Discharge product morphology versus operating temperature in non-aqueous lithium-air batteries

Abstract During the discharge process of non-aqueous lithium-air batteries, a solid product, Li 2 O 2 , forms in the pores of the porous cathode, and eventually causes the discharge process to cease. During the charge process, solid Li 2 O 2 needs to be electrochemically oxidized. The morphology of the discharge product is, therefore, critically related to the capacity and reversibility of the battery. In this work, we experimentally show that for a given design of the cathode, the shape of the discharge product Li 2 O 2 at a given discharge current density remains almost unchanged with a change in the operating temperature, but the size decreases with an increase in the temperature. We also demonstrate that the product shape varies with the discharge current density at a given temperature. The practical implication of these findings is that the capacity, charge voltage, and cyclability of a given non-aqueous lithium-air battery are affected by the operating temperature.

[1]  Hun‐Gi Jung,et al.  An improved high-performance lithium-air battery. , 2012, Nature chemistry.

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

[3]  Nancy J. Dudney,et al.  Current Collectors for Rechargeable Li-Air Batteries , 2011 .

[4]  Betar M. Gallant,et al.  All-carbon-nanofiber electrodes for high-energy rechargeable Li–O2 batteries , 2011 .

[5]  Si Hyoung Oh,et al.  Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries. , 2012, Nature chemistry.

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

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

[8]  D. Rolison,et al.  Carbon Nanofoam-Based Cathodes for Li–O2 Batteries: Correlation of Pore–Solid Architecture and Electrochemical Performance , 2013 .

[9]  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 .

[10]  P. Bruce,et al.  Reactions in the rechargeable lithium-O2 battery with alkyl carbonate electrolytes. , 2011, Journal of the American Chemical Society.

[11]  Yang Shao-Horn,et al.  Mechanisms of Morphological Evolution of Li2O2 Particles during Electrochemical Growth. , 2013, The journal of physical chemistry letters.

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

[13]  Sanjeev Mukerjee,et al.  Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery , 2010 .

[14]  Jun Lu,et al.  The effect of oxygen crossover on the anode of a Li-O(2) battery using an ether-based solvent: insights from experimental and computational studies. , 2013, ChemSusChem.

[15]  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 .

[16]  J. Nørskov,et al.  Electrical conductivity in Li2O2 and its role in determining capacity limitations in non-aqueous Li-O2 batteries. , 2011, The Journal of chemical physics.

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

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

[19]  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.

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

[21]  T. Zhao,et al.  A gradient porous cathode for non-aqueous lithium-air batteries leading to a high capacity , 2014 .

[22]  Samanvaya Srivastava,et al.  High energy lithium–oxygen batteries – transport barriers and thermodynamics , 2012 .

[23]  Yang Shao-Horn,et al.  Influence of Li2O2 morphology on oxygen reduction and evolution kinetics in Li–O2 batteries , 2013 .

[24]  Kwang‐Bum Kim,et al.  Electrochemical properties of graphene flakes as an air cathode material for Li-O2 batteries in an ether-based electrolyte. , 2013, Physical chemistry chemical physics : PCCP.

[25]  F. Faglioni,et al.  Predicting autoxidation stability of ether- and amide-based electrolyte solvents for Li-air batteries. , 2012, The journal of physical chemistry. A.

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

[27]  Wei Shyy,et al.  Prediction of the theoretical capacity of non-aqueous lithium-air batteries , 2013 .

[28]  Yang Shao-Horn,et al.  Lithium–oxygen batteries: bridging mechanistic understanding and battery performance , 2013 .

[29]  A. Gewirth,et al.  Investigating the Li-O2 Battery in an Ether-Based Electrolyte Using Differential Electrochemical Mass Spectrometry , 2013 .

[30]  Gregory V. Chase,et al.  The Identification of Stable Solvents for Nonaqueous Rechargeable Li-Air Batteries , 2012 .

[31]  Kai Xie,et al.  Investigation of oxygen reduction chemistry in ether and carbonate based electrolytes for Li–O2 batteries , 2012 .

[32]  B. McCloskey,et al.  Lithium−Air Battery: Promise and Challenges , 2010 .

[33]  Dan Xu,et al.  Novel DMSO-based electrolyte for high performance rechargeable Li-O2 batteries. , 2012, Chemical communications.

[34]  Linda F. Nazar,et al.  Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge , 2013 .

[35]  Jeffrey Read,et al.  Discharge characteristic of a non-aqueous electrolyte Li/O2 battery , 2010 .

[36]  Jim P. Zheng,et al.  Theoretical Energy Density of Li–Air Batteries , 2008 .

[37]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[38]  Wei Shyy,et al.  A carbon powder-nanotube composite cathode for non-aqueous lithium-air batteries , 2014 .

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

[40]  Yang-Kook Sun,et al.  Evidence for lithium superoxide-like species in the discharge product of a Li-O2 battery. , 2013, Physical chemistry chemical physics : PCCP.

[41]  Andrew G. Glen,et al.  APPL , 2001 .

[42]  In-Hwan Oh,et al.  Influence of temperature on lithium-oxygen battery behavior. , 2013, Nano letters.

[43]  Khalil Amine,et al.  Disproportionation in Li-O2 batteries based on a large surface area carbon cathode. , 2013, Journal of the American Chemical Society.

[44]  Zhe Hu,et al.  Size effect of lithium peroxide on charging performance of Li-O2 batteries. , 2014, Nanoscale.