Combining Solid-State Shear Milling and FFF 3D-Printing Strategy to Fabricate High-Performance Biomimetic Wearable Fish-Scale PVDF-Based Piezoelectric Energy Harvesters

High-performance flexible piezoelectric polymer–ceramic composites are in high demand for increasing wearable energy-harvesting applications. In this work, a strategy combining solid-state shear milling (S³M) and fused filament fabrication (FFF) 3D-printing technology is proposed for the fabrication of high-performance biomimetic wearable piezoelectric poly­(vinylidene fluoride) (PVDF)/tetraphenylphosphonium chloride (TPPC)/barium titanate (BaTiO₃) nanocomposite energy harvesters with a biomimetic fish-scale-like metamaterial. The S³M technology could greatly improve the dispersion of BaTiO₃ sub-micrometer particles and the interfacial compatibility, resulting in better processability and piezoelectric performance of the nanocomposites. Typically, the FFF 3D printed energy harvester incorporating 30 wt % BaTiO₃ showed the highest piezoelectric outputs with an open-circuit voltage of 11.5 V and a short-circuit current of 220 nA. It could hence drive nine green LEDs to work normally. In addition, a 3D-printed biomimetic wearable energy harvester inspired by an environmentally adaptive fish-scale-like metamaterial was further fabricated. The fish-scale-like energy harvester could harvest energy through different deformation motions and successfully recharge a 4.7 μF capacitor by being mounted on a bicycle tire and the tire’s rolling. This work not only provides a 3D printing strategy for designing diversified and complex geometric structures but also paves the way for further applications in flexible, wearable, self-powered electromechanical energy harvesters.