Pyroelectric Nanogenerator Based on an SbSI–TiO2 Nanocomposite

For the first time, a composite of ferroelectric antimony sulfoiodide (SbSI) nanowires and non-ferroelectric titanium dioxide (TiO2) nanoparticles was applied as a pyroelectric nanogenerator. SbSI nanowires were fabricated under ultrasonic treatment. Sonochemical synthesis was performed in the presence of TiO2 nanoparticles. The mean lateral dimension da = 68(2) nm and the length La = 2.52(7) µm of the SbSI nanowires were determined. TiO2 nanoparticles served as binders in the synthesized nanocomposite, which allowed for the preparation of dense films via the simple drop-casting method. The SbSI–TiO2 nanocomposite film was sandwiched between gold and indium tin oxide (ITO) electrodes. The Curie temperature of TC = 294(2) K was evaluated and confirmed to be consistent with the data reported in the literature for ferroelectric SbSI. The SbSI–TiO2 device was subjected to periodic thermal fluctuations. The measured pyroelectric signals were highly correlated with the temperature change waveforms. The magnitude of the pyroelectric current was found to be a linear function of the temperature change rate. The high value of the pyroelectric coefficient p = 264(7) nC/(cm2·K) was determined for the SbSI–TiO2 nanocomposite. When the rate of temperature change was equal dT/dt = 62.5 mK/s, the maximum and average surface power densities of the SbSI–TiO2 nanogenerator reached 8.39(2) and 2.57(2) µW/m2, respectively.

OPTIMIZATION OF TECHNOLOGY FOR PRODUCING A COMPOSITE BASED ON BARIUM FERRITE AND BARIUM TITANATE

В работе показано, что в результате спекания образцов композита титанат бария (80 объемных %) - феррит бария (20 объемных %) в фарфоровом тигле при температуре 1300 °С возникает эвтектика. В результате сравнения свойств образцов, полученных при различных температурах спекания, установлено, что оптимальные свойства имеют образцы, спеченные при 1250 °С. Проведено сравнение структуры и диэлектрических свойств образцов керамики титаната бария и композита титанат бария (80 объемных %) - феррит бария (20 объемных %), спеченных при температуре 1250°С. Показано, что добавление в состав титаната бария 20% феррита бария повышает значение диэлектрической проницаемости, пироэлектрического коэффициента и пьезоэлектрического модуля d композита в 1,5 - 2 раза по сравнению с керамикой титаната бария, тогда как значение пьезоэлектрического модуля d остается без изменения. Введение в состав керамики титаната бария 20 % феррита бария достаточно для того, чтобы полученный композит имел магнитные характеристики, соответствующий чистому ферриту бария. It is shown in the work that as a result of sintering of composite samples of barium titanate (80 vol. %) - barium ferrite (20 vol. %) in a porcelain crucible at a temperature of 1300 °C, a eutectic appears. As a result of comparing the properties of the samples obtained at different sintering temperatures, it was found that the samples sintered at 1250 °C have optimal properties. The structure and dielectric properties of barium titanate ceramic samples and barium titanate (80 vol. %) - barium ferrite (20 vol. %) composite sintered at a temperature of 1250 °C are compared. It has been shown that the addition of 20% barium ferrite to the composition of barium titanate increases the dielectric constant, pyroelectric coefficient, and piezoelectric modulus d of the composite of 1,5 - 2 times compared to barium titanate ceramics, while the value of the piezoelectric modulus d remains unchanged. The introduction of 20 % barium ferrite into the barium titanate ceramics is sufficient for the resulting composite to have magnetic characteristics corresponding to pure barium ferrite.

