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• The modification strategy with PDA@nano-TiO 2 was designed to enhance electrochemical performance of spinel LNMO. • PDA@TiO 2 -LNMO cathode showed high reversible capacities and good capacity retention. • The excellent performance was attributed to PDA@nano-TiO2 as protective layer and good conductor for Li+ diffusion. The surface modification of LiNi 0.5 Mn 1.5 O 4 cathode material with PDA@TiO 2 enable it gain the high reversible capacities and good capacity retention. [Display omitted] Improving the cycling performance without sacrificing its capacity is challenging for high-voltage LiNi 0.5 Mn 1.5 O 4 cathode due to the trade-off nature among the key properties. A self-polymerization process of dopamine was utilized to grow polydopamine (PDA)-nano titanium dioxide assembly. PDA@TiO 2 composite was demonstrated to be integrated with the particles of high-voltage spinel LiNi 0.5 Mn 1.5 O 4 cathodes via wet chemical method. PDA@TiO 2 decorated LNMO improved the long-term cycling performance and rate capability by suppressing detrimental side reactions in balancing the interfacial stability and Li+ diffusion kinetics of LNMO and consequently providing efficient conductive pathways. As a result, 2% PDA@TiO 2 modified LNMO cathode exhibited the high reversible capacity of 117 mAh g−1 after 1000 cycles with good capacity retention of 90.7% at 1 C, and superior rate capability (78.5 mAh g−1 at 5 C) at room temperature. Remarkably, a significant improvement in cycling stability at an elevated temperature (50 °C) was obtained for the PDA@TiO 2 -LNMO composite, giving a capacity retention of 93% after 100 cycles at 1 C. The mechanism of performance improvement could be attributed to the maintenance of the structural stability of LNMO cathode materials and the enhanced kinetics of the remarkable lithium-ion diffusion through the protective effect of PDA@TiO 2 decorating. [ABSTRACT FROM AUTHOR]