Direct Measurements Of Electrocaloric Effect Research Articles

Direct measurement of electrocaloric effect based on multi-harmonic lock-in thermography

We report on a direct measurement method for electrocaloric effects, the heating/cooling upon application/removal of an electric field in dielectric materials, based on a lock-in thermography technique. By use of sinusoidal excitation and multi-harmonic detection, the actual temperature change can be measured by a single measurement in the frequency domain even when the electrocaloric effect shows a nonlinear response to the excitation field. We demonstrated the method by measuring the temperature dependence of the electric-field-induced temperature change in two Sr-doped BaTiO3 systems with different ferroelectric-paraelectric phase transition temperatures, where we introduce the procedure for extracting the pure electrocaloric contribution free from heat losses and Joule heating due to leakage currents. This method can be used irrespective of the type of dielectric material and enables simultaneous estimation of the polarization change and power dissipation during the application of an electric field, making it a convenient imaging measurement method for the electrocaloric effect.

Direct measurement of electrocaloric effect in P(VDF-TrFE-CFE) film using infrared imaging

Poly (vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) P(VDF-TrFE-CFE) is a relaxor ferroelectric polymer, which exhibits a temperature-independent electrocaloric effect at room temperature. In this work, the electrocaloric effect in P(VDF-TrFE-CFE) film was directly analysed using infrared imaging. P(VDF-TrFE-CFE) 64.8%/27.4%/7.8% (in mole) film of (15 ± 1) μm thickness was deposited on polyethylene naphthalate substrate. Direct ECE of P(VDF-TrFE-CFE) film was measured from 15 to 35 °C at different electric fields. A maximum adiabatic temperature change (ΔTad) of 3.58 K was measured during the cooling cycle at a field of 100 V/μm at 30 °C. Finite element analysis of temperature dissipation through the sample estimated that the actual temperature change within P(VDF-TrFE-CFE) film was 4.3 K. Despite the thermal mass of the substrate, a substantial ECE was observed in P(VDF-TrFE-CFE) films. This electrocaloric terpolymer composition could be of interest for electrocaloric cooling applications.

Direct measurement of electrocaloric effect of BaTiO<sub>3</sub> using high-speed infrared camera

Direct measurement of electrocaloric effect of BaTiO<sub>3</sub> using high-speed infrared camera

Direct measurement of electrocaloric effect in lead-free (Na0.5Bi0.5)TiO3-based multilayer ceramic capacitors

Multilayer ceramic capacitors (MLCCs) of lead-free NBT-based ceramics are produced and their electrocaloric effect (ECE) is characterised for the first time. Dense MLCCs with 97μm-thick active layers are successfully produced by tape casting. Dielectric permittivity measurements reveal the MLCCs to have properties similar with that reported for the corresponding bulk ceramics, including Td∼50°C and TS∼100°C. Direct ECE measurements also reveal agreement and confirm the previously reported tendency of the high-field ECE peak to shift towards TS. The highest value of ECE, ΔTmax∼1.7K is measured at 90°C under 90kV/cm. A low breakdown strength of 93kV/cm needs to be solved to realise stronger electric fields and achieve commercially viable ECE values.

Quasi-adiabatic calorimeter for direct electrocaloric measurements.

The electrocaloric effect (ECE) in ferroelectric materials is a promising candidate for small, effective, low cost, and environmentally friendly solid state cooling applications. Instead of the commonly used indirect estimates based on Maxwell's relations, direct measurements of the ECE are required to obtain reliable values. In this work, we report on a custom-made quasi-adiabatic calorimeter for direct ECE measurements. The ECE is measured for two promising lead-free materials: Ba(Zr0.12Ti0.88)O3 and Ba(Zr0.2Ti0.8)O3 bulk ceramics. Adiabatic temperature changes of ΔTEC = 0.5 K at 355 K and ΔTEC = 0.3 K at 314 K were achieved under the application of an electric field of 2 kV/mm for the Ba(Zr0.12Ti0.88)O3 and Ba(Zr0.2Ti0.8)O3 samples, respectively. The quasi-adiabatic ECE measurements reliably match other direct EC measurements using a differential scanning calorimeter or an infrared camera. The data are compared to indirect EC estimations based on Maxwell's relations and show that the indirect measurements typically underestimate the effect to a certain degree.

