High‐energy storage density and excellent temperature stability in antiferroelectric/ferroelectric bilayer thin films

The antiferroelectric/ferroelectric (PbZrO₃/PbZr_0.52Ti_0.48O₃) bilayer thin films were fabricated on a Pt(111)/Ti/SiO₂/Si substrate using sol‐gel method. PbZr_0.52Ti_0.48O₃ layer acts as a buffered layer and template for the crystallization of PbZrO₃ layer. The PbZrO₃ layer with improved quality can share the external voltage due to its smaller dielectric constant and thinner thickness, resulting in the enhancements of electric field strength and energy storage density for the PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer thin film. The greatly improved electric breakdown strength value of 2615 kV/cm has been obtained, which is more than twice the value of individual PbZr_0.52Ti_0.48O₃ film. The enhanced energy storage density of 28.2 J/cm³ at 2410 kV/cm has been achieved in PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film at 20°C, which is higher than that of individual PbZr_0.52Ti_0.48O₃ film (15.6 J/cm³). Meanwhile, the energy storage density and efficiency of PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film increase slightly with the increasing temperature from 20°C to 120°C. Our results indicate that the design of antiferroelectric/ferroelectric bilayer films may be an effective way for developing high power energy storage density capacitors with high‐temperature stability.     

High energy storage performance in Ca-doped PbZrO3 antiferroelectric films

In this work, antiferroelectric Pb_1-xCa_xZrO₃ (PCZ) thin films with different concentrations of Ca²⁺ were prepared by chemical solution deposition, and the effects of Ca²⁺ concentration on the antiferroelectric properties and energy storage performance were investigated. The results show that the optimal Ca²⁺ concentration in the PCZ thin films is x = 0.12 for electric properties and energy storage performance. The recoverable energy storage density and energy storage efficiency is 50.2 J/cm³ and 83.1 % at 2800 kV/cm, which is 261 % and 44.8 % higher than those of the PbZrO₃ (PZ) films. These effects are attributed to the enhancement of stability of antiferroelectric phase, diffuseness in the field-induced phase transition and electric breakdown strength by Ca²⁺-doping in the PZ films. Our results demonstrate that doping an appropriate amount of Ca²⁺ ions in antiferroelectric thin films is an effective way to improve their energy storage performance.     

Phase transition and piezoelectricity of BaZrO3-modified (K,Na)NbO3 lead-free piezoelectric thin films

(K,Na)NbO₃ (KNN) is a promising lead-free ferroelectric/piezoelectric system, to which incorporating BaZrO₃ can greatly enhance its piezoelectricity, but the mechanism is not clear. This work was conducted to investigate the phase transition in the BaZrO₃-modifed KNN system and its contribution to piezoelectricity enhancement, using thin films with a fixed orientation and high compositional homogeneity fabricated by a sol-gel method. Two ferroelectric-to-ferroelectric phase transitions are revealed, which correspond to monoclinic M_C- M_A phase transition at higher temperature and rhombohedral-monoclinic M_C phase transition at lower temperature. It is difficult to distinguish these phases in KNN-based bulk materials, but their differences are clear when conducting high-resolution X-ray reciprocal space mapping (RSM) on the present thin films. Piezoresponse force microscopy experiments also revealed an interesting finding that local piezoelectricity of monoclinic phases was higher than that of rhombohedral ones in KNN-based thin films. This work could shed insights on the fundamental understandings for the effect of the chemical doping, and offer guidance for property optimization in the KNN-based lead-free piezoelectrics.     

Bismuth niobate thin films for dielectric energy storage applications

Low‐temperature processed bismuth niobate (BNO) thin films were explored in this work as a potential candidate for high‐energy density capacitors. The BNO samples were fabricated by the chemical solution deposition method followed by a series of ultraviolet (UV) exposure and heat treatments. A UV treatment prior to the final pyrolysis step was found to be useful in eliminating bound carbon. X‐ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) demonstrated that the residual carbon could be effectively removed at 350°C after UV exposure. Following a heat treatment at 450°C, the energy storage density of the BNO thin film reached 39 J/cm³ with an efficiency of 72%. Furthermore, 350°C and 375°C treated BNO samples showed high‐temperature stability such that the efficiencies of the films remained above 97% up to 150°C at 10 kHz under 1 MV/cm applied field.     

