Effect of glass addition into interfacial polarization and energy storage properties of (Na0.5Bi 0.5 )TiO3 based NaNbO3 ceramics

Effect of glass addition into interfacial polarization and energy storage properties of (Na0.5Bi 0.5 )TiO3 based NaNbO3 ceramics | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Effect of glass addition into interfacial polarization and energy storage properties of (Na 0.5 Bi 0.5 )TiO 3 based NaNbO 3 ceramics Anwar Farag Ali, A.A. Ebnalwaled, Moukhtar A. Hassan, Abd El-razek Mahmoud This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9295258/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract This study demonstrates a successful strategy for designing 0.25(Na 0.5 Bi 0.5 )TiO 3 -0.75NaNbO 3 (0.25BNT-0.75NN) based 0.025 (Ba 0.8 B 0.1 Ca 0.1 )(Zr0. 1 Ti 0.9 )O 3 (2.5% glass) phase for enhancement their energy storage properties and interfacial polarization suppression. The addition of glass phase foster cations disorder and disrupting long-range ordering (LRO) of BNT-NN ferroelectric phase and enhancement of relaxor degree. Furthermore, the increasing in grain resistance induced inhabitation of interfacial polarization subsequently enhancement of the dielectric breakdown strength (DBS). The activation energy (E a ) was elevated from 0.033eV in pure BNT-NN to 0.075eV IN BNT-NN-2.5%glass. Remarkable enhancement into energy storage density of (W rec ) = 1.45 J/cm 3 and superior energy storage efficiency (η) of 96.4%. Moreover, superior temperature stability across a broad temperature range up to 150°C was achieved in BNT-NN-based glass phase. The variant of W rec was observed less than 3% within the whole range of applied temperature. This work offers a promising approach for generating high-performance glass-ceramic materials for advanced energy storage applications. Relaxor-antiferroelectric Breakdown strength Interfacial polarization Thermal stability energy storage density Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction Nowadays, because of the current global energy crisis caused by the depletion of fossil fuels, the most attention has been paid to research into clean, efficient, and renewable energy sources like water, solar, wind, thermal, and wave energy [ 1 , 2 ]. Fuel cells, batteries, and dielectric capacitors are examples of energy storage systems that are becoming more and more necessary because these energies depend on them. Among them, lead-free dielectrics are currently more advantageous for renewable energy storage systems because of their low cost, great power density, and quick charging and discharge times (< 100ns), lack of chemical reaction during the charge and discharge processes, and greater mechanical and thermal robustness than the other systems [ 3 – 5 ]. However, these materials are not appropriate for energy storage applications, because of their lower DBS, lower η, and lower W rec [ 6 ]. Thus, developing a new ceramic material with remarkable energy storage properties-like high DBS, quick charge-discharge, thermal stability, and recoverable energy storage density is essential. Theoretically, the depolarization curve can be integrated via the polarization versus electric field (P–E) hysteresis loop using Eq. (1–3), to determine the W tot , W rec , and η of dielectric materials. respectively W tot = \(\:{\int\:}_{0}^{\varvec{P}\varvec{m}\varvec{a}\varvec{x}}\varvec{E}\varvec{d}\varvec{P}\) (1) W rec = \(\:{\int\:}_{\varvec{P}\varvec{r}}^{\varvec{P}\varvec{m}\varvec{a}\varvec{x}}\varvec{E}\varvec{d}\varvec{P}\) (2) η = \(\:\frac{\mathbf{W}\mathbf{r}\mathbf{e}\mathbf{c}}{\mathbf{W}\mathbf{t}\mathbf{o}\mathbf{t}}\) = \(\:\frac{\mathbf{W}\mathbf{r}\mathbf{e}\mathbf{c}}{\mathbf{W}\mathbf{r}\mathbf{e}\mathbf{c}+\mathbf{W}\mathbf{l}\mathbf{o}\mathbf{s}\mathbf{s}}\) (3) where W loss and E stand for the applied electric field and energy loss density, respectively. These equations indicate that in order to attain higher energy performance, dielectric capacitors with big P max - P r (ΔP), high DBS, and high η are essential. Thus far, the energy-storage properties have been applied to four different kinds of dielectric materials: relaxor-ferroelectric materials (RFEs), ferroelectric materials (FEs), anti-ferroelectric materials (AFEs), and linear dielectric materials (LDs) [ 7 ]. As a result, AFEs and RFEs exhibit considerable promise for energy-storage applications, and several different materials, such as Bi 0.5 Na 0.5 TiO 3 (BNT), K 0.5 Na 0.5 NbO 3 (KNN), NaNbO 3 (NN), Bi 0.5 Na 0.5 TiO 3 -BaTiO 3 (BNT-BT) have been investigated [8–11]. However, because to the significant loss caused by the huge hysteresis between the forward and backward between