Electroactive properties and piezo-tribo hybrid energy harvesting performances of PVDF-AlFeO3 composites: role of crystal symmetry and agglomeration of fillers.

Inorganic filler-loaded PVDF-based composites have been very widely used for electrical and energy harvesting applications in recent times. In this regard, the effects of different parameters of fillers like size, shape, chemical states, distribution, functional properties, and many others on the output performance of PVDF have been widely studied. However, the effect of another important parameter, namely the crystal symmetry of the filler, in tuning the energy harvesting performance of PVDF has been rarely explored. Therefore, to explore this fact, here we develop PVDF-based composite films by using two types of AlFeO3 fillers, one with rhombohedral R3̄c symmetry (AFRH) and another with an orthorhombic Pc21n structure. Ferrite-based oxides have been chosen here as fillers due to their good dielectric compatibility with PVDF. On the other hand, AlFeO3 has been chosen due to the simplicity of synthesizing it with both centrosymmetric and non-centrosymmetric crystal structures and the scarcity of reports exploring the energy-harvesting performance of AlFeO3-based polymer composites. A significant difference in particle agglomeration has also been observed here between the mentioned two types of AlFeO3 fillers which was mainly due to their specific synthesis conditions. The electroactive properties of PVDF have been observed to be mostly dependent on filler agglomeration. However, the crystal symmetry has shown a strong effect on the piezoelectric energy harvesting performances. As a result of these facts, the piezo-tribo hybrid energy harvesting performance, which depends on both the dielectric permittivity and piezoelectric activity, has been observed to be better for the AFRH5-based hybrid device (AFRH5H) (with ∼72 V open circuit voltage and ∼45 µW cm-2 power density) compared to that of the AFOR5-based hybrid device (AFOR5H). The real-life applications of all the energy harvesting devices have also been demonstrated here.

Nature-Driven Biocompatible Epidermal Electronic Skin for Real-Time Wireless Monitoring of Human Physiological Signals.

Wearable bioelectronic patches are creating a transformative effect in the health care industry for human physiological signal monitoring. However, the use of such patches is restricted due to the unavailability of a proper power source. Ideal biodevices should be thin, soft, robust, energy-efficient, and biocompatible. Here, we report development of a flexible, lightweight, and biocompatible electronic skin-cum-portable power source for wearable bioelectronics by using a processed chicken feather fiber. The device is fabricated with a novel, breathable composite of biowaste chicken feather and organic poly(vinylidene fluoride) (PVDF) polymer, where the chicken feather fiber constitutes the "microbones" of the PVDF, enhancing its piezoelectric phase content, biocompatibility, and crystallinity. Thanks to its outstanding pressure sensitivity, the fabricated electronic skin is used for the monitoring of different human physiological signals such as body motion, finger and joint bending, throat activities, and pulse rate with excellent sensitivity. A wireless system is developed to remotely receive the different physiological signals as captured by the electronic skin. We also explore the capabilities of the device as a power source for other small electronics. The piezoelectric energy harvesting device can harvest a maximum output voltage of ∼28 V and an area power density of 1.4 µW·cm-2 from the human finger imparting. The improved energy harvesting property of the device is related to the induced higher fraction of the electroactive phase in the composite. The easy process ability, natural biocompatibility, superior piezoelectric performance, high pressure sensitivity, and alignment toward wireless transmission of the captured data make the device a promising candidate for wearable bioelectronic patches and power sources.

Enhanced dielectric, ferroelectric, energy storage and mechanical energy harvesting performance of ZnO-PVDF composites induced by MWCNTs as an additive third phase.

The present work highlights an attempt of fabricating a nanocomposite by the addition of multi-walled carbon nanotubes (MWCNTs) as a third phase into flexible ZnO-poly(vinylidene fluoride) (ZnO-PVDF) composites. MWCNTs played a very important role in distributing ZnO fillers in the PVDF matrix more homogeneously and increased the connection capability. Enhancement of the piezoelectric phase, dielectric permittivity, ferroelectric polarization, energy storage density and mechanical energy harvesting performance of ZnO-PVDF composites after the addition of MWCNTs was confirmed from the respective characterization studies. The sensing capability was demonstrated by the generation of ∼22 V ac output voltage through the application of human finger tapping on 15 wt% ZnO and a 0.1 wt% MWCNT-loaded PVDF (15PZNT) based composite film. The rectified voltage from the fabricated 15PZNT film was used to charge a 10-µF capacitor up to ∼3 V which was used for the illumination of 30 commercial LEDs. The maximum power density from the film was found to be 21.41 µW cm-2 at 4 MΩ load resistance. The effect of the addition of MWCNTs was also verified by simulation using COMSOL Multiphysics software.

