In operando X-ray studies of the conversion reaction in Mn3O4 lithium battery anodes

The pursuit of energy storage systems with high energy density has revealed several exciting possibilities, including the unexpectedly reversible conversion reactions between metal oxides and lithium for lithium ion battery anodes. The mechanistic complexity of the drastic chemical and structural changes as well as the sensitivity of the reaction intermediates and products to ambient conditions mean that the reaction mechanism is best studied by non-destructive techniques in the native battery environment (in operando). This work applies synchrotron X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) to directly observe the conversion reaction of a Mn3O4 anode previously shown to have promising electrochemical performance. The results enable the assignment of electrochemical features to specific reactions, including the formation of LiMn3O4, MnO, metallic Mn, and non-metal-centered reactions, and elucidate the difference between the first and subsequent lithiation reactions. In operando XAS clearly shows that a significant fraction of the charge is stored in non-Mn-centered reactions, a result with serious implications for Mn3O4, in particular, and other metal oxide conversion anodes, in general. This study emphasizes the importance of in situ/in operando studies on next-generation electrode materials to confirm that the observed charge transfer is due to the desired electrochemical reactions.

[1]  Liquan Chen,et al.  Anodes based on oxide materials for lithium rechargeable batteries 1 1 Paper presented at the 1997 H , 1999 .

[2]  F. Farges.  Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials , 2005 .

[3]  A. West,et al.  Co-doped Mn3O4: a possible anode material for lithium batteries , 2005 .

[4]  P. Balaya,et al.  Li-Storage via Heterogeneous Reaction in Selected Binary Metal Fluorides and Oxides , 2004 .

[5]  M Newville,et al.  ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. , 2005, Journal of synchrotron radiation.

[6]  P. Eisenberger,et al.  The study of disordered systems by EXAFS: Limitations , 1979 .

[7]  Liquan Chen,et al.  Capacitive Energy Storage on Fe/Li3PO4 Grain Boundaries , 2011 .

[8]  K. Kang,et al.  Electrochemical and ex-situ analysis on manganese oxide/graphene hybrid anode for lithium rechargeable batteries , 2011 .

[9]  T. Phan,et al.  Influence of Annealing Temperature on Spin Dynamics of Mn in Metal Oxides: Electron Spin Resonance Study , 2010, IEEE Transactions on Magnetics.

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

[11]  J. Tarascon,et al.  On the Origin of the Extra Electrochemical Capacity Displayed by MO/Li Cells at Low Potential , 2002 .

[12]  J. Tarascon,et al.  High temperature lithium cells using conversion oxide electrodes , 2009 .

[13]  J. Dahn,et al.  Electrochemical and In Situ X‐Ray Diffraction Studies of Lithium Intercalation in Li x CoO2 , 1992 .

[14]  Quan Fan,et al.  Electrospun Manganese Oxide Nanofibers as Anodes for Lithium-Ion Batteries , 2007 .

[15]  Liquan Chen,et al.  Investigation on porous MnO microsphere anode for lithium ion batteries , 2011 .

[16]  A. P. Hammersley,et al.  Two-dimensional detector software: From real detector to idealised image or two-theta scan , 1996 .

[17]  R. Huggins,et al.  Thermodynamic investigations of ternary lithium-transition metal-oxygen cathode materials , 1980 .

[18]  Gavin Vaughan,et al.  In situ X-ray diffraction techniques as a powerful tool to study battery electrode materials , 2002 .

[19]  J. Tarascon,et al.  From the vanadates to 3d-metal oxides negative electrodes , 2000 .

[20]  A. Stoneham,et al.  The basic atomic processes of corrosion II. Defect structures and cation transport in transition-metal oxides , 1979 .

[21]  Liquan Chen,et al.  MnO powder as anode active materials for lithium ion batteries , 2010 .

[22]  Michael A. Lowe,et al.  Spongelike Nanosized Mn3O4 as a High-Capacity Anode Material for Rechargeable Lithium Batteries , 2011 .

[23]  M. Litt,et al.  Ring-opening polymerization of ethylene carbonate and depolymerization of poly(ethylene oxide-co-ethylene carbonate) , 2000 .

[24]  John B. Goodenough,et al.  Lithium insertion into manganese spinels , 1983 .

[25]  J. Tarascon,et al.  Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries , 2000, Nature.

[26]  J. Xie,et al.  Nanocrystal manganese oxide (Mn3O4, MnO) anchored on graphite nanosheet with improved electrochemical Li-storage properties , 2012 .

[27]  M. Thackeray,et al.  A preliminary investigation of the electrochemical performance of α-Fe2O3 and Fe3O4 cathodes in high-temperature cells , 1981 .

[28]  Yan Yu,et al.  Some new facts on electrochemical reaction mechanism for transition metal oxide electrodes , 2009 .

[29]  Michael F Toney,et al.  In Operando X-ray diffraction and transmission X-ray microscopy of lithium sulfur batteries. , 2012, Journal of the American Chemical Society.

[30]  E. Cairns,et al.  Electrochemical in situ reaction cell for X-ray scattering, diffraction and spectroscopy. , 2003, Journal of synchrotron radiation.

[31]  P. Kofstad.  Defects and diffusion in MnO , 1983 .

[32]  Yong‐Sheng Hu,et al.  Electrode reactions of manganese oxides for secondary lithium batteries , 2010 .

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

[34]  James McBreen,et al.  In situ X-ray diffraction and X-ray absorption studies of high-rate lithium-ion batteries , 2001 .

[35]  J. Cabana,et al.  Beyond Intercalation‐Based Li‐Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions , 2010, Advanced materials.

[36]  George Srajer,et al.  Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides , 2003 .

[37]  K. Lee,et al.  Polaronic conduction of electrons in α-Mn3O4 slightly doped with Li , 1993 .

[38]  Mao-Sung Wu,et al.  Synthesis of manganese oxide electrodes with interconnected nanowire structure as an anode material for rechargeable lithium ion batteries. , 2005, The journal of physical chemistry. B.

[39]  H. Dai,et al.  Mn3O4-graphene hybrid as a high-capacity anode material for lithium ion batteries. , 2010, Journal of the American Chemical Society.