Membrane distillation (MD) is a promising technology for treating high-salinity mine water. However, MD membranes are known to have low membrane flux and are prone to fouling. In this study, we used the cost-effective and controllable vapor-induced phase separation (VIPS) technology to prepare polyvinylidene difluoride (PVDF) membranes, replacing the traditional immersion precipitation method and optimizing the membrane structure by including LiCl and acetone as porogen in the casting solution. The results showed that the membrane prepared using the VIPS method exhibited a highly open interconnected porous surface. Unlike traditional MD membranes with a dense epidermal layer and large finger-like pores, these optimized membranes had a symmetrical and uniform internal structure, leading to a high flux of 8.62 kg·(m2·h)−1 during direct contact membrane distillation testing. Different porogens produced varied results on the VIPS process and varying effects on membrane structure. The use of LiCl promoted the formation of PVDF β-phase, resulting in a decrease in the number of spherical nodules on the membrane surface, as well as improved density and smoothness. Consequently, this reduced fouling risk during membrane distillation while slightly decreasing membrane flux. On the other hand, acetone rapidly evaporated during the VIPS process, facilitating pre-gelatinization and α-phase formation of PVDF. This concurrent effect effectively restricted excessive nodule growth on the membrane surface, endowing the membrane with antifouling capabilities while preserving high flux.
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