composed of ultrasmall cobalt phosphide nanoparticles supported by nitrogen‐, sulfur‐, phosphorus‐doped carbon matrix shows remarkable bifunctional activity close to that of the benchmark precious‐metal catalysts along with an excellent durability in the full potential range covering both the OER and ORR. The overall overpotential of the rechargeable ZABs can be greatly reduced with this bifunctional hybrid catalyst as an air‐electrode, and the cycling stability outperforms the commercial Pt/C catalyst. It is revealed that the cobalt phosphide nanoparticles are in situ converted to cobalt oxide under the accelerated conditions during OER (and/or ORR) of the ZABs and reduces the anodic current applied to the carbon. This contributes to the stability of the carbon material and in maintaining the high initial catalytic properties of the hybrid catalyst.

Authors:
 [1];  [1]
  1. Materials Science and Engineering Program and Texas Materials Institute The University of Texas at Austin Austin TX 78712 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1378112
Grant/Contract Number:  
DE‐SC0005397
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Small
Additional Journal Information:
Journal Name: Small Journal Volume: 13 Journal Issue: 40; Journal ID: ISSN 1613-6810
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Ahn, Sung Hoon, and Manthiram, Arumugam. Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long‐Life Rechargeable Zinc–Air Batteries. Germany: N. p., 2017. Web. doi:10.1002/smll.201702068.
Ahn, Sung Hoon, & Manthiram, Arumugam. Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long‐Life Rechargeable Zinc–Air Batteries. Germany. https://doi.org/10.1002/smll.201702068
Ahn, Sung Hoon, and Manthiram, Arumugam. Fri . "Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long‐Life Rechargeable Zinc–Air Batteries". Germany. https://doi.org/10.1002/smll.201702068.
@article{osti_1378112,
title = {Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient, Long‐Life Rechargeable Zinc–Air Batteries},
author = {Ahn, Sung Hoon and Manthiram, Arumugam},
abstractNote = {Abstract Metal phosphides and heteroatom‐doped carbons have been regarded as promising candidates as bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, both have suffered from stability issues during repeated ORR and OER operations in zinc–air batteries (ZABs). Herein, this study reports a versatile cobalt‐based hybrid catalyst with a 1D structure by integrating the metal‐organic framework‐derived conversion approach and an in situ crosslinking method. Among them, the 1D hybrid catalyst composed of ultrasmall cobalt phosphide nanoparticles supported by nitrogen‐, sulfur‐, phosphorus‐doped carbon matrix shows remarkable bifunctional activity close to that of the benchmark precious‐metal catalysts along with an excellent durability in the full potential range covering both the OER and ORR. The overall overpotential of the rechargeable ZABs can be greatly reduced with this bifunctional hybrid catalyst as an air‐electrode, and the cycling stability outperforms the commercial Pt/C catalyst. It is revealed that the cobalt phosphide nanoparticles are in situ converted to cobalt oxide under the accelerated conditions during OER (and/or ORR) of the ZABs and reduces the anodic current applied to the carbon. This contributes to the stability of the carbon material and in maintaining the high initial catalytic properties of the hybrid catalyst.},
doi = {10.1002/smll.201702068},
journal = {Small},
number = 40,
volume = 13,
place = {Germany},
year = {Fri Sep 01 00:00:00 EDT 2017},
month = {Fri Sep 01 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/smll.201702068

Citation Metrics:
Cited by: 80 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Nitrogen, phosphorus and sulfur co-doped ultrathin carbon nanosheets as a metal-free catalyst for selective oxidation of aromatic alkanes and the oxygen reduction reaction
journal, January 2016

  • Zhu, Ya-Nan; Cao, Chang-Yan; Jiang, Wen-Jie
  • Journal of Materials Chemistry A, Vol. 4, Issue 47
  • DOI: 10.1039/C6TA08335H

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

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


Ternary NiCo 2 P x Nanowires as pH-Universal Electrocatalysts for Highly Efficient Hydrogen Evolution Reaction
journal, December 2016


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
  • DOI: 10.1021/ja104587v

High-performance bi-functional electrocatalysts of 3D crumpled graphene–cobalt oxide nanohybrids for oxygen reduction and evolution reactions
journal, January 2014

  • Mao, Shun; Wen, Zhenhai; Huang, Taizhong
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE42696C

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

Recent advances in zinc–air batteries
journal, January 2014


Nitrogen-doped cobalt phosphate@nanocarbon hybrids for efficient electrocatalytic oxygen reduction
journal, January 2016

