This paper considered the electrochemical behavior of new electrospun separators for lithium-ion batteries on the basis of nano- and microfibers of polyvinylidene fluoride (PVDF) and its polymer composition, with polytetrafluoroethylene (PTFE) having advanced electroconductive properties over conventionally used separators based on polypropylene (PP) and glass-fibers (GF). Such advancement is associated with the low density of electrospun material leading to lower mechanical strengths. However, its use in the electrochemical systems with middle-voltage anode materials where dendrite growth is excluded is very prospective. The performance at the operation of the separators were investigated in the three-electrode-containing laboratory half-cells having Li4
as the electrode under investigation. Galvanostatic charge and discharge tests of cells were conducted under variation of the experimental conditions: the current varied in the range 0.1 C–1 C, and 1C cycling was conducted over 100 cycles. The working electrode and separator characteristics at cycling were monitored by the electrochemical impedance spectroscopy (EIS) method. The gradual decrease of Li4
transport characteristics at cycling was noticed for all the types of separators. However, the least degradation rate was associated with the PVDF and the PTFE-based separator. This fact is explained by the better conductivity of an electrospun separator compared to others, with therefore a better current distribution on the electrode surface and a lower concentration perturbation in the electrode.
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