| Summary: | The thermal stability of the polyethylene (PE) separator is of utmost importance for the safety of lithium-ion batteries. Although the surface coating of PE separator with oxide nanoparticles can improve thermal stability, some serious problems still exist, such as micropore blockage, easy detaching, and introduction of excessive inert substances, which negatively affects the power density, energy density, and safety performance of the battery. In this paper, TiO<sub>2</sub> nanorods are used to modify the surface of the PE separator, and multiple analytical techniques (e.g., SEM, DSC, EIS, and LSV) are utilized to investigate the effect of coating amount on the physicochemical properties of the PE separator. The results show that the thermal stability, mechanical properties, and electrochemical properties of the PE separator can be effectively improved via surface coating with TiO<sub>2</sub> nanorods, but the degree of improvement is not directly proportional to the coating amount due to the fact that the forces inhibiting micropore deformation (mechanical stretching or thermal contraction) are derived from the interaction of TiO<sub>2</sub> nanorods directly “bridging” with the microporous skeleton rather than those indirectly “glued” with the microporous skeleton. Conversely, the introduction of excessive inert coating material could reduce the ionic conductivity, increase the interfacial impedance, and lower the energy density of the battery. The experimental results show that the ceramic separator with a coating amount of ~0.6 mg/cm<sup>2</sup> TiO<sub>2</sub> nanorods has well-balanced performances: its thermal shrinkage rate is 4.5%, the capacity retention assembled with this separator was 57.1% under 7 C/0.2 C and 82.6% after 100 cycles, respectively. This research may provide a novel approach to overcoming the common disadvantages of current surface-coated separators.
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