Sustainable Vibration Energy Harvesting Based on Zr‐Doped PMN‐PT Piezoelectric Single Crystal Cantilevers

In this paper, we present the results of a preliminary study on the piezoelectric energy harvesting performance of a Zr‐doped PbMg_1/3Nb_2/3O₃‐PbTiO₃ (PMN‐PZT) single crystal beam. A novel piezoelectric beam cantilever structure is used to demonstrate the feasibility of generating AC voltage during a state of vibration. The energy‐harvesting capability of a PMN‐PZT beam is calculated and tested. The frequency response of the cantilever device shows that the first mode resonance frequency of the excitation model exists in the neighborhood of several hundreds of hertz, which is similar to the calculated value. These tests show that several significantly open AC voltages and sub‐mW power are achieved. To test the possibility of a small scale power source for a ubiquitous sensor network service, energy conversion and the testing of storage experiment are also carried out.     

In Vivo Self‐Powered Wireless Transmission Using Biocompatible Flexible Energy Harvesters

Additional surgeries for implantable biomedical devices are inevitable to replace discharged batteries, but repeated surgeries can be a risk to patients, causing bleeding, inflammation, and infection. Therefore, developing self‐powered implantable devices is essential to reduce the patient's physical/psychological pain and financial burden. Although wireless communication plays a critical role in implantable biomedical devices that contain the function of data transmitting, it has never been integrated with in vivo piezoelectric self‐powered system due to its high‐level power consumption (microwatt‐scale). Here, wireless communication, which is essential for a ubiquitous healthcare system, is successfully driven with in vivo energy harvesting enabled by high‐performance single‐crystalline (1 ? x )Pb(Mg_1/3Nb_2/3)O₃?(x )Pb(Zr,Ti)O₃ (PMN‐PZT). The PMN‐PZT energy harvester generates an open‐circuit voltage of 17.8 V and a short‐circuit current of 1.74 µA from porcine heartbeats, which are greater by a factor of 4.45 and 17.5 than those of previously reported in vivo piezoelectric energy harvesting. The energy harvester exhibits excellent biocompatibility, which implies the possibility for applying the device to biomedical applications.     

Giant Piezoelectric Coefficients in Relaxor Piezoelectric Ceramic PNN‐PZT for Vibration Energy Harvesting

It is well known that the piezoelectric performance of ferroelectric Pb(Zr,Ti)O₃ (PZT) based ceramics is far inferior to that of ferroelectric single crystals due to ceramics' polycrystalline nature. Herein, it is reported that piezoelectric stress coefficient e₃₃ = 39.24 C m^?2 (induced electric displacement under applied strain) in the relaxor piezoelectric ceramic 0.55Pb(Ni_1/3Nb_2/3)O₃–0.135PbZrO₃–0.315PbTiO₃ (PNN‐PZT) prepared by the solid state reaction method exhibits the highest value among various reported ferroelectric ceramic and single crystal materials. In addition, its piezoelectric coefficient d₃₃* = 1753 pm V^?1 is also comparable with that of the commercial Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (PMN‐PT) piezoelectric single crystal. The PNN‐PZT ceramic is then assembled into a cymbal energy harvester. Notably, its maximum output current at the acceleration of 3.5 g is 2.5 mA_pp, which is four times of the PMN‐PT single crystal due to the large piezoelectric e₃₃ constants; while the maximum output power is 14.0 mW, which is almost the same as the PMN‐PT single crystal harvester. The theoretical analysis on force‐induced power output is also presented, which indicates PNN‐PZT ceramic has great potential for energy device application.     

