Defect-rich carbon fiber electrocatalysts with porous graphene skin for flexible solid-state zinc–air batteries

Abstract Rechargeable flexible Zn–air batteries have attracted great attentions as promising next-generation energy storage devices for portable and wearable electronics. Bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) electrocatalysts on the air electrode are critical for improving the energy storage performance of Zn–air batteries. Free-standing electrocatalysts with superb OER/ORR reactivity render promising flexible power sources for the wearable and stretchable devices. In this contribution, a metal-free electrocatalyst based on surface modification of flexible carbon cloth is proposed. A coaxial cable-like structure with carbon fiber skeleton coated by nanostructured porous and defect-rich graphene skin is in situ fabricated through a facile H2 etching approach. With abundant heteroatoms and defects as active sites, the nanocarbon shells coated carbon cloth exhibits excellent OER/ORR bifunctional activity. The OER and ORR current densities on graphene skin modified carbon fiber are 20 and 3 times higher than those of pristine carbon cloth, respectively. This emerging carbon cloth derived electrocatalyst with porous graphene skin also serves as the air electrode in a rechargeable flexible solid-state Zn air battery with polymer gel electrolyte, and demonstrates stable charge/discharge cycling even under bending. This strategy of constructing nanostructures directly on carbon fibers benefits the rational design of flexible and functionalized materials for electrocatalytic energy applications.

[1]  C. Tung,et al.  NiFe Layered Double Hydroxide Nanoparticles on Co,N‐Codoped Carbon Nanoframes as Efficient Bifunctional Catalysts for Rechargeable Zinc–Air Batteries , 2017 .

[2]  Qiang Zhang,et al.  Nanocarbon for Oxygen Reduction Electrocatalysis: Dopants, Edges, and Defects , 2017, Advanced materials.

[3]  X. Liu,et al.  A two-step method for high efficient and continuous carbon fiber treatment with enhanced fiber strength and interfacial adhesion , 2017 .

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

[5]  Qiang Zhang,et al.  Defect Engineering toward Atomic Co–Nx–C in Hierarchical Graphene for Rechargeable Flexible Solid Zn‐Air Batteries , 2017, Advanced materials.

[6]  M. Antonietti,et al.  Synthesis of single-crystal-like nanoporous carbon membranes and their application in overall water splitting , 2017, Nature Communications.

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

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

[9]  Qiang Zhang,et al.  Bifunctional Transition Metal Hydroxysulfides: Room‐Temperature Sulfurization and Their Applications in Zn–Air Batteries , 2017, Advanced materials.

[10]  Y. Tong,et al.  A modified molecular framework derived highly efficient Mn-Co-carbon cathode for a flexible Zn-air battery. , 2017, Chemical communications.

[11]  X. Bao,et al.  Nitrogen-doped carbon nanotube encapsulating cobalt nanoparticles towards efficient oxygen reduction for zinc–air battery , 2017 .

[12]  Christopher L. Brown,et al.  Defect Graphene as a Trifunctional Catalyst for Electrochemical Reactions , 2016, Advanced materials.

[13]  Hui-Ming Cheng,et al.  A 3D bi-functional porous N-doped carbon microtube sponge electrocatalyst for oxygen reduction and oxygen evolution reactions , 2016 .

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

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

[16]  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 .

[17]  Abdullah M. Asiri,et al.  Acidically oxidized carbon cloth: a novel metal-free oxygen evolution electrode with high catalytic activity. , 2015, Chemical communications.

[18]  Yong Zhao,et al.  Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation , 2013, Nature Communications.

[19]  Xin-Bing Cheng,et al.  Nanostructured energy materials for electrochemical energy conversion and storage: A review , 2016 .

[20]  Yihua Gao,et al.  Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery. , 2018, ACS nano.

[21]  Qiang Zhang,et al.  A review of nanocarbons in energy electrocatalysis: Multifunctional substrates and highly active sites , 2017 .

[22]  Zhiqian Wang,et al.  Development of flexible zinc–air battery with nanocomposite electrodes and a novel separator , 2017 .

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

[24]  Baosheng Li,et al.  Free-standing vertically-aligned nitrogen-doped carbon nanotube arrays/graphene as air-breathing electrodes for rechargeable zinc–air batteries , 2017 .

[25]  Chun-Chen Yang,et al.  Improvement of high-rate capability of alkaline Zn–MnO2 battery , 2002 .

[26]  Jian Zhang,et al.  Facile Synthesis of Defect-Rich and S/N Co-Doped Graphene-Like Carbon Nanosheets as an Efficient Electrocatalyst for Primary and All-Solid-State Zn-Air Batteries. , 2017, ACS applied materials & interfaces.

[27]  Jing Pan,et al.  Advanced Architectures and Relatives of Air Electrodes in Zn–Air Batteries , 2018, Advanced science.

[28]  Birger Horstmann,et al.  Modeling nucleation and growth of zinc oxide during discharge of primary zinc-air batteries , 2016, 1612.03464.

[29]  Hua Zhang,et al.  Hierarchical Ni-Mo-S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte , 2015, Science Advances.

[30]  Hani E. Naguib,et al.  Double-layer membrane cathode with improved oxygen diffusivity in zinc-air batteries , 2017 .

[31]  Yao Zheng,et al.  Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. , 2015, Chemical Society reviews.

[32]  X. Yao,et al.  Recent Progress in Oxygen Electrocatalysts for Zinc–Air Batteries , 2017 .

[33]  Yun Tong,et al.  Metallic Co4N Porous Nanowire Arrays Activated by Surface Oxidation as Electrocatalysts for the Oxygen Evolution Reaction. , 2015, Angewandte Chemie.