AFE-FE and FE-AFE phase transitions, AFEs with macro domains often feature typical double P-E hysteresis loops with low η [12]. To overcome these limitations, RFEs materials have emerged as a pivotal class of dielectrics for the next generation of pulse power applications [13]. Unlike standard ferroelectrics, RFEs are characterized by the presence of polar nanoregions (PNRs) instead of long-range ordered domains, which allows for a highly reversible polarization response with minimal hysteresis [14]. The strategic advantage of RFEs lies in their unique ability to maintain a high maximum polarization (P max ) while simultaneously exhibiting a near-zero remnant polarization (P r ). This "slimming" of the P-E hysteresis loop is essential for maximizing the W rec . BNT material is a conventional lead-free ferroelectric material and one of the most promising energy storage technologies, due to it crystallizes in the rhombohedral symmetry (R, space group: R 3 c) with significant anti-phase octahedral rotation and considerable cation displacements along the [111] C polar axis [15]. Near T d (about 200°C), the tetragonal distortion (T, space group: P4bm) appears, and it subsequently predominates close to T m (around 320°C). An ideal cubic perovskite structure is seen when the temperature is raised over 540°C. R phase and T phase octahedral tilting are denoted by a − a − a − and a 0 a 0 c + , respectively. Therefore, it is proposed that a substantial polarization in BNT (about 43 µC/cm 2 ) results from strong hybridization between the Bi 3+ 6s and O 2− 2p orbitals [16]. Second, a change in the A-site ionic radius or valence bond type results in more local structural disorder and distortion, which is beneficial for generating high energy storage performances (ESP). However, Because of its high P r , low breakdown electric field (E b ), and strong nonlinear polarization response (early saturation polarization), pure BNT cannot be employed directly for energy storage. As previously studies, considerable major improvements have been made in improving the energy storage capacity of BNT-based ceramics; however, further work is still required to achieve ultrahigh W rec (≥ 8 J/cm 3 ) and η (≥ 90%), satisfying the requirements of modern electronic devices' lightweight and miniaturization [17,18]. Additionally, strong temperature stability is essential for dielectrics. It is suggested that adding AFE materials such as NN to BNT ceramics and designing RAFEs can result a stable AFE behavior, large E b , increase the degree of relaxor phase, hence obtain better energy storage characteristic of BNT ceramics [19,20]. To design RAFEs and enhance the ESP for BNT, NN ceramic was considered, this material is a promising lead-free AFE material garnered a lot of attention for energy storage [21–23]. When NN is introduced into BNT, it can promote a transition from a strong ferroelectric state towards a RFE or even an AFE-like behavior, which is very desirable for energy storage applications [24]. For example, studies have shown that incorporating NN into BNT-based ceramics can effectively reduce P r while maintaining a high maximum polarization (P max ), thus maximizing the W rec [25,26]. Furthermore, the introduction of NaNbO 3 can also significantly enhance the BDS of the BNT ceramic. This is often attributed to several factors, including grain refinement and the development of a more compact microstructure, which act as barriers to electrical breakdown [27]. The presence of NN can also create local random fields and induce structural disorder, suppressing large ferroelectric domains and promoting the formation of polar nano-regions (PNRs). These PNRs contribute to a more diffuse phase transition and can further improve the linearity of the P-E loop, leading to higher W rec [28]. For instance, He Qi, Ruzhong Zuo, et al examined how the 0.24BNT additive affected the energy storage capacity of 0.76 NN, obtaining W rec value of 12 J/cm 3 at E b =700kV/cm, however the system has a low η (69%) [27]. To further enhance energy density and efficiency, recent research has focused on enhancing these properties through compositional tuning and microstructure engineering, such as the introduction of glass phases or secondary additives. These modifications disrupt the coupling between dipoles, intensifying the relaxor behavior and effectively increasing DBS [29]. Furthermore, the dynamic response of PNRs in these materials enables them to operate efficiently over a wide range of temperatures and frequencies, making them indispensable for modern electronic devices and electric vehicle power modules. Consequently, understanding the transition from