A New Material for High‐Temperature Lead‐Free Actuators

Unimorph cantilevers are made from 0.5BaTiO₃‐0.5Sm₂O₃ (BTO‐SmO) self‐assembled vertical heteroepitaxial nanocomposite thin films, grown by PLD on (001) SrTiO₃ single crystal substrates. The films remain piezoelectric up to at least 250 °C without losing any actuation. The longitudinal piezoelectric coefficient, d₃₃, is ≈45 to 50 pm V^?1 measured from room temperature to 250 °C. The transverse piezoelectric coefficient, d₃₁, a key parameter of actuator performance, exceeds PZT (Pb_1–xZr_xTiO₃) films at >200 pm V^?1. Since the d₃₁ coefficient was found to be positive, this opens up exciting new applications opportunities. The possible reasons for d₃₁ > 0 are discussed in the light of 3D strain control in the nanocomposites.     

Temperature‐Insensitive (K,Na)NbO3‐Based Lead‐Free Piezoactuator Ceramics

The development of lead‐free piezoceramics has attracted great interest because of growing environmental concerns. A polymorphic phase transition (PPT) has been utilized in the past to tailor piezoelectric properties in lead‐free (K,Na)NbO₃ (KNN)‐based materials accepting the drawback of large temperature sensitivity. Here a material concept is reported, which yields an average piezoelectric coefficientd₃₃ of about 300 pC/N and a high level of unipolar strain up to 0.16% at room temperature. Most intriguingly, field‐induced strain varies less than 10% from room temperature to 175 °C. The temperature insensitivity of field‐induced strain is rationalized using an electrostrictive coupling to polarization amplitude while the temperature‐dependent piezoelectric coefficient is discussed using localized piezoresponse probed by piezoforce microscopy. This discovery opens a new development window for temperature‐insensitive piezoelectric actuators despite the presence of a polymorphic phase transition around room temperature.     

Hybrid Cd‐free CIGS solar cell/TEG device with ZnO nanowires

A green energy device with a CuInGaSe₂ (CIGS) photovoltaic (PV) cell covered with a passive light‐trapping structure (ZnO nanowires (NWs)) and connected to an active energy‐harvesting device (thermoelectric generator (TEG)) is presented. The efficiency of the ZnO NWs/CIGS PV device obtained using a deposition temperature of 550 °C and Cd‐free processes reaches 16.5%. The series‐connected CIGS PV cell with a TEG had a record‐high efficiency of 22% at a cool‐side temperature (T_c) below 5 °C. The open‐circuit voltage (V_oc) of the hybrid CIGS PV/TEG device was increased from 0.64 to 0.85 V. This technology has potential for high‐efficiency energy‐harvesting applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Performance Enhancement of Flexible Piezoelectric Nanogenerator via Doping and Rational 3D Structure Design For Self‐Powered Mechanosensational System

With the rapid development of the Internet of things (IoT), flexible piezoelectric nanogenerators (PENG) have attracted extensive attention for harvesting environmental mechanical energy to power electronics and nanosystems. Herein, porous piezoelectric fillers with samarium/titanium‐doped BiFeO₃ (BFO) are prepared by a freeze‐drying method, and then silicone rubber is filled into the microvoids of the piezoelectric ceramics, forming a unique structure based on silicone rubber matrix with uniformly distributed piezoelectric ceramic. When subjected to external force stimulation, compared with conventional piezocomposite films found on undoped BFO without a porous structure, the PENG possesses higher stress transfer ability and thus boosts output performance. The notable enhancement in the stress transfer ability and piezoelectric potential is proven by COMSOL simulations. The PENG can exhibit a maximum open‐circuit voltage (V_oc) of 16 V and short‐circuit current (I_sc) of 2.8 µA, which is 5.3 and 5.6 times higher than those of conventional piezocomposite films, respectively. The PENG can be used as a triggering signal to control the operation of fire extinguishers and household appliances. This work not only expands the application scope of lead‐free piezoelectric ceramic for energy harvesting, but also provides a novel solution for self‐powered mechanosensation and shows great potential application in IoT.     

