An Efficient, Scalable Route to Robust PVDF‐co‐HFP/SiO2 Separator for Long‐Cycle Lithium Ion Batteries

A highly uniform, heterogeneous‐phase composite separator is synthesized by a direct post‐solidation process from the mixture of nano‐SiO2/acetone monodisperse suspension and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP)/acetone gel, without any organic surfactants. This technique leads to the PVDF‐co‐HFP/SiO2 composite separator outstanding microstructural uniformity. The incorporation of SiO2 nanoparticles leads to reduced crystallinity (≈27%), enhanced wettability (≈14%), improved electrolyte uptake (≈420%), and enhanced mechanical strength (>14 MPa) of the composite separator. These enhanced properties of the separator translate into remarkable LiFePO4/Li battery performance with reduced polarization, a high room‐temperature capacity of 165 mAh g−1 at 0.5 C, a high thermal dimensional stability (≈4.5% shrinkage after annealing at 160 °C for 1 h) and 5.2% capacity degradation after 1500 charge/discharge cycles at 2 C.