ferroelectric to relaxor states is fundamental to achieving the synergistic balance of high W rec and superior discharge η required for contemporary energy storage technologies. BBCZT as a glass phase was incorporated into NN-NBT to improve antiferro-distortion and relaxor character BNT- NN -2.5% glass. Actually, breakdown field strengths more than 300 kV/cm are the primary determinant of large energy storage densities. It has been stated that glasses when add to ferroelectric ceramics have apparently been enhanced to enable their lowered sintering temperature and influence on the grain size and band gap [30,31], in addition to, a lot of studies have reported that addition of glass can increase their DBS, hence enhance ESP [32,33]. The motivation of BBCZT glass into BNT material was driven by three considerations; 1- Its low tolerance factor makes ferroelectricity more enhanced. 2Its large to electronegativity contrast and poor polarizability between Ca 2+ and Na + /Bi 3+ disturb the long- range order of polarization. 3- The incorporation of BBCZT glass can enhance the E b by broad the band gap and optimizing the grain size for the solid solution of BNT-NN ceramic. Where, both internal and exterior ceramic material characteristics, such as the relative dielectric constant (ɛ r ), band gap, grain size (G), sample size, suppression of the interfacial polarization, and test conditions, affect the E b of the dielectrics by the following relationships: E b α d − 0.5 G − a ɛ −0.5 [34,35]. Herein, we suggest using a synergistic approach (Fig. 1 (b)) to get a fully optimized W rec and η in BNT-NN-based ceramics by optimization of chemical composition, existence of PNRs, grain size refinement, suppression of the Interfacial polarization, and the 2p orbitals of O can hybridize with the lone pair electronic 6s 2 structure in Bi, producing significant saturation polarization in ceramics based on BNT. Based on this strategy, we demonstrate remarkable enhancements in the W rec and E b for the lead-free ceramics of BNT-NN by incorporation of 2.5% glass. As a result, BNT- NN -2.5% glass ceramic expected to improve the stored energy density by increase the breakdown strength, and maintains a high efficiency. Moreover, excellent temperature and frequency stabilities are expected to be achieved. 2. Material and methods 2.1. Preparation of BNT and NN ceramic by solid-state reaction method Initially, two distinct compositions of BNT and 0.25BNT- 0.75NN were created using a solid solution technique. High purity of Bi 2 O 3 (99.0%), Na 2 CO 3 (99.8%), Nb 2 O 5 (99.5%) and TiO 2 (nanoparticle) as raw materials. Powders were weighed in stoichiometric amounts in accordance with a compositional formula. Powders were measured using a compositional formula and weighed in stoichiometric amounts. The mixture was ball milled for 24 hours in a plastic container using absolute ethyl alcohol as a liquid medium. After drying, the powders were calcined for two hours at 850°C. After that, the calcined powders were crushed into pellets that were about 10 mm in diameter and 1 mm thick after being granulated with 10% polyvinyl alcohol (PVA). The ceramics were sintered for two hours at 1130°C in an alumina crucible following the burning of the PVA. 2.2. Preparation of BBCZT glass by melt quenching method and BNT-NN-2.5% BBCZT In the second batch, the glass phase was synthesized. The chemical formula BBCZT was used to weight each of them., which included BaCO 3 , CaCO 3 , BH 3 O 3 , ZrO 2 , and TiO 2 . The conventional melt quenching method was used to create the matching glass phase. In order to create the glass phase, the BBCZT calcined powder was ground into agate mortar, placed in platinum crucibles, and heated in an electric furnace to 1450°C for one hour while the crucibles were constantly stirred to eliminate air bubbles and produce a uniform molten solution. the solution was quenched between two slabs of stainless steel. After that, the molten solution was allowed to cool in air at room temperature. Then The BBCZT glass was ground by agate mortar to obtain the fine powder. After weighing the calcined BNT-NN and BBCZT glass powders using the formula (0.975(BNT-NN) − 0.025 BBCZT), they were combined by ball milling in ethanol with zirconia balls for five hours to create a uniform powder, which was then dried and sieved. The dried powder was combined with 5 weight percent polyvinyl alcohols (PVA) as a binder and compressed using a steel die to create pellets that were 10 mm in diameter and around 1 mm thick. this composition was sintered at a 1120 C, where the glass phase reacts as a sintering aid for decreasing the sintering temperature. 