Improved Performance of Graphite/ LiNi0.5Mn1.5O4 Cells Cycled to High Voltage (4.8 V) with Electrolyte Additives
The failure mechanism of graphite /LiNi0.5Mn1.5O4 cells cycled at 25 oC and 55 oC (1.2 M LiPF6 in 3:7 EC/EMC) have been analyzed by electrochemical methods and ex-situ surface analysis of the electrodes. Graphite /LiNi0.5Mn1.5O4 cells cycle well at 25 oC , but have rapid capacity fade upon cycling at 55 oC. Independent electrochemical analysis of anodes and cathodes extracted from cells cycled at 55 oC suggest that both electrodes have significant capacity loss, although the cathode capacity can be recovered with longer charging times. Ex-situ surface analysis of the cathode with SEM reveals that the bulk cathode particles and the cathode laminate are retained while XPS confirms the presence of a cathode electrolyte interface composed of the decomposition products of the electrolyte. Ex-situ analysis of the anode reveals a thick anode solid electrolyte interphase (SEI), anode delamination, and the presence of Mn. The results suggest that both the anode and the cathode contribute to performance loss in graphite/LiNi0.5Mn1.5O4cells.
We are using this mechanistic information about capacity fade in graphite/LiNi0.5Mn1.5O4 cells to develop novel additives to improve the performance of LiNi0.5Mn1.5O4 cycled to high voltage (4.9 V vs Li). The additives include Lewis basic species which inhibit the thermal decomposition of LiPF6 and cathode film forming additives. Preliminary investigations suggest that incorporation of the novel additives into graphite/ LiNi0.5Mn1.5O4 cells significantly improves the capacity retention upon cycling at high voltage (4.9 V vs Li) and moderately elevated temperature (55 oC). Ex-situ surface analysis of the electrodes after cycling suggest that the additives modify the surface of the LiNi0.5Mn1.5O4cathode via the formation of a stable cathode electrolyte interface (CEI). The presence of the CEI inhibits the oxidation of the electrolyte and dissolution of Mn and Ni from the surface of the cathode particles. The additives, also stabilize the SEI on the anode by preventing Mn deposition on the anode surface and damage of the anode SEI.
The details of our experimental results and our mechanistic interpretation will be presented.
This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, Subcontract No 6879235 under the Batteries for Advanced Transportation Technologies (BATT) Program. In addition, we thank BASF-SE for financial support of this research.