High-performance non-spinel cobalt–manganese mixed oxide-based bifunctional electrocatalysts for rechargeable zinc–air batteries

Abstract Development of efficient bifunctional electrocatalysts from earth abundant elements, simultaneously active for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), remains to be a grand challenge for electrocatalysis. Herein we firstly synthesized a new type of bifunctional catalyst (NCNT/CoxMn1−xO) consisting of non-spinel cobalt–manganese oxide supported on N-doped carbon nanotubes through a simple non-surfactant assistant hydrothermal method. This hybrid catalyst exhibits much higher OER activity than that of IrO2, and comparable ORR activity to Pt/C with identical onset potential (0.96 V) in alkaline media. Furthermore, the NCNT/CoxMn1−xO catalyst was studied as a cathode in both primary and rechargeable zinc–air batteries demonstrating similar performance to commercial Pt/C or (Pt/C+IrO2), respectively. Primary zinc–air battery tests show a gravimetric energy density of 695 W h  kg Zn - 1 , and the rechargeable battery exhibits a high round-trip efficiency evidenced by a low discharge–charge voltage gap (0.57 V) at a current density of 7 mA cm−2.

[1]  P. Strasser,et al.  Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions. , 2015, ChemSusChem.

[2]  Ruiguo Cao,et al.  Nanostructured carbon-based cathode catalysts for nonaqueous lithium-oxygen batteries. , 2014, Physical chemistry chemical physics : PCCP.

[3]  M. Swihart,et al.  Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction. , 2015, Nanoscale.

[4]  Lin Guo,et al.  CoO Hollow Cube/Reduced Graphene Oxide Composites with Enhanced Lithium Storage Capability , 2014 .

[5]  John B. Shoven,et al.  I , Edinburgh Medical and Surgical Journal.

[6]  C. Wong,et al.  Designed functional systems from peapod-like Co@carbon to Co3O4@carbon nanocomposites. , 2010, ACS nano.

[7]  A. Khodakov,et al.  Pore-Size Control of Cobalt Dispersion and Reducibility in Mesoporous Silicas , 2001 .

[8]  James R. McKone,et al.  Solar water splitting cells. , 2010, Chemical reviews.

[9]  Yong‐Mook Kang,et al.  Syntheses and Characterization of Wurtzite CoO, Rocksalt CoO, and Spinel Co3O4 Nanocrystals: Their Interconversion and Tuning of Phase and Morphology , 2010 .

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

[11]  K. Müllen,et al.  High‐Performance Electrocatalysts for Oxygen Reduction Derived from Cobalt Porphyrin‐Based Conjugated Mesoporous Polymers , 2014, Advanced materials.

[12]  D. Schmeißer,et al.  Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides. , 2014, Journal of the American Chemical Society.

[13]  Wensheng Yang,et al.  Facile fabrication of Chinese lantern-like MnO@N–C: a high-performance anode material for lithium-ion batteries , 2014 .

[14]  Zhen He,et al.  Electrodeposition of Crystalline Co3O4—A Catalyst for the Oxygen Evolution Reaction , 2012 .

[15]  L. Christophorou Science , 2018, Emerging Dynamics: Science, Energy, Society and Values.

[16]  Joseph F. Parker,et al.  Wiring zinc in three dimensions re-writes battery performance—dendrite-free cycling , 2014 .

[17]  Shihe Yang,et al.  Bio-inspired synthesis of NaCl-type CoxNi1−xO (0 ≤ x < 1) nanorods on reduced graphene oxide sheets and screening for asymmetric electrochemical capacitors , 2012 .

[18]  Li-ping Zhu,et al.  Porous CoO Nanostructure Arrays Converted from Rhombic Co(OH)F and Needle-like Co(CO3)0.5(OH)·0.11H2O and Their Electrochemical Properties , 2013 .

[19]  M. Inaba,et al.  Silica-supported cobalt catalysts for the selective reduction of nitrogen monoxide with propene , 1996 .

[20]  Gang Wu,et al.  High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt , 2011, Science.

[21]  Jian‐Qiang Wang,et al.  Active Coordinatively Unsaturated Manganese Monoxide-Containing Mesoporous Carbon Catalyst in Wet Peroxide Oxidation , 2012 .

[22]  Hailiang Wang,et al.  Strongly coupled inorganic/nanocarbon hybrid materials for advanced electrocatalysis. , 2013, Journal of the American Chemical Society.

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

[24]  Jian Wang,et al.  Oxygen reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes. , 2012, Journal of the American Chemical Society.

