Florian Le Goupil

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.

Electrocaloric enhancement near the morphotropic phase boundary in lead-free NBT-KBT ceramics

The electrocaloric effects (ECEs) of the morphotropic phase boundary (MPB) composition 0.82(Na0.5Bi0.5)TiO3-0.18(K0.5Bi0.5)TiO3 (NBT-18KBT) are studied by direct measurements. The maximum ECE ΔTmax = 0.73 K is measured at 160 °C under 22 kV/cm. This corresponds to an ECE responsivity (ΔT/ΔE) of 0.33 × 10−6 K m/V, which is comparable with the best reported values for lead-free ceramics. A comparison between the direct and indirect ECE measurements shows significant discrepancies. The direct measurement of both positive and negative electrocaloric effect confirms the presence of numerous polar phases near the MPB of NBT-based materials and highlights their potential for solid-state cooling based on high field-induced entropy changes.

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.

Effect of Ce doping on the electrocaloric effect of SrxBa1−xNb2O6 single crystals

The electrocaloric effect (ECE) of SrxBa(1−x)Nb2O6 (SBN100x) single crystals, with a tetragonal tungsten bronze structure and a high ECE near room temperature, is studied by direct measurements. It is shown that although the onset of the ECE peak is closer to room temperature in SBN80 than in SBN75, the effect of the increase of the strontium content is very detrimental to the ECE performances with a decrease to ΔTEC = 0.23 K for SBN80 from the reported value of ΔTEC = 0.42 K under 10 kV/cm for SBN75 [F. Le Goupil et al., “Anisotropy of the electrocaloric effect in lead-free relaxor ferroelectrics,” Adv. Energy Mater. (published online)]. However, when 1.40% of cerium is introduced in SBN61, the temperature of depolarisation is shifted below 30 °C, while an ECE above 0.6 K is maintained over more than 70 K for a low electric field of 28 kV/cm. The maximum ECE ΔTEC = 0.85 K is measured at 61 °C. In addition to having an ECE peak close to room temperature, the ECE measured in Ce-doped SBN61 is comparable wi...

Upper limit of the electrocaloric peak in lead-free ferroelectric relaxor ceramics

The electrocaloric effect (ECE) of two compositions (x = 0.06 and 0.07) of (1 − x)(Na0.5Bi0.5)TiO3-xKNbO3 in the vicinity of the morphotropic phase boundary is studied by direct measurements. ΔTmax = 1.5 K is measured at 125 °C under 70 kV/cm for NBT-6KN while ΔTmax = 0.8 K is measured at 75 °C under 55 kV/cm for NBT-7KN. We show that the “shoulder,” TS, in the dielectric permittivity, marks the upper limit of the ECE peak under high applied electric fields. These results imply that the range of temperature with high ECE can be quickly identified for a given composition, which will significantly speed up the process of materials selection for ECE cooling.

Lead-Free and “Exotic” Electrocaloric Materials

This chapter describes lead-free electrocaloric materials and will mostly concentrate on bulk form. The materials will be described by their reported electrocaloric (EC) values or other essential factors associated with the electrocaloric effect such as ferroelectric phase transition, polarization, dipole entropy or heat capacity evaluations.