Electrocaloric Materials Research Articles

Effect of unsaturated or saturated ferroelectric polarization on electrocaloric effect

The pursuit of high-efficiency and zero-emission refrigeration technologies has spurred interest in electrocaloric (EC) refrigeration utilizing ferroelectric (FE) materials, where accurate characterization of the EC effect is crucial for comprehending its underlying physical mechanisms and for developing high-performance EC materials. In this study, we investigate the influence of unsaturated vs saturated FE polarization characteristics on EC effects using Pb0.99Nb0.02[(Zr0.6Sn0.4)0.85Ti0.15]0.98O3 ceramics. Direct EC measurement reveals that unsaturated loops can introduce substantial errors and even fake negative EC effects when employing the Maxwell approach for indirect EC measurement. In contrast, relatively accurate indirect EC results can be obtained using saturated FE hysteresis loops. Furthermore, it also highlights the necessity for saturated polarization conditions to achieve optimal EC performance in FEs. This work not only emphasizes the importance of carefully selecting polarization data for indirect EC measurements, but also presents a universal strategy to enhance EC effects in various materials.

Perspectives and Energy Applications of Magnetocaloric, Pyromagnetic, Electrocaloric, and Pyroelectric Materials

AbstractThis perspective provides an overview of the state of research and innovation in the areas of magnetocaloric and pyromagnetic materials, and electrocaloric and pyroelectric materials, including the overlapping sub‐areas of multicaloric and multipyro materials that can operate simultaneously under the application of magnetic and electric fields. These materials are critically examined for their potential to revolutionize cooling, heating, and energy‐harvesting applications. This perspective first summarizes the state‐of‐the‐art advancements and highlights recent significant developments. Then, it is identified and discussed that the prevailing challenges hindering the widespread adoption of technologies based on these materials. In this context, after consulting with members of the caloric and pyro communities, a technology roadmap is outlined to guide research efforts in overcoming current barriers to applications, with the goal of achieving impactful results by 2040. This roadmap emphasizes the importance of focusing on under‐researched materials, novel devices, and application spaces, paving the way for interdisciplinary efforts that can lead to significant reductions in carbon dioxide emissions.

Energy storage efficiency and electrocaloric performances in lead-free Ba0.87Ca0.13(Ti0.9Zr0.1)0.98(Zn1/3Nb2/3)0.02O3 ceramic

Ba0.87Ca0.13(Ti0.9Zr0.1)0.98(Zn1/3Nb2/3)0.02O3 ceramic was prepared using a solid-state reaction method. This work investigates their dielectric, ferroelectric, energy storage, and electrocaloric properties. X-ray diffraction analysis confirms a pure perovskite structure. The dielectric constant reaches a maximum of 9364 at 326 K. Enhanced total energy density, recovered energy density, and energy storage efficiency are observed between 303 K and 363 K. Artificial neural networks (ANNs) are employed for the indirect determination of large ECE and responsivity based solely on measured ferroelectric polarization (P(E,T)). This approach offers rapid and accurate predictions with minimal experimental data, significantly accelerating the characterization of novel electrocaloric materials. The maximum ECE occurs above the Curie temperature (TC) and increases with higher electric fields. The ceramic exhibits significant ECE parameters around TC with a broad electrocaloric temperature span. Various figures of merit, including relative cooling power, refrigerant capacity, and temperature-averaged entropy change, are explored under different electric fields, demonstrating the material's potential for green cooling devices. These figures improve monotonically with increasing field strength. A comprehensive analysis of the field dependence of ΔS (entropy change) confirms the second-order nature of the electric phase transition through master curve analysis. In conclusion, these lead-free ceramics exhibit promising applications in high-performance energy storage devices and solid-state refrigeration technology.

Engineering Multiphase Phase Transitions for Exceptional Electrocaloric Performance and Ultraweak Electrostrictive Response in Ferroelectrics.

