Metal-organic framework derived ZnO/ZnFe2O4/C nanocages as stable cathode material for reversible lithium-oxygen batteries.

Tremendous efforts have been devoted to exploring various Li-O2 cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, most of the high-activity ORR/OER catalysts can also accelerate side-reactions, such as electrolyte degradation on cycling. To address this issue, we change our strategy from pursuing highly active catalysts to developing stable cathodes that are compatible with the electrolyte. In this work, hierarchical mesoporous ZnO/ZnFe2O4/C (ZZFC) nanocages are synthesized from the templates of metal-organic framework (MOF) nanocages. Such ZZFC nanocages have lower ORR/OER catalytic activity as compared with the widely used catalysts for fuel cells, but they do not catalyze the degradation of organic electrolyte during operation. Furthermore, the optimized porosity and conductivity can fit well the needs of the Li-O2 cathode. When employed in a Li-O2 battery, the ZZFC cathode delivers a primary discharge/charge capacity exceeding 11 000 mAh g(-1) at a current density of 300 mA g(-1) and an improved cyclability with capacity of 5000 mAh g(-1) for 15 cycles. The superior electrochemical performance is ascribed to the hierarchical porosity and little degradation of the organic electrolyte.

[1]  A. Manthiram,et al.  Decoupled bifunctional air electrodes for high-performance hybrid lithium-air batteries , 2014 .

[2]  Yunhui Huang,et al.  MOF‐Derived Porous ZnO/ZnFe2O4/C Octahedra with Hollow Interiors for High‐Rate Lithium‐Ion Batteries , 2014, Advanced materials.

[3]  M. Olivares-Marín,et al.  Simple Method to Relate Experimental Pore Size Distribution and Discharge Capacity in Cathodes for Li/O2 Batteries , 2014 .

[4]  Yang Shao-Horn,et al.  Chemical Instability of Dimethyl Sulfoxide in Lithium-Air Batteries. , 2014, The journal of physical chemistry letters.

[5]  A. Manthiram,et al.  Advanced hybrid Li–air batteries with high-performance mesoporous nanocatalysts , 2014 .

[6]  Zhian Zhang,et al.  Hierarchical mesoporous γ-Fe2O3/carbon nanocomposites derived from metal organic frameworks as a cathode electrocatalyst for rechargeable Li-O2 batteries , 2014 .

[7]  A. Manthiram,et al.  O‐ and N‐Doped Carbon Nanowebs as Metal‐Free Catalysts for Hybrid Li‐Air Batteries , 2014 .

[8]  Dan Xu,et al.  3D ordered macroporous LaFeO3 as efficient electrocatalyst for Li–O2 batteries with enhanced rate capability and cyclic performance , 2014 .

[9]  Dan Sun,et al.  A solution-phase bifunctional catalyst for lithium-oxygen batteries. , 2014, Journal of the American Chemical Society.

[10]  David G. Kwabi,et al.  Materials challenges in rechargeable lithium-air batteries , 2014 .

[11]  Ziyang Guo,et al.  Metal–Organic Frameworks as Cathode Materials for Li–O2 Batteries , 2014, Advanced materials.

[12]  Ping He,et al.  Core-shell-structured CNT@RuO(2) composite as a high-performance cathode catalyst for rechargeable Li-O(2) batteries. , 2014, Angewandte Chemie.

[13]  Wei He,et al.  Well-defined metal-organic framework hollow nanocages. , 2014, Angewandte Chemie.

[14]  Young-Bum Kim,et al.  Corrigendum: Clusterin and LRP2 are critical components of the hypothalamic feeding regulatory pathway , 2013 .

[15]  Xiaogang Zhang,et al.  Mesoporous N-containing carbon nanosheets towards high-performance electrochemical capacitors , 2013 .

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

[17]  Dan Sun,et al.  A high-capacity lithium–air battery with Pd modified carbon nanotube sponge cathode working in regular air , 2013 .