[25]  Shouheng Sun,et al.  Co/CoO nanoparticles assembled on graphene for electrochemical reduction of oxygen. , 2012, Angewandte Chemie.

[26]  Soo Min Hwang,et al.  One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries , 2015, Scientific Reports.

[27]  A. Lösch Nano , 2012, Ortsregister.

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

[29]  W. Schuhmann,et al.  Mn(x)O(y)/NC and Co(x)O(y)/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes. , 2014, Angewandte Chemie.

[30]  Shouheng Sun,et al.  Monodisperse M(x)Fe(3-x)O4 (M = Fe, Cu, Co, Mn) nanoparticles and their electrocatalysis for oxygen reduction reaction. , 2013, Nano letters.

[31]  S. Walsh Rock salt vs. wurtzite phases of Co1−xMnxO: control of crystal lattice and morphology at the nanoscale , 2013 .

[32]  Piotr Zelenay,et al.  Nanostructured nonprecious metal catalysts for oxygen reduction reaction. , 2013, Accounts of chemical research.

[33]  X. Lou,et al.  Shape-controlled synthesis of porous Co3O4 nanostructures for application in supercapacitors , 2010 .

[34]  Shaoming Huang,et al.  A Facile and General Approach for the Direct Fabrication of 3D, Vertically Aligned Carbon Nanotube Array/Transition Metal Oxide Composites as Non‐Pt Catalysts for Oxygen Reduction Reactions , 2014, Advanced materials.

[35]  T. Jaramillo,et al.  In situ X-ray absorption spectroscopy investigation of a bifunctional manganese oxide catalyst with high activity for electrochemical water oxidation and oxygen reduction. , 2013, Journal of the American Chemical Society.

[36]  E. Zhecheva,et al.  Lithium storage mechanisms and effect of partial cobalt substitution in manganese carbonate electrodes. , 2012, Inorganic chemistry.

[37]  Lauren R. Grabstanowicz,et al.  Highly Efficient Non‐Precious Metal Electrocatalysts Prepared from One‐Pot Synthesized Zeolitic Imidazolate Frameworks , 2014, Advanced materials.

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

[39]  A. Bell,et al.  Size-Dependent Activity of Co 3 O 4 Nanoparticle Anodes for Alkaline Water Electrolysis , 2009 .

[40]  I. Takeuchi,et al.  La(0.8)Sr(0.2)MnO(3-δ) decorated with Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ): a bifunctional surface for oxygen electrocatalysis with enhanced stability and activity. , 2014, Journal of the American Chemical Society.

[41]  Shiva Gupta,et al.  Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media. , 2016, Chemistry, an Asian journal.

[42]  M. Antonietti,et al.  Blood Ties: Co3O4 Decorated Blood Derived Carbon as a Superior Bifunctional Electrocatalyst , 2014 .

[43]  Hui Li,et al.  Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application. , 2011, Nano letters.

[44]  L. Dai,et al.  Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. , 2011, Journal of the American Chemical Society.

[45]  M. Itoh,et al.  Correlation between Magnetic Properties and Mn/Co Atomic Order in LaMn0.5Co0.5O3+δ: I. Second-Order Nature in Mn/Co Atomic Ordering and Valence State , 2003 .

[46]  Min Gyu Kim,et al.  Fabrication of Ba0.5Sr0.5Co0.8Fe0.2O3–δ Catalysts with Enhanced Electrochemical Performance by Removing an Inherent Heterogeneous Surface Film Layer , 2015, Advanced materials.

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

[48]  Tom Regier,et al.  Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts. , 2012, Journal of the American Chemical Society.

[49]  Mietek Jaroniec,et al.  Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes. , 2014, Journal of the American Chemical Society.

[50]  M. Prabu,et al.  Hierarchical nanostructured NiCo2O4 as an efficient bifunctional non-precious metal catalyst for rechargeable zinc-air batteries. , 2014, Nanoscale.

[51]  S. Bent,et al.  Active MnOx Electrocatalysts Prepared by Atomic Layer Deposition for Oxygen Evolution and Oxygen Reduction Reactions , 2012 .

[52]  Jaephil Cho,et al.  Nanocarbon Electrocatalysts for Oxygen Reduction in Alkaline Media for Advanced Energy Conversion and Storage , 2014 .

[53]  M. Willinger,et al.  Spinel Mn-Co oxide in N-doped carbon nanotubes as a bifunctional electrocatalyst synthesized by oxidative cutting. , 2014, Journal of the American Chemical Society.

[54]  Haitao Zhang,et al.  Morphology-controllable synthesis and characterization of hierarchical 3D Co1-xMnxO nanostructures. , 2006, The journal of physical chemistry. B.