Hollow Co3O4 Nanosphere Embedded in Carbon Arrays for Stable and Flexible Solid‐State Zinc–Air Batteries

Highly active and durable air cathodes to catalyze both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are urgently required for rechargeable metal-air batteries. In this work, an efficient bifunctional oxygen catalyst comprising hollow Co3 O4 nanospheres embedded in nitrogen-doped carbon nanowall arrays on flexible carbon cloth (NC-Co3 O4 /CC) is reported. The hierarchical structure is facilely derived from a metal-organic framework precursor. A carbon onion coating constrains the Kirkendall effect to promote the conversion of the Co nanoparticles into irregular hollow oxide nanospheres with a fine scale nanograin structure, which enables promising catalytic properties toward both OER and ORR. The integrated NC-Co3 O4 /CC can be used as an additive-free air cathode for flexible all-solid-state zinc-air batteries, which present high open circuit potential (1.44 V), high capacity (387.2 mAh g-1 , based on the total mass of Zn and catalysts), excellent cycling stability and mechanical flexibility, significantly outperforming Pt- and Ir-based zinc-air batteries.

[1]  Minjoon Park,et al.  All‐Solid‐State Cable‐Type Flexible Zinc–Air Battery , 2015, Advanced materials.

[2]  Yao Zheng,et al.  Graphene oxide-polydopamine derived N, S-codoped carbon nanosheets as superior bifunctional electrocatalysts for oxygen reduction and evolution , 2016 .

[3]  Yaobing Wang,et al.  Scalable Fabrication of Nanoporous Carbon Fiber Films as Bifunctional Catalytic Electrodes for Flexible Zn‐Air Batteries , 2016, Advanced materials.

[4]  Wei Wang,et al.  NiO/CoN Porous Nanowires as Efficient Bifunctional Catalysts for Zn-Air Batteries. , 2017, ACS nano.

[5]  F. Wei,et al.  An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. , 2012, Nature nanotechnology.

[6]  Jung-Ho Lee,et al.  Scalable 3-D Carbon Nitride Sponge as an Efficient Metal-Free Bifunctional Oxygen Electrocatalyst for Rechargeable Zn-Air Batteries. , 2017, ACS nano.

[7]  Yadong Li,et al.  Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction. , 2017, Angewandte Chemie.

[8]  Karren L. More,et al.  Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces , 2014, Science.

[9]  Min Gyu Kim,et al.  Single crystalline pyrochlore nanoparticles with metallic conduction as efficient bi-functional oxygen electrocatalysts for Zn–air batteries , 2017 .

[10]  Min Gyu Kim,et al.  Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc-Air Batteries. , 2015, Angewandte Chemie.

[11]  R. Johnston,et al.  One‐Pot Synthesis of Dealloyed AuNi Nanodendrite as a Bifunctional Electrocatalyst for Oxygen Reduction and Borohydride Oxidation Reaction , 2017 .

[12]  Guozhao Fang,et al.  MOFs nanosheets derived porous metal oxide-coated three-dimensional substrates for lithium-ion battery applications , 2016 .

[13]  X. Duan,et al.  High-performance transition metal–doped Pt3Ni octahedra for oxygen reduction reaction , 2015, Science.

[14]  Yayuan Liu,et al.  Direct and continuous strain control of catalysts with tunable battery electrode materials , 2016, Science.

[15]  Jun Chen,et al.  Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. , 2012, Chemical Society reviews.

[16]  Tom Regier,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.

[17]  B. Liu,et al.  Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst , 2016, Science Advances.

[18]  Meilin Liu,et al.  Recent Progress in Non‐Precious Catalysts for Metal‐Air Batteries , 2012 .

[19]  Tao Ling,et al.  Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis , 2016, Nature Communications.

[20]  D. Ivey,et al.  Electrocatalytic Activity of Non-Stoichiometric Perovskites toward Oxygen Reduction Reaction in Alkaline Electrolytes , 2011 .

[21]  Guosong Hong,et al.  Advanced zinc-air batteries based on high-performance hybrid electrocatalysts , 2013, Nature Communications.

[22]  Hongjie Dai,et al.  Recent advances in zinc-air batteries. , 2014, Chemical Society reviews.

[23]  Colin F. Dickens,et al.  Combining theory and experiment in electrocatalysis: Insights into materials design , 2017, Science.

[24]  Wei Li,et al.  Atomic Modulation of FeCo–Nitrogen–Carbon Bifunctional Oxygen Electrodes for Rechargeable and Flexible All‐Solid‐State Zinc–Air Battery , 2017 .

