PbZrO3 has been broadly considered as a prototypical antiferroelectric material for high-power energy storage. A recent theoretical study suggests that the ground state of PbZrO3 is threefold-modulated ferrielectric, which challenges the generally accepted antiferroelectric configuration. However, such a novel ferrielectric phase was predicted only to be accessible at low temperatures. Here, we successfully achieve the room-temperature construction of the strongly competing ferrielectric and antiferroelectric state by strain-mediated phase separation in PbZrO3/SrTiO3 thin film. We demonstrate that the phase separation occurs spontaneously in quasi-periodic stripe-like patterns under a compressive misfit strain and can be tailored by varying the film thickness. The ferrielectric phase strikingly exhibitsa threefold modulation period with a nearly up-up-down configuration, which could be stabilized and manipulated by the formation and evolution of interfacial defects under applied strain. The present results construct a fertile ground for further exploring the physical properties and applications based on the novel ferrielectric phase.
Dielectric ceramics with ultrahigh polarization and energy density are the core components used in next-generation pulse power generators based on explosive energy conversion. However, the low polarization of ferroelectric materials and high depolarized pressure hinder their development toward miniaturization, light weight, and integration, while antiferroelectric materials possessing larger nonlinear saturated polarization and rich phase structure are neglected in pulse power energy conversion. Here, an effective strategy of constructing antiferroelectric-to-ferroelectric overlap zone is achieved in binary system (1 - x)(Pb,La)(Zr,Ti)O3-xBa(Al1/2Nb1/2)O3 antiferroelectric ceramics to realize an excellent polarization of 41 µC/cm2 and a large depolarization efficiency of >99% under 150 MPa as well as a record high energy harvesting density of 2.5 J/cm3 under 400 MPa. The excellent comprehensive energy conversion and energy harvesting performance is mainly attributed to the strategy of antiferroelectric-to-ferroelectric overlap zone and improved microdomain density, at which orthorhombic-to-rhombohedral structure evolution is confirmed by transmission electron microscopy, piezo-response force microscopy, and Raman spectrum, resulting in substantially enhanced remanent polarization compared to ferroelectric ceramics. Besides, excellent temperature stability (â¼180 °C) and optimized depolarization pressure also support that this binary system is a candidate for energy conversion and energy harvesting application. This work demonstrates that antiferroelectric-to-ferroelectric overlap based on antiferroelectric materials is an excellent strategy to develop dielectric materials with excellent depolarized polarization and energy harvesting density for energy conversion and harvesting.
The recently discovered plastic/ductile inorganic thermoelectric (TE) materials open a new avenue for the fabrication of high-efficiently flexible TE devices, which can utilize the small temperature difference between human body and environment to generate electricity. However, the maximum power factor (PF) of current plastic/ductile TE materials is usually around or less than 10 µW cm-1 K-2 , much lower than the classic brittle TE materials. In this work, a record-high PF of 18.0 µW cm-1 K-2 at 375 K in plastic/ductile bulk SnSe2 -based crystals is reported, superior to all the plastic inorganic TE materials and flexible organic TE materials reported before. The origin of such high PF is from the modulation of material's stacking forms and polymorph crystal structures via simultaneously doping Cl/Br at Se-site and intercalating Cu inside the van der Waals gap, leading to the significantly enhanced carrier concentrations and mobilities. An in-plane fully flexible TE device made of the plastic/ductile SnSe2 -based crystals is successfully developed to show a record-high normalized maximum power density to 0.18 W m-1 under a temperature difference of 30 K. This work indicates that the plastic/ductile material can realize high TE power factor to achieve large output electric power density in flexible TE technology.
The most promising candidates for energy storage capacitor application are relaxor ferroelectrics, among which, the perovskite structure ferroelectric ceramics have witnessed great development progress. However, less attention has been paid on tetragonal tungsten bronze structure (TTBS) ceramics because of their lower breakdown strength and polarization. Herein, a multiscale regulation strategy is proposed to tune the energy storage performances (ESP) of TTBS ceramics from grain, domain, and macroscopic scale. The enhanced relaxor behavior with dynamic polar nanodomains guarantees low remanent polarization, while the refined grains and enlarged bandgap ensure increased breakdown strength. Hence, excellent ESP is realized in unfilled TTBS Sr0.425 La0.1 â¡0.05 Ba0.425 Nb1.4 Ta0.6 O6 (SLBNT) ceramics with an ultrahigh recoverable energy density of 5.895 J cm-3 and a high efficiency of 85.37%. This achievement notably surpasses previous studies in TTBS ceramics and is comparable to that of perovskite components. Meanwhile, the energy density exhibits a wide temperature, frequency, and cycling fatigue stability. In addition, high power density (257.89 MW cm-3 ), especially the ultrafast discharge time (t0.9 = 16.4 ns) are achieved. The multiscale regulation strategy unlocks the energy storage potential of TTBS ceramics and thus highlights TTBS ceramics as promising candidates for energy storage, like perovskite structured ceramics.