Structure variation and energy storage properties of acceptor-modified PBLZST antiferroelectric ceramics

Energy storage capacitors with high recoverable energy density and efficiency are greatly desired in pulse power system. In this study, the energy density and efficiency were enhanced in Mn-modified (Pb_0.93Ba_0.04La_0.02)(Zr_0.65Sn_0.3Ti_0.05)O₃ antiferroelectric ceramics via a conventional solid-state reaction process. The improvement was attributed to the change in the antiferroelectric-to-ferroelectric phase transition electric field (E_F) and the ferroelectric-to-antiferroelectric phase transition electric field (E_A) with a small Mn addition. Mn ions as acceptors, which gave rise to the structure variation, significantly influenced the microstructures, dielectric properties and energy storage performance of the antiferroelectric ceramics. A maximum recoverable energy density of 2.64 J/cm³ with an efficiency of 73% was achieved when x = 0.005, which was 40% higher than that (1.84 J/cm³, 68%) of the pure ceramic counterparts. The results demonstrate that the acceptor modification is an effective way to improve the energy storage density and efficiency of antiferroelectric ceramics by inducing a structure variation and the (Pb_0.93Ba_0.04La_0.02)(Zr_0.65Sn_0.3Ti_0.05)O₃-xMn₂O₃ antiferroelectric ceramics are a promising energy storage material with high-power density.     

Electric field tunable thermal stability of energy storage properties of PLZST antiferroelectric ceramics

The electrical hysteresis behaviors and energy storage performance of Pb_0.97La_0.02(Zr_0.58Sn_0.335Ti_0.085)O₃ antiferroelectric (AFE) ceramics were studied under the combined effects of electric field and temperature. It was observed that the temperature dependence of recoverable energy density (W_re) of AFE ceramics depends critically on the applied electric field. While W_re at lower electric fields (<8 kV/mm) shows increasing tendency with increasing temperature from 20°C to 100°C, W_re at higher electric fields (>8 kV/mm) demonstrates decreasing dependence. There exists an appropriate electric field (8 kV/mm) under which the AFE ceramics exhibit nearly temperature‐independent W_re (the variation is less than 0.5% per 10°C). The underlying physical principles were also discussed in this study. These results indicate that the temperature dependence of W_re of AFE materials can be tuned through selecting appropriate electric fields and provide an avenue to obtain thermal stable energy storage capacitors, which should be of great interest to modern energy storage community.     

Excellent energy storage performance in La and Ta co-doped AgNbO3 antiferroelectric ceramics

Lead-free dielectric materials with high breakdown electric field strength and energy density are required for pulsed power devices with high level of integration. This work describes: (Ag_0.94La_0.02)(Nb_1-xTa_x)O₃ lead-free antiferroelectric ceramics, which were prepared by rolling process. Following composition engineering, an outstanding energy density of 6.9 J cm^-3 at electric field of 490 kV cm^-1 was achieved, coupled with remarkable frequency stability (<1% over 1-100 Hz under E = 420 kV cm^-1) for (Ag_0.94La_0.02)(Nb_0.80Ta_0.20)O₃ ceramics. Moreover, it also shows excellent charge-discharge properties (discharge density = 1429 A cm^-2, power density = 144 MW cm^-3). The addition of La³⁺ and Ta⁵⁺ induced a disordered local structure, which gradually decreased the phase transition temperature of M₂-M₃ to room temperature, reflecting the enhanced antiferroelectricity. All advantageous properties observed for the La and Ta co-doped AgNbO₃ ceramics highlight their significant potential for energy storage applications.     

