Direct Electrocaloric Effect Research Articles

Enhanced electrocaloric effect over a broad temperature range in lead‐free Na0.5Bi0.5TiO3‐based relaxor ferroelectrics via doping with Bi(Mg0.5Zr0.5)O3

AbstractWith an increasing demand for environmentally friendly refrigeration, the solid‐state refrigeration based on the electrocaloric effect (ECE) has been drawn extensive attention. It is a challenge to maintain a large adiabatic temperature change (∆T) over a broad temperature span. Herein, the authors designed and synthesised (0.74‐x) Na0.5Bi0.5TiO3‐0.06BaTiO3‐0.2SrTiO3‐xBi(Mg0.5Zr0.5)O3 (abbreviated as NBT‐xBMZ) (x = 0, 0.02, 0.04, 0.06 and 0.08) lead‐free relaxor ferroelectrics. Their microstructures, dielectric properties, ferroelectric properties, ECEs and the structure‐property relationships were investigated. Via doping with BMZ, an enhanced relaxor feature and a wider temperature range where multi‐phases coexist were achieved. The relaxor ferroelectric characteristics were illustrated using the Vogel‐Fulcher relation. The indirectly calculated ECE results showed that the optimal ΔT of 1.11 K was obtained for the x = 0.02 sample at 90°C and 70 kV/cm over a wide Tspan of 120°C, providing a potential ECE material. The direct ECE results procured using thermocouple indicated that the maximal ∆T of 2.14 K and ∆T/∆E of 0.31 K m/MV were achieved in the same sample at 70°C and 7 MV/m and the variation trend of ECE results was consistent with the indirect results. Moreover, the multi‐phases coexistent strategy can be extended to other materials system to generate a large ΔT over a wide temperature range.

Influence of voltage amplitude parameters on the electrocaloric response in ferroelectric materials

Direct electrocaloric effect of BaTiO3-based ceramic materials was measured during poling and partial reverse poling using a square-wave electric field. A strong influence of the amplitude of the reverse bias field on the electrocaloric response was found. With increasing amplitude of the reverse bias field, the electrocaloric response was suppressed depending on the coercive field of the material and nature of the ferroelectric-to-paraelectric phase transition.

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.

Large electrocaloric effect obtained in Ba(SnxTi1−x)O3 lead-free ceramics using direct and indirect measurements

The electrocaloric effect (ECE) in lead-free BaSnxTi[Formula: see text]O3 (BSnT, [Formula: see text], 0.10 and 0.15) ceramics were investigated using a direct ECE measurement. Results indicate that the maximum ECE occurs near the Curie temperature and it slightly shifts towards high temperatures. The directly measured ECE is larger than that calculated using the Maxwell relation and P-E loops. A maximum electrocaloric efficiency [Formula: see text][Formula: see text]KmV[Formula: see text] was procured for the composition with [Formula: see text] at [Formula: see text][Formula: see text]K. And it also shows a broad peak in the temperature range of 250–320[Formula: see text]K.

Electrocaloric effect in lead-free 0.5Ba(Zr0.2Ti0.8) O3-0.5(Ba0.7Ca0.3) TiO3 ceramic measured by direct and indirect methods

Lead-free 0.5BZT-0.5BCT ferroelectric ceramic was fabricated through the conventional solid-state reaction method. The electrocaloric effect (ECE) of 0.5BZT-0.5BCT was systematically investigated by both direct and indirect methods over a wide temperature range and electric field range. The maximum direct ECE ΔTEC = 0.464 K occurs at 100 °C under the electric field of 6 kV/mm, while the obtained maximum indirect ECE ∆TECID is 0.26 K when the electric filed is 2 kV/mm at 70 °C. ECE of 0.5BZT-0.5BCT ceramic exhibits a fast response speed (2–3 s), good cycle stability, and a wide working temperature range (80–140 °C) with ΔTEC ≥ 0.2 K, which indicates the promising candidate for applications in cooling technologies.

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.

Large electrocaloric efficiency over a broad temperature span in lead-free BaTiO3-based ceramics near room temperature

We report a large electrocaloric efficiency of 0.029 K cm kV−1 at 303 K and in a wide operating temperature range of 293 K to 313 K in a lead-free Ba0.9Sr0.1(Ti0.9Zr0.1)0.95Sn0.05O3 ceramic by using direct electrocaloric effect (ECE) measurements. Sn4+ doping in Ba0.9Sr0.1Ti0.9Zr0.1O3 not only tunes the rhombohedral-to-paraelectric phase transition temperature to room temperature but also slightly widens the phase transition region, by slightly strengthening the diffuse character and maintaining its good ferroelectricity. Also, polar nanoregions embedded in the matrix facilitate polarization rotation because of a flat energy landscape associated with the relaxor-to-ferroelectric phase transition, inducing enhanced entropy changes and consequently excellent ECE performance.

Direct and indirect measurement of electrocaloric effect in lead-free (100-x)Ba(Hf0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 ceramics near multi-phase boundary

In this work, the (100-x)Ba(Hf0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 (BHT–xBCT) ferroelectric ceramics were fabricated by a conventional solid-state reaction method. The electrocaloric effect (ECE) of these ceramics was studied by both indirect and direct methods over a wide temperature range with the composition changing from x = 20 to 50. The most excellent direct ECE occurs in the BHT–50BCT with a good direct ΔTEC = 0.27 K (at 92 °C) under the electric field of 10 kV/cm. What's more, the direct EC effect peaks not only locates at near the Curie temperature, but also at the phase-transition temperatures corresponding to the transitions between different ferroelectric phases. In particular, it is found that BHT–50BCT exhibits a direct ECE anomaly ΔTEC = 0.1 K at 30 °C under an electric field of 10 kV/cm, which can be ascribed to the orthorhombic to tetragonal phase transition, proposing that one can achieve a broad temperature window by tuning the temperature gap between ferroelectric (FE) to paraelectric (PE) boundary and FE-FE boundary. In addition, BHT–30BCT shows good stability of indirect ΔTEC,max/ΔE and a broad ECE peak at a higher electric field, indicating that it is possible for electrocaloric temperature ΔTEC to be tuned linearly by electric field. Overall, our results imply that the BHT– xBCT ceramics are promising candidates for lead-free cooling refrigeration applications.

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.