Antiferroelectric thin-film capacitors with ultralow remanent polarization and fast discharge speed have attracted extensive attention for energy storage applications. A multilayer heterostructure is considered to be an efficient approach to enhance the breakdown strength and improve the functionality. Here, we report a high-performance multilayer heterostructure (PbZrO3/PbTiO3)n with a maximum recoverable energy storage density of 36.4 J/cm3 due to its high electric breakdown strength (2.9 MV/cm) through the heterostructure strategy. The positive effect of interfacial blockage and the negative effect of local strain defects competitively affect the breakdown strength, showing an inflection point at n = 3. The atomic-scale characterizations reveal the underlying microstructure mechanism of the interplay between the heterointerface dislocations and the decreased energy storage performance. This work offers the potential of well-designed multilayers with high energy storage performance through heterostructure engineering.
Thermal conductivity k dominates in a heat transfer medium, and a field modulated k would facilitate delicate control in thermal management technology, yet it is hardly realized in a single solid material unless with changing temperature. Herein, in BaTiO3 ceramic, a modulated k was discovered by adjusting ferroelectric polarization P, which was a conventional strategy in ferroelectric functional materials. Four different states (P1, P2, P3, P4) were obtained by controlling poling time and field strength, showing that k leaped from 2.704 ± 0.054 to 3.201 ± 0.070 W (m K)-1 with increased P. Moreover, the strong correlation between P and k was also verified by the thermal depolarization measurement from room temperature to Curie temperature. The underlying origin of P modulated k was attributed to the internal bias field, which is born in the oriented ferroelectric domains, tightening special phonon modes in BaTiO3 ceramics. Raman spectrum, P-E loops, first-order reversible curve, XRD analysis, and PFM measurement were then employed to clarify how ferroelectric polarization structurally influences phonon transport and subsequent thermal conductivity. This work will pave a brand-new research route for conventional ferroelectric ceramic, also potentiating the idea of the electric field-controlled k component and active solid heat-transport device in the future.
The recently discovered ductile/plastic inorganic semiconductors pave a new avenue toward flexible thermoelectrics. However, the power factors of current ductile/plastic inorganic semiconductors are usually low (below 5 µW cm-1 K-2 ) as compared with classic brittle inorganic thermoelectric materials, which greatly limit the electrical output power for flexible thermoelectrics. Here, large plasticity and high power factor in bulk two-dimensional van der Waals (2D vdW) single-crystalline SnSe2 are reported. SnSe2 crystals exhibit large plastic strains at room temperature and they can be morphed into various shapes without cracking, which is well captured by the inherent large deformability factor. As a semiconductor, the electrical transport properties of SnSe2 can be readily tuned in a wide range by doping a tiny amount of halogen elements. A high power factor of 10.8 µW cm-1 K-2 at 375 K along the in-plane direction is achieved in plastic single-crystalline Br-doped SnSe2 , which is the highest value among the reported flexible inorganic and organic thermoelectric materials. Combining the good plasticity, excellent power factors, as well as low-cost and nontoxic elements, bulk 2D vdW single-crystalline SnSe2 shows great promise to achieve high power density for flexible thermoelectrics.
The devil's staircase, describing step-like function for two competing frequencies, is well known over a wide range of dynamic systems including Huyghens' clocks, Josephson junction, and chemical reaction. In condensed matter physics, the devil's staircase has been observed in spatially modulated structures, such as magnetic ordering. It draws widespread attentions because it plays a crucial role in the fascinating phenomena including phase-locking behaviors, commensurate-incommensurate phase transition, and spin-valve effect. Here, we report the observation of polymorphic phase transitions consisting of several steps in PbZrO3-based system-namely, electric devil's staircase-originated from competing ferroelectric and antiferroelectric interactions. We fully characterize a specific electric dipole configuration by decomposing this competitive interaction in terms of basic structure and modulation function. Of particular interest is that the occurrence of many degenerate electric dipole configurations in devil's staircase enables superior energy storage performance. These observations are of great significance for exploring more substantive magnetic-electric correspondence and engineering practical high-power antiferroelectric capacitors.