Variations in the glass transition temperature of polyester with special architectures confined in thin films

Variations of the polymer dynamic of different systematically varied polyester architectures in the confinement of thin films were studied by temperature dependent spectroscopic vis-ellipsometry. The architectures were tailored in order to evaluate (a) the impact of different polymer backbones (hyperbranched, branched or linear and aromatic, aromatic-aliphatic or aliphatic), (b) the influence of functional groups (hydroxyl, benzoyl, tert-butyldimethylsilyl) and (c) the role of interfacial interactions (attractive, repulsive) with the silicon substrate. Possible reasons for the deviation of the glass transition temperature T_g in thin polymer films (10-800 nm) from the bulk value are described and compared to the literature. It was found that the functional groups of the applied polymers have the largest effect on T_g. Beside interfacial interactions, chemical and physical reactions in the polymer film are playing a significant role.     

Enhanced energy storage density in Ca and Ta co-doped AgNbO3 antiferroelectric ceramics

Ca and Ta co-doped AgNbO₃ antiferroelectric lead-free ceramics were fabricated by rolling process technique, and improved energy storage properties were obtained. X-ray diffraction and Raman spectra indicate a single perovskite structure for (Ag_1-2xCa_x)(Nb_1-xTa_x)O₃ ceramics. The dielectric performances were also investigated, showing that increasing the content of Ca and Ta from 0.1 to 5 mol% gradually decreased the temperatures of the phase transition of monoclinic M₁-M₂ and M₂-M₃. This proved the enhanced antiferroelectricity stability associated with the enlarged low temperature phase transition region. The obtained (Ag_0.90Ca_0.05)(Nb_0.95Ta_0.05)O₃ ceramics exhibit an enhanced recoverable energy storage density (3.36 J/cm³) and efficiency (58.3%) with good temperature and frequency stability. The same composition shows excellent charge and discharge properties with a discharge current as high as 91.5 A and fast discharge speed (150 ns discharge period). All these merits demonstrate that AgNbO₃-based antiferroelectric ceramics are competitive with other lead-based and lead-free dielectric capacitors, which are promising candidates for dielectric energy storage applications.     

Thickness-dependent glass transition temperature of hydroxyethyl cellulose thin films based on dielectric properties

Hydroxyethyl cellulose (HEC) thin films with a molecular weight of 720,000 g/mol deposited by thermal evaporation in a thickness range of 250, 500, and 750 nm were measured in a frequency range of 1–10⁵ Hz and a temperature range of 233–373 K for dielectric characterization with increments of 10 K. Dielectric results were used to derive and evaluate the glass transition temperature and ductility, which are essential parameters for structural analysis. Results showed that the thickness of HEC thin films was an effective parameter on dielectric and structural properties. Because of the increasing thickness, the dielectric constant has values between 22 and 143 at 1 kHz, and glass transition temperature and ductility change between 211–175 K and 15–20, respectively. Based on the literature and the compatible results, the main effect of these variations could be dead layers and voids in structure. The effect of the dead layer gave an important idea about the adjustability of mechanical properties of HEC thin films depending on the thickness. In this way, it would be possible to use these thin films deposited from HEC with 720,000 g/mol molecular weight, especially in drug delivery, electrophoresis technologies, biomedical devices, and coverage applications.     

高分子固-固相变储能材料的研究与应用

综述了各类高分子固-固相变储能材料的性能、储能机理及其优缺点,介绍了此类材料的各种应用, 并对其发展前景做了探讨和展望。高分子固-固相变储能材料具有储能密度大,相变温度恒定,体积变化小,相变过程无液体泄漏等诸多优点,已成为能源开发利用和材料科学研究的新热点。     

Cracking and loss of adhesion of Si3N4 and SiO2:P films deposited on Al substrates

Tensile tests in a scanning electron microscope have been performed to study the mechanical stability of different film/substrate systems consisting of films of Si₃N₄ and SiO₂ :4.5 wt% P deposited on Al substrates. Successive stages of crack development were observed: transverse through-thickness cracking of the film precedes its loss of adhesion and buckling, induced by the transverse contraction of the substrate. It was observed that the presence of a thermally grown Al₂O₃ interlayer improved the adhesion of the films by delaying the de-adhesion process. The influence of roughness on the interfacial strength was analysed from the observation of the de-adhesion of a SiO₂ :4.5 wt% P film deposited on a scratched Al substrate. The critical strain for the through-thickness cracking of each film was calculated. Then the multiple film cracking was analysed through the evolution of the crack density with the longitudinal strain. Finally, by using the point at which the film de-adhered, an interfacial fracture energy was calculated for each system.     