[34]  Xiaodong He,et al.  Study of structure–mechanical heterogeneity of polyacrylonitrile-based carbon fiber monofilament by plasma etching-assisted radius profiling , 2017 .

[35]  L. Dai,et al.  Defect Chemistry of Nonprecious‐Metal Electrocatalysts for Oxygen Reactions , 2017, Advanced materials.

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

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

[38]  B. Liu,et al.  A flexible high-performance oxygen evolution electrode with three-dimensional NiCo2O4 core-shell nanowires , 2015 .

[39]  Jiaqi Huang,et al.  Toward Full Exposure of “Active Sites”: Nanocarbon Electrocatalyst with Surface Enriched Nitrogen for Superior Oxygen Reduction and Evolution Reactivity , 2014 .

[40]  Mietek Jaroniec,et al.  Phosphorus-doped graphitic carbon nitrides grown in situ on carbon-fiber paper: flexible and reversible oxygen electrodes. , 2015, Angewandte Chemie.

[41]  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.

[42]  Jun Chen,et al.  Studies on the vapour-transport synthesis and electrochemical properties of zinc micro-, meso- and nanoscale structures , 2007 .

[43]  Mietek Jaroniec,et al.  Nitrogen and Oxygen Dual‐Doped Carbon Hydrogel Film as a Substrate‐Free Electrode for Highly Efficient Oxygen Evolution Reaction , 2014, Advanced materials.

[44]  Jun Chen,et al.  Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts. , 2011, Nature chemistry.

[45]  Xunyu Lu,et al.  Electrocatalytic oxygen evolution at surface-oxidized multiwall carbon nanotubes. , 2015, Journal of the American Chemical Society.

[46]  Yanhui Yang,et al.  Core-shell carbon materials derived from metal-organic frameworks as an efficient oxygen bifunctional electrocatalyst , 2016 .

[47]  Chao Ma,et al.  Electrochemical approach to prepare integrated air electrodes for highly stretchable zinc-air battery array with tunable output voltage and current for wearable electronics , 2017 .

[48]  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.

[49]  M. Jaroniec,et al.  Ionic liquid-assisted synthesis of N/S-double doped graphene microwires for oxygen evolution and Zn–air batteries , 2015 .

[50]  Min Wei,et al.  Directed synthesis of carbon nanotube arrays based on layered double hydroxides toward highly-efficient bifunctional oxygen electrocatalysis , 2017 .

[51]  T. Jaramillo,et al.  A bifunctional nonprecious metal catalyst for oxygen reduction and water oxidation. , 2010, Journal of the American Chemical Society.

[52]  Maria-Magdalena Titirici,et al.  Active sites engineering leads to exceptional ORR and OER bifunctionality in P,N Co-doped graphene frameworks , 2017 .

[53]  Hongbing Ji,et al.  A monolithic metal-free electrocatalyst for oxygen evolution reaction and overall water splitting , 2016 .

[54]  Hui Xu,et al.  Transition metal (Fe, Co, Ni, and Mn) oxides for oxygen reduction and evolution bifunctional catalysts in alkaline media , 2016 .

[55]  Tingzheng Hou,et al.  Topological Defects in Metal‐Free Nanocarbon for Oxygen Electrocatalysis , 2016, Advanced materials.

[56]  Zhaolin Liu,et al.  A Near-Neutral Chloride Electrolyte for Electrically Rechargeable Zinc-Air Batteries , 2014 .

[57]  Qiang Zhang,et al.  Multiscale Principles To Boost Reactivity in Gas-Involving Energy Electrocatalysis. , 2018, Accounts of chemical research.

[58]  Cailing Xu,et al.  Atomic‐Level Coupled Interfaces and Lattice Distortion on CuS/NiS2 Nanocrystals Boost Oxygen Catalysis for Flexible Zn‐Air Batteries , 2017 .

[59]  John Wang,et al.  Hollow Co3O4 Nanosphere Embedded in Carbon Arrays for Stable and Flexible Solid‐State Zinc–Air Batteries , 2017, Advanced materials.

[60]  Zifeng Wang,et al.  Texturing in situ: N,S-enriched hierarchically porous carbon as a highly active reversible oxygen electrocatalyst , 2017 .

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

[62]  Volkmar M. Schmidt,et al.  Influence of CO2 on the stability of bifunctional oxygen electrodes for rechargeable zinc/air batteries and study of different CO2 filter materials , 2001 .

[63]  Jin-Young Yu,et al.  Highly active and durable carbon nitride fibers as metal-free bifunctional oxygen electrodes for flexible Zn-air batteries. , 2017, Nanoscale horizons.

[64]  Quan Quan,et al.  Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives. , 2017, Chemical Society reviews.

[65]  Yong Wang,et al.  Flexible and rechargeable Zn–air batteries based on green feedstocks with 75% round-trip efficiency , 2017 .

[66]  Zhenhai Xia,et al.  A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. , 2015, Nature nanotechnology.

[67]  Minghai Chen,et al.  Crosslinked Carbon Nanotube Aerogel Films Decorated with Cobalt Oxides for Flexible Rechargeable Zn-Air Batteries. , 2017, Small.

[68]  Yanyong Wang,et al.  In Situ Exfoliated, Edge‐Rich, Oxygen‐Functionalized Graphene from Carbon Fibers for Oxygen Electrocatalysis , 2017, Advanced materials.

[69]  Qiang Zhang,et al.  Structural evolution during annealing of thermally reduced graphene nanosheets for application in supercapacitors , 2012 .