Enhanced electrocaloric analysis and energy-storage performance of lanthanum modified lead titanate ceramics for potential solid-state refrigeration applications

The unique properties and great variety of relaxer ferroelectrics make them highly attractive in energy-storage and solid-state refrigeration technologies. In this work, lanthanum modified lead titanate ceramics are prepared and studied. The giant electrocaloric effect in lanthanum modified lead titanate ceramics is revealed for the first time. Large refrigeration efficiency (27.4) and high adiabatic temperature change (1.67 K) are achieved by indirect analysis. Direct measurements of electrocaloric effect show that reversible adiabatic temperature change is also about 1.67 K, which exceeds many electrocaloric effect values in current direct measured electrocaloric studies. Both theoretical calculated and direct measured electrocaloric effects are in good agreements in high temperatures. Temperature and electric field related energy storage properties are also analyzed, maximum energy-storage density and energy-storage efficiency are about 0.31 J/cm3 and 91.2%, respectively.

Direct measurement of electrocaloric effect in lead-free Ba(SnxTi1-x)O3 ceramics

In this study, we report on investigation of the electrocaloric (EC) effect in lead-free Ba(SnxTi1-x)O3 (BSnT) ceramics with compositions in the range of 0.08 ≤ x ≤ 0.15 by the direct measurement method using a differential scanning calorimeter. The maximum EC temperature change, ΔTEC-max = 0.63 K under an electric field of 2 kV/mm, was observed for the composition with x = 0.11 at ∼44 °C around the multiphase coexistence region. We observed that the EC effect also peaks at transitions between ferroelectric phases of different symmetries. Comparison with the results of indirect EC measurements from our previous work shows that the indirect approach provides reasonable estimations of the magnitude of the largest EC temperature changes and EC strength. However, it fails to describe correctly temperature dependences of the EC effect for the compositions showing relaxor-like behaviour (x = 0.14 and 0.15) because of their non-ergodic nature. Our study provides strong evidence supporting that looking for multiphase ferroelectric materials can be very useful to optimize EC performance.

Direct measurements of electrocaloric effect in ferroelectrics using thin-film thermocouples

A direct measurement method for investigating the electrocaloric (EC) effect was developed using a thin-film thermocouple deposited on samples. A T-type thin-film thermocouple was fabricated by RF magnetron sputtering at room temperature. Two types of measurement were carried out using rectangular pulses and sine waves with a DC offset. The EC coefficients (ΔT/ΔE) of BaTiO3 ceramics were determined as 0.35 × 10−6 and 0.48 × 10−6 K·m/V in the measurements at Curie temperature. The EC temperature change of a (Ba0.9,Ca0.1)TiO3 thin film was measured using sine waves with the DC offset. The EC coefficient was 0.0018 × 10−6 K·m/V at room temperature. These results suggest that thin-film thermocouples are useful for the direct measurement of the EC effect.

Modified Differential Scanning Calorimeter for Direct Electrocaloric Measurements

Solid-state refrigeration using the electrocaloric effect (ECE) in ferroelectric materials is a promising alternative to the conventional vapor-compression technology. In spite of growing interest to the investigation of the ECE, direct measurements of the effect are still rare. In this paper, we report on a modification of a differential scanning calorimeter for direct ECE measurements. The importance of proper estimation of the thermal correction factor and use of proper values of the heat capacitance for correct ECE measurements is discussed. The ECE measurements were performed for Ba(Zr0.2Ti0.8)O3 and Ba(Zr0.12Ti0.88)O3 bulk ceramics. Large electrocaloric temperature changes of 0.54 and 0.34 K are achieved under the application of an electric field of 2 kV/mm for the Ba(Zr0.12Ti0.88)O3 and Ba(Zr0.2Ti0.8)O3 samples, respectively. The relation between the directly measured ECE values and frequently used indirect estimation based on Maxwell's relations is discussed.

Large room-temperature electrocaloric effect in lead-free BaHfxTi1−xO3 ceramics under low electric field

Ferroelectrics are promising candidate materials for electrocaloric refrigeration. Materials with a large electrocaloric effect (ECE) near room temperature and a broad working temperature range are getting closer to practical applications. However, the enhanced ECE is always achieved under high electric field, which limits their wide cooling applications. In this paper, the phase diagram of lead-free BaHfxTi1−xO3 (BHT) ferroelectric ceramics was established. A large ECE under relatively low electric field (ΔE = 10 kV/cm) is firstly reported in BHT ferroelectric ceramics. The direct temperature change (ΔT = 0.35 °C under 10 kV/cm) in BHT ceramics is comparable with those reported in the literature under high electric fields. Meanwhile, the electrocaloric efficiency (ΔT/ΔE = 0.35 K mm kV−1 under 10 kV/cm) is thirteen percent higher than the best value reported previously under high electric field (ΔE = 145 kV/cm). We demonstrate that the ECE can be greatly enhanced by tuning the composition of the lead-free BHT ceramics to its first-order phase transition (FPT), invariant critical point (ICP) or diffuse phase transition (DPT). It is shown that the enhancement in ECE is strongly dependent on the nature of structural phase transition and electric field coupling effect, which has been confirmed by both the indirect and direct ECE measurements. A phenomenological explanation based on Landau model was also proposed to understand this phenomenon. Our findings in this work may provide a better understanding and design methodology for developing more practically useful electrocaloric materials.

