Hierarchical Mesoporous/Macroporous Co-doped NiO Nanosheet Arrays as Free-standing Electrode Materials for Rechargeable Li-O2 Batteries.

Lithium-oxygen (Li-O2) batteries have been widely recognized as appealing power systems for their extremely highest energy density versus common Li-ion batteries. However, there are still lots of issues that need to be addressed towards the practical application. Here, free-standing Co-doped NiO three-dimensional nanosheets were prepared by a hydrothermal synthesis method and directly employed as air-breathing cathode of Li-O2 battery. The morphological phenomenon and electrochemical performance of the as-prepared cathode material were characterized by high-resolution scanning electron microscopy (HRSEM), X-ray diffraction (XRD), cyclic voltammetry (CV), galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy (EIS) measurements. The Co-doped NiO electrode delivered a maximum discharge capacity of around 12857 mAh g-1 with a low overpotential (0.82 V) at 200 mA g-1. Under upper-limit specific capacities of 500 mAh g-1 at 400 mA g-1, the Li-O2 batteries exhibited a long cycle-life of 165 cycles. Compared with the undoped NiO electrode, the Li-O2 battery based on the Co-doped NiO cathode showed significantly higher oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities. This superior electrochemical performance is because the partial substitution of Ni2+ in the NiO matrix by Co2+ to improve the p-type electronic conductivity of NiO. In addition, the morphology and specific surface area of NiO are affected by Co doping, which can expand electrode-electrolyte contact area and lead to sufficient space for Li2O2 deposition. This approach harnesses the great potential of Co-doped NiO nanosheets for practical applications as advanced electrodes for rechargeable lithium-oxygen batteries.

[1]  Zhixing Wang,et al.  Non-aqueous dual-carbon lithium-ion capacitors: a review , 2019, Journal of Materials Chemistry A.

[2]  P. Hu,et al.  Co3O4 nanocage derived from metal-organic frameworks: An excellent cathode catalyst for rechargeable Li-O2 battery , 2019, Nano Research.

[3]  Qiaobao Zhang,et al.  Advances in nanostructures fabricated via spray pyrolysis and their applications in energy storage and conversion. , 2019, Chemical Society reviews.

[4]  Y. Zhai,et al.  Synthesis of morphology controllable free-standing Co3O4 nanostructures and their catalytic activity for Li O2 cells , 2019, Electrochimica Acta.

[5]  Zhiwei Zhang,et al.  Hierarchical NiCo2S4@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O2 Batteries , 2019, Advanced Energy Materials.

[6]  Fang Wang,et al.  Hierarchical porous FeCo2O4@Ni as a carbon- and binder-free cathode for lithium−oxygen batteries , 2019, Journal of Alloys and Compounds.

[7]  Xin-bo Zhang,et al.  Designing a self-healing protective film on a lithium metal anode for long-cycle-life lithium-oxygen batteries , 2019, Energy Storage Materials.

[8]  S. Dou,et al.  Understanding the Reaction Chemistry during Charging in Aprotic Lithium–Oxygen Batteries: Existing Problems and Solutions , 2019, Advanced materials.

[9]  T. Zhao,et al.  V2O5-NiO composite nanowires: A novel and highly efficient carbon-free electrode for non-aqueous Li-air batteries operated in ambient air , 2019, Journal of Power Sources.

[10]  Yong‐Mook Kang,et al.  α-MnO2 Nanowire-Anchored Highly Oxidized Cluster as a Catalyst for Li-O2 Batteries: Superior Electrocatalytic Activity and High Functionality. , 2018, Angewandte Chemie.

[11]  Y. Liu,et al.  Metalorganic Quantum Dots and Their Graphene‐Like Derivative Porous Graphitic Carbon for Advanced Lithium‐Ion Hybrid Supercapacitor , 2018, Advanced Energy Materials.

[12]  Xin-bo Zhang,et al.  Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy–O2 batteries , 2018, Nature Chemistry.

[13]  Hee Jo Song,et al.  Synergistic Effect of CuGeO3/Graphene Composites for Efficient Oxygen–Electrode Electrocatalysts in Li–O2 Batteries , 2018, Advanced Energy Materials.

[14]  Xin-bo Zhang,et al.  In Situ CVD Derived Co-N-C Composite as Highly Efficient Cathode for Flexible Li-O2 Batteries. , 2018, Small.

[15]  S. Cai,et al.  A Synergistic Catalytic Mechanism for Oxygen Evolution Reaction in Aprotic Li–O2 Battery , 2018, ACS Catalysis.

[16]  P. He,et al.  Research progresses on materials and electrode design towards key challenges of Li-air batteries , 2018, Energy Storage Materials.

[17]  Jinhua Ye,et al.  Photo-enhanced lithium oxygen batteries with defective titanium oxide as both photo-anode and air electrode , 2018 .

