Ultrathin Co3O4 Layers with Large Contact Area on Carbon Fibers as High‐Performance Electrode for Flexible Zinc–Air Battery Integrated with Flexible Display

A facile and binder-free method is developed for the in situ and horizontal growth of ultrathin mesoporous Co3O4 layers on the surface of carbon fibers in the carbon cloth (ultrathin Co3O4/CC) as high-performance air electrode for the flexible Zn–air battery. In particular, the ultrathin Co3O4 layers have a maximum contact area on the conductive support, facilitating the rapid electron transport and preventing the aggregation of ultrathin layers. The ultrathin feature of Co3O4 layers is characterized by the transmission electron microscopy, Raman spectra, and X-ray absorption fine structure spectroscopy. Benefiting from the high utilization degree of active materials and rapid charge transport, the mass activity for oxygen reduction and evolution reactions of the ultrathin Co3O4/CC electrode is more than 10 times higher than that of the carbon cloth loaded with commercial Co3O4 nanoparticles. Compared to the commercial Co3O4/CC electrode, the flexible Zn–air battery using ultrathin Co3O4/CC electrode exhibits excellent rechargeable performance and high mechanical stability. Furthermore, the flexible Zn–air battery is integrated with a flexible display unit. The whole integrated device can operate without obvious performance degradation under serious deformation and even during the cutting process, which makes it highly promising for wearable and roll-up optoelectronics.

[1]  Zhongwei Chen,et al.  3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries. , 2016, Small.

[2]  Vishal M. Dhavale,et al.  Low surface energy plane exposed Co3O4 nanocubes supported on nitrogen-doped graphene as an electrocatalyst for efficient water oxidation. , 2015, ACS applied materials & interfaces.

[3]  CoOOH Nanosheets with High Mass Activity for Water Oxidation. , 2015, Angewandte Chemie.

[4]  Jingde Li,et al.  Pomegranate-Inspired Design of Highly Active and Durable Bifunctional Electrocatalysts for Rechargeable Metal-Air Batteries. , 2016, Angewandte Chemie.

[5]  Zhongwei Chen,et al.  Self-Assembled NiO/Ni(OH)2 Nanoflakes as Active Material for High-Power and High-Energy Hybrid Rechargeable Battery. , 2016, Nano letters.

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

[7]  Bing Chen,et al.  Improving the Electrocatalytic Activity of Pt Monolayer Catalysts for Electrooxidation of Methanol, Ethanol and Ammonia by Tailoring the Surface Morphology of the Supporting Core , 2016 .

[8]  Sun Tai Kim,et al.  Metal–Air Batteries with High Energy Density: Li–Air versus Zn–Air , 2010 .

[9]  Zhong Lin Wang,et al.  Ultrathin mesoporous Co3O4 nanosheets with excellent photo-/thermo-catalytic activity , 2016 .

[10]  M. Tadé,et al.  Manganese oxides at different oxidation states for heterogeneous activation of peroxymonosulfate for phenol degradation in aqueous solutions , 2013 .

[11]  Teng Zhai,et al.  Solid‐State Supercapacitor Based on Activated Carbon Cloths Exhibits Excellent Rate Capability , 2014, Advanced materials.

[12]  Hua Zhang,et al.  High‐Performance Flexible Solid‐State Ni/Fe Battery Consisting of Metal Oxides Coated Carbon Cloth/Carbon Nanofiber Electrodes , 2016 .

[13]  Shuang Yuan,et al.  Advances and challenges for flexible energy storage and conversion devices and systems , 2014 .

[14]  S. Joo,et al.  Ordered mesoporous Co3O4 spinels as stable, bifunctional, noble metal-free oxygen electrocatalysts , 2013 .

[15]  Lei Liu,et al.  Sub-3 nm Co3O4 nanofilms with enhanced supercapacitor properties. , 2015, ACS nano.

