Engineering efficient bifunctional electrocatalysts for rechargeable zinc–air batteries by confining Fe–Co–Ni nanoalloys in nitrogen-doped carbon nanotube@nanosheet frameworks

Tang, Xiannong; Cao, Rui; Li, Longbin; Huang, Bingyu; Zhai, Weijuan; Yuan, Kai; Chen, Yiwang

doi:10.1039/d0ta09580j

Engineering efficient bifunctional electrocatalysts for rechargeable zinc–air batteries by confining Fe–Co–Ni nanoalloys in nitrogen-doped carbon nanotube@nanosheet frameworks

Journal Article · Tue Nov 17 23:00:00 EST 2020 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d0ta09580j· OSTI ID:1767949

^[1]; Cao, Rui ^[2]; Li, Longbin ^[1]; Huang, Bingyu ^[1]; Zhai, Weijuan ^[1]; ^[1]; ^[3]

Nanchang Univ. (China)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Nanchang Univ. (China); Jiangxi Normal Univ., Nanchang (China)

Developing precious-metal-free bifunctional oxygen reduction and evolution reaction (ORR/OER) electrocatalysts is of great significance for several key energy conversion and storage systems, yet remains a formidable challenge. In this work, we systematically designed Fe–Co–Ni trimetallic nanoalloys encapsulated in nitrogen-doped carbon nanotube@nanosheet frameworks (FeCoNi-NC) for application as effective bifunctional ORR/OER electrocatalysts. The rational structural design of FeCoNi-NC provides hierarchical porosity coupled with greatly increased effective electrochemical specific area for exposing abundant active sites and enhanced mass-transfer capability toward the ORR/OER. Experimental observations and theoretical calculations confirmed that Fe–Co–Ni nanoalloys interacting with pyridinic nitrogen-rich carbon synergistically optimized the adsorption/desorption free energies of oxygen intermediates, thus significantly enhancing the intrinsic ORR/OER activity. Consequently, FeCoNi-NC exhibits remarkable bifunctionality for the ORR (half-wave potential of 0.89 V) and OER (1.54 V at 10 mA cm^–2) with ΔE = 0.65 V, and even outperforms Pt/C–RuO₂ benchmarks. Moreover, the corresponding zinc–air battery shows large power density (315.2 mW cm^–2), high capacity (803.78 mA h g^–1 at 100 mA cm^–2) and excellent cycling durability (over 100 hours at 50 mA cm^–2), further testifying its practical applications. This work demonstrates an effective pathway to highly active non-precious-metal bifunctional catalysts toward sustainable energy technologies.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NNSFC); Natural Science Foundation of Jiangxi Province; China Postdoctoral Science Foundation; National Postdoctoral Program for Innovative Talents

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1767949

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 48 Vol. 8; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