Significantly improved energy storage properties and cycling stability in La-doped PbZrO3 antiferroelectric thin films by chemical pressure tailoring

In this work, Pb_1−3x/2La_xZrO₃ (x = 0–0.12) (PLZ-x) antiferroelectric thin films were fabricated on Pt(111)/TiO₂/SiO₂/Si substrates using chemical solution method. Smaller cations (La³⁺) and vacancies were introduced into A-sites of perovskite structure to construct chemical pressure. According to phenomenological theory, chemical pressure can increase the energy barrier between antiferroelectric (AFE) and ferroelectric (FE) phase, and enhance antiferroelectricity of the system. As a result, a large energy storage density (W_re) of 23.1 J cm⁻³ and high efficiency (η) of 73% were obtained in PLZ-0.10 films, while PLZ-0 films displayed lower W_re (15.1 J cm⁻³) and η (56%). More importantly, PLZ-0.10 films exhibited an excellent cycling stability with a variation of ˜2% after 1 × 10⁸ cycles. The results demonstrate that heavily La-doped PbZrO₃ films with high energy storage density, high efficiency and excellent cycling stability can be considered as potential candidates for energy storage applications.     

Structural phase transition,electrical and photoluminescent properties of Pr3+-doped (1-x)Na0.5Bi0.5TiO3-xSrTiO3 lead-free ferroelectric thin films

Lead-free ferroelectric Pr³⁺-doped (1-x)Na_0.5Bi_0.5TiO₃-xSrTiO₃ (x?=?0–0.5) (hereafter abbreviated as Pr-NBT-xSTO) thin films were prepared on Pt/Ti/SiO₂/Si and fused silica substrates by a chemical solution deposition method combined with a rapid thermal annealing process at 700?°C, and their structural phase transition, dielectric, ferroelectric, and photoluminescent properties were investigated as a function of STO content. Raman analysis shows that with increasing STO content, the phase structures evolve from rhombohedral phase to coexistence of rhombohedral and tetragonal phases (i.e. morphotropic phase boundary), and then to tetragonal phase. The structural phase transition behavior has been well confirmed by temperature- and frequency- dependent dielectric measurements. Meanwhile, the variation in photoluminescence intensity of Pr³⁺ ions with different STO content in the NBT-xSTO thin films also indicates that there exists a clear structural phase transition when the film composition is close to the morphotropic phase boundary. Superior dielectric and ferroelectric properties are obtained in the Pr-NBT-0.24STO thin films due to the formation of morphotropic phase boundary. Our study suggests that Pr-NBT-xSTO thin films be promising multifunctional materials for optoelectronic device applications.     

Revealing the solid-state processing mechanisms of antiferroelectric AgNbO3 for energy storage

AgNbO₃ is one of the prominent lead-free antiferroelectric (AFE) oxides, which readily exhibits a field-induced AFE to ferroelectric phase transition and thus a high energy storage density. The solid-state synthesis of AgNbO₃ is considered difficult and an oxidizing atmosphere is typically employed during AgNbO₃ processing, on the premise that oxygen can prevent possible decomposition of the silver oxide at high temperatures. However, details about the influence of processing parameters on the functional properties of AFE AgNbO₃ are insufficiently understood. In this work, the solid-state reaction of a stoichiometric AgO and Nb₂O₅ mixture was investigated. We found that ball milling can convert AgO into metallic Ag, which is beneficial for lowering the reaction temperature for the formation of the perovskite phase to 500‒600℃. Moreover, the influence of the processing atmosphere (air, O₂, and N₂) was investigated by thermal analysis and in situ X-ray diffraction. Since the reaction between Ag and Nb₂O₅ to form AgNbO₃ requires oxygen uptake, AgNbO₃ was only found to form in air and O₂, whereby the kinetics were faster in the latter case. All the sintered AgNbO₃ samples exhibited a similar crystallographic structure, although the samples processed in O₂ had a lower oxygen vacancy concentration. Despite this, well-defined AFE double polarization loops were obtained in all cases. Our results indicate that decomposition of sliver oxide during ball milling is beneficial for the solid-state reaction, while a pure O₂ atmosphere is not essential for the synthesis of high-quality AgNbO₃. These findings may simplify the processing and facilitate further research of AgNbO₃-based antiferroelectrics.     