Strongly (001) Oriented Bimorph PZT Film on Metal Foils Grown by rf‐Sputtering for Wrist‐Worn Piezoelectric Energy Harvesters

For piezoelectric energy harvesters, a large volume of piezoelectric material with a high figure of merit is essential to obtain a higher power density. The work describes the growth of highly (001) oriented sputtered lead zirconate titanate (PZT) films (f ≈ 0.99) exceeding 4 µm in thickness on both sides of an Ni foil to produce a bimorph structure. These films are incorporated in novel wrist‐worn energy harvesters (<16 cm²) in which piezoelectric beams are plucked magnetically using an eccentric rotor with embedded magnets to implement frequency up‐conversion. The resulting devices successfully convert low‐frequency vibration sources (i.e., from walking, rotating the wrist, and jogging) to higher frequency vibrations of the PZT beams (100–200 Hz). Measured at resonance, six beams producing an output of 1.2 mW is achieved at 0.15 G acceleration. For magnetic plucking of a wrist‐worn nonresonant device, 40–50 µW is produced during mild activity.     

Ultrahigh Energy‐Storage Density in NaNbO3‐Based Lead‐Free Relaxor Antiferroelectric Ceramics with Nanoscale Domains

Dielectric energy‐storage capacitors have received increasing attention in recent years due to the advantages of high voltage, high power density, and fast charge/discharge rates. Here, a new environment‐friendly 0.76NaNbO₃–0.24(Bi_0.5Na_0.5)TiO₃ relaxor antiferroelectric (AFE) bulk ceramic is studied, where local orthorhombic Pnma symmetry (R phase) and nanodomains are observed based on high‐resolution transmission electron microscopy, selected area electron diffraction, and in/ex situ synchrotron X‐ray diffraction. The orthorhombic AFE R phase and relaxor characteristics synergistically contribute to the record‐high energy‐storage density W_rec of ≈12.2 J cm^?3 and acceptable energy efficiency η ≈ 69% at 68 kV mm^?1, showing great advantages over currently reported bulk dielectric ceramics. In comparison with normal AFEs, the existence of large random fields in the relaxor AFE matrix and intrinsically high breakdown strength of NaNbO₃‐based compositions are thought to be responsible for the observed energy‐storage performances. Together with the good thermal stability of W_rec (>7.4 J cm^?3) and η (>73%) values at 45 kV mm^?1 up to temperature of 200 °C, it is demonstrated that NaNbO₃‐based relaxor AFE ceramics will be potential lead‐free dielectric materials for next‐generation pulsed power capacitor applications.     

Efficient Piezoelectric Energy Harvesters Utilizing (001) Textured Bimorph PZT Films on Flexible Metal Foils

Extracting energy from low vibration frequencies (<10 Hz) using piezoelectric energy harvester promises continuous self‐powering for sensors and wearables. The piezoelectric compliant mechanism (PCM) design provides a significantly higher efficiency by fostering a uniform strain for its 1st mode shape, and so is interesting for this application. In this paper, a PCM energy harvester with bimorph Pb(Zr,Ti)O₃ (PZT) films on Ni foil deposited by rf magnetron sputtering is shown to have high efficiency and large power for low frequency mechanical vibration. In particular, {001} textured PZT films are deposited on both sides of polished Ni foils with (100) oriented LaNiO₃ seed layers on HfO₂ buffer layers. The performance of PCM with an active area of 5.2 cm² is explored for various excitation accelerations (0.02–0.16 g [g = 9.8 m s^?2]) around 6 Hz. The PCM device provides a power level of 3.9 mW cm^?2 g² and 65% mode shape efficiencies.     

