Functionality Tuning in Hierarchically Engineered Magnetoelectric Nanocomposites for Energy-Harvesting Applications.

The ß-phase of the copolymer poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) possesses the highest dipole moment among all the functional polymers. It remains a key component of flexible energy-harvesting devices based on piezoelectricity and triboelectricity in the last decade. However, the quest for P(VDF-TrFE)-based magnetoelectric (ME) nanocomposites with enhanced ferroelectric, piezoelectric, and triboelectric properties remains elusive. The magnetostrictive inclusion in the copolymer matrix forms electrically conducting pathways and degrades ß-phase crystallinity significantly, deteriorating the functional properties of the nanocomposite films. To address this issue, we report the synthesis of magnetite (Fe3O4) nanoparticles on micron-scale magnesium hydroxide [Mg(OH)2] templates. These hierarchical structures were incorporated within the P(VDF-TrFE) matrix rendering composites with enhanced energy-harvesting capability. The Mg(OH)2 template prevents the formation of a continuous network of magnetic fillers, leading to lower electrical leakage in the composite. The addition of dual-phase fillers with 5 wt % only increases remanent polarization (Pr) values by ∼44%, owing to the presence of the ß-phase with significant crystallinity and increased interfacial polarization. The composite film exhibits a quasi-superparamagnetic nature and a significant magnetoelectric coupling coefficient (αME) of 30 mV/cm Oe. The film was also employed for triboelectric nanogenerator applications, exhibiting five times higher power density than the pristine film. We finally explored the integration of our ME devices with an internet of things platform to monitor the operational status of electrical appliances remotely. In light of these findings, the present work opens the path for future self-powered, multifunctional, and flexible ME devices with new application domains.

Exfoliated Molybdenum Disulfide-Wrapped CdS Nanoparticles as a Nano-Heterojunction for Photo-Electrochemical Water Splitting.

We developed a heterojunction photocathode, MoS2@CdS, based on the wrapping of CdS nanoparticles by the MoS2 nanocrystals. The liquid-phase exfoliation method was adopted for preparing few-layer MoS2 nanocrystals of a layer thickness of ∼7.9 nm, whereas CdS nanoparticles of an average diameter of ∼17 nm were synthesized by the one-step hydrothermal process. The synthesized nanocrystals and nanoparticles were characterized by AFM, FESEM, HRTEM, STEM, XRD, GIXRD, UV-vis absorption, fluorescence emission, and Raman spectroscopy. The difference between two modes in the Raman spectrum of MoS2 indicates the formation of few-layer MoS2. The photoelectrochemical performance of the heterojunction photocathode was excellent. The MoS2@CdS heterostructure photocathode increased the photocurrent density (JPh) under 100 mW/cm2 illumination. We obtained the maximum applied biased photoconversion efficiency (ABPE) of ∼1.2% of the MoS2@CdS heterojunction photocathode in optimum device configuration. The production of H2 was measured as ∼72 µmol/h for the MoS2@CdS heterostructure with a cyclic stability of up to 7500 s.

Milli-Watt Power Harvesting from Dual Triboelectric and Piezoelectric Effects of Multifunctional Green and Robust Reduced Graphene Oxide/P(VDF-TrFE) Composite Flexible Films.

For a variety of mechanical energy harvesting as well as biomedical device applications, flexible energy devices are useful which require the development of environment-friendly and robust materials and devices. In this manuscript, we demonstrate a lead-free, facile, low-cost, sol-gel-processed reduced graphene oxide (rGO)/P(VDF-TrFE) nanocomposite with multipurpose capability demonstration as a piezoelectric nanogenerator (PENG) and hybrid piezoelectric triboelectric nanogenerator (HPTENG) devices. The structural analysis of the materials shows that the interactions between the rGO and P(VDF-TrFE) matrix help in breaking the centrosymmetry of rGO, resulting in a strong enhancement in the piezoelectric, ferroelectric, and triboelectric properties of composites over pristine P(VDF-TrFE) films. In the case of PENG, the composite devices showed >22 times improvement in the piezoelectric output voltage over the pristine P(VDF-TrFE) PENG device with the highest output voltage of 89.7 V for the 0.5 wt % rGO composite. Also, HPTENG devices based on composite films generated an average VOC of 227 V, much higher than the pristine P(VDF-TrFE)-based devices. Maximum output power densities measured were 0.28 W/cm3 and 0.34 mW/cm3 for hybrid piezoelectric-triboelectric and piezoelectric devices, respectively. The triboelectric devices demonstrated lighting of 45 blue light-emitting diodes directly, connected in series, by harvesting mechanical energy generated by repeated finger tapping. The study highlights the promise of rGO/P(VDF-TrFE) composites for PENG and HPTENG devices with dramatically improved electrical output.

Significantly Enhanced Energy Density by Tailoring the Interface in Hierarchically Structured TiO2-BaTiO3-TiO2 Nanofillers in PVDF-Based Thin-Film Polymer Nanocomposites.

Dielectric polymer nanocomposites with a high breakdown field and high dielectric constant have drawn significant attention in modern electrical and electronic industries due to their potential applications in dielectric and energy storage systems. The interfaces of the nanomaterials play a significant role in improving the dielectric performance of polymer nanocomposites. In this work, polydopamine (dopa)-functionalized TiO2-BaTiO3-TiO2 (TiO2-BT-TiO2@dopa) core@double-shell nanoparticles have been developed as novel nanofillers for high-energy-density capacitor applications. The hierarchically designed nanofillers help in tailoring the interfaces surrounding the polymer matrix as well as act as individual capacitors in which the core and outer TiO2 shell function as a capacitor plate because of their high electrical conductivity while the middle BT layer functions as a dielectric medium due to high dielectric constant. Detailed electrical characterizations have revealed that TiO2-BT-TiO2@dopa/poly(vinylidene fluoride) (PVDF) possesses a higher relative dielectric permittivity (εr), breakdown strength ( Eb), and energy density as compared to those of PVDF, TiO2/PVDF, TiO2@dopa/PVDF, and TiO2-BT@dopa/PVDF polymer nanocomposites. The εr and energy density of TiO2-BT-TiO2@dopa/PVDF were 12.6 at 1 kHz and 4.4 J cm-3 at 3128 kV cm-1, respectively, which were comparatively much higher than those of commercially available biaxially oriented polypropylene having εr of 2.2 and the energy density of 1.2 J cm-3 at a much higher electric field of 6400 kV cm-1. It is expected that these results will further open new avenues for the design of novel architecture for high-performance polymer nanocomposite-based capacitors having core@multishell nanofillers with tailored interfaces.