High cooling performance in a double-loop electrocaloric heat pump.

Cooling through solid-state electrocaloric materials is an attractive replacement for vapor compression. Despite recent efforts, devices that are potentially commercially competitive have not been developed. We present an electrocaloric cooler with a maximum temperature span of 20.9 kelvin and a maximum cooling power of 4.2 watts under the moderate applied electric field of 10 volts per micrometer without any observed breakdown. Moreover, the maximum coefficient of performance, even taking into account energy expended on fluid pumping, reaches 64% of Carnot's efficiency as long as energy is properly recovered. We believe that this demonstration shows electrocaloric cooling to be a very promising alternative to vapor compression cooling.

Direct Electrocaloric Characterization of Ceramic Films.

Reliable and accurate characterization of the electrocaloric effect is necessary to understand the intrinsic properties of materials. To date, several methods are developed to directly measure the electrocaloric effect. However, each of them has some limitations, making them less suitable for characterizing ceramic films, which rely almost exclusively on less accurate indirect methods. Here, a new approach is proposed to address the process of rapid heat dissipation in ceramic films and to detect the electrically induced temperature change before it thermally bonds with the surrounding elements. By using a polymer substrate that slows heat dissipation to the substrate and fast infrared imaging, a substantial part of the adiabatic electrocaloric effect in Pb(Mg1/3 Nb2/3 )O3 -based ceramic films is captured. Infrared imaging provides a robust technique to reduce the ratio between the adiabatic and the measured electrocaloric temperature change in micrometer-sized ceramic films to a single-digit number, ≈3.5. The obtained results are validated with another direct thermometric method and compared with the results obtained with an indirect approach. Despite different measurement principles, the results obtained with the two direct methods agree well. The proposed approach is timely and can open a door to verify the predicted giant electrocaloric effects in ceramic films.

Large harvested energy with non-linear pyroelectric modules.

Coming up with sustainable sources of electricity is one of the grand challenges of this century. The research field of materials for energy harvesting stems from this motivation, including thermoelectrics1, photovoltaics2 and thermophotovoltaics3. Pyroelectric materials, converting temperature periodic variations in electricity, have been considered as sensors4 and energy harvesters5-7, although we lack materials and devices able to harvest in the joule range. Here we develop a macroscopic thermal energy harvester made of 42 g of lead scandium tantalate in the form of multilayer capacitors that produces 11.2 J of electricity per thermodynamic cycle. Each pyroelectric module can generate up to 4.43 J cm-3 of electric energy density per cycle. We also show that two of these modules weighing 0.3 g are sufficient to sustainably supply an autonomous energy harvester embedding microcontrollers and temperature sensors. Finally, we show that for a 10 K temperature span these multilayer capacitors can reach 40% of Carnot efficiency. These performances stem from (1) a ferroelectric phase transition enabling large efficiency, (2) low leakage current preventing losses and (3) high breakdown voltage. These macroscopic, scalable and highly efficient pyroelectric energy harvesters enable the reconsideration of the production of electricity from heat.

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.

Heterogeneity Challenges in Multiple-Element-Modified Lead-Free Piezoelectric Ceramics.

We report on a heterogeneity study, down to the atomic scale, on a representative multiple-element-modified ceramic based on potassium sodium niobate (KNN): 0.95(Na0.49K0.49Li0.02)(Nb0.8Ta0.2)O3-0.05CaZrO3 with 2 wt % MnO2. We show that different routes for incorporating the MnO2 (either before or after the calcination step) affect the phase composition and finally the functionality of the material. According to X-ray diffraction and scanning electron microscopy analyses, the ceramics consist of orthorhombic and tetragonal perovskite phases together with a small amount of Mn-rich secondary phase. The addition of MnO2 after the calcination results in better piezoelectric properties, corresponding to a ratio between the orthorhombic and tetragonal perovskite phases that is closer to unity. We also show, using microscopy techniques combined with analytical tools, that Zr-rich, Ta-rich and Mn-rich segregations are present on the nano and atomic levels. With this multi-scale analysis approach, we demonstrate that the functional properties are sensitive to minor modifications in the synthesis route, and consequently to different material properties on all scales. We believe that detecting and learning how to control these modifications will be a step forward in overcoming the irreproducibility problems with KNN-based materials.

Investigations of ferroelectric polycrystalline bulks and thick films using piezoresponse force microscopy.

In recent years, ferroelectric/piezoelectric polycrystalline bulks and thick films have been extensively studied for different applications, such as sensors, actuators, transducers and caloric devices. In the majority of these applications, the electric field is applied to the working element in order to induce an electromechanical response, which is a complex phenomenon with several origins. Among them is the field-induced movement of domain walls, which is nowadays extensively studied using piezoresponse force microscopy (PFM), a technique derived from atomic force microscopy. PFM is based on the detection of the local converse piezoelectric effect in the sample; it is one of the most frequently applied methods for the characterization of the ferroelectric domain structure due to the simplicity of the sample preparation, its non-destructive nature and its relatively high imaging resolution. In this review, we focus on the PFM analysis of ferroelectric bulk ceramics and thick films. The core of the paper is divided into four sections: (i) introduction; (ii) the preparation of the samples prior to the PFM investigation; (iii) this is followed by reviews of the domain structures in polycrystalline bulks; and (iv) thick films.

Structure and Dynamics of Ferroelectric Domains in Polycrystalline Pb(Fe1/2Nb1/2)O3.

A complex domain structure with variations in the morphology is observed at ambient temperature in monoclinic Pb(Fe1/2Nb1/2)O3. Using electron microscopy and piezoresponse force microscopy, it is possible to reveal micrometre-sized wedge, lamellar-like, and irregularly shaped domains. By increasing the temperature, the domain structure persists up to 80 °C, and then starts to disappear at around 100 °C due to the proximity of the ferroelectric-paraelectric phase transition, in agreement with macroscopic dielectric measurements. In order to understand to what degree domain switching can occur in the ceramic, the mobility of the domain walls was studied at ambient temperature. The in situ poling experiment performed using piezoresponse force microscopy resulted in an almost perfectly poled area, providing evidence that all types of domains can be easily switched. By poling half an area with 20 V and the other half with -20 V, two domains separated by a straight domain wall were created, indicating that Pb(Fe1/2Nb1/2)O3 is a promising material for domain-wall engineering.

Preparation and Investigation of the Thermal Stability of Phosphate-modified TiO2 Anatase Powders and Thin Films.

The temperature dependence of the anatase-to-rutile phase transition of TiO2 powders and thin films was studied. In order to shift the phase transition to higher temperature, samples were doped with a different amount of phosphate ions and their influence on the structure and thermal stability of the anatase phase was investigated. In addition, the effect of the catalyst form (powders or thin films) on the temperature of the anatase-to-rutile phase transition was observed. TiO2 thin films and powders were prepared using a simple sol-gel method with an alkoxide precursor and citric acid. The thin films were deposited on silicon and aluminum substrates using the dip-coating technique. The content of the anatase phase and the crystallite size at different annealing temperatures were monitored using X-ray diffraction. The course of the thermal decomposition was followed using thermal analyses. The morphology, particle size, shape and elemental makeup of the samples were investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that the phosphate ions successfully inhibited the growth of the anatase nanoparticles and delayed the phase transition to the rutile phase.