In the pursuit of eco-friendly alternatives for refrigeration technology, electrocaloric materials have emerged as promising candidates for efficient solid-state refrigeration due to their high efficiency and integrability. However, current advancements in electrocaloric effects (ECEs) are often constrained by high temperatures and elevated electric fields (E-field), limiting practical applicability. Informed by phase-field simulation, this study introduces a (1-x)Pb(Yb1/2Nb1/2)O3-xPb(Mg1/3Nb2/3)O3 system, strategically engineered to incorporate highly ordered YN and disordered MN mixtures. The synergistic interplay between E-field/temperature-induced polarization reorientation and cation shift initiates multiple ferroelectric-antiferroelectric-paraelectric phase transitions. Our results demonstrate that under a moderate E-field of 50 kV cm-1, the x = 0.22 composition achieves remarkable performance with a giant temperature change (ΔT) of 3.48 K, a robust ECE strength (ΔT/ΔE) of 0.095 K cm kV-1, and a wide temperature span (Tspan) of 38 °C. Notably, the disrupted lattice structure contributes to ultralow electrostrains below 0.008%, with an average electrostrictive coefficient Q33 of 0.007 m4 C-2. The significantly weakened electrostrictive activity favors enhancing the performance stability of subsequent devices. This work introduces an innovative strategy for developing robust electrocaloric materials, offering substantial ΔT and low electrostrains, presenting promising advancements in ECE applications with an extended lifetime.

Synergy of Oxygen Octahedra Distortion and Polar Nanodomains Induced Emergent Electrocaloric Effect in NaNbO3-Based Ceramics.

High-performance electrocaloric materials are essential for the development of solid-state cooling technologies; however, the contradiction of the electrocaloric effect (ECE) and temperature span in ferroelectrics frustrates practical applications. In this work, through modulating oxygen octahedra distortion and short-range polar nanodomains with moderate coupling strength, an EC value of ΔT ∼ 0.30 K with an ultrawide temperature span of 85 K is obtained in the x = 0.04 composition [(0.88 - x)NaNbO3-0.12BaTiO3-xLiSbO3 (x = 0-0.06)]. The LiSbO3 dopant induces a P4bm-to-R3cH phase transition and intensifies the oxygen octahedra distortion degree, accompanied by the ferroelectric domain smashing into polar nanodomains. Also, LiSbO3 addition enhances the relaxation degree with a downshift of Tfd (ferroelectric-to-diffuse phase transition temperature) and TJ (temperature of the maximal current density value), and Tfd is shifted to near room temperature with an absence of TJ in x = 0.04. Local energy barriers induced by oxygen octahedra distortion inhibit the phase transition in conjunction with activation of short-range polar order switching under thermal stimuli, which is the underlying mechanism for an excellent EC performance for x = 0.04. This work not only clarifies that ferroelectrics with oxygen octahedra distortion and short-range polar order are expected to achieve remarkable EC performances but also provides a design strategy to seek emergent EC behaviors in complex oxygen-octahedra-distortion materials.

Achieving large negative electrocaloric effect in AgNbO3-based antiferroelectric ceramics based on dipole disordering

The electrocaloric effect (ECE) is considered as an environmentally friendly refrigeration technology, which can be used to replace vapor compression refrigeration. Lead-free antiferroelectric (AFE) ceramics are promising electrocaloric materials because of large saturation polarization and polarization change with temperature, which can generate large positive or negative ECE. In this work, the lead-free Ag(Nb1-0.8xHfx)O3 (x = 0, 0.001 and 0.003) AFE ceramics are fabricated through a conventional solid-state reaction method which shows a decreased the phase transition temperature of M1 - M2 toward room temperature (RT), and a large negative ECE (ΔT = −2.3 K under 130 kV cm−1) is obtained near the ambient temperature by using an indirect measurement in ANH0.001 AFE ceramic. The large negative ECE behavior is ascribed to dipole disordering (i.e. the anti-parallel dipoles are broken and gradually becomes disordered under an external electric field) resulting from the field-induced phase transition under a modest electric field. This work shows that AgNbO3-based AFE ceramics could be used in the refrigeration devices as an electrocaloric material.

