Electrospinning as a versatile technique producing nanofibers was employed to study the influence of the processing parameters and chemical and physical parameters of solutions on poly(vinylidene fluoride) (PVDF) fibers’ morphology, crystallinity, phase composition and dielectric and piezoelectric characteristics. PVDF fibrous layers with nano- and micro-sized fiber diameters were prepared by a controlled and reliable electrospinning process. The fibers with diameters from 276 nm to 1392 nm were spun at a voltage of 25 kV–50 kV from the pure PVDF solutions or in the presence of a surfactant—Hexadecyltrimethylammonium bromide (CTAB). Although the presence of the CTAB decreased the fibers’ diameter and increased the electroactive phase content, the piezoelectric performance of the PVDF material was evidently deteriorated. The maximum piezoelectric activity was achieved in the fibrous PVDF material without the use of the surfactant, when a piezoelectric charge of 33 pC N⁻¹ was measured in the transversal direction on a mean fiber diameter of 649 nm. In this direction, the material showed a higher piezoelectric activity than in the longitudinal direction.

Utilizing the triboelectric effect of the fibrous structure, a very low cost and straightforward sensor or an energy harvester can be obtained. A device of this kind can be flexible and, moreover, it can exhibit a better output performance than a device based on the piezoelectric effect. This study is concerned with comparing the properties of triboelectric devices prepared from polyvinylidene fluoride (PVDF) fibers, polyamide 6 (PA) fibers, and fibrous structures consisting of a combination of these two materials. Four types of fibrous structures were prepared, and then their potential for use in triboelectric devices was tested. Namely, individual fibrous mats of (i) PVDF and (ii) PA fibers, and their combination—(iii) PVDF and PA fibers intertwined together. Finally, the fourth kind was (iv), a stratified three-layer structure, where the middle layer from PVDF and PA intertwined fibers was covered by PVDF fibrous layer on one side and by PA fibrous layer on the opposite side. Dielectric properties were examined and the triboelectric response was investigated in a simple triboelectric nanogenerator (TENG) of individual or combined (i–iv) fibrous structures. The highest triboelectric output voltage was observed for the stratified three-layer structure (the structure of iv type) consisting of PVDF and PA individual and intertwined fibrous layers. This TENG generated 3.5 V at peak of amplitude at 6 Hz of excitation frequency and was most sensitive at the excitation signal. The second highest triboelectric response was observed for the individual PVDF fibrous mat, generating 2.8 V at peak at the same excitation frequency. The uniqueness of this work lies in the dielectric and triboelectric evaluation of the fibrous structures, where the materials PA and PVDF were electrospun simultaneously with two needles and thus created a fibrous composite. The structures showed a more effective triboelectric response compared to the fibrous structure electrospun by one needle.

Global concerns over energy availability and the environment impose an urgent requirement for sustainable manufacturing, usage, and disposal of electronic components. Piezoelectric and photovoltaic components are being extensively used. They contain the hazardous element, Pb (e.g., in widely used and researched Pb(Zr,Ti)O₃ and halide perovskites), but they are not being properly recycled or reused. This work demonstrates the fabrication of upside‐down composite sensor materials using crushed ceramic particles recycled from broken piezoceramics, polycrystalline halide perovskite powder collected from waste dye‐sensitized solar cells, and crystal particles of a Cd‐based perovskite composition, C₆H₅N(CH₃)₃CdBr_3xCl_3(1–x). The piezoceramic and halide perovskite particles are used as filler and binder, respectively, to show a proof of concept for the chemical and microstructural compatibility between the oxide and halide perovskite compounds while being recycled simultaneously. Production of the recycled and reusable materials requires only a marginal energy budget while achieving a very high material densification of >92%, as well as a 40% higher piezoelectric voltage coefficient, i.e., better sensing capability, than the pristine piezoceramics. This work thus offers an energy‐ and environmentally friendly approach to the recycling of hazardous elements as well as giving a second life to waste piezoelectric and photovoltaic components.