Melting behavior and superheating capacity of REBa2Cu3Oy films with nano‐layer buffered structures

Using high temperature‐optical microscopy, in situ investigations were conducted on melting and superheating behaviors of REBa₂Cu₃O_7?δ (RE123, RE = Nd, Gd) films, which were grown on nano‐layer buffered substrates. The results demonstrate that all buffered RE123 films have improved crystallinity and in‐plane alignments, leading to the higher superheating capability. In the first case, due to its good lattice match with the buffer material of Y123, the Nd123 film with the minimal extrinsic property grew from the superior interface. In the second circumstance, because of its stronger chemical bonding with the buffer layer of Gd₂O₃, the pure c‐axis oriented Gd123 film was fabricated. Moreover, the optimized thickness of buffer layer plays an important role in reducing interface energy of RE123 films and enhancing its superheating capacity.     

Relaxation behavior of PbZrO3-SrTiO3 thin film for enhancing energy storage performances

In recent years, antiferroelectric materials have attracted significant attention as energy storage materials in pulsed power systems. In this study, (1-x)PbZrO₃-xSrTiO₃ (PZO-STO) antiferroelectric films were prepared, and the effects of the STO content on the microstructure and energy storage performance of the thin films were investigated in detail. The results showed that when the PZO/STO ratio was near the morphotropic phase boundary, the long-range PZO-STO-ordered structure could be broken by the paraelectric nanograins generated at the grain boundary. The number of nanoparticles increased gradually with an increase in the STO content, thereby leading to the microstructure transformation of the thin films from antiferroelectric to relaxation ferroelectric. When the STO content was 20%, the as-prepared thin film had a maximum energy storage density of 15.26 J/cm³, which was 117.14% higher than that of the pure PZO thin film.     

Investigation of Tb-doping on structural transition and multiferroic properties of BiFeO3 thin films

Pure BiFeO₃ (BFO) and Bi_1−xTb_xFeO₃ (BTFO) thin films were successfully prepared on FTO (fluorine doped tin oxide) substrates by the sol–gel spin-coating method. The effects of Tb-doping on the structural transition, leakage current, and dielectric and multiferroic properties of the BTFO thin films have been investigated systematically. XRD, Rietveld refinement and Raman spectroscopy results clearly reveal that a structural transition occurs from the rhombohedral (R3c:H) to the biphasic structure (R3c:H+R-3m:R) with Tb-doping. The leakage current density of BTFO_x=0.10 thin film is two orders lower than that of the pure BFO, i.e. 5.1×10⁻⁷ A/cm² at 100 kV/cm. Furthermore, the electrical conduction mechanism of the BTFO thin films is dominated by space-charge-limited conduction. The two-phase coexistence of BTFO_x=0.10 gives rise to the superior ferroelectric (2P_r=135.1 μC/cm²) and the enhanced ferromagnetic properties (M_s=6.3 emu/cm³). The optimal performance of the BTFO thin films is mainly attributed to the biphasic structure and the distorted deformation of FeO₆ octahedra.     

Thermoelectric properties of thin films of bismuth telluride electrochemically deposited on stainless steel substrates

Bismuth telluride thin films have been synthesized by electrochemical deposition onto stainless steel substrates from acidic solutions. The influence of deposition variables on film composition, morphology and crystal orientation associated with the growth of the film was investigated by means of constant potential deposition and pulsed potential deposition. In-plane thermoelectric and transport properties of the electrodeposited films were measured. The carrier concentration of the electrodeposited films was found to be one order of magnitude larger than typically reported for optimized bulk bismuth telluride, which explains the unusually low Hall mobility and Seebeck coefficient values found for the electrodeposited films. Pulse deposited films showed slightly lower electrical resistivity and higher Seebeck coefficient due to the lower porosity and less preferred crystal orientation of the films compared to the continuously deposited films. Improvements of the film properties are necessary to make them viable for applications.