2.3. Characterizations measurements Phase composition was determined by X-ray diffraction (XRD) using a PANalytical X'Pert diffractometer with n (XRD with 0.15 nm of CuKα). The sintered ceramic's morphology was examined using a scanning electron microscope (SEM) (JEOL JSM-840A). The ceramics were polished and silver electrodes were placed on both sides of them to measure their electrical properties. By using an LCR meter (TH2826 LCR Meter 20Hz-5MHz), the temperature dependency of ε r and loss (tan δ) were measured at four various frequencies in the 1 kHz–1000 kHz range. In order to assess the energy density properties of manufactured samples, P-E hysteresis loops including bi-polar, mono-polar in addition to piezoelectric were obtained using (RADIANT Precision Premium II Multiferroic Ferroelectric Test System 10kV HVI-SC Model 609B) at various temperatures and electric field intensities. 3. Results and discussion 3.1. Crystallization and morphology properties Figure 2 (a) shows the XRD pattern of BNT, BNT-NN, and BNT-NN-2.5% glass ceramics at ambient temperature. It can be observed that all of the compositions under examination have formed a suitable single phase perovskite structure with no any obvious detection of secondary phases under the detection limit of XRD, suggesting that NN and the glass phases were successfully interacted into BNT lattices during the sintering process resulting in a single-structure solid solution. XRD of as-quenched glass at room temperature is displayed in the inset of Fig. 2 . It shows that there isn't a peak, confirming that glass is amorphous. For additional crystal structure analysis, the change of the (200) in the 2θ range of 45 ~ 48° expanded diffraction peaks were carefully shown in Fig. 2 (b). The patterns revealed that, the peaks moved towards the higher angles compared to pure BNT, indicating a decrease in the lattice volume which might be ascribed to the lower ionic radius of NN. This causes the lattice's volume cell to shrink [36]. Additionally, the enlarging patterns display hump and slight splitting diffraction peaks suggests a typical rhombohedral (R-phase, space group R 3c ) phase for the pure BNT ceramic (x = 0). The substitution of NN for BNT makes (200) peak more split and displays a small shoulder at the lower-degree side of (200) diffraction lines, suggesting the phase transition from rhombohedral to rhombohedral- orthorhombic coexistence phases in other samples (R&O phases, with space group R 3C and Pbma, respectively. An increase in splitting peak of O-phase at 2θ = 46 in BNT-NN-2.5% glass show greater compositional fluctuation and cation disorder at room temperature, which may be advantageous for increasing the degree of relaxor phase by adding glass [37]. The microstructural homogeneity and properties of the sintered pellets were examined at the room temperature using a scanning electron microscope (SEM). Figure 3 demonstrates the typical surface microstructure morphologies and the distribution of grains for each sintered ceramics. All samples revealed a very dense microstructure homogenous of grain size, while tiny pores exist among the grain boundaries of the BNT-NN ceramic, due to the high temperature of sintering. The presence of the glass phase entirely suppressed the pores, leading to improve the surface morphology. The grain size (G) distribution was determined by Image J software, it dropped from 2.05 µm for pure BNT to 1.63663 µm for BNT-NN and decreased to a sub-micrometer of 0.903µm by adding the glass phase. Furthermore, adding BBCZT glass caused the grain size to decrease because the substitution of different ionic radius may raise the lattice strain energy, which in turn may cause the grain boundary mobility to be disrupted [38]. Ceramics' small grain size helps to increase the breakdown strength via the relationship of E b α G −α , which raises the energy storage density [39]. 3.2 Dielectric properties and AC-properties: Figure 4 . (a,b,c) demonstrates the temperature dependence of the ε r along with dielectric loss (tan δ) for the virgin sintered ceramic at four different frequencies (0.5, 1, 10, and 100 KHz) for BNT, BNT-NN, and BNT-NN-2.5% glass ceramic within the temperature range of (25-300 o C). As can be seen, each sample exhibits distinct behavior from the others indicates the superior effect of adding of NN and the glass phase into dielectric characteristics of BNT ceramic. In pure BNT, two permittivity peaks were appeared, the first peak was known as the depolarization temperature (T d ~ 285 ◦ C), at which the crossover of one ferroelectric phase to another with a various crystal structure can be observed, while the second peak is known