Hydroxylated BiFeO3 as efficient fillers in poly(vinylidene fluoride) for flexible dielectric, ferroelectric, energy storage and mechanical energy harvesting application.

Here we report the effect of surface hydroxylation of BiFeO3 fillers on the dielectric, ferroelectric, energy storage and mechanical energy harvesting performance of poly(vinylidene fluoride). Surface hydroxylation helped to improve the interfacial interaction between the filler and PVDF matrix by introducing a strong hydrogen bonding between the -OH group of the hydroxylated BiFeO3 filler surface and the -CF2 dipole of PVDF in place of electrostatic interfacial interaction between non-hydroxylated BiFeO3 and the -CH2 dipole of PVDF. The amount of polar phase increased to around 91% for a 7 wt% hydroxylated BiFeO3 loaded PVDF film (7BFOH) by this new type of interfacial interaction. The dielectric, ferroelectric, energy storage and mechanical energy harvesting performance of the PVDF based composite films also improved by the above said technique. Upon repeated human finger tapping, the 7BFOH film delivered ∼18 V output peak to peak open circuit ac voltage (VOC). After rectification, the VOC of the 7BFOH film was able to charge a 10 µF capacitor up to ∼3 V which was able to light up some LEDs (connected in parallel) together instantaneously, which proved the real life applicability of the composite films in low power consuming self-powered electronic devices.

Nano-ZnO decorated ZnSnO3 as efficient fillers in PVDF matrixes: toward simultaneous enhancement of energy storage density and efficiency and improved energy harvesting activity.

Here, we report the effect of ZnO decoration on ZnSnO3 fillers on the dielectric property, energy storage behaviour and mechanical energy harvesting performance of PVDF matrixes. More enhanced dielectric constant and reduction in dielectric loss were achieved in PVDF-ZnO@ZnSnO3 (PVDF-ZNZS) films than in PVDF-ZnSnO3 (PVDF-ZS) films for the same concentration of filler loading. Similarly, PVDF-ZNZS films showed simultaneous enhancement in electrical energy storage density and storage efficiency compared to PVDF-ZS composites. As all the constituent materials (PVDF, ZnSnO3 and ZnO) were piezoelectric, the resulting composite film showed improved piezoelectric energy harvesting performance too. After rectification, the output ac voltage was used to charge a 10 µF capacitor up to ∼5 V dc which was further used to light up some LEDs. Furthermore, in order to exhibit improved sensitive output, a hybrid piezo-tribo nanogenerator was fabricated which was demonstrated as a motion sensor, a weight sensor and a human body movement sensor as part of a real life application.

Frequency dependent energy storage and dielectric performance of Ba-Zr Co-doped BiFeO3 loaded PVDF based mechanical energy harvesters: effect of corona poling.

Bi0.95Ba0.05Fe0.95Zr0.05O3 (BBFZO) nanoparticles were synthesized by a sol-gel technique to develop a filler material with lower leakage current and oxygen vacancies compared to the host BiFeO3. In this work, we report the enhanced dielectric, ferroelectric, energy storage and energy harvesting performance of BBFZO incorporated PVDF composites. 15 wt% BBFZO loaded PVDF (15BBFZO) exhibited improved polarity (F(EA) = 77.42%) compared to neat PVDF (F(EA) = 37.01%). At an applied field of ∼14 kV cm-1 (1 Hz), this film (15BBFZO) exhibited a maximum energy storage density of 151.18 µJ cm-3 (at 1 Hz). Upon repeated human finger tapping, an average open circuit peak to peak a.c. voltage (VOC) ∼ 20 V was obtained from 15BBFZO. A comprehensive study of frequency dependent D-E loops and an extensive study of the effect of electrical poling on the output performance of the developed composite films have been performed. An improvement of the dipolar polarization was established through a frequency dependent D-E loop study of unpoled and poled 15BBFZO and from other experiments. After poling the energy storage density and VOC of 15BBFZO were 154.66 µJ cm-3 (at 1 Hz) and ∼30 V, respectively. After rectification this output electrical signal was able to charge a 10 µF commercial capacitor up to ∼5.5 V. After poling, the energy storage efficiency (η) of 15BBFZO also improved from 52.49% to 67.85% (at 1 Hz). The frequency dependence of the storage efficiency for all the samples has also been extensively investigated here. At 1 kHz, η improved to 93.30% for poled 15BBFZO.

