The benefits of combining 1D and 3D nanofillers in a piezocomposite nanogenerator for biomechanical energy harvesting.

Mechanical energy harvesting using piezoelectric nanogenerators (PNGs) offers an attractive solution for driving low-power portable devices and self-powered electronic systems. Here, we designed an eco-friendly and flexible piezocomposite nanogenerator (c-PNG) based on H2(Zr0.1Ti0.9)3O7 nanowires (HZTO-nw) and Ba0.85Ca0.15Zr0.10Ti0.90O3 multipods (BCZT-mp) as fillers and polylactic acid (PLA) as a biodegradable polymer matrix. The effects of the applied stress amplitude, frequency and pressing duration on the electric outputs in the piezocomposite nanogenerator (c-PNG) device were investigated by simultaneous recording of the mechanical input and the electrical outputs. The fabricated c-PNG shows a maximum output voltage, current and volumetric power density of 11.5 V, 0.6 µA and 9.2 mW cm-3, respectively, under cyclic finger imparting. A high-pressure sensitivity of 0.86 V kPa-1 (equivalent to 3.6 V N-1) and fast response time of 45 ms were obtained in the dynamic pressure sensing. Besides this, the c-PNG demonstrates high-stability and durability of the electrical outputs for around three months, and can drive commercial electronics (charging capacitor, glowing light-emitting diodes and powering a calculator). Multi-physics simulations indicate that the presence of BCZT-mp is crucial in enhancing the piezoelectric response of the c-PNG. Accordingly, this work reveals that combining 1D and 3D fillers in a polymer composite-based PNG could be beneficial in improving the mechanical energy harvesting performances in flexible piezoelectric nanogenerators for application in electronic skin and wearable devices.

Design of lead-free BCZT-based ceramics with enhanced piezoelectric energy harvesting performances.

The design of lead-free ceramics for piezoelectric energy harvesting applications has become a hot topic. Among these materials, Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) and BaTi0.89Sn0.11O3 (BTSn) are considered as potential candidates due to their enhanced piezoelectric properties. Here, the structural, electrical, piezoelectric and piezoelectric energy harvesting properties of the (1 - x)Ba0.85Ca0.15Zr0.10Ti0.90O3-xBaTi0.89Sn0.11O3 (xBTSn, x = 0.2, 0.4 and 0.6) system are investigated. A systematic study of the structural properties of the xBTSn samples was carried out using X-ray diffraction, Raman spectroscopy, and dielectric measurements. The addition of BTSn allows a successive phase transition, which broadens the application temperature range. The enhanced piezoelectric energy harvesting properties were found in the 0.2BTSn ceramic, where the large-signal and small-signal piezoelectric coefficients, piezoelectric voltage and the piezoelectric figure of merit reached 245 pm V-1, 228 pC N-1, 16.2 mV m N-1 and 3.7 pm2 N-1, respectively. Consequently, the combination of BCZT and BTSn could provide suitable lead-free materials with enhanced piezoelectric energy harvesting performances.

Thermal-stability of the enhanced piezoelectric, energy storage and electrocaloric properties of a lead-free BCZT ceramic.

The lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) relaxor ferroelectric ceramic has aroused much attention due to its enhanced piezoelectric, energy storage and electrocaloric properties. In this study, the BCZT ceramic was elaborated by the solid-state reaction route, and the temperature-dependence of the structural, electrical, piezoelectric, energy storage and electrocaloric properties was investigated. X-ray diffraction analysis revealed a pure perovskite phase, and the temperature-dependence of Raman spectroscopy, dielectric and ferroelectric measurements revealed the phase transitions in the BCZT ceramic. At room temperature, the strain and the large-signal piezoelectric coefficient reached a maximum of 0.062% and 234 pm V-1, respectively. Furthermore, enhanced recovered energy density (W rec = 62 mJ cm-3) and high-energy storage efficiency (η) of 72.9% at 130 °C were found. The BCZT ceramic demonstrated excellent thermal stability of the energy storage variation (ESV), less than ±5.5% in the temperature range of 30-100 °C compared to other lead-free ceramics. The electrocaloric response in the BCZT ceramic was explored via the indirect approach by using the Maxwell relation. Significant electrocaloric temperature change (ΔT) of 0.57 K over a broad temperature span (T span = 70 °C) and enhanced coefficient of performance (COP = 11) were obtained under 25 kV cm-1. The obtained results make the BCZT ceramic a suitable eco-friendly material for energy storage and solid-state electrocaloric cooling devices.