[18]  B. Wei,et al.  High rate capability of hydrogen annealed iron oxide-single walled carbon nanotube hybrid films for lithium-ion batteries. , 2013, ACS applied materials & interfaces.

[19]  Dan Xu,et al.  Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries , 2013, Nature Communications.

[20]  Yang Shao-Horn,et al.  Reactivity of carbon in lithium-oxygen battery positive electrodes. , 2013, Nano letters.

[21]  Tao Zhang,et al.  Challenges of non-aqueous Li–O2 batteries: electrolytes, catalysts, and anodes , 2013 .

[22]  Yuyan Shao,et al.  Making Li‐Air Batteries Rechargeable: Material Challenges , 2013 .

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

[24]  Yang Shao-Horn,et al.  Probing the Reaction Kinetics of the Charge Reactions of Nonaqueous Li-O2 Batteries. , 2013, The journal of physical chemistry letters.

[25]  Linda F Nazar,et al.  The role of catalysts and peroxide oxidation in lithium-oxygen batteries. , 2013, Angewandte Chemie.

[26]  Bryan D. McCloskey,et al.  On the Mechanism of Nonaqueous Li–O2 Electrochemistry on C and Its Kinetic Overpotentials: Some Implications for Li–Air Batteries , 2012 .

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

[28]  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 .

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

[30]  Z. Wen,et al.  A tubular polypyrrole based air electrode with improved O2 diffusivity for Li–O2 batteries , 2012 .

[31]  J. Nørskov,et al.  Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li-O2 Batteries. , 2012, The journal of physical chemistry letters.

[32]  Linda F. Nazar,et al.  Screening for superoxide reactivity in Li-O2 batteries: effect on Li2O2/LiOH crystallization. , 2012, Journal of the American Chemical Society.

[33]  Z. Wen,et al.  Mesoporous carbon nitride loaded with Pt nanoparticles as a bifunctional air electrode for rechargeable lithium-air battery , 2012, Journal of Solid State Electrochemistry.

[34]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

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

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

[37]  W. Bennett,et al.  Hierarchically porous graphene as a lithium-air battery electrode. , 2011, Nano letters.

[38]  刘宇,et al.  A free-standing-type design for cathodes of rechargeable Li-O(2) batteries , 2011 .

[39]  Yuhui Chen,et al.  The lithium-oxygen battery with ether-based electrolytes. , 2011, Angewandte Chemie.

[40]  Duncan Graham,et al.  Oxygen reactions in a non-aqueous Li+ electrolyte. , 2011, Angewandte Chemie.

[41]  Jagjit Nanda,et al.  Spectroscopic Characterization of Solid Discharge Products in Li–Air Cells with Aprotic Carbonate Electrolytes , 2011 .

[42]  R M Shelby,et al.  Solvents' Critical Role in Nonaqueous Lithium-Oxygen Battery Electrochemistry. , 2011, The journal of physical chemistry letters.

[43]  Ji‐Guang Zhang,et al.  Investigation on the charging process of Li2O2-based air electrodes in Li–O2 batteries with organic carbonate electrolytes , 2011 .

[44]  Haoshen Zhou,et al.  Li-air rechargeable battery based on metal-free graphene nanosheet catalysts. , 2011, ACS nano.

[45]  Ji-Guang Zhang,et al.  Air electrode design for sustained high power operation of Li/air batteries , 2009 .

[46]  Sanjeev Mukerjee,et al.  Elucidating the Mechanism of Oxygen Reduction for Lithium-Air Battery Applications , 2009 .

[47]  A S Bondarenko,et al.  Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. , 2009, Nature chemistry.

[48]  L. Dao,et al.  New Class of Carbon‐Nanotube Aerogel Electrodes for Electrochemical Power Sources , 2008 .

[49]  T. Yamashita,et al.  Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials , 2008 .

[50]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[51]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode , 2004 .

[52]  K. M. Abraham,et al.  A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery , 1996 .