Direct simultaneous measurement of electrocaloric effect and hysteresis loss heating in ferroelectrics

Electrocaloric effect and loss-induced self-heating are simultaneously investigated in single-crystalline relaxor 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 by a direct, high-resolution method. Transients of the total temperature change for few-cycle electric field pulses allow to distinguish and individually determine the contributions from electrocaloric effect and self-heating with millikelvin temperature and submillisecond temporal resolution. Simultaneous dielectric measurements make the comparison of observed self-heating to hysteresis losses possible, where very good agreement is found. The loss factor as a figure of merit for electrocaloric materials is directly obtained from the combined determination of caloric temperature change and losses.

Large room-temperature electrocaloric response achieved by tailoring the first-order orthorhombic-tetragonal phase transition in BaTiO3-based ferroelectric ceramics

The development of refrigeration technology has burgeoned in response to the challenges posed by global warming. Notably, electrocaloric materials have garnered significant attention for their potential in miniaturization and high efficiency. However, investigations into the electrocaloric response in proximity to orthorhombic-tetragonal phase transition in BaTiO3-based ferroelectric ceramics remain scarce. In this study, we employ a lead-free x(Ba0.7Sr0.3)TiO3-(1-x)Ba(Zr0.2Ti0.8)O3 polycrystalline ceramics fabricated through the solid-state reaction method. The comprehensive analysis includes elucidation of the phase structure, surface morphologies, dielectric properties, domain switching behavior, and the electrocaloric effect. Integrating these findings with the phase diagram unveils optimal adiabatic temperature change (ΔT) achieved within the quadruple point coexistence region. That is, the highest ΔT of 0.53 K is achieved for x = 0.4 ceramic, which is attributed to the increased entropy resulting from multiple polar phases. Remarkably, the highest ΔT of 0.3 K is attained in x = 0.6 ceramic under a low driving electric field of 30 kV/cm at room temperature, precisely within the orthorhombic-tetragonal transition temperature. The investigation underscores the efficacy of regulating the first-order orthorhombic-tetragonal phase transition to achieve exceptional electrocaloric responses at room temperature.

Highly reversible extrinsic electrocaloric effects over a wide temperature range in epitaxially strained SrTiO3 films

Electrocaloric effects have been experimentally studied in ferroelectrics and incipient ferroelectrics, but not incipient ferroelectrics driven ferroelectric using strain. Here we use optimally oriented interdigitated surface electrodes to investigate extrinsic electrocaloric effects in low-loss epitaxial SrTiO3 films near the broad second-order 243 K ferroelectric phase transition created by biaxial in-plane coherent tensile strain from DyScO3 substrates. Our extrinsic electrocaloric effects are an order of magnitude larger than the corresponding effects in bulk SrTiO3 over a wide range of temperatures including room temperature, and unlike electrocaloric effects associated with first-order transitions they are highly reversible in unipolar applied fields. Additionally, the canonical Landau description for strained SrTiO3 films works well if we set the low-temperature zero-field polarization along one of the in-plane pseudocubic <100> directions. In future, similar strain engineering could be exploited for other films, multilayers and bulk samples to increase the range of electrocaloric materials for energy efficient cooling.