Role of suppressed oxygen vacancies in the BiFeO3 nanofiller to improve the polar phase and multifunctional performance of poly(vinylidene fluoride).

In the present work, we report the enhanced dielectric, ferroelectric, energy storage and energy harvesting performance of a citrate-gel synthesized Bi1-xBaxFeO3 (x = 0, 0.05, 0.10) incorporated poly(vinylidene fluoride) (PVDF) matrix. Doping with aliovalent ions has been shown to improve the multiferroic properties of BiFeO3. Though Ba2+ doping has been expected to introduce more oxygen vacancies, here we found a decrease in oxygen vacancies with increasing Ba2+ up to 10% doping. This suppression of oxygen vacancies through Ba2+ doping in BiFeO3 helped in the formation of the polar PVDF phase in the composite through interfacial interaction. The polar phase fraction (F(EA)) increases to 82.4% for the 7 wt% Bi0.9Ba0.1FeO3 incorporated PVDF film from 38.2% for the neat PVDF. This film also showed the highest energy storage density of 5.4 mJ cm-3 at a 110 kV cm-1 applied field and the highest energy harvesting performance of ∼20 V open circuit output voltage after application of repeated human finger tapping and releasing motion, due to its enhanced piezoelectric property. Here, we also demonstrate the enhanced energy harvesting capability of the said PVDF-Bi0.9Ba0.1FeO3 composite by charging a 10 µF commercial capacitor up to ∼5 V in 270 s, which can comfortably light up about 50 LEDs instantaneously.

Improved dielectric constant and breakdown strength of γ-phase dominant super toughened polyvinylidene fluoride/TiO2 nanocomposite film: an excellent material for energy storage applications and piezoelectric throughput.

Titanium dioxide (TiO2) nanoparticles (NPs) embedded γ-phase containing polyvinylidene fluoride (PVDF) nanocomposite (PNC) film turns to an excellent material for energy storage application due to an increased dielectric constant (32 at 1 kHz), enhanced electric breakdown strength (400 MV m-1). It also exhibits a high energy density of 4 J cm-3 which is 25 times higher than that of virgin PVDF. 98% of the electroactive γ-phase has been acheived by the incorporation of TiO2 NPs and the resulting PNC behaves like a super-toughened material due to a dramatic improvement (more than 80%) in the tensile strength. Owing to their electroactive nature and extraordinary mechanical properties, PNC films have a strong ability to fabricate the piezoelectric nanogenerators (PNGs) that have recently been an area of focus regarding mechanical energy harvesting. The feasibility of piezoelectric voltage generation from PNGs is demostrated under the rotating fan that also promises further utility such as rotational speed (RPM) determination.

The preparation of γ-crystalline non-electrically poled photoluminescant ZnO-PVDF nanocomposite film for wearable nanogenerators.

Polyvinylidene fluoride (PVDF) films are filled with various mass fractions (wt%) of zinc oxide nanoparticles (ZnO-NPs) to fabricate the high performance of a wearable polymer composite nanogenerator (PCNG). The ZnO-NPs can induced a fully γ-crystalline phase in PVDF, where traditional electrical poling is not necessary for the generation of piezoelectric properties. The PCNG delivers up to 28 V of open circuit voltage and 450 nA of short circuit current by simple repeated human finger imparting (under a pressure amplitude of 8.43 kPa) that generates sufficient power to turn on at least 48 commercial blue light emitting diodes (LEDs) instantly. Furthermore, it also successfully charged the capacitors, signifying practical applicability as a piezoelectric based nanogenerator for self-powering devices. The applicability of PCNG by wearable means is clarified when it gives rise to a sensible response, say up to 400 mV of output voltage synchronized with the PCNG embedded human finger in a bending and releasing gesture. UV-visible absorption spectral analysis revealed the possibility of estimating a change in the optical band gap value (E g), refractive index (n) and optical activation energy (E a) in different concentrations of ZnO-NP incorporated PVDF nanocomposite films, and it possesses a useful methodology where ZnO-NPs can be used as an optical probe. Near blue light emission is observed from photoluminescence spectra, which are clearly shown from a Commission Internationale de L'Eclairage (CIE) diagram. The piezoelectric charge coefficient of the nanocomposite film is estimated to be -6.4 pC/N, where even electrical poling treatment is not employed. In addition, dielectric properties have been studied to understand the role of molecular kinetic and interfacial polarization occurring in nanocomposite films at different applied frequencies.