  • Zhou, Tianhua; Du, Yonghua; Yin, Shengming
  • Energy & Environmental Science, Vol. 9, Issue 8
  • DOI: 10.1039/C6EE01297C

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

A general approach to cobalt-based homobimetallic phosphide ultrathin nanosheets for highly efficient oxygen evolution in alkaline media
journal, January 2017

  • Xiao, Xiaofen; He, Chun-Ting; Zhao, Shenlong
  • Energy & Environmental Science, Vol. 10, Issue 4
  • DOI: 10.1039/C6EE03145E

Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media
journal, September 2015

  • Gupta, Shiva; Kellogg, William; Xu, Hui
  • Chemistry - An Asian Journal, Vol. 11, Issue 1
  • DOI: 10.1002/asia.201500640

Nitrogen, Phosphorus, and Fluorine Tri-doped Graphene as a Multifunctional Catalyst for Self-Powered Electrochemical Water Splitting
journal, October 2016

  • Zhang, Jintao; Dai, Liming
  • Angewandte Chemie International Edition, Vol. 55, Issue 42
  • DOI: 10.1002/anie.201607405

A Bifunctional Perovskite Catalyst for Oxygen Reduction and Evolution
journal, March 2014

  • Jung, Jae-Il; Jeong, Hu Young; Lee, Jang-Soo
  • Angewandte Chemie International Edition, Vol. 53, Issue 18
  • DOI: 10.1002/anie.201311223

Scalable 3-D Carbon Nitride Sponge as an Efficient Metal-Free Bifunctional Oxygen Electrocatalyst for Rechargeable Zn–Air Batteries
journal, December 2016


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

Nitrogen, Phosphorus, and Sulfur Co-Doped Hollow Carbon Shell as Superior Metal-Free Catalyst for Selective Oxidation of Aromatic Alkanes
journal, February 2016

  • Yang, Shuliang; Peng, Li; Huang, Peipei
  • Angewandte Chemie International Edition, Vol. 55, Issue 12
  • DOI: 10.1002/anie.201600455

Designing an improved transition metal phosphide catalyst for hydrogen evolution using experimental and theoretical trends
journal, January 2015

  • Kibsgaard, Jakob; Tsai, Charlie; Chan, Karen
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/C5EE02179K

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

Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction
journal, January 2016

  • Yu, Xin-Yao; Feng, Yi; Guan, Buyuan
  • Energy & Environmental Science, Vol. 9, Issue 4
  • DOI: 10.1039/C6EE00100A

Texturing in situ: N,S-enriched hierarchically porous carbon as a highly active reversible oxygen electrocatalyst
journal, January 2017

  • Pei, Zengxia; Li, Hongfei; Huang, Yan
  • Energy & Environmental Science, Vol. 10, Issue 3
  • DOI: 10.1039/C6EE03265F

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

A nickel iron diselenide-derived efficient oxygen-evolution catalyst
journal, August 2016

  • Xu, Xiang; Song, Fang; Hu, Xile
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12324

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

A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions
journal, April 2015

  • Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.48

From Bimetallic Metal-Organic Framework to Porous Carbon: High Surface Area and Multicomponent Active Dopants for Excellent Electrocatalysis
journal, July 2015

  • Chen, Yu-Zhen; Wang, Chengming; Wu, Zhen-Yu
  • Advanced Materials, Vol. 27, Issue 34
  • DOI: 10.1002/adma.201502315

An efficient bifunctional two-component catalyst for oxygen reduction and oxygen evolution in reversible fuel cells, electrolyzers and rechargeable air electrodes
journal, January 2016

  • Dresp, Sören; Luo, Fang; Schmack, Roman
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C6EE01046F

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

Versatile nanoporous bimetallic phosphides towards electrochemical water splitting
journal, January 2016

  • Tan, Yongwen; Wang, Hao; Liu, Pan
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/C6EE01109H

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


Disclosing the High Activity of Ceramic Metallics in the Oxygen Evolution Reaction: Nickel Materials as a Case Study
journal, September 2016

  • Ledendecker, Marc; Yang, Xiaofei; Antonietti, Markus
  • ChemSusChem, Vol. 9, Issue 20
  • DOI: 10.1002/cssc.201601128

Novel Hydrogel-Derived Bifunctional Oxygen Electrocatalyst for Rechargeable Air Cathodes
journal, September 2016