[18]  Kaixue Wang,et al.  Strategies toward High-Performance Cathode Materials for Lithium-Oxygen Batteries. , 2018, Small.

[19]  Shichao Wu,et al.  A single ion conducting separator and dual mediator-based electrolyte for high-performance lithium–oxygen batteries with non-carbon cathodes , 2018 .

[20]  Tong Liu,et al.  Blood‐Capillary‐Inspired, Free‐Standing, Flexible, and Low‐Cost Super‐Hydrophobic N‐CNTs@SS Cathodes for High‐Capacity, High‐Rate, and Stable Li‐Air Batteries , 2018 .

[21]  Le Zhou,et al.  Phosphorus and Aluminum Codoped Porous NiO Nanosheets as Highly Efficient Electrocatalysts for Overall Water Splitting , 2018 .

[22]  Zhen Zhou,et al.  Binder-free NiFe 2 O 4 /C nanofibers as air cathodes for Li-O 2 batteries , 2018 .

[23]  Wei Lu,et al.  3D Foam-Like Composites of Mo2C Nanorods Coated by N-Doped Carbon: A Novel Self-Standing and Binder-Free O2 Electrode for Li-O2 Batteries. , 2018, ACS applied materials & interfaces.

[24]  Xiaowei Li,et al.  MnCo2 O4 /MoO2 Nanosheets Grown on Ni foam as Carbon- and Binder-Free Cathode for Lithium-Oxygen Batteries. , 2018, ChemSusChem.

[25]  L. Gu,et al.  Enhancing the Catalytic Activity of Co3O4 for Li–O2 Batteries through the Synergy of Surface/Interface/Doping Engineering , 2018 .

[26]  L. Jian,et al.  Bifunctional catalyst of well-dispersed RuO2 on NiCo2O4 nanosheets as enhanced cathode for lithium-oxygen batteries , 2018 .

[27]  Zhanhu Guo,et al.  Urchin-like NiO-NiCo2O4 heterostructure microsphere catalysts for enhanced rechargeable non-aqueous Li-O2 batteries. , 2018, Nanoscale.

[28]  Shichao Zhang,et al.  Mesoporous Pd/Co 3 O 4 nanosheets nanoarrays as an efficient binder/carbon free cathode for rechargeable Li-O 2 batteries , 2017 .

[29]  Yu Zhang,et al.  High‐Performance Integrated Self‐Package Flexible Li–O2 Battery Based on Stable Composite Anode and Flexible Gas Diffusion Layer , 2017, Advanced materials.

[30]  Hye Ryung Byon,et al.  Unexpected Li2O2 Film Growth on Carbon Nanotube Electrodes with CeO2 Nanoparticles in Li-O2 Batteries. , 2016, Nano letters.

[31]  Kyeongse Song,et al.  Achieving outstanding Li+-ORR and -OER activities via edge- and corner-embedded bimetallic nanocubes for rechargeable Li–O2 batteries , 2015 .

[32]  Hui Xu,et al.  Facile hydrothermal synthesis of flower-like Co-doped NiO hierarchical nanosheets as anode materials for lithium-ion batteries , 2015 .

[33]  Alok Kumar Rai,et al.  High performance of Co-doped NiO nanoparticle anode material for rechargeable lithium ion batteries , 2015 .

[34]  Won‐Hee Ryu,et al.  Simple synthesis of highly catalytic carbon-free MnCo2O4@Ni as an oxygen electrode for rechargeable Li–O2 batteries with long-term stability , 2015, Scientific Reports.

[35]  Tianyi Kou,et al.  Ultrathin mesoporous NiO nanosheet-anchored 3D nickel foam as an advanced electrode for supercapacitors , 2015 .

[36]  Ping He,et al.  Mesoporous NiO with a single-crystalline structure utilized as a noble metal-free catalyst for non-aqueous Li–O2 batteries , 2015 .

[37]  A. Yu,et al.  Hierarchical porous NiCo2O4@Ni as carbon-free electrodes for Lithium–oxygen batteries , 2015 .

[38]  Youngmin Kim,et al.  MnCo2O4 nanowires anchored on reduced graphene oxide sheets as effective bifunctional catalysts for Li-O2 battery cathodes. , 2015, ChemSusChem.

[39]  A. Pearse,et al.  DMSO-Li2O2 Interface in the Rechargeable Li-O2 Battery Cathode: Theoretical and Experimental Perspectives on Stability. , 2015, ACS applied materials & interfaces.

[40]  Lifang Jiao,et al.  Copper-doped dual phase Li4Ti5O12-TiO2 nanosheets as high-rate and long cycle life anodes for high-power lithium-ion batteries. , 2015, ChemSusChem.

