In recent years, wearable sensors and energy harvesters have shown great potential for a wide range of applications in personalized healthcare, robotics, and human-machine interfaces. Among different types of materials used in wearable electronics, piezoelectric materials have gained enormous attention due to their exclusive ability to harvest energy from ambient sources. Piezoelectric materials can be utilized as sensing elements in wearable sensors while harvesting biomechanical energy. Electrospun piezoelectric polymer nanofibers are extensively investigated due to their high flexibility, ease of processing, biocompatibility, and higher piezoelectric property (in contrast to their corresponding cast films). However, as compared to piezoceramic materials, they mostly exhibit relatively lower piezoelectric coefficients. Therefore, considerable efforts have been devoted to improving the piezoelectricity of electrospun polymer nanofibers recently, resulting in significant advances. This review presents a broad overview of these advances including new material, structure designs as well as new strategies to enhance piezoelectricity of electrospun polymer nanofibers. The challenges in achieving high mechanical performance as well as high piezoelectricity are particularly discussed. The main motivation of this review is to examine these challenges and highlight effective approaches to achieving high-performance piezoelectric sensors and energy harvesters for wearable technologies.

Polyvinylidene fluoride (PVDF) is a piezo‐polymer which among its crystalline phases, the β‐phase has been researched for the improvement of piezoelectric properties. In this study, to improve the β‐phase contents and thereby the piezoelectric response of the polymer, the effect of adding self‐synthesized ionic liquid surfactant (ILS) in PVDF nanofibers is studied. This material is added in different weight percentages into the PVDF solution and the nanofibers are produced by electrospinning to prepare active piezoelectric thin layers. SEM, XRD, FTIR, and piezo‐tests are employed for assessing the effect of the ILS on the enhancement of β‐phase in electrospun nanofibers and their piezoelectric performance. The results indicate ≈98.6% β‐phase formation in the sample containing 4 wt% ILS and in comparison with the pure nanofibers, the output voltage and its power density are improved 186.9% and 275%, respectively. Considering the results, it is suggested that the ILS can improve the piezoelectric response of the polymer in the fabricated structure by simple mixing in solution compared to other additives.