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

[17]  Lele Peng,et al.  Two dimensional nanomaterials for flexible supercapacitors. , 2014, Chemical Society reviews.

[18]  Lin Yang,et al.  Flexible High‐Energy Polymer‐Electrolyte‐Based Rechargeable Zinc–Air Batteries , 2015, Advanced materials.

[19]  Ja-Yeon Choi,et al.  Morphologically controlled Co3O4 nanodisks as practical bi-functional catalyst for rechargeable zinc–air battery applications , 2014 .

[20]  Cuie Wen,et al.  High Energy Density Metal-Air Batteries: A Review , 2013 .

[21]  Wei Liu,et al.  Flexible and Stretchable Energy Storage: Recent Advances and Future Perspectives , 2017, Advanced materials.

[22]  John Wang,et al.  A Flexible Quasi‐Solid‐State Nickel–Zinc Battery with High Energy and Power Densities Based on 3D Electrode Design , 2016, Advanced materials.

[23]  Ja-Yeon Choi,et al.  Advanced Extremely Durable 3D Bifunctional Air Electrodes for Rechargeable Zinc‐Air Batteries , 2014 .

[24]  Yi Xie,et al.  Ultrathin Co3O4 Layers Realizing Optimized CO2 Electroreduction to Formate. , 2016, Angewandte Chemie.

[25]  Min Gyu Kim,et al.  Optimizing nanoparticle perovskite for bifunctional oxygen electrocatalysis , 2016 .

[26]  Xin-bo Zhang,et al.  Direct electrodeposition of cobalt oxide nanosheets on carbon paper as free-standing cathode for Li–O2 battery , 2014 .

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

[28]  Qiuyun Ouyang,et al.  Three-dimensional hierarchical MoS2 nanoflake array/carbon cloth as high-performance flexible lithium-ion battery anodes , 2014 .

[29]  Viktor G. Hadjiev,et al.  The Raman spectra of Co3O4 , 1988 .

[30]  Y. Bando,et al.  Self-stacked Co3O4 nanosheets for high-performance lithium ion batteries. , 2011, Chemical communications.

[31]  Wenbin Hu,et al.  NiCo2S4 nanocrystals anchored on nitrogen-doped carbon nanotubes as a highly efficient bifunctional electrocatalyst for rechargeable zinc-air batteries , 2017 .

[32]  Vishal M. Dhavale,et al.  Surface-Tuned Co3O4 Nanoparticles Dispersed on Nitrogen-Doped Graphene as an Efficient Cathode Electrocatalyst for Mechanical Rechargeable Zinc-Air Battery Application. , 2015, ACS applied materials & interfaces.

[33]  Jing Zhang,et al.  Laminated Cross‐Linked Nanocellulose/Graphene Oxide Electrolyte for Flexible Rechargeable Zinc–Air Batteries , 2016 .

[34]  R. Ruoff,et al.  Two‐Dimensional Materials for Beyond‐Lithium‐Ion Batteries , 2016 .

[35]  Byron D. Gates.  Flexible Electronics , 2009, Science.

[36]  Jing Zhang,et al.  A flexible solid-state electrolyte for wide-scale integration of rechargeable zinc–air batteries , 2016 .

[37]  Jian Jiang,et al.  Recent Advances in Metal Oxide‐based Electrode Architecture Design for Electrochemical Energy Storage , 2012, Advanced materials.

[38]  W. Hu,et al.  Pt-Decorated highly porous flower-like Ni particles with high mass activity for ammonia electro-oxidation , 2016 .

[39]  Weiwei Ben,et al.  General Polyethyleneimine‐Mediated Synthesis of Ultrathin Hexagonal Co3O4 Nanosheets with Reactive Facets for Lithium‐Ion Batteries , 2016 .

[40]  Yanguang Li,et al.  Metallic Cobalt Nanoparticles Encapsulated in Nitrogen‐Enriched Graphene Shells: Its Bifunctional Electrocatalysis and Application in Zinc–Air Batteries , 2016 .