[41]  Jong-Won Lee,et al.  Carbon-, binder-, and precious metal-free cathodes for non-aqueous lithium-oxygen batteries: nanoflake-decorated nanoneedle oxide arrays. , 2014, ACS applied materials & interfaces.

[42]  Dongxiao Wang,et al.  NiO thin films grown directly on Cu foils by pulsed laser deposition as anode materials for lithium ion batteries , 2014 .

[43]  Guofa Cai,et al.  Co-doped NiO nanoflake array films with enhanced electrochromic properties , 2014 .

[44]  Seong‐Hyeon Hong,et al.  SnO2@Co3O4 hollow nano-spheres for a Li-ion battery anode with extraordinary performance , 2014, Nano Research.

[45]  Heinz Pitsch,et al.  Solvent Degradation in Nonaqueous Li-O2 Batteries: Oxidative Stability versus H-Abstraction. , 2014, The journal of physical chemistry letters.

[46]  Luzhuo Chen,et al.  An efficient bifunctional catalyst of Fe/Fe3C carbon nanofibers for rechargeable Li–O2 batteries , 2014 .

[47]  Shichao Zhang,et al.  Direct Growth of Flower‐Like δ‐MnO2 on Three‐Dimensional Graphene for High‐Performance Rechargeable Li‐O2 Batteries , 2014 .

[48]  Donald J. Siegel,et al.  Enhanced Charge Transport in Amorphous Li2O2 , 2014 .

[49]  H. Pitsch,et al.  Identifying Descriptors for Solvent Stability in Nonaqueous Li-O2 Batteries. , 2014, The journal of physical chemistry letters.

[50]  Kyeongse Song,et al.  Ultra-low overpotential and high rate capability in Li–O2 batteries through surface atom arrangement of PdCu nanocatalysts , 2014 .

[51]  W. Pan,et al.  Enhanced conductivity and gating effect of p-type Li-doped NiO nanowires. , 2014, Nanoscale.

[52]  Trang Vu Thi,et al.  Improving the electrochemical performance of anatase titanium dioxide by vanadium doping as an anode material for lithium-ion batteries , 2013 .

[53]  Kyeongse Song,et al.  β-FeOOH nanorod bundles with highly enhanced round-trip efficiency and extremely low overpotential for lithium-air batteries. , 2013, Nanoscale.

[54]  Yuhui Chen,et al.  A stable cathode for the aprotic Li-O2 battery. , 2013, Nature materials.

[55]  Tao Zhang,et al.  Ru/ITO: a carbon-free cathode for nonaqueous Li-O2 battery. , 2013, Nano letters.

[56]  Yin Yang,et al.  A hierarchical three-dimensional NiCo2O4 nanowire array/carbon cloth as an air electrode for nonaqueous Li-air batteries. , 2013, Physical chemistry chemical physics : PCCP.

[57]  Rak-Hyun Song,et al.  Carbon-free cobalt oxide cathodes with tunable nanoarchitectures for rechargeable lithium-oxygen batteries. , 2013, Chemical communications.

[58]  Donald J. Siegel,et al.  Charge transport in lithium peroxide: relevance for rechargeable metal–air batteries , 2013, 1305.2904.

[59]  Cheng-Fu Yang,et al.  Developing high-transmittance heterojunction diodes based on NiO/TZO bilayer thin films , 2013, Nanoscale Research Letters.

[60]  Stefan A Freunberger,et al.  The carbon electrode in nonaqueous Li-O2 cells. , 2013, Journal of the American Chemical Society.

[61]  L. Nazar,et al.  The role of vacancies and defects in Na0.44MnO2 nanowire catalysts for lithium–oxygen batteries , 2012 .

[62]  Ji‐Guang Zhang,et al.  The stability of organic solvents and carbon electrode in nonaqueous Li-O2 batteries , 2012 .

[63]  Xin-bo Zhang,et al.  Graphene Oxide Gel‐Derived, Free‐Standing, Hierarchically Porous Carbon for High‐Capacity and High‐Rate Rechargeable Li‐O2 Batteries , 2012 .

[64]  P. Bruce,et al.  A Reversible and Higher-Rate Li-O2 Battery , 2012, Science.

[65]  Qianfei Zhou,et al.  Transparent p-type conducting K-doped NiO films deposited by pulsed plasma deposition , 2012 .

[66]  Chan‐Jin Park,et al.  Al-doped Ceria: A New Cathode Catalyst for Li–O2 Batteries , 2012 .

[67]  Y. Sohn,et al.  Interfacial Natures and Controlling Morphology of Co Oxide Nanocrystal Structures by Adding Spectator Ni Ions , 2012 .

[68]  Z. Wen,et al.  A free-standing-type design for cathodes of rechargeable Li–O2 batteries , 2011 .

[69]  D. Bethune,et al.  On the efficacy of electrocatalysis in nonaqueous Li-O2 batteries. , 2011, Journal of the American Chemical Society.