• Energy Research

AbstractThe occurrence of the inverse (or negative) electrocaloric effect, where the isothermal application of an electric field leads to an increase in entropy and the removal of the field decreases the entropy of the system under consideration, is discussed and analyzed. Inverse electrocaloric effects have been reported to occur in several cases, for example, at transitions between ferroelectric phases with different polarization directions, in materials with certain polar defect configurations, and in antiferroelectrics. This counterintuitive relationship between entropy and applied field is intriguing and thus of general scientific interest. The combined application of normal and inverse effects has also been suggested as a means to achieve larger temperature differences between hot and cold reservoirs in future cooling devices. A good general understanding and the possibility to engineer inverse caloric effects in terms of temperature spans, required fields, and operating temperatures are thus of fundamental as well as technological importance. Here, the known cases of inverse electrocaloric effects are reviewed, their physical origins are discussed, and the different cases are compared to identify common aspects as well as potential differences. In all cases the inverse electrocaloric effect is related to the presence of competing phases or states that are close in energy and can easily be transformed with the applied field.

The temperature dependence of the dielectric permittivity and polarization hysteresis loops of P(VDF-TrFE-CFE) polymer films with different compositions are studied. Among them, the three compositions, 51.3/48.7/6.2, 59.8/40.2/7.3, and 70/30/8.1, are characterized for the first time. Relaxor behavior is confirmed for all studied samples. Increasing the CFE content results in lowering the freezing temperature and stabilizes the ergodic relaxor state. The observed double hysteresis loops are related to the field-induced transition to a ferroelectric state. The critical field corresponding to this transition varies with the composition and temperature; it becomes larger for temperatures far from the freezing temperature. The energy storage performance is evaluated from the analysis of unipolar polarization hysteresis loops. P(VDF-TrFE-CFE) 59.8/40.2/7.3 shows the largest energy density of about 5 J·cm−3 (at the field of 200 MV·m−1) and a charge–discharge efficiency of 63%, which iscomparable with the best literature data for the neat terpolymers.

Polymer materials are actively used in dielectric capacitors, in particular for energy storage applications. An enhancement of the stored energy density can be achieved in composites of electroactive polymers and dielectric inorganic fillers with a high dielectric permittivity. In this article, we report on the energy storage characteristics of composites of relaxor terpolymer P(VDF-TrFE-CFE) and BaZr0.2Ti0.8O3 (BZT) nanoparticles. The choice of materials was dictated by their large dielectric permittivity in the vicinity of room temperature. Free-standing composite films, with BZT contents up to 5 vol.%, were prepared by solution casting. The dielectric properties of the composites were investigated over a wide range of frequencies and temperatures. It was shown that the addition of the BZT nanoparticles does not affect the relaxor behavior of the polymer matrix, but significantly increases the dielectric permittivity. The energy storage parameters were estimated from the analysis of the unipolar polarization hysteresis loops. The addition of the BZT filler resulted in the increasing discharge energy density. The best results were achieved for composites with 1.25–2.5 vol.% of BZT. In the range of electric fields to 150 MV/m, the obtained materials demonstrate a superior energy storage density compared to other P(VDF-TFE-CFE) based composites reported in the literature.

AbstractLead‐free relaxor ferroelectrics are promising materials for energy storage applications. To find new material systems for electrostatic capacitors, many researches have dedicated their work to formulate new ecologically safe compositions. In our study, we have prepared (1−x)Ba(Ti0.93Sn0.07)O3−xBiYO3 (BTS7‐BY) solid solutions via the solid‐state method. The parent composition, Ba(Ti0.93Sn0.07)O3 is a ferroelectric‐relaxor crossover material. It reduces its remanent polarization while still maintaining a high maximum polarization. Moderate substitution with BiYO3 further lowers the remanent polarization, resulting in slimmer polarization loops and increasing the energy storage efficiency to 90 %. Samples with x ≥ 0.06 show a true relaxor behavior with linear‐like polarization loops with character of weakly‐coupled relaxors. Breakdown strength measurements reveal a reduced breakdown strength with increasing BY content. Further investigations of the electrostriction, the band gap, and the electrical microstructure link the homogeneity and grain size of the microstructure to the resulting breakdown strength. This highlights the importance of a homogenous and small‐grained microstructure for enhancing the energy storage properties. Samples with x = 0.06 exhibit the best energy storage properties with a recoverable energy density of 1.11 J/cm3 at 189 kV/cm with an energy storage efficiency of 74%.

Abstract Thin film Cu2ZnSnSe4 (CZTSe) solar cells can be grown on flexible and lightweight metal substrates allowing their direct integration on bendable surfaces and where the weight of solar cell is an important criterion. Flexible substrates make it possible to use the roll-to-roll technology of solar cells, which leads to an additional reduction in the cost of production and final cost of solar cells. The CZTSe thin films were fabricated by selenization of electrodeposited metallic precursors onto tantalum (Ta) flexible substrates at different temperature and time. The results of the effect of selenization temperature and time on the morphology, structural, and optical property of the CZTSe films are presented in this work. It was found that the morphology of the CZTSe thin films depend on their elemental composition and time of selenization. Experimental data indicate that composition of the CZTSe films selenized within 10 and 20 min at 560 °C have the CZTSe basic phase and secondary phases (CuSe, SnSe and ZnSe). In contrast, the increase in selenization temperature and/or time leads to disappearing of the secondary phases (CuSe, SnSe) and better crystallization of the CZTSe films. It was found that films selenized at 560 and 580 °C within the same time have similar characteristics. Depending on selenization time and temperature of the CZTSe, thin films exhibited a shift in band gap from 1.16 to 1.19 and to 1.22 eV, respectively. The change of band gap of the CZTSe thin films is associated with changes of elemental and phase compositions, and thickness of the film. These results showed that the received CZTSe films on Ta foil can be used for fabrication of thin film solar cells.

Abstract Piezoelectric energy harvesters (PEH) hold enormous potential for converting mechanical energy from our surrounding environment into electrical energy that can be used for powering portable electronics. Potassium sodium niobate (KNN) is one of the promising alternatives to replace lead-based piezoelectric materials. This work presents a cutting-edge demonstration of synthesis-function-device integration of piezoelectric nanofibers, where the morphology and the composition are engineered towards achieving high device output. We report a flexible nanogenerator based on electrospun Li and Ta-modified lead-free KNN nanofibers yielding a high voltage output of 5.6 V, which is around 9-fold higher than for the Mn-doped KNN nanofibers reported previously. The influence of Li and Ta-incorporation into the KNN lattice on the electromechanical coupling and the effect of a nanofiber morphology are investigated. The net-shaped KNN and Li and Ta-modified KNN nanofibers, synthesized by electrospinning of appropriate sols, maintain their structural integrity upon calcination and firing steps. The phase analysis (XRD) confirms the formation of single-phase (KNN) material. Li and Ta are found to be incorporated on the A and B-sites of the perovskite lattice, respectively. Piezo force microscopy data show the heat-treated nanofibers to exhibit multi-domain ferroelectric properties.

In the ferroelectric phase, the change of polarization with temperature from partially switched polarization hysteresis loops has no relation with the electrocaloric effect (ECE) and hence cannot be used in Maxwell relation to deducing ECE.