Large electrocaloric effect and wide working area in the transition from ferroelectric to nanodomains

AbstractA large adiabatic temperature change along with a wide operating temperature region is usually required for the electrocaloric materials to fulfill their refrigeration function. In general, doping foreign ions into BaTiO3 is the frequently utilized strategy in order to obtain excellent electrocaloric materials for the practical application. In the current paper, BaTiO3 lead‐free ferroelectric ceramics were doped by Ca2+ and Sn4+ simultaneously in order to generate a coexistence state at room temperature, where ferroelectric domains and nanodomains exit. As a result, a large polarization and a wide operating temperature range were finally induced. It is found that Ba0.9Ca0.1Ti0.85Sn0.15O3 has a maximum adiabatic temperature change of 0.85 K and an excellent working temperature region (65 K, ∆T &gt; 90% Tmax) was achieved under an electric field of 50 kV/cm. The above phenomenon indicates that the modified BaTiO3 ceramics can be a good potential electrocaloric material in the state of cross‐existence of ferroelectric domains and nanodomains.

Strong electrocaloric response with ultrawide working temperature span in lead-free BaTiO3-based ceramics by composition design

Solid-state refrigeration technology based on electrocaloric effect provides a cost-effective and convenient approach for microelectronic device cooling. However, the working temperature range of electrocaloric materials is often narrow and incommensurate with that required by many microelectronic devices including computer chips and CPUs. In this work, the working temperature span of electrocaloric response in BaTiO3 ceramics were tuned by the simultaneous introduction of Sr and Hf (abbreviated as BSHT). Through rational variation of Sr and Hf content, not only the Curie temperature is reduced to ∼80 °C, but also the room-temperature phase structure of the ceramics can be effectively tuned from a single rhombohedral phase to coexistence of rhombohedral + orthorhombic or orthorhombic + tetragonal phases. Relaxor behavior of BSHT ceramics is evident by the frequency-dispersion of dielectric permittivity and the increased relaxor diffuseness factor γ. Temperature-dependent Raman spectra confirm that Ba0.85Sr0.15Hf0.06Ti0.94O3 (0.6BSHT) sustain a two-phase coexistence state over a broad temperature range. 0.6BSHT ceramics render a large adiabatic temperature change ΔT of 0.91 K under 40 kV cm−1 with a broad temperature span of ∼57 °C, covering the working temperature window of most microelectronic devices. Moreover, the electrocaloric response of 0.6BSHT shows excellent fatigue endurance, i.e., the adiabatic temperature change shows a trivial degradation of <4.4 % after 106 cycles. This work demonstrates that BaTiO3-based ceramics remain one of the most promising electrocaloric candidates and compositional modification is an effective route to tune the electrocaloric response for fulfilling the requirements of practical applications.

P(VDF-TrFE-CFE) polymer based electrocaloric device design for battery cooling

Electrocaloric (EC) cooling has the potential to be an alternative to traditional cooling methods. The polyvinylidene fluoride-trifluoro ethylene-chlorofluoroethylene terpolymer (P(VDF-TrFE-CFE) is used as electrocaloric material. A 3D equation-based modeling and finite element simulations are performed for EC cooling, where the battery's heat generation is considered a heat source for analysis. The electric field waveform has been varied to obtain the maximum possible ECE. Electric field cycles with 0.3 sec holding provide the maximum EC temperature change. The magnitude of the electric field is also varied and a maximum adiabatic temperature change of 5.41 K is achieved under 100 MV/m. The EC effect shows that the heat transfer from the source (battery surface) to the sink (environment) is faster than without EC.

Synergistically optimizing electrocaloric effect over a wider temperature span utilizing structural overlap zone

An overlap zone based on tetragonal, rhombohedral or pseudo-cubic states around a morphotropic phase boundary is designed through composition engineering to optimize EC response (∼1.58 K) and temperature stability under a wider temperature window (∼100 °C).