Piezoelectric A15B16C17 Compounds and Their Nanocomposites for Energy Harvesting and Sensors: A Review

Interest in pyroelectrics and piezoelectrics has increased worldwide on account of their unique properties. Applications based on these phenomena include piezo- and pyroelectric nanogenerators, piezoelectric sensors, and piezocatalysis. One of the most interesting materials used in this growing field are A15B16C17 nanowires, an example of which is SbSI. The latter has an electromechanical coupling coefficient of 0.8, a piezoelectric module of 2000 pC/N, and a pyroelectric coefficient of 12 × 10−3 C/m2K. In this review, we examine the production and properties of these nanowires and their composites, such as PAN/SbSI and PVDF/SbSI. The generated electrical response from 11 different structures under various excitations, such as an impact or a pressure shock, are presented. It is shown, for example, that the PVDF/SbSI and PAN/SbSI composites have well-arranged nanowires, the orientation of which greatly affects the value of its output power. The power density for all the nanogenerators based upon A15B16C17 nanowires (and their composites) are recalculated by use of the same key equation. This enables an accurate comparison of the efficiency of all the configurations. The piezo- and photocatalytic properties of SbSI nanowires are also presented; their excellent ability is shown by the high reaction kinetic rate constant (7.6 min−1).

Pyroelectric properties of 91.5Na0.5Bi0.5TiO3–8.5K0.5Bi0.5TiO3 lead-free single crystal

The dielectric and pyroelectric performances of 91.5Na[Formula: see text]Bi[Formula: see text]TiO3–8.5K[Formula: see text]Bi[Formula: see text]TiO3 lead-free single crystal were investigated. The depolarization temperature of the crystal is about 153[Formula: see text]C. Among the [Formula: see text]001[Formula: see text], [Formula: see text]110[Formula: see text], and [Formula: see text]111[Formula: see text] crystallographic orientations, the [Formula: see text]111[Formula: see text]-oriented crystal possesses the highest pyroelectric coefficient and the largest figures of merit, and the values of [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text]are 5.63× 10[Formula: see text] C/m2 ⋅ K, 0.06 m2/C, and 21.5 [Formula: see text]Pa[Formula: see text] for the [Formula: see text]111[Formula: see text]-oriented crystal at room temperature. The [Formula: see text]and [Formula: see text]exhibit weak frequency dependence in the range of 100–300 Hz. With the increase of the temperature, the value of [Formula: see text]increases, while the [Formula: see text] value of [Formula: see text] decreases from 18[Formula: see text]C to 103 [Formula: see text]C.

Improved Non-Piezoelectric Electric Properties Based on La Modulated Ferroelectric-Ergodic Relaxor Transition in (Bi0.5Na0.5)TiO3-Ba(Ti, Zr)O3 Ceramics

The characteristic transition from ferroelectric (FE) to ergodic relaxor (ER) state in (Bi0.5Na0.5)TiO3 (BNT) based lead-free ceramics provides an efficient approach to bring a highly ordered phase back to a disordered one. It would be rational to utilize this transition to improve relevant non-piezoelectric properties based on domain decomposition. In this work, different La contents were introduced to 0.93(Bi0.5Na0.5)TiO3-0.07Ba(Ti0.945Zr0.055)O3 ceramics (BNT-BZT-xLa) to induce evolution of ergodic degree. The results reveal that with increasing La content, both the FE-ER transition temperature TF-R and depolarization temperature Td shift towards room temperature, implying a deepened ergodic degree. By modulation of ergodic degree, thermally stimulated depolarization current experiment shows a higher current density peak, and corresponding pyroelectric coefficient increases from 2.46 to 2.81 μC/(cm2∙°C) at Td. For refrigeration, the indirect measurement demonstrates the ΔT maximum increases from 1.1 K to 1.4 K, indicating an enhanced electrocaloric effect. Moreover, the optimized energy storage effect is observed after La doping. With appearance of “slimmer” P-E loops, both calculated recoverable energy storage density Wrec and storage efficiency η increase to 0.23 J/cm3 and 22.8%, respectively. These results denote La doping conduces to the improvement of non-piezoelectric properties of BNT-based ceramics in a certain range. Therefore, La doping should be an adopted modification strategy for lead-free ceramics used in areas like refrigerator and pulse capacitors.

