Li–O2 Battery Degradation by Lithium Peroxide (Li2O2): A Model Study

The chemical stability of the Li-O-2 battery components (cathode and electrolyte) in contact with lithium peroxide (Li2O2) was investigated using X-ray photoelectron spectroscopy (XPS). XPS is a versatile method to detect amorphous as well as crystalline decomposition products of both salts and solvents. Two strategies were employed. First, cathodes including carbon, alpha-MnO2 catalyst, and Kynar binder (PVdF-HFP) were exposed to Li2O2 and LiClO4 in propylene carbonate (PC) or tetraethylene glycol dimethyl ether (TEGDME) electrolytes. The results indicated that Li2O2 degrades TEGDME to carboxylate containing species and that the decomposition products, in turn, degraded the Kynar binder. The alpha-MnO2 catalyst was unaffected. Second, Li2O2 model surfaces were kept in contact with different electrolytes to investigate the chemical stability and also the resulting surface layer on Li2O2. Further, the XPS experiments revealed that the Li salts such as LiPF6, LiBF4, and LiC!

[1]  H. Zhang,et al.  Ab initio calculations of structural, elastic and electronic properties of Li2O2 , 2007 .

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

[3]  J. Kerr,et al.  Chemical reactivity of PF{sub 5} and LiPF{sub 6} in ethylene carbonate/dimethyl carbonate solutions , 2001 .

[4]  N. Dudney,et al.  Influence of Lithium Salts on the Discharge Chemistry of Li-Air Cells. , 2012, The journal of physical chemistry letters.

[5]  Jun Lu,et al.  Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes , 2011 .

[6]  L. Nazar,et al.  Decomposition Reaction of Lithium Bis(oxalato)borate in the Rechargeable Lithium-Oxygen Cell , 2011 .

[7]  R. Dedryvère,et al.  XPS valence characterization of lithium salts as a tool to study electrode/electrolyte interfaces of Li-ion batteries. , 2006, The journal of physical chemistry. B.

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

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

[10]  M. Seah An accurate and simple universal curve for the energy‐dependent electron inelastic mean free path , 2012 .

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

[12]  A. Clover THE AUTOXIDATION OF ETHYL ETHER , 1922 .

[13]  Andrea G. Bishop,et al.  The influence of lithium salt on the interfacial reactions controlling the thermal stability of graphite anodes , 2002 .

[14]  S. Oswald,et al.  XPS investigations of electrolyte/electrode interactions for various Li-ion battery materials , 2011, Analytical and bioanalytical chemistry.

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

[16]  K. Kanamura,et al.  XPS Analysis of the Surface of a Carbon Electrode Intercalated by Lithium Ions , 1997 .

[17]  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.

[18]  L. G. Cota,et al.  On the structure of lithium peroxide, Li2O2. , 2005, Acta Crystallographica Section B Structural Science.

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

[20]  Y. Shao-horn,et al.  Probing the Origin of Enhanced Stability of AlPO4 Nanoparticle Coated LiCoO2 during Cycling to High Voltages: Combined XRD and XPS Studies , 2009 .

[21]  J. Tarascon,et al.  Contribution of X-ray Photoelectron Spectroscopy to the Study of the Electrochemical Reactivity of CoO toward Lithium , 2004 .

[22]  K. Edström,et al.  The SEI layer formed on lithium metal in the presence of oxygen: A seldom considered component in the development of the Li–O2 battery , 2013 .

[23]  K. Edström,et al.  Electrochemically lithiated graphite characterised by photoelectron spectroscopy , 2003 .

[24]  K. Edström,et al.  Influence of the cathode porosity on the discharge performance of the lithiumoxygen battery , 2011 .

[25]  K. Kang,et al.  Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries , 2012 .

[26]  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.

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

[28]  Jasim Ahmed,et al.  A Critical Review of Li/Air Batteries , 2011 .

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

[30]  Yair Ein-Eli,et al.  Review on Liair batteriesOpportunities, limitations and perspective , 2011 .

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

[32]  Kristina Edström,et al.  The cathode-electrolyte interface in the Li-ion battery , 2004 .

[33]  Kang Xu,et al.  Reaction mechanisms for the limited reversibility of Li–O2 chemistry in organic carbonate electrolytes , 2011 .

[34]  K. Edström,et al.  The Cathode Surface Composition of a Cycled Li–O2 Battery: A Photoelectron Spectroscopy Study , 2012 .

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

[36]  T. Laino,et al.  A new piece in the puzzle of lithium/air batteries: computational study on the chemical stability of propylene carbonate in the presence of lithium peroxide. , 2012, Chemistry.

[37]  Haoshen Zhou,et al.  A lithium-air fuel cell using copper to catalyze oxygen-reduction based on copper-corrosion mechanism. , 2010, Chemical communications.

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

[39]  B. Lucht,et al.  Reactivity of Electrolytes for Lithium-Oxygen Batteries with Li2O2 , 2012 .

[40]  Kristina Edström,et al.  Ether Based Electrolyte, LiB(CN)4 Salt and Binder Degradation in the Li-O2 Battery Studied by Hard X-ray Photoelectron Spectroscopy (HAXPES) , 2012 .

[41]  Fuminori Mizuno,et al.  Rechargeable Li-Air Batteries with Carbonate-Based Liquid Electrolytes , 2010 .

[42]  R. Muller,et al.  Composition of Surface Layers on Li Electrodes in PC, LiClO4 of Very Low Water Content , 1985 .