Phase boundary provides a fertile ground for exploring emergent phenomena and understanding order parameters couplings in condensed-matter physics. In Pb(Zr1-xTix)O3, there are two types of composition-dependent phase boundary with both technological and scientific importance, i.e. morphotropic phase boundary (MPB) separating polar regimes into different symmetry and ferroelectric/antiferroelectric (FE/AFE) phase boundary dividing polar and antipolar dipole configurations. In contrast with extensive studies on MPB, FE/AFE phase boundary is far less explored. Here, we apply atomic-scale imaging and Rietveld refinement to directly demonstrate the intermediate phase at FE/AFE phase boundary exhibits a rare multipolar Pb-cations ordering, i.e. coexistence of antipolar or polar displacement, which manifests itself in both periodically gradient lattice spacing and anomalous initial hysteresis loop. In-situ electron/neutron diffraction reveals that the same parent intermediate phase can transform into either FE or AFE state depending on suppression of antipolar or polar displacement, coupling with the evolution of long-/short-range oxygen octahedra tilts. First-principle calculations further show that the transition between AFE and FE phase can occur in a low-energy pathway via the intermediate phase. These findings enrich the structural understanding of FE/AFE phase boundary in perovskite oxides.
Antiferroelectric materials has become one of the most promising candidates for pulsed power capacitors. The polarization versus electric-field hysteresis loop is the key electrical property for evaluating their energy-storage performance. Here, we applied in situ biasing transmission electron microscopy to decode two representative energy-storage behaviors-namely, multiple and double hysteresis loops-in (Pb,La)(Zr,Sn,Ti)O3 system. Simultaneous structural examination and domain/defects observation establish a direct relationship between phase transitions and hysteresis loops. Sustaining a smaller period of modulated structure to a certain applied electric field and then undergoing additional transitions among varying antiferroelectric phases with increasing modulation periods before the final antiferroelectric-ferroelectric transition leads to the favorable multiple-loop configuration that realizes a high energy-storage performance. Such phenomenon is described by a model in terms of defect-driven phase transition. The distinctive mechanisms of multiple phase transition will inspire future composition-design for high switch-fielding antiferroelectric materials.
PbZr0.35Ti0.65O3 (PZT), PbZrO3 (PZO), and PZT/PZO ferroelectric/antiferroelectric multilayer films were prepared on a Pt/Ti/SiO2/Si substrate using the sol-gel method. Microstructures and physical properties such as the polarization behaviors, leakage current, dielectric features, and energy-storage characteristics of the three films were systematically explored. All electric field-dependent phase transitions, from sharp to diffused, can be tuned by layer structure, indicated by the polarization, shift current, and dielectric properties. The leakage current behaviors suggested that the layer structure could modulate the current mechanism, including space-charge-limited bulk conduction for single layer films and Schottky emission for multilayer thin films. The electric breakdown strength of a PZT/PZO multilayer structure can be further enhanced to 1760 kV/cm, which is higher than PZT (1162 kV/cm) and PZO (1373 kV/cm) films. A recoverable energy-storage density of 21.1 J/cm3 was received in PZT/PZO multilayers due to its high electric breakdown strength. Our results demonstrate that a multilayer structure is an effective method for enhancing energy-storage capacitors.
Pb0.6Sr0.4TiO3/La0.7Sr0.3MnO3/La0.7Ca0.3MnO3 (PST/LSMO/LCMO) film is grown on Si substrate by chemical solution deposition method. The film crystallizes perfectly into perovskite phases with a random crystalline orientation. The La0.7Sr0.3MnO3/La0.7Ca0.3MnO3/Si layer exhibits low resistivity and obvious negative magnetoresistivity (MR); the PST/LSMO/LCMO film shows notable magnetocapacitance (MC) above 350 K, from 102.9% to 29.5%. Near room temperature, there is no distinguished magnetoelectric coupling; the MC is 34.3% @ 250 K, 29.5% @ 300 K and 32.8% @ 350 K respectively. The mechanism can be explained in light of the Maxwell-Wagner (MW) model and the enhanced MR origin from the successive mixed manganite phases and spin dependent tunneling across the junctions of PST/LSMO/LCMO. This work provides a new approach for designing and developing novel composites with promising MC.
Dynamic temperature sensing and infrared detection/imaging near room temperature are critical in many applications including invasive safety alarming, energy conversion, and public health, in which ferroelectric (FE) materials play an extremely important role due to their pyroelectricity. As a result, over the past few decades many efforts have been made to improve the understanding of pyroelectrics, explore new pyroelectric materials, and promote their practical applications. In this review, we consider the pyroelectric parameters and the two pyroelectric operation modes. Then based on the operation modes, we review recent achievements in the FE ceramic materials for pyroelectric detection applications, including Pb(Zr,Ti)O3-based, (Bi,Na)TiO3-based, (Sr,Ba)NbO3-based, Pb(Sc,Ta)O3-based, (Ba,Sr)TiO3-based, and Pb(Zr,Sn,Ti)O3-based systems. This review will attempt to provide guidance for further improvements of the pyroelectric properties of these materials and consider future exploration of new FE and other material candidates for use in temperature and infrared sensing/detection applications.