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

Dependence of the dielectric properties of barium titanate ceramics and a composite based on it on the sintering temperature

In this paper, we compare the structure and dielectric properties of the samples of barium titanate ceramics that have been sintered at temperatures of 1100, 1150, 1200, 1250 and 1350 °C and dielectric characteristics of the samples of barium titanate (80 vol.%) — barium ferrite (20 vol.%). It is shown that only samples sintered at the temperature of 1250 and 1350 °C have polarization sufficient for the existence of the piezoelectric effect. For the same samples, the pyroelectric coefficient and reversal polarization significantly exceed those for samples sintered at lower temperatures. Analysis of the samples structure confirmed the dependence of the dielectric properties of the barium titanate ceramics on the grain size and, as a consequence, on the sintering temperature. Based on the studies carried out, the optimal temperature (1250 °С) for obtaining composite samples of barium titanate (80 vol.%) — barium ferrite (20 vol.%) was selected. The temperature dependence of the dielectric constant for the composite samples based on barium ferrite — barium titanate with a sintering temperature of 1250 °C is similar to the dependence for the BaTiO3 ceramic samples sintered at 1350 °C. At room temperatures, the permittivity of the composite samples is also significantly higher than that of the barium titanate ceramic samples obtained at the same sintering temperatures. The addition of barium ferrite to the barium titanate not only increased the permittivity of the composite, but also led to a diffusing of the ferroelectric phase transition and a shift in the temperature of the maximum of the dielectric constant by 10 degrees towards high temperatures.

Manipulating electron redistribution to achieve exotic electronic pyroelectricity in dynamic [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for the practical uses remains a formidable challenge, because in conventional ferroelectric materials the pyroelectric effect promptly declines upon cooling from the transition temperature. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice resulting in the electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin transition and redistribution of electron density between redox isomers of high-spin Fe through a charge transfer between the Fe atom and redox active ligand. As a result, temperature dependence of the pyroelectric behavior reported here is opposite and originates from the interconversion between three distinct electronic states. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

Improper molecular ferroelectrics with simultaneous ultrahigh pyroelectricity and figures of merit

Although ferroelectric materials exhibit large pyroelectric coefficients, their pyroelectric figures of merit (FOMs) are severely limited by their high dielectric constants because of the inverse relationship between FOMs and dielectric constant. Here, we report the molecular ferroelectric [Hdabco]ClO4 and [Hdabco]BF4 (dabco = diazabicyclo[2.2.2]octane) exhibiting improper ferroelectric behavior and pyroelectric FOMs outperforming the current ferroelectrics. Concurrently, the improper molecular ferroelectrics have pyroelectric coefficients that are more than one order of magnitude greater than the state-of-the-art pyroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3. Our first-principles and thermodynamic calculations show that the strong coupling between the order parameters, i.e., the rotation angle of anions and polarization, is responsible for the colossal pyroelectric coefficient of the molecular ferroelectrics. Along with the facile preparation and self-poling features, the improper molecular ferroelectrics hold great promise for high-performance pyroelectric devices.

Effect of sintering temperature on dielectric properties of barium titanate ceramics and composite

The structure and dielectric properties of barium titanate ceramics samples sintered at 1100, 1150, 1200, 1250 and 1350 °C have been compared with the dielectric properties of 80 vol.% barium titanate + 20 vol.% barium ferrite composite samples sintered at 1150, 1200 and 1250 °C. It has been shown that polarization sufficient for existence of the piezoelectric effect is only achieved in barium titanate samples sintered at 1250 and 1350 °C. Furthermore the pyroelectric coefficient and reversal polarization of these samples are far higher than those of samples sintered at lower temperatures. Analysis of the sample structures has confirmed that the dielectric properties of barium titanate ceramics depend on grain size and therefore on sintering temperature. Based on the experimental results we have selected the optimum sintering temperature for 80 vol.% barium titanate + 20 vol.% barium ferrite composite to be 1250 °С. Further increase in sintering temperature to 1300 °C showed that this composite has a eutectic. The temperature dependence of the permittivity of the barium titanate / barium ferrite composite sintered at 1250 °С is similar to that of BaTiO3 ceramics samples sintered at 1350 °С. The room temperature permittivity of the composite samples also proves to be far higher than that of barium titanate ceramics samples sintered at the same temperatures. Barium ferrite addition to barium titanate increases the permittivity of the composite and also diffuses the ferroelectric phase transition and shifts the permittivity maximum temperature by 10 °C towards higher temperatures.