An Ideal Structure for Li-Ion Battery Separators
Authors: Luiso Salvatore , Williams Austin H , Velev Orlin D. , Pourdeyhimi Behnam , Fedkiw Peter S. 
Published: December 2020

Among all types of Li-ion battery (LIB) separators, fibrous mats have the advantage of low cost, low mass, and high porosity. Fibrous Poly(Vinylidene difluoride) (PVDF) shows promising results because of its stability and affinity for electrolytes commonly employed in Li-ion cells. Despite numerous studies published on LIB separators, none reports structure-property relationships for the identification of an ideal structure. We investigated the properties of a melt-blowable PVDF and produced meltblown PVDF mats in scale-up equipment with the objective of elucidating its performance as a LIB separator. We also present a new class of LIB separators, PVDF-based highly-branched, colloidal polymer particulates called soft dendritic colloids that are produced by shear-driven polymer precipitation within a highly turbulent nonsolvent flow, followed by filtration. We show that the morphology of the resulting PVDF particulates can be modulated from fibrous soft dendritic colloids (SDC) to thin and highly porous sheet-like particles.
Through a scale-up system, we obtained high-quality meltblown PVDF with high homogeneity, low number of defects, an average fiber diameter of 1.4 μm, and pore size as low as 0.9 μm. Small fiber diameter provides high-surface area and high-electrolyte uptake. We show interactions of the meltblown PVDF with the electrolyte lead to a morphology change in the fibers. The highest ionic conductivity was ~ 9.6 mS/cm, and the first-cycle capacity was 140 mAh/g (Li/LiCoO2). After melt-pressing, the thickness and pore size decrease, but the mats electrolyte absorbency and conductivity decrease commensurately. PVDF SDC separators show high porosity (up to 80%) and high particle surface area, which results in high conductivity (1.2 mS/cm), high-electrolyte uptake (325%), and high-cell capacity (112 mAh/g in Li/LiCoO2 cell) with <10% loss after 50 cycles. Both processes yield separators with low thermal shrinkage (<5% at 90 ºC) and high tensile strength (<0.5% offset at 1000 psi), with the highest-performing separator possessing low average fiber diameter with a wide diameter distribution.
Both meltblowing and shear-driven precipitation are facile and versatile processes for high-volume fabrication of LIB separators with one single polymer without necessarily requiring post-processing and with characteristics similar to commercially available battery separators. Our findings show that battery separators should be fabricated with a low pore size (<2 µm) but also with a wide pore distribution. When the strength and openness of the micropores are coupled with a dense net of nanopores, an ideal Li-ion battery separator is obtained.
References:

Luiso, S., Henry, J. J., Pourdeyhimi, B. & Fedkiw, P. S. (2020). Fabrication and Characterization of Meltblown Poly(vinylidene difluoride) Membranes. ACS Appl. Polym. Mater., 2, 2849–2857.

S. Roh, A. H. Williams, R. S. Bang, S. D. Stoyanov, and O. D. Velev (2019). Soft dendritic microparticles with unusual adhesion and structuring properties. Nature Materials, vol. 18, no. 12. pp. 1315–1320.