Successive phase transitions–induced multiple boundaries and unprecedented electrocaloric effect in Pb(Yb1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3 system

AbstractTemperature stability of electrocaloric effect (ECE) is a thorny problem in ferroelectrics (FE). A general method is to design ferroelectric‐to‐relaxor phase transition at a sacrifice of electrocaloric (EC) strength. The Pb(Yb1/2Nb1/2)O3 antiferroelectrics (AFE) + Pb(Mg1/3Nb2/3)O3 relaxors strategy designed in this work is effective to tackle this dilemma [(1 − x)PYN–xPMN, x = 0.08–0.36]. PMN addition induces a successive phase transition and dual phase boundaries of ferrielectric (FIE)‐nonergodic relaxor (NER) and NER‐ergodic relaxor (ER), where ferroelectric polarization/strain and ECE reach a local maximum. Thermally stable ΔT is unexpectedly achieved in FIE (x = 0.14) and NER (x = 0.24), except for a generality for ER state (x = 0.30). A dome‐like variation trend is observed in x = 0.14 and 0.24 with a wide temperature span of ∼60 and ∼55 K (±15%ΔTmax). Notably, x = 0.24 NER possesses a large directly measured ΔTmax ∼0.64 K simultaneously. Dielectric/ferroelectric properties clarify that two‐stage transition of AFE rigid‐order de‐texture and dissociation of de‐textured AFE domains into polar nano‐entities accounts for thermal stability of ΔT as the alternation of ordered antipolar domains to disorder relaxors serves as a buffer to compensate for the thermal‐shock enhanced random field. This work not only accounts for the underlying mechanism for thermal stability of ΔT at FIE and NER side for the first time in physics but also provides an exotic approach to seek for high‐performance EC materials in practical applications.

Optimized Electrocaloric Refrigeration in Lead-Free NaNbO3-Based Ceramics via AFE ↔ FE Phase Transition Modulation.

An outstanding challenge for eco-friendly ferroelectric (FE) refrigeration is to achieve a large adiabatic temperature change within a broad temperature range originating from the electrocaloric (EC) effect, which is expected to be realized in antiferroelectric (AFE) materials owing to the large entropy change during electric field and thermally induced phase transition. In this work, a large EC response over a wide response temperature range can be achieved slightly above room temperature via designing the phase transition of NaNbO3. An irreversible to reversible AFE-FE phase transition on heating induced by the introduction of CaZrO3 into NaNbO3 plays a key role in the optimized electrocaloric refrigeration. Accordingly, accompanying the local structure transformation corresponding to the B-site ions, the transition temperature between the square polarization-electric field (P-E) hysteresis loop (the irreversible AFE-FE phase transition induced by the electric field) and the repeatable double P-E hysteresis loop (the electric field induced reversible AFE-FE phase transition) was tailored to around room temperature, in favor of extending large entropy change to the wide temperature range. This work provides an efficient approach to designing lead-free EC materials with excellent EC performance, promoting the advancement of environmentally friendly solid-state cooling technology.

Achieving improved electrocaloric effect and broad operation temperature by tailoring phase fraction in BaTiO3-based ceramics

Ferroelectric electrocaloric (EC) materials are a pivotal part of sustainable micro-cooling, which complements conventional cooling methods in miniaturized devices. However, the application of EC materials is largely limited by the unsatisfactory room-temperature EC response and narrow operation temperature window. In this work, with careful tuning the composition of BaTiO3 (BT)-based ceramics through the conventional doping method, enhanced EC properties were achieved in Ba0.8Sr0.2Zrx(Ti0.999Mn0.001)1-xO3 (BSZMT) (x = 0.05, 0.10, 0.15, and 0.20). We especially found that the electrocaloric temperature change (ΔT) of > 0.50 K was achieved in a broaden temperature ranging from 20 °C to 95 °C and a peak ΔT value of 1.08 K was achieved at temperature of 70 °C in our BSZMT with x = 0.15. To ascertain the physical mechanism, we employed hybrid characterization methods including XRD, Raman, and dielectric analysis together with Density Functional Theory (DFT) calculation. Our results clearly show that the doped Zr and Mn at B site of BSZMT effectively modulate the microstructure leading to coexistence of different ferroelectric phases and broken long-range ferroelectric order, which subsequently results in the enhanced EC performance and broad operating temperature window.