as curie temperature (T c ) is ascribed to the phase transition from the ferroelectric to the paraelectric occurred at ~ 350 ◦ C [40]. The observed significant dependence of permittivity values on applied frequency suggests the presence of a microscopic domain structure, large domain size, and LRO of ferroelectricity. In BNT-NN sample, the behavior was completely different, where no discernible phase transition could be seen in temperature range of 25 to 300 o C, and the ε r decreased as temperature increased. In BNT-NN-2.5% glass sample, a further decreasing in the permittivity and increasing thermal stability were happened, higher thermal stability was noted across a broad temperature range, and the permittivity is not affected by the frequency, can contribute to the existence of the nano-domain of the relaxor phase and the cation disorder effect resulting from adding the glass phase produced relaxor phase and break the LRO of ferroelectricity for BNT [41,42] a significant reduction in dielectric loss has been accomplished at BNT-NN-2.5% glass sample due to current cation vacancies in the A-site of the lattice caused by the substitution the monovalent Na + 1 ion for the trivalent Bi + 3 ions, which can result in the formation of a relaxor phase and slim hysteresis loop by pinching the remaining polarization. η can be improved by reduced dielectric loss. Because of the conduction process and inadequate electric insulation at high temperatures, values have been seen to slightly increase. One of the main factors that is directly connected to interfacial polarization and breakdown strength is the activation energy (Ea), which may be calculated using the Arrhenius equation as follows. δ dc = δ o e –Ea /KBT (4) Where, δo refers to the pre-exponential factor, T represents the kelvin temperature, and K B refers to Boltzmann constant. Figure 4 (d, e) illustrated the variation of Lnδ with T and the activation energy values for the current ceramics, the results verified that Ea increases as adding NN and the glass phase, with a maximum value of 0.075 in BNT-NN-2.5% glass sample. Impedance spectroscopy is a technique used to investigating the electrical characteristics of materials. The interface polarization can be suppressed by increasing the resistance of grain (R g ) until the difference between R g and resistance of grain boundary (R gb ) is mismatched, Thus, in addition to the real impedance Z' and imagined impedance Z″ we examined the imagined part of modules M analysis examined. Figure 5 (a,b,c) shows the data of Neqyest plot of impedance (Zʹ & Z″) of the present ceramics in the frequency range (20Hz -5MHz with 20000Hz as frequency step) at various temperatures (550 and 650 ◦ C). As can be seen, all sintered ceramics produced semicircles in the cole-cole plots, indicating that the graphs are influenced by both the grain and the grain boundary. Additionally, the BNT-NN-2.5% glass sample has the biggest radius of the impedance spectrum arc, indicating the highest R g . It is possible to interpret the increased R g that suppresses the oxygen vacancies effect lead to enhancing E b and ESP. For studying the suppression of interfacial polarization and determining how the values of R g and R gb changed. The comparing the Z''− f and M"− f spectra of the samples recorded at 650 ◦ C was displayed in Fig .5 (d,e,f) to unequivocally support this claim, where the value of R g is gave by the variation of Z''− f, while R gb is reflected by M"− f variation [43]. In all samples the present Z″ and M″ peaks is observed, indicate the present of R g and R gb effect. When peaks overlapping between Z'' and M'' decrease, the interfacial polarization of ceramics is reduced where R g and R gb values would be near one another. According to a number of earlier researches, the interfacial polarization can be determined by the value of frequency gab (Δf) or the difference between the R g and R gb values [40]. The BNT-NN-2.5% glass ceramic has the lowest Δf, indicating the grain's elevation resistance and, consequently, a smaller R g -R gb difference at this sample. Stated differently, interfacial polarization and oxygen vacancy effects can be suppressed by high grain resistance. The current findings clearly show that high-entropy materials with high grain resistance can simultaneously improve ESP, synergistic DBS, and the interfacial polarization effect. 