Sputtering graphite coating to improve the elevated-temperature cycling ability of the LiMn2O4 electrodeElectronic supplementary information (ESI) available: Raman spectra of samples before and after 30 min graphite sputtering; video images presenting the electrolyte dispersion into the BLMO and GLMO-30 electrodes as a function of time. See DOI: 10.1039/c4cp01069h

To improve the cycle performance of LiMn 2 O 4 at elevated temperature, a graphite layer is introduced to directly cover the surface of a commercial LiMn 2 O 4 -based electrode via room-temperature DC magnetron sputtering. The as-modified cathodes display improved capacity retention as compared to the bare LiMn 2 O 4 cathode (BLMO) at 55 °C. When sputtering graphite for 30 min, the sample shows the best cycling performance at 55 °C, maintaining 96.2% capacity retention after 200 cycles. Reasons with respect to the graphite layer for improving the elevated-temperature performance of LiMn 2 O 4 are systematically investigated via the methods of cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectrometry, scanning and transmission electron microscopy, X-ray diffraction and inductively coupled plasma-atomic emission spectrometry. The results demonstrate that the graphite coated LiMn 2 O 4 cathode has much less increased electrode polarization and electrochemical impedance than BLMO during the elevated-temperature cycling process. Furthermore, the graphite layer is able to alleviate the severe dissolution of manganese ions into the electrolyte and mitigate the morphological and structural degradation of LiMn 2 O 4 during cycling. A model for the electrochemical kinetics process is also suggested for explaining the roles of the graphite layer in suppressing the Mn dissolution. The graphite layer acts as a barrier against HF corrosion to LiMn 2 O 4 , thus improving its high-temperature cycle performance.