A High Power Density Intermediate‐Temperature Solid Oxide Fuel Cell with Thin (La0.9Sr0.1)0.98(Ga0.8Mg0.2)O3‐δ Electrolyte and Nano‐Scale Anode

Solid oxide fuel cells (SOFCs) with thin (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3‐δ (LSGM) electrolytes are primary candidates for achieving high (> 1 W cm^‐2) power density at intermediate (< 650 °C) temperatures. Although high power density LSGM‐electrolyte SOFCs have been reported, it is still necessary to develop a fabrication process suitable for large‐scale manufacturing and to minimize the amount of LSGM used. Here we show that SOFCs made with a novel processing method and a Sr_0.8La_0.2TiO_{3‐ α} (SLT) oxide support can achieve high power density at intermediate temperature. The SLT support is advantageous, especially compared to LSGM supports, because of its low materials cost, electronic conductivity, and good mechanical strength. The novel process is to first co‐fire the ceramic layers – porous SLT support, porous LSGM layer, and dense LSGM layer – followed by infiltration of nano‐scale Ni into the porous layers. Low polarization resistance of 0.188 Ωcm² was achieved at 650 °C for a cell with an optimized anode functional layer (AFL) and an (La,Sr)(Fe,Co)O₃ cathode. Maximum power density reached 1.12 W cm^?2 at 650 °C, limited primarily by cathode polarization and ohmic resistances, so there is considerable potential to further improve the power density.     

Piezoelectric Nylon‐11 Nanowire Arrays Grown by Template Wetting for Vibrational Energy Harvesting Applications

Piezoelectric polymers, capable of converting mechanical vibrations into electrical energy, are attractive for use in vibrational energy harvesting due to their flexibility, robustness, ease, and low cost of fabrication. In particular, piezoelectric polymers nanostructures have been found to exhibit higher crystallinity, higher piezoelectric coefficients, and “self‐poling,” as compared to films or bulk. The research in this area has been mainly dominated by polyvinylidene fluoride and its copolymers, which while promising have a limited temperature range of operation due to their low Curie and/or melting temperatures. Here, the authors report the fabrication and properties of vertically aligned and “self‐poled” piezoelectric Nylon‐11 nanowires with a melting temperature of ≈200 °C, grown by a facile and scalable capillary wetting technique. It is shown that a simple nanogenerator comprising as‐grown Nylon‐11 nanowires, embedded in an anodized aluminium oxide (AAO) template, can produce an open‐circuit voltage of 1 V and short‐circuit current of 100 nA, when subjected to small‐amplitude, low‐frequency vibrations. Importantly, the resulting nanogenerator is shown to exhibit excellent fatigue performance and high temperature stability. The work thus offers the possibility of exploiting a previously unexplored low‐cost piezoelectric polymer for nanowire‐based energy harvesting, particularly at temperatures well above room temperature.     

A Flexible Dual‐Ion Battery Based on Sodium‐Ion Quasi‐Solid‐State Electrolyte with Long Cycling Life

Sodium‐based dual‐ion batteries (SDIBs) have attracted much attention for their advantages of high operating voltage, environmental friendliness, and especially low cost. However, the electrochemical performances of the reported SDIBs are still unsatisfied due to the decomposition problem of traditional liquid electrolyte under high working voltage. Development of quasi‐solid‐state electrolytes (QSSEs) with excellent electrochemical stability at high voltage is a possible means to improve their properties. In this work, a flexible SDIB based on a QSSE, consisting of poly(vinylidene ?uoride‐co‐hexa?uoropropylene) (PVDF‐HFP) three‐dimensionally cross‐linked with Al₂O₃ nanoparticles, which exhibits a porous 3D structure with dramatically enhanced ionic conductivity up to ≈1.3 × 10^?3 S cm^?1, facilitating fast ionic migration of both anions and cations, is reported. This quasi‐state SDIB exhibits a high specific capacity of 96.8 mAh g^?1 at a current rate of 5 C and excellent cycling stability with a capacity retention of 97.5% after 600 cycles at 5 C, which is the best performance of the SDIBs. Moreover, excellent flexibility and a wide working temperature range (?20 to 70 °C) have been realized for this battery, suggesting its potential for high‐performance flexible energy storage applications.     