Improved breakdown strength and electrical energy storage performance of γ-poly(vinylidene fluoride)/unmodified montmorillonite clay nano-dielectrics.

A remarkable improvement in the dielectric breakdown strength (Eb) and discharge energy density (U e) of flexible polymer nanocomposites is realized by the incorporation of unmodified smectite montmorillonite (MMT) nanoclay into a poly(vinylidene fluoride) (PVDF) matrix. The resulting PVDF/MMT clay nanocomposite (PCN) films stabilize the γ phase and increase the path tortuosity via strong intercalation of the PVDF matrix into inorganic layered silicates without sacrificing the quality of surface morphology. The PCN films exhibits superior dielectric properties (up to ε r ∼ 28 and tan δ ∼ 0.032 at 1 kHz) than those of pure PVDF. As a result, a large increase in E b of 873 MV m(-1) and U e of 24.9 J cm(-3) is achieved. Subsequently, the PCN films possess more than 60% charge-discharge efficiency even at higher electric field and thus provide a scope to develop high energy density flexible and transparent materials for energy storage technologies.

The influence of hydrogen bonding on the dielectric constant and the piezoelectric energy harvesting performance of hydrated metal salt mediated PVDF films.

Polyvinylidene fluoride (PVDF) films are filled with various mass fractions (wt%) of hydrated metal salt (MgCl2·6H2O) (Mg-salt) to fabricate high performance piezoelectric energy harvesters (PEHs). They deliver up to 4 V of open circuit voltage by simply repeated human finger imparting (under a pressure of ∼4.45 kPa) and also generate sufficient power to turn on at least ten commercial blue light emitting diodes (LEDs) instantly. The enhanced piezo-response is attributed to the combined effect of the change in the inherent dipole moment of the electroactive phase containing PVDF itself and H-bonding arising between the Mg-salt filler and PVDF via electrostatic interactions. Furthermore, it also successfully charged the capacitors, signifying practical applicability as a piezoelectric based energy harvester power source. UV-visible optical absorption spectral analysis revealed the possibility to estimate a change in the optical band gap value at different concentrations of Mg-salt filler added PVDF films that possess a useful methodology where the Mg-salt can be used as an optical probe. In addition dielectric properties have been studied to understand the role of molecular kinetic and interfacial polarization occurs in H-bond PVDF films at different applied frequencies at room temperature.

Self-poled transparent and flexible UV light-emitting cerium complex-PVDF composite: a high-performance nanogenerator.

Cerium(III)-N,N-dimethylformamide-bisulfate [Ce(DMF)(HSO4)3] complex is doped into poly(vinylidene fluoride) (PVDF) to induce a higher yield (99%) of the electroactive phases (ß- and γ-phases) of PVDF. A remarkable enhancement of the output voltage (∼32 V) of a nanogenerator (NG) based on a nonelectrically poled cerium(III) complex containing PVDF composite film is achieved by simple repeated human finger imparting, whereas neat PVDF does not show this kind of behavior. This high electrical output resembles the generation of self-poled electroactive ß-phase in PVDF due to the electrostatic interactions between the fluoride of PVDF and the surface-active positive charge cloud of the cerium complex via H-bonding and/or bipolar interaction among the opposite poles of cerium complex and PVDF, respectively. The capacitor charging capability of the flexible NG promises its applicability as piezoelectric-based energy harvester. The cerium(III) complex doped PVDF composite film exhibit an intense photoluminescence in the UV region, which might be due to a participation of electron cloud from negative pole of bipolarized PVDF. This fact may open a new area for prospective development of high-performance energy-saving flexible solid-state UV light emitters.