This study is focused on the characterization and investigation of polyvinylidene fluoride (PVDF) nanofibers from the point of view of macro- and nanometer level. The fibers were produced using electrostatic spinning process in air. Two types of fibers were produced since the collector speed (300 rpm and 2000 rpm) differed as the only one processing parameter. Differences in fiber’s properties were studied by scanning electron microscopy (SEM) with cross-sections observation utilizing focused ion beam (FIB). The phase composition was determined by Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy. The crystallinity was determined by differential scanning calorimetry (DSC), and chemical analysis of fiber’s surfaces and bonding states were studied using X-ray photoelectron spectroscopy (XPS). Other methods, such as atomic force microscopy (AFM) and piezoelectric force microscopy (PFM), were employed to describe morphology and piezoelectric response of single fiber, respectively. Moreover, the wetting behavior (hydrophobicity or hydrophilicity) was also studied. It was found that collector speed significantly affects fibers alignment and wettability (directionally ordered fibers produced at 2000 rpm almost super-hydrophobic in comparison with disordered fibers spun at 300 rpm with hydrophilic behavior) as properties at macrolevel. However, it was confirmed that these differences at the macrolevel are closely connected and originate from nanolevel attributes. The study of single individual fibers revealed some protrusions on the fiber’s surface, and fibers spun at 300 rpm had a core-shell design, while fibers spun at 2000 rpm were hollow.

This review summarizes the current trends and developments in the field of polyvinylidene fluoride (PVDF) for use mainly as a nanogenerator. The text covers PVDF from the first steps of solution mixing, through production, to material utilization, demonstration of results, and future perspective. Specific solvents and ratios must be selected when choosing and mixing the solution. It is necessary to set exact parameters during the fabrication and define whether the material will be flexible nanofibers or a solid layer. Based on these selections, the subsequent use of PVDF and its piezoelectric properties are determined. The most common degradation phenomena and how PVDF behaves are described in the paper. This review is therefore intended to provide a basic overview not only for those who plan to start producing PVDF as energy nanogenerators, active filters, or sensors but also for those who are already knowledgeable in the production of this material and want to expand their existing expertise and current overview of the subject.