Ni3Fe‐N Doped Carbon Sheets as a Bifunctional Electrocatalyst for Air Cathodes

A promising bifunctional electrocatalyst is reported for air cathodes consisting of Ni3Fe nanoparticles embedded in porous nitrogen‐doped carbon sheets (Ni3Fe/N‐C sheets) by a facile and effective pyrolysis‐based route with sodium chloride (NaCl) crystals as a template. The Ni3Fe/N‐C sheets show excellent catalytic activity, selectivity, and durability toward both the oxygen‐reduction and oxygen‐evolution reactions (ORR and OER). They are shown to provide a superior, low‐cost cathode for a rechargeable Zn‐air battery. At a discharge–charge current density of 10 mA cm−2, the Ni3Fe/N‐C sheets enable a Zn–air battery to cycle steadily up to 420 h with only a small increase in the round‐trip overpotential, outperforming the more costly Pt/C + IrO2 mixture catalyst (160 h). With the simplicity and scalability of the synthetic approach and its remarkable bifunctional electrocatalytic performance, the Ni3Fe/N‐C sheets offer a promising rechargeable air cathode operating at room temperature in an alkaline electrolyte.

[1]  R. L. Tichenor Nickel Oxides-Relation Between Electrochemical and Foreign Ion Content , 1952 .

[2]  A. Salkind,et al.  Alkaline Storage Batteries , 1970 .

[3]  Yumin Du,et al.  Chitosan- metal complexes as antimicrobial agent: Synthesis, characterization and Structure-activity study , 2005 .

[4]  F. Du,et al.  Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction , 2009, Science.

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

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

[7]  J. Goodenough,et al.  Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. , 2011, Nature chemistry.

[8]  Yan-Jie Wang,et al.  Noncarbon support materials for polymer electrolyte membrane fuel cell electrocatalysts. , 2011, Chemical reviews.

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

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

[11]  M. Jaroniec,et al.  Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. , 2012, Angewandte Chemie.

[12]  Klaus Müllen,et al.  3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction. , 2012, Journal of the American Chemical Society.

[13]  Hao Gong,et al.  Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction , 2012 .

[14]  Yaming Yu,et al.  Chitosan-functionalized carbon nanotubes as support for the high dispersion of PtRu nanoparticles and their electrocatalytic oxidation of methanol. , 2012, Chemistry, an Asian journal.

[15]  Hoon T. Chung,et al.  Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction , 2013, Nature Communications.

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

[17]  D. Van dyck,et al.  Fe-vacancy order and superconductivity in tetragonal β-Fe1-xSe , 2013, Proceedings of the National Academy of Sciences.

[18]  H. Byon,et al.  Promoting formation of noncrystalline Li2O2 in the Li-O2 battery with RuO2 nanoparticles. , 2013, Nano letters.

[19]  G. Fu,et al.  One-Pot Water-Based Synthesis of Pt–Pd Alloy Nanoflowers and Their Superior Electrocatalytic Activity for the Oxygen Reduction Reaction and Remarkable Methanol-Tolerant Ability in Acid Media , 2013 .

[20]  Jiajun Li,et al.  Carbon-encapsulated Fe3O4 nanoparticles as a high-rate lithium ion battery anode material. , 2013, ACS nano.

[21]  Jun Chen,et al.  Ultrasmall Sn nanoparticles embedded in nitrogen-doped porous carbon as high-performance anode for lithium-ion batteries. , 2014, Nano letters.

[22]  Shun Mao,et al.  High-performance bi-functional electrocatalysts of 3D crumpled graphene–cobalt oxide nanohybrids for oxygen reduction and evolution reactions , 2014 .

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

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

[25]  Min Gyu Kim,et al.  A bifunctional perovskite catalyst for oxygen reduction and evolution. , 2014, Angewandte Chemie.

[26]  Hongjie Dai,et al.  A mini review of NiFe-based materials as highly active oxygen evolution reaction electrocatalysts , 2014, Nano Research.

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

[28]  Xiulei Ji,et al.  Pyrolysis of cellulose under ammonia leads to nitrogen-doped nanoporous carbon generated through methane formation. , 2014, Nano letters.

[29]  Klaus Müllen,et al.  Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction , 2014, Nature Communications.

[30]  Yao Zheng,et al.  Mesoporous MnCo2O4 with abundant oxygen vacancy defects as high-performance oxygen reduction catalysts , 2014 .

[31]  S. Qiao,et al.  Fe–N Decorated Hybrids of CNTs Grown on Hierarchically Porous Carbon for High‐Performance Oxygen Reduction , 2014, Advanced materials.

[32]  Xinglong Gou,et al.  Nitrogen and Phosphorus Dual-Doped Graphene/Carbon Nanosheets as Bifunctional Electrocatalysts for Oxygen Reduction and Evolution , 2015 .

[33]  Qiang Zhang,et al.  Spatially Confined Hybridization of Nanometer‐Sized NiFe Hydroxides into Nitrogen‐Doped Graphene Frameworks Leading to Superior Oxygen Evolution Reactivity , 2015, Advanced materials.

[34]  Xunyu Lu,et al.  Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities , 2015, Nature Communications.

[35]  Shun Mao,et al.  Rational design of mesoporous NiFe-alloy-based hybrids for oxygen conversion electrocatalysis , 2015 .

[36]  Yan Zhang,et al.  Ultrathin Two-Dimensional Free-Standing Sandwiched NiFe/C for High-Efficiency Oxygen Evolution Reaction. , 2015, ACS applied materials & interfaces.

[37]  Yu Zhu,et al.  Core-shell Si/C nanospheres embedded in bubble sheet-like carbon film with enhanced performance as lithium ion battery anodes. , 2015, Small.

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

[39]  Yang Shao-Horn,et al.  Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis , 2015 .

[40]  Jianglan Shui,et al.  N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells , 2015, Science Advances.

[41]  A. Hirata,et al.  3D Nanoporous Nitrogen‐Doped Graphene with Encapsulated RuO2 Nanoparticles for Li–O2 Batteries , 2015, Advanced materials.

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

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

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

[45]  B. Geng,et al.  Facile synthesis of Fe/Ni bimetallic oxide solid-solution nanoparticles with superior electrocatalytic activity for oxygen evolution reaction , 2015, Nano Research.

[46]  S. Qiao,et al.  An Fe/N co-doped graphitic carbon bulb for high-performance oxygen reduction reaction. , 2015, Chemical communications.

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

[48]  Xi-hong Lu,et al.  Chitosan Waste-Derived Co and N Co-doped Carbon Electrocatalyst for Efficient Oxygen Reduction Reaction , 2015 .

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

[50]  Yongye Liang,et al.  Facile Synthesis of Nickel–Iron/Nanocarbon Hybrids as Advanced Electrocatalysts for Efficient Water Splitting , 2016 .

[51]  D. Chi,et al.  In-grown structure of NiFe mixed metal oxides and CNT hybrid catalysts for oxygen evolution reaction. , 2016, Chemical communications.

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

[53]  Shiva Gupta,et al.  Carbon nanocomposite catalysts for oxygen reduction and evolution reactions: From nitrogen doping to transition-metal addition , 2016 .

[54]  Arumugam Manthiram,et al.  Long‐Life, High‐Voltage Acidic Zn–Air Batteries , 2016 .

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