3.3. Ferroelectric and piezoelectric properties : The bipolar P-E and I-E loops of BNT, BNT-NN, and BNT-NN-2.5% glass sintered ceramics at RT, applied electric field (E = 50 kV/cm), and 10Hz are displayed in Fig. 6 . A strong normal ferroelectric P-E loop was seen in pure BNT, with a large value of P max =37µC/cm 2 and P r =32µC/cm 2 . This is due to the perovskite's rhombohedral structure [42]. High P r is attributed to a high degree of domain wall displacement caused by external influences, whereas high P max was attributed to high hybridization between Bi 3+ 6P and O 2 − 2P.. In NBT-NN ceramic, the pinched double-like P-E loops is observed and both P max and P r decrease with adding NN phase, where the values of P max decreased from 37 to 7.52 µC/cm 2 . While P r drops dramatically from approximately 32 to 0.65 µC/cm 2 reveal the AFE characteristic of this ceramics [44]. By adding the glass phase, the shape of P – E loops tend to be slimmer with P max 7 µC/cm 2 and a decreasing can be observed in P r to 0.38 µC/cm 2 , indicating the improvement of relaxation behavior. As shown, despite a drop of P max , the attenuation of about 90% in P r eventually dominates the energy-storage performances of NBT-NN-2.5% glass ceramic because of the resulting slim P-E loop with greatly reduced electric hysteresis loss. Meanwhile, P max and P r of BNT-NN and BNT-NN-2.5% glass ceramics would decrease as a result of the local random field created due to the variable valence and ionic radius, which the long-range dipole alignment would be broken into short-range polar clusters [45]. The relaxor phase can also be confirmed by the current loop, which shows a definite increase in current values as E increases and reaches its maximum values (E max ). At BNT, there was just one sharp current peak; this behavior confirms the presence of the ferroelectric phase. However, a weak current peak with a rectangular I-E loop form was seen in the BNT-NN sample, which was attributed to a phase change from ferroelectric to relaxor due to the domain switching effect. While, the current peak at BNT-NN-2.5% glass sample dropped and was entirely disappeared with the rectangular I-E loop shape, indicating an enhanced relaxor degree. 3.4.2. Energy Storage Properties The energy storage performance of the BNT-NN, and BNT-NN-2.5% glass sintered ceramics dependent electric fields (50-150kV/cm) was systematically investigated through the analysis of the unipolar P-E loops illustrated in Fig. 7 (a,b) respectively. The outstanding energy storage characterization of these compositions can be understood as follow: In the BNT-NN sample (Fig. 7 (a)), the curves exhibit a relatively wider curve with a noticeable P r =1.14 µC/cm 2 . However, as observed in Fig. 7 (b), the 2.5% glass-modified ceramic exhibits a slender and delayed ferroelectric hysteresis loop, which is a characteristic feature of RFE. At an applied electric field of 150 kV/cm, the ceramic reaches a P max of approximately 19.89 µC/cm 2 , while maintaining a remarkably low P r of nearly 0.5 µC/cm 2 . The reduction in P r and the maintenance of a high P max in the glass-modified sample lead to a substantial enhancement in W rec . This "slimming" of the loop is a hallmark of improved relaxor ferroelectric behavior, where the LRO of ferroelectric is disrupted into PNRs, allowing for rapid polarization switching with minimal energy loss [46]. Based on the numerical integration of the discharge curve, the calculated W rec is approximately 1.45 J/cm 3 at 150 kV/cm. The narrow gap between the charging and discharging curves indicates minimal W loss , resulting in an ultrahigh ɳ = 96.4% is higher than that of unmodified BNT and BNT–NN ceramic. This dramatic improvement is primarily ascribed to the "pinning effect" and the disruption of the LRO of ferroelectric caused by the NN substitution and the glass phase [47]. Consequently, this improvement can be attributed to the optimized interfacial polarization that occurs at the ceramic-glass grain boundaries. As previously noted, the superior interfacial polarization in sample (b) allows for more effective charge trapping and distribution, which prevents local field concentrations and suppresses leakage currents [29]. In the other hand, the liquid-phase sintering aided by the glass additive promotes a dense, pore-free microstructure and glass additive acts as an insulating barrier resulting in a much denser microstructure that can effectively increases the E b which, allowing the material to withstand higher E compared to the pure ceramic [48,49]. Moreover, the grain size is reduced which caused by incorporating the glass phase as a sintering aid result in optimizing the DBS, thus induce an ultrahigh W rec , where the correlation between the grain size and E b is explained by the following equation [41]: E b α G − a (5) Where G is the grain size and (a) is constant between 0.2 and 0.4. Also, reducing the grain size leads to raise the density of