[25]  Cheng Hou,et al.  Nitrogen‐Doped Co3O4 Mesoporous Nanowire Arrays as an Additive‐Free Air‐Cathode for Flexible Solid‐State Zinc–Air Batteries , 2017, Advanced materials.

[26]  Gabor A. Somorjai,et al.  Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect , 2004, Science.

[27]  John Wang,et al.  Rational Design of Metal‐Organic Framework Derived Hollow NiCo2O4 Arrays for Flexible Supercapacitor and Electrocatalysis , 2017 .

[28]  Charles W. Tobias,et al.  The solubility and diffusion coefficient of oxygen in potassium hydroxide solutions , 1967 .

[29]  M. G. Park,et al.  Electrically Rechargeable Zinc–Air Batteries: Progress, Challenges, and Perspectives , 2017, Advanced materials.

[30]  Jia Huo,et al.  Cobalt nanoparticle-embedded carbon nanotube/porous carbon hybrid derived from MOF-encapsulated Co3O4 for oxygen electrocatalysis. , 2016, Chemical communications.

[31]  Xin-bo Zhang,et al.  Integrated Three-Dimensional Carbon Paper/Carbon Tubes/Cobalt-Sulfide Sheets as an Efficient Electrode for Overall Water Splitting. , 2016, ACS nano.

[32]  Yong Wang,et al.  All‐Solid‐State, Foldable, and Rechargeable Zn‐Air Batteries Based on Manganese Oxide Grown on Graphene‐Coated Carbon Cloth Air Cathode , 2017 .

[33]  Dingshan Yu,et al.  Three-dimensional B,N-doped graphene foam as a metal-free catalyst for oxygen reduction reaction. , 2013, Physical chemistry chemical physics : PCCP.

[34]  Y. Tong,et al.  Engineering Thin MoS2 Nanosheets on TiN Nanorods: Advanced Electrochemical Capacitor Electrode and Hydrogen Evolution Electrocatalyst , 2017 .

[35]  Hua Zhang,et al.  Cobalt oxide and N-doped carbon nanosheets derived from a single two-dimensional metal-organic framework precursor and their application in flexible asymmetric supercapacitors. , 2017, Nanoscale horizons.

[36]  Zhongwei Chen,et al.  Flexible Rechargeable Zinc‐Air Batteries through Morphological Emulation of Human Hair Array , 2016, Advanced materials.

[37]  Y. Tong,et al.  Achieving Ultrahigh Energy Density and Long Durability in a Flexible Rechargeable Quasi‐Solid‐State Zn–MnO2 Battery , 2017, Advanced materials.

[38]  Gengfeng Zheng,et al.  Nanostructured Bifunctional Redox Electrocatalysts. , 2016, Small.

[39]  Bin Liu,et al.  Ultrathin Co3O4 Layers with Large Contact Area on Carbon Fibers as High‐Performance Electrode for Flexible Zinc–Air Battery Integrated with Flexible Display , 2017 .

[40]  H. Alshareef,et al.  Plasma-Assisted Synthesis of NiCoP for Efficient Overall Water Splitting. , 2016, Nano letters.

[41]  Hangxun Xu,et al.  A Highly Efficient Metal‐Free Oxygen Reduction Electrocatalyst Assembled from Carbon Nanotubes and Graphene , 2016, Advanced materials.

[42]  J. Tu,et al.  Efficient oxygen reduction reaction using mesoporous Ni-doped Co3O4 nanowire array electrocatalysts , 2015 .

[43]  Dang Sheng Su,et al.  Assembly of three-dimensional hetero-epitaxial ZnO/ZnS core/shell nanorod and single crystalline hollow ZnS nanotube arrays. , 2012, ACS nano.

[44]  M. Yousaf,et al.  Novel Pliable Electrodes for Flexible Electrochemical Energy Storage Devices: Recent Progress and Challenges , 2016 .

[45]  Li An,et al.  A novel CoN electrocatalyst with high activity and stability toward oxygen reduction reaction , 2014 .

[46]  Xueping Gao,et al.  A High‐Efficiency Sulfur/Carbon Composite Based on 3D Graphene Nanosheet@Carbon Nanotube Matrix as Cathode for Lithium–Sulfur Battery , 2017 .

[47]  W. Schuhmann,et al.  Co@Co3O4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode. , 2016, Angewandte Chemie.

[48]  Y. Tong,et al.  Flexible Ultrafast Aqueous Rechargeable Ni//Bi Battery Based on Highly Durable Single‐Crystalline Bismuth Nanostructured Anode , 2016, Advanced materials.

[49]  Xin Wang,et al.  A metal–organic framework-derived bifunctional oxygen electrocatalyst , 2016, Nature Energy.