Lithium ion battery technology is the heart in operating modern technology devices such as mobile phones and laptops. However, as our society is moving towards the utilization of sustainable energy sources, batteries can be foreseen to become an even more important part of the energy infrastructure. They will be used not only for transportation, but also for medium and short term storage as well as for frequency stabilization in intermittent grid scale energy sources such as solar and wind. Thus, the development of new cheaper and safer battery materials with high energy and power density is very important for a successful worldwide energy transition. The understanding of structural and compositional changes of bulk electrodes in batteries is undoubtedly important. However, it is often transport of electrons and ions across and through interfaces  (e.g., between lithiated and delithiated domains) which limits the obtainable power density and battery life time. A challenging and important task is to obtain in situ information about the formation and evolution of interfaces in an operating battery system. This work addresses these challenges and for this purpose we have developed a special microcapillary battery cell allowing diffraction information to be obtained from only the active material during battery operation . High resolution synchrotron x-ray powder diffraction technique has been undertaken to obtain detailed structural and compositional information during lithiation/delithiation of commercial LiFePO4 materials . We report results from the first in situ time resolved high resolution powder diffraction experiments at beamline ID22/31 at the European Synchrotron Radiation Facility, ESRF. We follow the structural changes during charge of commercial LiFePO4 based battery materials using the Rietveld method. Conscientious Rietveld analysis shows slight but continuous deviation of lattice parameters from those of the fully stoichiometric end members LiFePO4 and FePO4 indicating a subsequent variation of stoichiometry during cathode delithiation. The application of an intermittent current pulses during charge using GITT technique shows an oscillation of lattice constants that correlates with the applied current and electrochemical relaxation sequence and may indicate the existence of metastable non-stoichiometric states. References  R. Malik, F. Zhou, and G. Ceder, Nat. Mater., 10, 587 (2011).  R. E. Johnsen, and P. Norby, J. Appl. Crystallogr., 46, 1537 (2013).  A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, J. Electrochem. Soc., 144, 1188 (1997).
|Electrochemical Society. Meeting Abstracts (Online)
|Number of pages
|Published - 2015
|227th ECS Meeting - Chicago, IL, United States
Duration: 24 May 2015 → 28 May 2015
|227th ECS Meeting
|24/05/2015 → 28/05/2015