Thermally-stable high energy storage performances and large electrocaloric effect over a broad temperature span in lead-free BCZT ceramic.

Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) relaxor ferroelectric ceramics exhibit enhanced energy storage and electrocaloric performances due to their excellent dielectric and ferroelectric properties. In this study, the temperature-dependence of the structural and dielectric properties, as well as the field and temperature-dependence of the energy storage and the electrocaloric properties in BCZT ceramics elaborated at low-temperature hydrothermal processing are investigated. X-ray diffraction and Raman spectroscopy results confirmed the ferroelectric-paraelectric phase transition in the BCZT ceramic. At room temperature and 1 kHz, the dielectric constant and dielectric loss reached 5000 and 0.029, respectively. The BCZT ceramic showed a large recovered energy density (W rec) of 414.1 mJ cm-3 at 380 K, with an energy efficiency of 78.6%, and high thermal-stability of W rec of 3.9% in the temperature range of 340-400 K. The electrocaloric effect in BCZT was explored via an indirect approach following the Maxwell relation at 60 kV cm-1. The significant electrocaloric temperature change of 1.479 K at 367 K, a broad temperature span of 87 K, an enhanced refrigerant capacity of 140.33 J kg-1, and a high coefficient of performance of 6.12 obtained at 60 kV cm-1 make BCZT ceramics potentially useful coolant materials in the development of future eco-friendly solid-state refrigeration technology.

Structural, Dielectric, and Magnetic Properties of Multiferroic ( 1 - x ) La0.5Ca0.5MnO3-( x ) BaTi0.8Sn0.2O3 Laminated Composites.

High-performance lead-free multiferroic composites are desired to replace the lead-based ceramics in multifunctional device applications. Laminated compounds were prepared from ferroelectric and ferromagnetic materials. In this work, we present the laminated ceramics compound by considering the ferromagnetic La0.5Ca0.5MnO3 (LCMO) and the ferroelectric BaTi0.8Sn0.2O3 (BTSO) in two different proportions. Compounds ( 1-x ) LCMO-( x ) BTSO with x = 1 and 0 (pure materials) were synthesized by the sol-gel method, and x = 0.7 and 0.5 (laminated) compounds were elaborated by welding appropriate mass ratios of each pure material by using the silver paste technique. Structural, dielectric, ferroelectric, microstructure, and magnetic characterizations were conducted on these samples. X-ray scattering results showed pure perovskite phases confirming the successful formation of both LCMO and BTSO. Scanning electron microscope (SEM) images evidenced the laminated structure and good quality of the interfaces. The laminated composite materials have demonstrated a multiferroic behavior characterized by the ferroelectric and the ferromagnetic hysteresis loops. Furthermore, the enhancement of the dielectric constant in the laminated composite samples is mainly attributed to the Maxwell-Wagner polarization.

Giant Nernst-Ettingshausen oscillations in semiclassically strong magnetic fields.

We consider the Nernst-Ettingshausen (NE) effect in the presence of semiclassically strong magnetic fields for a quasi-two-dimensional system with a parabolic or linear dispersion of carriers. We show that the occurring giant oscillations of the NE coefficient are coherent with the recent experimental observation in graphene, graphite, and bismuth. In the 2D case we find the exact shape of these oscillations and show that their magnitude decreases (increases) with enhancement of the Fermi energy for Dirac fermions (normal carriers). With a crossover to the 3D spectrum the phase of the oscillations shifts, their amplitude decreases, and the peaks become asymmetric.

Mesoscopic metal-insulator transition at ferroelastic domain walls in VO2.