High‐Performance [001]c‐Textured PNN‐PZT Relaxor Ferroelectric Ceramics for Electromechanical Coupling Devices

[001]_C‐Textured 0.55Pb(Ni_1/3Nb_2/3)O₃–0.15PbZrO₃–0.3PbTiO₃ (PNN‐PZT) ceramics are prepared by the templated grain‐growth method using BaTiO₃ (BT) platelet templates. Samples with different template contents are fabricated and compared in terms of texture fraction, microstructure, and piezoelectric, ferroelectric and dielectric properties. High piezoelectric performance (d₃₃ = 1210 pC N^?1, d₃₃* = 1773 pm V^?1 at 5 kV cm^?1) and high figure of merit g₃₃?d₃₃ (21.92 × 10^?12 m² N^?1) are achieved in the [001]_C‐textured PNN‐PZT ceramic with 2 vol% BaTiO₃ template, for which the texture fraction is 82%. In addition, domain structures of textured PNN‐PZT ceramics are observed and analyzed, which provide clues to the origin of the giant piezoelectric and electromechanical coupling properties of PNN‐PZT ceramics.     

Unidirectional High‐Power Generation via Stress‐Induced Dipole Alignment from ZnSnO3 Nanocubes/Polymer Hybrid Piezoelectric Nanogenerator

The extremely stable high‐power generation from hybrid piezoelectric nanogenerator (HP‐NG) based on a composite of single‐crystalline piezoelectric perovskite zinc stannate (ZnSnO₃) nanocubes and polydimethylsiloxane without any electrical poling treatment is reported. The HP‐NG generates large power output under only vertical compression, while there is negligible power generation with other configurations of applied strain, such as bending and folding. This unique high unidirectionality of power generation behavior of the HP‐NG provides desirable features for large‐area piezoelectric power generation based on vertical mechanical compression such as moving vehicles, railway transport, and human walking. The HP‐NGs of ZnSnO₃ nanocubes exhibit high mechanical durability, excellent robustness, and high power‐generation performance. A large recordable output voltage of about 20 V and an output current density value of about 1 μA cm^?2 are successfully achived, using a single cell of HP‐NG obtained under rolling of a vehicle tire.     

An Amphiphobic Hydraulic Triboelectric Nanogenerator for a Self‐Cleaning and Self‐Charging Power System

Raindrop falling, which is one kind of water motions, contains large amount of mechanical energy. However, harvesting energy from the falling raindrop to drive electronics continuously is not commonly investigated. Therefore, a self‐cleaning/charging power system (SPS) is reported, which can be exploited to convert and store energy from falling raindrop directly for providing a stable and durable output. The SPS consists of a hydraulic triboelectric nanogenerator (H‐TENG) and several embedded fiber supercapacitors. The surface of H‐TENG is amphiphobic, enabling the SPS self‐cleaning. The fiber supercapacitor which uses α‐Fe₂O₃/reduced graphene oxide composite possesses remarkable specific capacitance, excellent electrical stability, and high flexibility. These properties of the fiber supercapacitor make it suitable for a wearable power system. A power raincoat based on the SPS is demonstrated as application. After showering by water flow, which simulates falling raindrops, for 100 s, the power raincoat achieves an open‐circuit voltage of 4 V and lights a light‐emitting diode for more than 300 s. With features of low cost, easy installation, and good flexibility, the SPS harvesting energy from the falling raindrop renders as a promising sustainable power source for wearable and portable electronics.     

Sustainable Nanotextured Wave Energy Harvester Based on Ferroelectric Fatigue‐Free and Flexoelectricity‐Enhanced Piezoelectric P(VDF‐TrFE) Nanofibers with BaSrTiO3 Nanoparticles