A Review of Precious-Metal-Free Bifunctional Oxygen Electrocatalysts: Rational Design and Applications in Zn−Air Batteries Wang, Hao-Fan; Tang, Cheng; Zhang, Qiang Advanced Functional Materials, Vol. 28, Issue 46 https://doi.org/10.1002/adfm.201803329	journal	August 2018
Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution Liu, Shaohong; Wang, Zhiyu; Zhou, Si Advanced Materials, Vol. 29, Issue 31 https://doi.org/10.1002/adma.201700874	journal	June 2017
Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis Wan, Gang; Yang, Ce; Zhao, Wanpeng Advanced Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adma.201703436	journal	November 2017
Atomic Modulation and Structure Design of Carbons for Bifunctional Electrocatalysis in Metal–Air Batteries Huang, Yiyin; Wang, Yueqing; Tang, Cheng Advanced Materials, Vol. 31, Issue 13 https://doi.org/10.1002/adma.201803800	journal	September 2018
Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO ₂ RR) Kim, Cheonghee; Dionigi, Fabio; Beermann, Vera Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201805617	journal	December 2018
Pt‐Based Nanocrystal for Electrocatalytic Oxygen Reduction Zhao, Zipeng; Chen, Changli; Liu, Zeyan Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201808115	journal	December 2018
Hierarchically Porous Carbon Plates Derived from Wood as Bifunctional ORR/OER Electrodes Peng, Xinwen; Zhang, Lei; Chen, Zhongxin Advanced Materials, Vol. 31, Issue 16 https://doi.org/10.1002/adma.201900341	journal	February 2019
A Hydrangea‐Like Superstructure of Open Carbon Cages with Hierarchical Porosity and Highly Active Metal Sites Hou, Chun‐Chao; Zou, Lianli; Xu, Qiang Advanced Materials, Vol. 31, Issue 46 https://doi.org/10.1002/adma.201904689	journal	September 2019
Engineering Catalytic Active Sites on Cobalt Oxide Surface for Enhanced Oxygen Electrocatalysis Han, Xiaopeng; He, Guowei; He, Yu Advanced Energy Materials, Vol. 8, Issue 10 https://doi.org/10.1002/aenm.201702222	journal	December 2017
Graphitic‐Shell Encapsulation of Metal Electrocatalysts for Oxygen Evolution, Oxygen Reduction, and Hydrogen Evolution in Alkaline Solution Khani, Hadi; Grundish, Nicholas S.; Wipf, David O. Advanced Energy Materials, Vol. 10, Issue 1 https://doi.org/10.1002/aenm.201903215	journal	November 2019
Atomically Dispersed Iron-Nitrogen Species as Electrocatalysts for Bifunctional Oxygen Evolution and Reduction Reactions Chen, Pengzuo; Zhou, Tianpei; Xing, Lili Angewandte Chemie International Edition, Vol. 56, Issue 2 https://doi.org/10.1002/anie.201610119	journal	December 2016
NiFe Alloy Nanoparticles with hcp Crystal Structure Stimulate Superior Oxygen Evolution Reaction Electrocatalytic Activity Wang, Changhong; Yang, Hongchao; Zhang, Yejun Angewandte Chemie International Edition, Vol. 58, Issue 18 https://doi.org/10.1002/anie.201902446	journal	April 2019
FeCoNi Alloy as Noble Metal-Free Electrocatalyst for Oxygen Evolution Reaction (OER) Saha, Soumen; Ganguli, Ashok K. ChemistrySelect, Vol. 2, Issue 4 https://doi.org/10.1002/slct.201601243	journal	February 2017
Simultaneously Integrating Single Atomic Cobalt Sites and Co ₉ S ₈ Nanoparticles into Hollow Carbon Nanotubes as Trifunctional Electrocatalysts for Zn–Air Batteries to Drive Water Splitting Li, Yizhe; Cao, Rui; Li, Longbin Small, Vol. 16, Issue 10 https://doi.org/10.1002/smll.201906735	journal	March 2020
Porphyrin-like Fe-N4 sites with sulfur adjustment on hierarchical porous carbon for different rate-determining steps in oxygen reduction reaction Wu, Konglin; Chen, Xin; Liu, Shoujie Nano Research, Vol. 11, Issue 12 https://doi.org/10.1007/s12274-018-2149-y	journal	August 2018
Defect-enriched, nitrogen-doped graphitic carbon microspheres within 3D interconnected super-macropores as efficient oxygen electrocatalysts for breathing Zn-Air battery Cheng, Dan; Wang, Zhe; Chen, Chang Carbon, Vol. 145 https://doi.org/10.1016/j.carbon.2019.01.010	journal	April 2019
Review of Metal Catalysts for Oxygen Reduction Reaction: From Nanoscale Engineering to Atomic Design Wang, Xiaoqian; Li, Zhijun; Qu, Yunteng Chem, Vol. 5, Issue 6 https://doi.org/10.1016/j.chempr.2019.03.002	journal	June 2019