grain boundary which works as the barrier areas between the grains with a high resistivity leading to enhancing the insulation characteristics and decrease the pores which are beneficial factors in increasing E b . Furthermore, the addition of the glass phase plays an essential role in improvement of relaxation property. By introducing structural disorder into the perovskite lattice, the glass phase promotes a faster polarization response and recovery during the field-removal stage, which is essential for high-power pulse applications [14]. This explains why the area inside the hysteresis loop representing the energy loss is drastically reduced in Fig. 7 (b) compared to the pure sample in Fig. 7 (a) resulting in a dramatic increase in ɳ, where, the high efficiency is critical for preventing thermal runaway in high-power electronic applications. Ultimately, the integration of 2.5% glass proves to be a decisive factor in achieving a superior balance between moderate W rec and exceptionally high ɳ, making it an ideal candidate for high-stability pulse power capacitors. The thermal reliability of the BNT-NN-2.5% glass sintered ceramic was investigated through unipolar hysteresis measurements across a temperature gradient from from RT to 150°C at 10Hz at field of 100 kV/cm is illustrated in Fig. 8 (a), and the conducted of W rec and ƞ were shown in Fig. 8 .(b). It's noteworthy that The material maintains a series of exceptionally slender hysteresis loops, exhibiting a high degree of temperature independence. Quantitatively, P max showed remarkable consistency, decreasing only slightly from only from 13.6 𝜇C/cm 2 to at 25°C to 12.9 𝜇C/cm 2 at 150°C. This decreasing in W rec may be related to decreasing the ε r value. The calculated energy storage parameters further confirm this robustness. ƞ also decreased slightly by increasing the applied temperature. This superior stability is primarily attributed to the relaxor phase characterized by a nano-domain structure PNRs. This level of stability is superior to many reported BNT-based systems and highlights the effectiveness of glass-phase engineering in developing high-performance, thermally reliable dielectric capacitors for harsh environments. CONCLUSION In summary, this work successfully demonstrates a robust strategy to improve the performance of energy storage of 0.25(Na 0.5 Bi 0.5 )TiO 3 -0.75NaNbO 3 (0.25BNT-0.75NN) based through the incorporation of a 0.025 (Ba 0.8 B 0.1 Ca 0.1 )(Zr 0.1 Ti 0.9 )O 3 (2.5% glass) based glass phase. The addition of the glass phase played a pivotal role in disrupting the long-range ferroelectric order (LRO) and promoting a higher degree of relaxor behavior, which is essential for achieving high efficiency (ɳ). One of the most significant findings is the profound impact of the glass phase on the dielectric breakdown strength (DBS) and charge transport mechanisms. By increasing the grain boundary resistance, the interfacial polarization (Maxwell-Wagner-Sillars effect) was effectively suppressed. This was quantitatively confirmed by the substantial rise in activation energy (Ea) from 0.033 eV to 0.075 eV, indicating a higher barrier for ionic and space charge migration. As a result of these synergistic effects, the glass-modified ceramic achieved a remarkable recoverable energy density (W rec ) of 1.45 J/cm 3 and a superior ɳ of 96.4% at 150 kV/cm. Furthermore, the material exhibited exceptional thermal reliability, with a small fluctuations in energy storage parameters up to 150°C. These findings underscore the potential of glass-ceramic composites as a promising materials for high-stability, high-efficiency pulse power capacitors in advanced electronic systems. Declarations Funding: This research received no external funding. Competing interests The authors declare no competing interests. Data availability The datasets used and/or analysed during the current study available from the corresponding author on reasonable request. References L. Yang, X. Kong, F. Li, H. Hao, Z. Cheng, H. Liu, J. Li, S. Perovskite lead-free dielectrics for energy storage applications. ‏Prog. Mater Sci. 102 (2019) 72–108. Sun, Z., Wang, Z., Tian, Y., Wang, G., Wang, W., Yang, M., ... & Pu, Y. Progress, outlook, and challenges in lead free energy storage ferroelectrics. Adv Elect Mater , 6 (1), 1900698.‏ Jiang, Jie, et al. "Ultrahigh energy storage density in lead-free relaxor antiferroelectric ceramics via domain engineering." Energy Storage Materials 43 (2021): 383-390. Pan, Yue, et al. "Enhanced energy storage properties of Bi (Ni 2/3 Nb 1/6 Ta 1/6 ) O 3 –NaNbO 3 solid solution lead-free ceramics." Ceramics International 48.18 (2022): 26466-26475. Yan, Fei, et al. "Progress and outlook on lead-free ceramics for energy storage applications." Nano Energy (2024): 109394. ang, Z., Du, H., Jin, L., & Poelman, D. (2021). High-performance lead-free bulk ceramics for electrical energy storage applications: design strategies and challenges. J. of Materials Chemistry A , 9 (34), 18026-18085.