Tuning the electrocaloric enhancement near the morphotropic phase boundary in lead-free ceramics.

The need for more energy-efficient and environmentally-friendly alternatives in the refrigeration industry to meet global emission targets has driven efforts towards materials with a potential for solid state cooling. Adiabatic depolarisation cooling, based on the electrocaloric effect (ECE), is a significant contender for efficient new solid state refrigeration techniques. Some of the highest ECE performances reported are found in compounds close to the morphotropic phase boundary (MPB). This relationship between performance and the MPB makes the ability to tune the position of the MPB an important challenge in electrocaloric research. Here, we report direct ECE measurements performed on MPB tuned NBT-06BT bulk ceramics with a combination of A-site substitutions. We successfully shift the MPB of these lead-free ceramics closer to room temperature, as required for solid state refrigeration, without loss of the criticality of the system and the associated ECE enhancement.

Interpretation of the Electrocaloric Effect in Na1/2Bi1/2TiO3-SrTiO3-PbTiO3 Solid Solutions

Results of direct measurements of electrocaloric effect and polarization are mutually compared in solid solutions 0.4Na1/2Bi1/2TiO3-(0.6-x)SrTiO3-xPbTiO3. Three temperature regions are distinguished in respect of a phase transition temperature. Above the phase transition, electrocaloric effect is determined by orientation of polar nanoregions by electric field. In wide temperature regions above and below the phase transition temperature, the difference between results, obtained from direct electrocaloric effect measurements and from polarization hysteresis loops, is explained by temperature dependence of concentration of polar nanoregions, oriented by electric field. Existence of a common ΔT(P) curve for all temperatures in the ferroelectric state indicates that polarization can be treated as a parameter, which solely determines electrocaloric effect in this state.

Direct and indirect electrocaloric measurements on 〈001〉-PbMg1/3Nb2/3O3-30PbTiO3 single crystals

A direct electrocaloric effect (ECE) measurement system, based on a modified-differential scanning calorimeter (DSC), allowing the acquisition of both thermal (ECE, heat capacity) and electrical (P-E loops, leakage current) information simultaneously, was used to analyze 〈001〉-oriented PbMg1/3Nb2/3O3-30PbTiO3 single crystals. Different electric-field-induced phase transitions were identified on direct ECE measurements and confirmed by dielectric measurements. The strongest ECE (ΔTEC = 0.65 K) was measured for an applied electric field E = 10 kV/cm just above the temperature of depolarization. The direct ECE measurements were compared with indirect measurements obtained from dielectric polarization measurements versus electric field and temperature and a very good agreement was found. A region with negative ΔTEC was identified by both direct and indirect measurements. This phenomenon was attributed to the formation of a reversible field-induced phase transition towards a state with a different polar direction.

Direct Measurements of the Electrocaloric Effect in Bulk PbMg1/3Nb2/3O3 (PMN) Ceramics

Electrocaloric effect (ECE), i.e., a reversibly change in the temperature of an electrocaloric material due to the adiabatically applied electric field, is very attractive phenomenon due to its applications, for example in electric refrigeration. The first observations of the giant ECE were based on indirect measurements of the electric polarization and not on direct measurements of the ECE itself. By using direct measurements of ECE we show existence of the giant ECE in PMN ceramics near the electric field-induced ferroelectric phase transition.

Direct Measurements of the Giant Electrocaloric Effect in Soft and Solid Ferroelectric Materials

The giant electrocaloric (EC) effect is of great importance for application in cooling or heating devices of new generation, which would be friendlier for environment. Recent predictions of the existence of the giant EC effect in polymeric and inorganic ferroelectric relaxors are based solely on the indirect measurements of the electric polarization and not on a direct measurement of the EC effect itself. Here a method and analysis of direct measurements of the giant EC effect in various soft and solid ferroelectric materials in the form of thick and thin films is presented. The field dependence of the EC effect is shown for PbMg1/3Nb2/3O3 (PMN) ceramics and P(VDF-TrFE) (68/32 mol%) copolymers.