Biomass-derived FeNi alloy and nitrogen-codoped porous carbons as highly efficient oxygen reduction and evolution bifunctional electrocatalysts for rechargeable Zn-air battery Yang, Liu; Zeng, Xiaofei; Wang, Di Energy Storage Materials, Vol. 12 https://doi.org/10.1016/j.ensm.2018.02.011	journal	May 2018
Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications Chen, Yuanjun; Ji, Shufang; Chen, Chen Joule, Vol. 2, Issue 7 https://doi.org/10.1016/j.joule.2018.06.019	journal	July 2018
Searching for Highly Active Catalysts for Hydrogen Evolution Reaction Based on O-Terminated MXenes through a Simple Descriptor Ling, Chongyi; Shi, Li; Ouyang, Yixin Chemistry of Materials, Vol. 28, Issue 24 https://doi.org/10.1021/acs.chemmater.6b03972	journal	December 2016
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
Spinels: Controlled Preparation, Oxygen Reduction/Evolution Reaction Application, and Beyond Zhao, Qing; Yan, Zhenhua; Chen, Chengcheng Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00051	journal	July 2017
Cobalt Single Atoms Immobilized N-Doped Carbon Nanotubes for Enhanced Bifunctional Catalysis toward Oxygen Reduction and Oxygen Evolution Reactions Dilpazir, Sobia; He, Hongyan; Li, Zehui ACS Applied Energy Materials, Vol. 1, Issue 7 https://doi.org/10.1021/acsaem.8b00490	journal	June 2018
Template-Grown MoS ₂ Nanowires Catalyze the Hydrogen Evolution Reaction: Ultralow Kinetic Barriers with High Active Site Density Ling, Chongyi; Ouyang, Yixin; Shi, Li ACS Catalysis, Vol. 7, Issue 8 https://doi.org/10.1021/acscatal.7b01595	journal	July 2017
Microporous Framework Induced Synthesis of Single-Atom Dispersed Fe-N-C Acidic ORR Catalyst and Its in Situ Reduced Fe-N ₄ Active Site Identification Revealed by X-ray Absorption Spectroscopy Xiao, Meiling; Zhu, Jianbing; Ma, Liang ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.8b00138	journal	February 2018
Synergetic Contribution of Boron and Fe–N _x Species in Porous Carbons toward Efficient Electrocatalysts for Oxygen Reduction Reaction Yuan, Kai; Sfaelou, Stavroula; Qiu, Ming ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01188	journal	November 2017
Tuning of Trifunctional NiCu Bimetallic Nanoparticles Confined in a Porous Carbon Network with Surface Composition and Local Structural Distortions for the Electrocatalytic Oxygen Reduction, Oxygen and Hydrogen Evolution Reactions Ahsan, Md Ariful; Puente Santiago, Alain R.; Hong, Yu Journal of the American Chemical Society, Vol. 142, Issue 34 https://doi.org/10.1021/jacs.0c06960	journal	July 2020
Constructing NiCo/Fe ₃ O ₄ Heteroparticles within MOF-74 for Efficient Oxygen Evolution Reactions Wang, Xiaolu; Xiao, Hai; Li, Ang Journal of the American Chemical Society, Vol. 140, Issue 45 https://doi.org/10.1021/jacs.8b08744	journal	October 2018
Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination Yuan, Kai; Lützenkirchen-Hecht, Dirk; Li, Longbin Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b11852	journal	January 2020
Carbon-based metal-free catalysts Liu, Xien; Dai, Liming Nature Reviews Materials, Vol. 1, Issue 11 https://doi.org/10.1038/natrevmats.2016.64	journal	September 2016
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Alloys of platinum and early transition metals as oxygen reduction electrocatalysts Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S. Nature Chemistry, Vol. 1, Issue 7, p. 552-556 https://doi.org/10.1038/nchem.367	journal	September 2009
Molecular metal–Nx centres in porous carbon for electrocatalytic hydrogen evolution Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8992	journal	August 2015
A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.48	journal	April 2015
Seed-mediated atomic-scale reconstruction of silver manganate nanoplates for oxygen reduction towards high-energy aluminum-air flow batteries Ryu, Jaechan; Jang, Haeseong; Park, Joohyuk Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06211-3	journal	September 2018