The novel phenomena induced by symmetry breaking at homointerfaces between ferroic variants in ferroelectric and ferroelastic materials have attracted recently much attention. Using variable temperature scanning microwave microscopy, we demonstrate the mesoscopic strain-induced metal-insulator phase transitions in the vicinity of ferroelastic domain walls in the semiconductive VO(2) that nucleated at temperatures as much as 10-12 degrees C below bulk transition, resulting in the formation of conductive channels in the material. Density functional theory is used to rationalize the process low activation energy. This behavior, linked to the strain inhomogeneity inherent in ferroelastic materials, can strongly affect interpretation of phase-transition studies in VO(2) and similar materials with symmetry-lowering transitions, and can also be used to enable new generations of electronic devices though strain engineering of conductive and semiconductive regions.

Interplay between ferroelastic and metal-insulator phase transitions in strained quasi-two-dimensional VO2 nanoplatelets.

Formation of ferroelastic twin domains in vanadium dioxide (VO(2)) nanosystems can strongly affect local strain distributions, and hence couple to the strain-controlled metal-insulator transition. Here we report polarized-light optical and scanning microwave microscopy studies of interrelated ferroelastic and metal-insulator transitions in single-crystalline VO(2) quasi-two-dimensional (quasi-2D) nanoplatelets (NPls). In contrast to quasi-1D single-crystalline nanobeams, the 2D geometric frustration results in emergence of several possible families of ferroelastic domains in NPls, thus allowing systematic studies of strain-controlled transitions in the presence of geometrical frustration. We demonstrate the possibility of controlling the ferroelastic domain population by the strength of the NPl-substrate interaction, mechanical stress, and by the NPl lateral size. Ferroelastic domain species and domain walls are identified based on standard group-theoretical considerations. Using variable temperature microscopy, we imaged the development of domains of metallic and semiconducting phases during the metal-insulator phase transition and nontrivial strain-driven reentrant domain formation. A long-range reconstruction of ferroelastic structures accommodating metal-insulator domain formation has been observed. These studies illustrate that a complete picture of the phase transitions in single-crystalline and disordered VO(2) structures can be drawn only if both ferroelastic and metal-insulator strain effects are taken into consideration and understood.

Universal properties of ferroelectric domains.

Based on the Ginzburg-Landau approach, we generalize the Kittel theory and derive the interpolation formula for the temperature evolution of a multidomain polarization profile P(x,z). We resolve the long-standing problem of the near-surface polarization behavior in ferroelectric domains and demonstrate polarization vanishing instead of the usually assumed fractal domain branching. We propose an effective scaling approach to compare the properties of different domain-containing ferroelectric plates and films.

Lattice-induced double-valley degeneracy lifting in graphene by a magnetic field.

We show that the recently discovered double-valley splitting of the Landau levels in the quantum Hall effect in graphene can be explained as the perturbative orbital interaction of intravalley and intervalley microscopic orbital currents with a magnetic field. This effect is facilitated by the translationally noninvariant terms that correspond to graphene's crystallographic honeycomb symmetry but do not exist in the relativistic theory of massless Dirac fermions in quantum electrodynamics. We discuss recent data in view of these findings.

Dirac and normal fermions in graphite and graphene: implications of the quantum Hall effect.

Spectral analysis of the Shubnikov-de Haas magnetoresistance oscillations and the quantum Hall effect (QHE) measured in quasi-2D highly oriented pyrolytic graphite (HOPG) [Phys. Rev. Lett. 90, 156402 (2003)] reveals two types of carriers: normal (massive) electrons with Berry phase 0 and Dirac-like (massless) holes with Berry phase pi. We demonstrate that recently reported integer- and semi-integer QHEs for bilayer and single-layer graphenes take place simultaneously in HOPG samples.

Phase analysis of quantum oscillations in graphite.

The quantum de Haas-van Alphen (dHvA) and Shubnikov-de Haas oscillations measured in graphite were decomposed by pass-band filtering onto contributions from three different groups of carriers. Generalizing the theory of dHvA oscillations for 2D carriers with an arbitrary spectrum and by detecting the oscillation frequencies using a method of two-dimensional phase-frequency analysis which we developed, we identified these carriers as (i) minority holes having a 2D parabolic massive spectrum p(2)(perpendicular)/2m(perpendicular), (ii) massive majority electrons with a 3D spectrum and (iii) majority holes with a 2D Dirac-like spectrum +/-vp(perpendicular) which seems to be responsible for the unusual strongly-correlated electronic phenomena in graphite.