Ceramics , Titanium , Temperature
Benefitting from the reversible phase transition between antiferroelectric and ferroelectric states, antiferroelectric materials have recently received widespread attentions for energy storage applications. Antiferroelectric configuration with specific antiparallel dipoles has been used to establish antiferroelectric theories and understand its characteristic behaviors. Here, we report that the so-called antiferroelectric (Pb,La)(Zr,Sn,Ti)O3 system is actually ferrielectric in nature. We demonstrate different ferrielectric configurations, which consists of ferroelectric ordering segments with either magnitude or angle modulation of dipoles. The ferrielectric configurations are mainly contributed from the coupling between A-cations and O-anions, and their displacement behavior is dependent largely on the chemical doping. Of particular significance is that the width and net polarization of ferroelectric ordering segments can be tailored by composition, which is linearly related to the key electrical characteristics, including switching field, remanent polarization and dielectric constant. These findings provide opportunities for comprehending structure-property correlation, developing antiferroelectric/ferrielectric theories and designing novel ferroic materials.
Explosive energy conversion materials with extremely rapid response times have broad and growing applications in energy, medical, defense, and mining areas. Research into the underlying mechanisms and the search for new candidate materials in this field are so limited that environment-unfriendly Pb(Zr,Ti)O3 still dominates after half a century. Here, we report the discovery of a previously undiscovered, lead-free (Ag0.935K0.065)NbO3 material, which possesses a record-high energy storage density of 5.401 J/g, enabling a pulse current ~ 22 A within 1.8 microseconds. It also exhibits excellent temperature stability up to 150°C. Various in situ experimental and theoretical investigations reveal the mechanism underlying this explosive energy conversion can be attributed to a pressure-induced octahedral tilt change from a - a - c + to a - a - c -/a - a - c +, in accordance with an irreversible pressure-driven ferroelectric-antiferroelectric phase transition. This work provides a high performance alternative to Pb(Zr,Ti)O3 and also guidance for the further development of new materials and devices for explosive energy conversion.
The phase boundaries of dielectric materials have constantly been valuable for instructing the design of phase structures, revealing correlations between compositions and structures, and attaining the desired functional properties for piezoelectric, pyroelectric, electrostriction, electrocaloric, energy storage and energy harvesting applications. We here observe a new type of phase boundary in a solid solution of xPbTiO3·(1 - x)Pb(Yb1/2Nb1/2)O3 (x = 0.00-0.20), which is between an antiferroelectric (AFE) phase and a relaxor ferroelectric (RFE) phase. x = 0.10 is confirmed as the phase boundary. XRD, TEM, PFM and Raman spectroscopy analysis reveal two fundamental traits of the phase structure: (1) the polar state changes from AFE to FE order; and (2) the domain range evolves from micrometer-sized to nanometer-sized, both of which are normally separated but coexist around the phase boundary. The intriguing phase structure contributes to the distinctive dielectric properties: (1) a broad compositional zone (x < 0.10 and x ≥ 0.14) features low remnant polarization, low hysteresis and highly reversible domain wall motion, and is expected to be utilized for dielectric energy storage and electrostriction applications; and (2) a narrow nonergodic RFE zone (0.10 ≤ x < 0.14) demonstrates remnant and maximum polarization, co-dominated by composition and temperature, and has potential for pyroelectric and electrocaloric applications.
As a promising candidate material replacing Pb(ZrTi)O3 (PZT), the lead-free Bi0.5Na0.5TiO3 (BNT) system exhibits outstanding piezoelectric and ferroelectric properties. However, the weak thermal stability of these electric properties hampers its practical applications. In this work, we designed and prepared novel Nb-doped 0.76Bi0.5Na0.5TiO3-0.24Bi0.5K0.5TiO3 (BNT-BKT) ceramics with superior temperature stability of electric properties. Both strain as well as discharging properties of 5% Nb-doped BNT-BKT ceramics varied less than 3% and 12.5% respectively from room temperature to 160 °C, ascribed to the enlarged gap between the depolarized temperature (T d or T F-R) and the maximum dielectric temperature (T m). In addition, we investigated the impacts of Nb doping on the phase transition, dielectric, piezoelectric and ferroelectric behaviors of BNT-BKT ceramics in detail. Temperature dependent dielectric spectrums indicated that T d decreased below room temperature with Nb modifying, revealing that the phase structure transformed from ferroelectric into ergodic relaxor. Accordingly, the maximum strain value of 0.21% and recoverable energy storage of 1.2 J cm-3 were simultaneously acquired at the critical composition of 5% Nb incorporation. Our results provide an effective means of obtaining BNT-based ceramics with simultaneously thermally stable strain and discharge properties for wide temperature actuator and capacitor applications.