A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts Zhu, Youqi; Sun, Wenming; Luo, Jun Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06296-w	journal	September 2018
A review of oxygen reduction mechanisms for metal-free carbon-based electrocatalysts Ma, Ruguang; Lin, Gaoxin; Zhou, Yao npj Computational Materials, Vol. 5, Issue 1 https://doi.org/10.1038/s41524-019-0210-3	journal	July 2019
Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction Yang, Hong Bin; Hung, Sung-Fu; Liu, Song Nature Energy, Vol. 3, Issue 2 https://doi.org/10.1038/s41560-017-0078-8	journal	February 2018
Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis Chattot, Raphaël; Le Bacq, Olivier; Beermann, Vera Nature Materials, Vol. 17, Issue 9 https://doi.org/10.1038/s41563-018-0133-2	journal	July 2018
PdMo bimetallene for oxygen reduction catalysis Luo, Mingchuan; Zhao, Zhonglong; Zhang, Yelong Nature, Vol. 574, Issue 7776 https://doi.org/10.1038/s41586-019-1603-7	journal	September 2019
General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities Fei, Huilong; Dong, Juncai; Feng, Yexin Nature Catalysis, Vol. 1, Issue 1 https://doi.org/10.1038/s41929-017-0008-y	journal	January 2018
Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells Li, Jiazhan; Chen, Mengjie; Cullen, David A. Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0164-8	journal	October 2018
Recent advances in zinc–air batteries Li, Yanguang; Dai, Hongjie Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00015C	journal	January 2014
Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives Suen, Nian-Tzu; Hung, Sung-Fu; Quan, Quan Chemical Society Reviews, Vol. 46, Issue 2 https://doi.org/10.1039/C6CS00328A	journal	January 2017
Boosting oxygen reduction catalysis with abundant copper single atom active sites Li, Feng; Han, Gao-Feng; Noh, Hyuk-Jun Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE01169A	journal	January 2018
Layered and two dimensional metal oxides for electrochemical energy conversion Browne, Michelle P.; Sofer, Zdeněk; Pumera, Martin Energy & Environmental Science, Vol. 12, Issue 1 https://doi.org/10.1039/C8EE02495B	journal	January 2019
Fe 3 O 4 -Encapsulating N-doped porous carbon materials as efficient oxygen reduction reaction electrocatalysts for Zn–air batteries Li, Longbin; Li, Yizhe; Xiao, Yingbo Chemical Communications, Vol. 55, Issue 52 https://doi.org/10.1039/C9CC03153G	journal	January 2019
Confining ultrasmall bimetallic alloys in porous N–carbon for use as scalable and sustainable electrocatalysts for rechargeable Zn–air batteries Liu, Jingjing; He, Ting; Wang, Qichen Journal of Materials Chemistry A, Vol. 7, Issue 20 https://doi.org/10.1039/C9TA02264C	journal	January 2019
Transition metal–assisted carbonization of small organic molecules toward functional carbon materials Wu, Zhen-Yu; Xu, Shi-Long; Yan, Qiang-Qiang Science Advances, Vol. 4, Issue 7 https://doi.org/10.1126/sciadv.aat0788	journal	July 2018
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017
Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks Chong, Lina; Wen, Jianguo; Kubal, Joseph Science, Vol. 362, Issue 6420 https://doi.org/10.1126/science.aau0630	journal	November 2018
Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells Tian, Xinlong; Zhao, Xiao; Su, Ya-Qiong Science, Vol. 366, Issue 6467 https://doi.org/10.1126/science.aaw7493	journal	November 2019

Similar Records

Ni₃FeN-Supported Fe₃Pt Intermetallic Nanoalloy as a High-Performance Bifunctional Catalyst for Metal-Air Batteries

Journal Article · Fri Jun 30 00:00:00 EDT 2017 · Angewandte Chemie (International Edition) · OSTI ID:1533116

Ni ₃ FeN‐Supported Fe ₃ Pt Intermetallic Nanoalloy as a High‐Performance Bifunctional Catalyst for Metal–Air Batteries

Journal Article · Thu Jul 13 00:00:00 EDT 2017 · Angewandte Chemie · OSTI ID:1378298

Related Subjects

25 ENERGY STORAGE

Engineering efficient bifunctional electrocatalysts for rechargeable zinc–air batteries by confining Fe–Co–Ni nanoalloys in nitrogen-doped carbon nanotube@nanosheet frameworks

Citation Formats

References (52)

Similar Records

Related Subjects