A surface coating of SiO2 is applied to a Ni rich LiNi0.6Co0.2Mn0.2O2 cathode material in a bid to improve its electrochemical and thermal properties. A uniform coating is achieved through a wet process using nano-sized SiO2 powder, and though the coated electrode is found to exhibit a reduced rate capability, its cycle performance at a high temperature of 60 °C is greatly enhanced. The effect of this SiO2 coating is further investigated by electrochemical impedance spectroscopy, which confirms that it suppresses the growth of interfacial impedance during progressive cycles. The SiO2 coating also demonstrates good HF scavenging ability, producing a subsequent reduction in the degradation of the active core material. The thermal properties of LiNi0.6Co0.2Mn0.2O2 are also improved by the SiO2 coating due to a reduction in the direct contact between the electrode and electrolyte. On the basis of these results, SiO2 coating is considered a viable surface modification method for improving the electrochemical and thermal properties of LiNi0.6Co0.2Mn0.2O2.