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Polyethylene (PE) membranes coated with nano-Al₂O₃ have been improved with water-dispersed poly(p-phenylene terephthamide) (PPTA). From the scanning electron microscope (SEM) images, it can be seen that a layer with a honeycombed porous structure is formed on the membrane. The thus-formed composite separator imbibed with the electrolyte solution has an ionic conductivity of 0.474 mS/cm with an electrolyte uptake of 335%. At 175 °C, the assembled battery from the synthesized composite separator explodes at 3200 s, which is five times longer than the battery assembled from an Al₂O₃-coated polyethylene (PE) membrane. The open circuit voltage of the assembled battery using a composite separator drops to zero at 600 s at an operating temperature of 185 °C, while the explosion of the battery with Al₂O₃-coated PE occurs at 250 s. More importantly, the interface resistance of the cell assembled from the composite separator decreases to 65 Ω. Hence, as the discharge rate increases from 0.2 to 1.0 C, the discharge capacity of the battery using composite separator retains 93.5%. Under 0.5 C, the discharge capacity retention remains 99.4% of its initial discharge capacity after 50 charge−discharge cycles. The results described here demonstrate that Al₂O₃/PPTA-coated polyethylene membranes have superior thermal stability and ion diffusion.