Theoretical Model and Outstanding Performance from Constructive Piezoelectric and Triboelectric Mechanism in Electrospun PVDF Fiber Film

Abstract Flexible materials with high electromechanical coupling performance are highly demanded for wide applications for electromechanical sensors and transducers, including mechanical energy harvesters. Here, outstanding electromechanical performance is obtained in electrospun‐aligned polyvinylidene fluoride (PVDF) fiber film. A theoretical model is developed from systematic theoretical analyses to clarify the underlying constructive piezoelectric‐triboelectric mechanism in the polarized PVDF fiber films that explains the experimental observations well. The electrospinning process induces polarization alignment and thus tunes the electron affinity for PVDF fibers with different polarization terminals, which results in the constructive piezoelectric and triboelectric responses in the obtained PVDF fiber films. Extremely large effective piezoelectric performance properties are achieved in the direct piezoelectric measurements, reaching the maximum effective piezoelectric strain and voltage coefficients of −1065 pm V −1 and −9178 V mm N −1 , respectively, at 100 Hz. In the converse piezoelectric measurements without a significant contribution from reversible triboelectric effect, the maximum effective piezoelectric strain and voltage coefficients are −166 pm V −1 and −1499 V mm N −1 , respectively. The theoretical analyses and experimental results show the great potential of the electrospun aligned polar PVDF fiber material for various electromechanical device applications, particularly for mechanical energy harvesting.