Nanogenerator power output: influence of particle size and crystallinity of BaTiO₃

Lead-free piezoelectric nanogenerators made with BaTiO₃ offer an attractive energy harvesting solution towards portable, battery-free medical devices such as self-powered pacemakers. Here, we assembled nanogenerators made of thin, flexible poly(vinylidene fluoride-co-hexafluoropropylene) films containing either polycrystalline BaTiO₃ nanoparticles of various sizes or commercial monocrystalline particles of 64 or 278 nm in average diameter. The nanoparticles were prepared by hydrogen-driven flame aerosol technology and had an average diameter of 24-50 nm with an average crystal size of about 10 nm. The rapid cooling during nanoparticle formation facilitated the synthesis of polycrystalline, multi-domain, piezoelectrically active tetragonal BaTiO₃ with a high c/a lattice ratio. Using these particles, 2 μm thin polymer nanocomposites were formed, assembled into nanogenerators that exhibited a 1.4 V time-averaged output, almost twice that of the best commercial BaTiO₃ particles. That output was maintained stable for over 45 000 cycles with each cycle corresponding to a heartbeat of 60 bpm. The exceptional piezoelectric performance of these nanogenerators is traced to their constituent polycrystalline nanoparticles, having high degree of domain orientation upon poling and exhibiting the flexoelectric effect, polarization induced by a strain gradient.