The performance of the Li/LiNi
0.5Mn
1.5O
4 cells cycled to 5.0 V (vs. Li/Li
+) using 1.0 M LiPF
6-EC/DMC (1/1, v/v) with and without dimethoxydiphenylsilane (DDS) at 25°C has been investigated. Cells with 1% DDS added deliver slightly lower initial discharge capacity than the cells with baseline electrolyte, 115.3 vs. 120.9 mAh g
−1. Electrochemical methods and ex-situ analytical techniques, including TGA and SEM, are employed to conduct the interfacial chemistry of LiNi
0.5Mn
1.5O
4/electrolyte to better understand the improved electrochemical performances of the cells with introduction of DDS. The results indicate that DDS can be electro-oxidized and participates in the formation of the surface layer on cathode electrode, which prevents electrolyte from further decomposition and promotes Li
+ conduction of the cathode/electrolyte interphase, thus improves the electrochemical performances of Li/LiNi
0.5Mn
1.5O
4 cells.
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