Here, ultrathin, flexible, and sustainable nanofiber‐based piezoelectric nanogenerators (NF‐PENGs) are fabricated and applied as wave energy harvesters. The NF‐PENGs are composed of poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) nanofibers with embedded barium strontium titanate (BaSrTiO₃) nanoparticles, which are fabricated by using facile, scalable, and cost‐effective fiber‐forming methods, including electrospinning and solution blowing. The inclusion of ferroelectric BaSrTiO₃ nanoparticles inside the electrospun P(VDF‐TrFE) nanofibers enhances the sustainability of the NF‐PENGs and results in unique flexoelectricity‐enhanced piezoelectric nanofibers. Not only do these NF‐PENGs yield a superior performance compared to the previously reported NF‐PENGs, but they also exhibit an outstanding durability in terms of mechanical properties and cyclability. Furthermore, a new theoretical estimate of the energy harvesting efficiency from the water waves is introduced here, which can also be employed in future studies associated with various nanogenerators, including PENGs and triboelectric nanogenerators.     

Boosting Piezoelectricity by 3D Printing PVDF-MoS2 Composite as a Conformal and High-Sensitivity Piezoelectric Sensor

Additively manufactured flexible and high-performance piezoelectric devices are highly desirable for sensing and energy harvesting of 3D conformal structures. Herein, the study reports a significantly enhanced piezoelectricity in polyvinylidene fluoride (PVDF) achieved through the in situ dipole alignment of PVDF within PVDF-2D molybdenum disulfide (2D MoS₂) composite by 3D printing. The shear stress-induced dipole poling of PVDF and 2D MoS₂ alignment are harnessed during 3D printing to boost piezoelectricity without requiring a post-poling process. The results show a remarkable, more than the eight-fold increment in the piezoelectric coefficient (d₃₃) for 3D printed PVDF-8wt.% MoS₂ composite over cast neat PVDF. The underlying mechanism of piezoelectric property enhancement is attributed to the increased volume fraction of β phase in PVDF, filler fraction, heterogeneous strain distribution around PVDF-MoS₂ interfaces, and strain transfer to the nanofillers as confirmed by microstructural analysis and finite element simulation. These results provide a promising route to design and fabricate high-performance 3D piezoelectric devices via 3D printing for next-generation sensors and mechanical–electronic conformal devices.     

UV‐Light‐Driven Oxygen Pumping in a High‐Temperature Solid Oxide Photoelectrochemical Cell

A solid‐state photoelectrochemical cell is operated between 400 and 500 °C under 365 nm UV light. The cell consists of a photovoltaic part, based on a La_0.8Sr_0.2CrO₃/SrTiO₃ junction, and an electrochemical part including a zirconia solid electrolyte with a shared (La,Sr)FeO₃ electrode. The photovoltaic cell part leads to open circuit voltages up to 920 mV at 400 °C. Upon UV light, this driving force is used in the electrochemical part of the cell to pump oxygen from low to high partial pressures, i.e., to convert radiation energy to chemical energy. This demonstrates the feasibility of high‐temperature photoelectrochemical cells for solar energy storage. The detailed characterization of the different resistance contributions in the system by DC and AC methods reveals the parts of the cell to be optimized for finally achieving high‐temperature photoelectrochemical water splitting.     

High‐Performance Flexible Thermoelectric Devices Based on All‐Inorganic Hybrid Films for Harvesting Low‐Grade Heat

The fabrication of a flexible thermoelectric (TE) device that contains flexible, all‐inorganic hybrid thin films (p‐type single‐wall carbon nanotubes (SWCNTs)/Sb₂Te₃ and n‐type reduced graphene oxide (RGO)/Bi₂Te₃) is reported. The optimized power factors of the p‐type and n‐type hybrid thin films at ambient temperature are about 55 and 108 µW m^?1 K^?2, respectively. The high performance of these films that are fabricated through the combination of vacuum filtration and annealing can be attributed to their planar orientation and network structure. In addition, a TE device, with 10 couples of legs, shows an output power of 23.6 µW at a temperature gradient of 70 K. A prototype of an integrated photovoltaic‐TE (PV‐TE) device demonstrates the ability to harvest low‐grade “waste” thermal energy from the human body and solar irradiation. The flexible TE and PV‐TE device have great potential in wearable energy harvesting and management.