[41]  Chong Xiao,et al.  Low overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. , 2014, Journal of the American Chemical Society.

[42]  Huisheng Peng,et al.  Integration: An Effective Strategy to Develop Multifunctional Energy Storage Devices , 2016 .

[43]  Jing Xu,et al.  Flexible electronics based on inorganic nanowires. , 2015, Chemical Society reviews.

[44]  Dan Xu,et al.  Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes. , 2014, Chemical Society reviews.

[45]  Jun Chen,et al.  Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis , 2015, Nature Communications.

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

[47]  W. Shin,et al.  CO oxidation performance of Au/Co3O4 catalyst on the micro gas sensor device , 2013 .

[48]  X. Lou,et al.  Growth of ultrathin mesoporous Co3O4 nanosheet arrays on Ni foam for high-performance electrochemical capacitors , 2012 .

[49]  H. Che,et al.  Facile synthesis of three-dimensional hierarchical Co3O4 peony-like microspheres and their lithium storage performance , 2015 .

[50]  Zhiqian Wang,et al.  Fabrication of High‐Performance Flexible Alkaline Batteries by Implementing Multiwalled Carbon Nanotubes and Copolymer Separator , 2014, Advanced materials.

[51]  Yi Xie,et al.  Atomically-thin non-layered cobalt oxide porous sheets for highly efficient oxygen-evolving electrocatalysts , 2014 .

[52]  K. Ho,et al.  Synthesis of Co3O4 nanosheets via electrodeposition followed by ozone treatment and their application to high-performance supercapacitors , 2012 .

[53]  Yi Xie,et al.  Ultrathin two-dimensional inorganic materials: new opportunities for solid state nanochemistry. , 2015, Accounts of chemical research.

[54]  Huisheng Peng,et al.  Flexible, Stretchable, and Rechargeable Fiber-Shaped Zinc-Air Battery Based on Cross-Stacked Carbon Nanotube Sheets. , 2015, Angewandte Chemie.

[55]  Youhong Tang,et al.  Three‐Dimensional Smart Catalyst Electrode for Oxygen Evolution Reaction , 2015 .

[56]  Juan Li,et al.  Effect of CoOOH loading on the photoelectrocatalytic performance of WO3 nanorod array film , 2013 .

[57]  Di Bao,et al.  In Situ Coupling of Strung Co4N and Intertwined N-C Fibers toward Free-Standing Bifunctional Cathode for Robust, Efficient, and Flexible Zn-Air Batteries. , 2016, Journal of the American Chemical Society.

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

[59]  Shuai Wang,et al.  Surface Structure Dependent Electrocatalytic Activity of Co3O4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction , 2013, Scientific Reports.

[60]  Pan Xu,et al.  Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal–air batteries , 2016 .

[61]  Minghao Yu,et al.  A Novel Exfoliation Strategy to Significantly Boost the Energy Storage Capability of Commercial Carbon Cloth , 2015, Advanced materials.

[62]  H. Alshareef,et al.  Enhanced rate performance of mesoporous Co(3)O(4) nanosheet supercapacitor electrodes by hydrous RuO(2) nanoparticle decoration. , 2014, ACS applied materials & interfaces.

[63]  Eunkyoung Kim,et al.  Hierarchically Ordered Porous CoOOH Thin‐Film Electrodes for High‐Performance Supercapacitors , 2015 .

[64]  Yi Xie,et al.  Atomically thick bismuth selenide freestanding single layers achieving enhanced thermoelectric energy harvesting. , 2012, Journal of the American Chemical Society.

[65]  S. Yoon,et al.  Thin bonding layer using sulfonated poly(arylene ether sulfone)/PVdF blends for hydrocarbon-based membrane electrode assemblies , 2015 .

[66]  Soojin Park,et al.  Flexible high-energy Li-ion batteries with fast-charging capability. , 2014, Nano letters.