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.

Tunable electrocaloric effect in selective ferroelectric bilayers via electrostatics for solid-state refrigeration and microelectronics thermal management

Ferroelectric (FE) electrocaloric materials research has been blossoming worldwide for solid-state refrigeration and potential cooling systems replacing thermoelectric Peltier coolers in microelectronics. In this work, we report the outcomes from a systematic study of combined phase transition (thermodynamics) based on the phenomenological Landau theory and distributed electric field (electrostatics of thin film interfaces) in FE bilayer films. Specifically, the compositional variation of ferroelectric bilayers results in broken spatial inversion symmetry leading to asymmetric thermodynamic potentials due to a combination of normal (first- and second-order phase transition) and relaxor (dispersive dielectric constant) ferroelectric behaviors devised for efficient electrocaloric cooling effects. Extensive theoretical analyses conducted for bilayers consisting of insulating materials highlight modified phase transition temperature behavior and self-poling by effective electric field amplification arising due to bilayers’ electrostatic coupling yielding significant changes in isothermal entropy (ΔS) and adiabatic temperature (ΔT). The theoretical calculation insights supported with experimental results signify, through case studies for a combination of materials experimental parameters, that amplification of the local electric field and materials engineering maximize the number of coexisting phases at or away from the morphotropic phase boundary of constituent layers in bilayer thin film architectures, which can be applicable toward other classes of materials and multilayer systems. These are effective ways for efficient cooling, in general, and for microelectronics thermal management either directly or by developing a thermal switch with phase change materials integrated with thermoelectric coolers for residual heat dissipation, both at the system and on-chip levels.

Modified (Ba,Sr)(Sn,Ti)O3 via hydrothermal synthesis for electrocaloric application

Electrocaloric cooling systems require components with large entropy change at the desired working temperature, high electric breakdown strength and low dielectric losses. We here report on hydrothermal synthesis (HTS) route for preparation of lead-free electrocaloric (EC) material Ba0.82Sr0.18Sn0.065Ti0.935O3 (BSSnT-18-6.5) with a median particle size of d50 = 150 nm. Influence of molar ratio (Ba,Sr):(Sn,Ti) on the purity and particle size of hydrothermally synthesized powders is investigated. The sintering behavior and the resulting microstructure of bulk ceramic samples prepared with HTS powders as well as their dielectric, ferroelectric, and electrocaloric properties are analyzed and discussed in detail. By using HTS powders we could significantly reduce sintering temperature from 1400 °C to 1275 °C. Samples prepared with a molar ratio (Ba,Sr):(Sn,Ti) of 1.6 show a maximum EC temperature change |ΔTEC| of 0.59 K around 30 °C with a broad peak of |ΔTEC| > 0.3 K in the temperature range from 5 °C to 65 °C under an applied electric field change of 5 V μm−1. Our results show that hydrothermal synthesis is well suited to produce starting powders of lead-free electrocaloric materials for future fabrication of multilayer ceramic (MLC) components.

How highly efficient power electronics transfers high electrocaloric material performance to heat pump systems

Electrocaloric heat pumps for cooling or heating are an emerging emission-free technology, which could replace vapor-compression systems, harmful refrigerants, and mechanical compressors by a solid-state solution with theoretically even higher coefficient of performance. Existing electrocaloric ceramics could reach around 85% of the Carnot-limit, and existing electrocaloric polymers could enable a compact and high power density system. However, the performance of published system demonstrators stays significantly below this performance, partly because of the external electronic charging loss (cyclic charging/discharging of electrocaloric capacitors). This work analyzes how the latest 99.74% ultra-efficient power electronics enables to maintain a high performance even at the system level. A first-principle analysis on material and system parameters also shows the effect of significantly different material properties of ceramics (PMN, PST) and PVDF-based polymers on system parameters. A system benchmark provides insight into system characteristics not covered by material analysis.Graphical abstract