Improving the performance of cathodes by using surface coatings has proven to be an effective method for improving the stability of Li-ion batteries (LIBs), while a high-quality film satisfying all requirements of electrochemical inertia, chemical stability, and lithium ion conductivity has not been found. In this study, a composite film composed of Al 2 O 3 and AlF 3 layers was coated on the surface of Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 (Li-rich NMC) based electrodes by atomic layer deposition (ALD). By varying the ratio of Al 2 O 3 and AlF 3 , an optimal coating was achieved. The electrochemical characterization results indicated that the coating with 1 cycle of AlF 3 ALD on 5 cycles of Al 2 O 3 ALD (1AlF 3 -5Al 2 O 3 ) significantly improved the cycling stability and alleviated the voltage attenuation problem of Li-rich NMC based electrodes by suppressing side reactions between the electrolyte and electrode, as well as inhibiting the transformation of layered Li 2 MnO 3 into a spinel-like phase. After 200 cycles of charge-discharge, the discharge capacity retention of LIB half cells based on 1AlF 3 -5Al 2 O 3 coated Li-rich NMC electrodes kept at 84%, much higher than that of the uncoated Li-rich NMC (the capacity retention less than 20%).