Capturing Solid Solutions during a First-Order Phase Transition of Li1+XMn2O4

Wednesday, 4 October 2017
Prince George's Exhibit Hall D/E (Gaylord National Resort and Convention Center)
B. Song, G. M. Veith, P. Whitfield, R. Schmidt, M. J. Kirkham, and A. Huq (Oak Ridge National Laboratory)
Lithium-ion batteries (LIBs) offering the highest energy density among the known battery chemistries are the major contenders for both transportation and stationary storage applications. In order to satisfy the demands of energy density for these applications, new full cell configuration with either improved working voltage or specific capacity is needed to further enlarge its energy density. One candidate that has received a great deal of attention is the spinel cathode LiMn2O4, which offers the advantages of a high operating voltage (4.0 V vs. Li+/Li) and an excellent rate capability. Nonetheless, the relatively low specific capacity of 125 mAh·g-1 is mainly due to the restricted operating voltage between 3 and 4.5 V. In theory, LiMn2O4 cathode can deliver a capacity of ∼297 mAh·g-1 when 2 mole of lithium ions are inserted/extracted into/from both 8a tetrahedral and 16c octahedral sites of the spinel lattice at the voltages of, respectively, ∼4.0 and ∼2.7 V.1 Phase transition related to 4.0 V plateau is highly reversible, involving only two similar cubic spinel phases. However, phase transition related to 2.7 V plateau is partly reversible because a cubic spinel transforms to a tetragonal spinel with Jahn-Teller distortion occurring as a result of Mn3+ formation. The increase in the axial ratio from c/a = 1.0 in the cubic phase to c/a = 1.6 in the tetragonal phase due to the cooperative Jahn-Teller distortion leads to a fracture of large particles, which induces a loss of electrical contact with the current collector upon cycles.2 These effects cause serious capacity fading. However, the dynamic process of this phase transition has never been fully understood due to a lack of characterization techniques.

Based on the above considerations, we report an in operando neutron diffraction study to fully understand the ~2.7 V related phase transition in the Li1+xMn2O4 spinel upon electrochemical cycling. We found solid solution formation upon reversible discharge and charge process, although a first-order phase transition is widely believed. The solid solution formation is possibly due to a thick electrode configuration that we applied and a large overpotential it could generate, which is cosistent with the phenomenon that observed under high-rate charging/discharging of LiFePO4 using in situ synchrotron XRD.3

  1. J. B. Goodenough, M. M. Thackeray, W. I. F. David, P. G. Bruce, Rev. Chim. Miner., 1984, 21, 435.
  2. S.-H. Kang, J. B. Goodenough, and L. K. Rabenberg, Chemistry of Materials, 2001, 13, 1758-1764.
  3. H. Liu, F. C. Strobridge, O. J. Borkiewicz, K. M. Wiaderek, K. W. Chapman, P. J. Chupas, C. P. Grey, Science 344, 7 (2014).