Time-Dependent in-Situ Neutron Diffraction Investigation of a Li(Co0.16Mn1.84)O4 Cathode

Real-time in-situ neutron diffraction data reveal for the first time that the Li(Co0.16Mn1.84)O4 cathode undergoes current-free discharge. We find that current-free discharge occurs in a partially charged Li(Co0.16Mn1.84)O4 cathode during its first charge cycle over a period of 11 h resulting in a 44(2)% expansion of the crystal lattice. The rate of change in the lattice parameter during the current-free discharge process is half the rate and more linear than for an applied-current discharge of −0.5 mA. The origins of current-free discharge are discussed along with the implications of nonequilibrium relaxation processes in in-situ neutron and X-ray diffraction studies. We show that the lattice does not return to the predischarge values after either current-applied or current-free discharge, indicating a limited ability for Li reinsertion (capacity loss) in partially charged Li(Co0.16Mn1.84)O4 batteries.

[1]  D. Richard,et al.  Analysis and Visualisation of Neutron-Scattering Data , 1996 .

[2]  Neeraj Sharma,et al.  In-situ neutron diffraction study of the MoS2 anode using a custom-built Li-ion battery , 2011 .

[3]  J. Tarascon,et al.  In SituStructural Study of 4V-Range Lithium Extraction/Insertion in Fluorine-Substituted LiMn2O4 , 1999 .

[4]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[5]  M. Hagen,et al.  WOMBAT: The High Intensity Powder Diffractometer at the OPAL Reactor , 2006 .

[6]  Smith,et al.  Neutron powder-diffraction studies of lithium, sodium, and potassium metal. , 1989, Physical review. B, Condensed matter.

[7]  Jean-Marie Tarascon,et al.  Materials' effects on the elevated and room temperature performance of CLiMn2O4 Li-ion batteries , 1997 .

[8]  P. Novák,et al.  A novel electrochemical cell for in situ neutron diffraction studies of electrode materials for lithium-ion batteries , 2008 .

[9]  E. Kelder,et al.  Neutron diffraction study of stoichiometric spinel Li1+xMn2–xO4 showing octahedral 16c-site Li-occupation , 1999 .

[10]  Petr Novák,et al.  Insertion Electrode Materials for Rechargeable Lithium Batteries , 1998 .

[11]  B. Chowdari,et al.  Synthesis of compounds, Li(MMn11/6)O4 (M = Mn1/6, Co1/6, (Co1/12Cr1/12), (Co1/12Al1/12), (Cr1/12Al1/12)) by polymer precursor method and its electrochemical performance for lithium-ion batteries , 2010 .

[12]  Josh Thomas,et al.  Neutron diffraction study of electrochemically delithiated LiMn2O4 spinel , 1999 .

[13]  Mark Hilary Van Benthem,et al.  In situ analysis of LiFePO4 batteries: Signal extraction by multivariate analysis , 2010, Powder Diffraction.

[14]  H. Berg,et al.  The LiMn2O4 to λ-MnO2 phase transition studied by in situ neutron diffraction , 2001 .

[15]  Michael M. Thackeray,et al.  Improved capacity retention in rechargeable 4 V lithium/lithium- manganese oxide (spinel) cells , 1994 .

[16]  S. Mukerjee,et al.  Structural evolution of Li{sub x}Mn{sub 2}O{sub 4} in lithium-ion battery cells measured in situ using synchrotron X-ray diffraction techniques , 1998 .

[17]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[18]  J. Tarascon,et al.  On the origin of the 3.3 and 4.5 V steps observed in LiMn{sub 2}O{sub 4}-based spinels , 2000 .

[19]  J. Goodenough.  Challenges for Rechargeable Li Batteries , 2010 .

[20]  M. Wakihara.  Recent developments in lithium ion batteries , 2001 .

[21]  M. Hagen,et al.  Echidna—the new high-resolution powder diffractometer being built at OPAL , 2006 .

[22]  Kristina Edström,et al.  A neutron diffraction cell for studying lithium-insertion processes in electrode materials , 1998 .

[23]  J. Rodríguez-Carvajal,et al.  Cubic ↔ Orthorhombic Transition in the Stoichiometric Spinel LiMn2 O 4 , 1999 .

[24]  Brian H. Toby,et al.  EXPGUI, a graphical user interface for GSAS , 2001 .

[25]  A. D. Kock,et al.  Spinel Electrodes from the Li‐Mn‐O System for Rechargeable Lithium Battery Applications , 1992 .

[26]  Dominique Guyomard,et al.  The carbon/Li1+xMn2O4 system , 1994 .

[27]  Neeraj Sharma,et al.  Structural changes in a commercial lithium-ion battery during electrochemical cycling: An in situ neutron diffraction study , 2010 .

[28]  Mark A. Rodriguez,et al.  Simultaneous in situ-neutron diffraction studies of the anode and cathode in a lithium-ion cell , 2003 .

[29]  K. Nikolowski,et al.  Design and performance of an electrochemical in-situ cell for high resolution full-pattern X-ray powder diffraction , 2005 .

[30]  Dominique Guyomard,et al.  Self-discharge of LiMn2O4/C Li-ion cells in their discharged state: Understanding by means of three-electrode measurements , 1998 .

[31]  R. Frech,et al.  In situ Raman spectroscopic studies of electrochemical intercalation in LixMn2O4-based cathodes , 1999 .

[32]  Petr Novák,et al.  In situ neutron diffraction study of Li insertion in Li4Ti5O12 , 2010 .

[33]  H. M. Otte,et al.  X‐Ray Diffractometer Determination of the Thermal Expansion Coefficient of Aluminum near Room Temperature , 1963 .