‏ Qi, He, et al. "Emerging antiferroelectric phases with fascinating dielectric, polarization and strain response in NaNbO 3 -(Bi 0.5 Na 0.5 ) TiO 3 lead-free binary system." Acta Materialia 208 (2021): 116710.. Jiang, Zehua, et al. "Enhanced breakdown strength and energy storage density of lead-free Bi 0.5 Na 0.5 TiO 3 -based ceramic by reducing the oxygen vacancy concentration." Chemical Engineering Journal 414 (2021): 128921.. Hreščak, Jitka, et al. "Donor doping of K 0.5 Na 0.5 NbO 3 ceramics with strontium and its implications to grain size, phase composition and crystal structure." Journal of the European Ceramic Society 37.5 (2017): 2073-2082.. Dong, Xiaoyan, et al. "Effective strategy to realise excellent energy storage performances in lead-free barium titanate-based relaxor ferroelectric." Ceramics International 47.5 (2021): 6077-6083. ] Y. Shen, L. Wu, J. Zhao, J. Liu, L. Tang, X. Chen, Z. Pan, Constructing novel binary Bi 0.5 Na 0.5 TiO 3 -based composite ceramics for excellent energy storage performances via defect engineering, Chem. Eng. J. 439 (2022), 135762. Tian, Y., Jin, L., Zhang, H., Xu, Z., Wei, X., Politova, E. D., ... & Yan, H. (2016). High energy density in silver niobate ceramics. J. Mater. Chem. A 2016 , 4 , 17279. Yang, Letao, et al. "Perovskite lead-free dielectrics for energy storage applications." Progress in Materials Science 102 (2019): 72-108. Su, Xiaopo, et al. "Large electrocaloric effect over a wide temperature span in lead-free bismuth sodium titanate-based relaxor ferroelectrics." Journal of Materiomics 9.2 (2023): 289-298. Hu, Qingyuan, et al. "Achieve ultrahigh energy storage performance in BaTiO3–Bi (Mg1/2Ti1/2) O3 relaxor ferroelectric ceramics via nano-scale polarization mismatch and reconstruction." Nano Energy 67 (2020): 104264. i, X. Hou, J. Wang, H. Zeng, B. Shen, J. Zhai, Structure-design strategy of 0–3 type (Bi0.32Sr0.42Na0.20)TiO3/MgO composite to boost energy storage density, efficiency and charge-discharge performance, J. Eur. Ceram. Soc. 39 (2019: (2889–2898. Wang, Hua, et al. "Enhanced energy density and discharged efficiency of lead-free relaxor (1-x)[(Bi 0.5 Na 0.5 )0.94Ba 0.06 ]0.98La 0.02 TiO 3 -xKNb 0.6 Ta 0.4 O 3 ceramic capacitors." Chemical Engineering Journal 394 (2020): 124879. Xi, Jiachen, et al. "Compromise boosted high capacitive energy storage in lead-free (Bi 0.5 Na 0.5 ) TiO 3 − based relaxor ferroelectrics by phase structure modulation and defect engineering." Chemical Engineering Journal 502 (2024): 157986. Qi, He, et al. "Ultrahigh energy‐storage density in NaNbO 3 ‐based lead‐free relaxor antiferroelectric ceramics with nanoscale domains." Advanced Functional Materials 29.35 (2019): 1903877. Meng, Xiangyu, et al. "Local structural origin of relaxor antiferroelectric behavior in NaNbO 3 -based ceramics." Chemical Engineering Journal (2025): 163109. Shi, Ruike, et al. "A novel lead-free NaNbO 3 –Bi (Zn 0.5 Ti 0.5 )O 3 ceramics system for energy storage application with excellent stability." Journal of Alloys and Compounds 815 (2020): 152356. Xu, Mingzhao, et al. "Optimize energy storage performance of NaNbO 3 ceramics by multivariable control strategy." Journal of the European Ceramic Society 44.11 (2024): 6460-6469. Qi, He, et al. "Large (anti) Ferro distortive NaNbO 3 -based lead-free relaxors: Polar nanoregions embedded in ordered oxygen octahedral tilt matrix." Materials Today 60 (2022): 91-97. Wang, Hua, et al. "Achieving ultrahigh energy storage density and efficiency in 0.90 NaNbO 3 –0.10 BaTiO 3 ceramics via a composition modification strategy." Dalton Transactions 51.26 (2022): 10085-10094. Wei, Kun, et al. "Achieving ultrahigh energy storage performance for NaNbO 3 -based lead-free antiferroelectric ceramics via the coupling of the stable antiferroelectric R phase and nanodomain engineering." ACS Applied Materials & Interfaces 15.41 (2023): 48354-48364. Qi, He, et al. "Emerging antiferroelectric phases with fascinating dielectric, polarization and strain response in NaNbO 3 -(Bi 0.5 Na 0.5 )TiO 3 lead-free binary system." Acta Materialia 208 (2021): 116710. Qi, He, et al. "Ultrahigh energy‐storage density in NaNbO 3 ‐based lead‐free relaxor antiferroelectric ceramics with nanoscale domains." Advanced Functional Materials 29.35 (2019): 1903877. Hui, Jiejie, et al. "Improving energy storage properties of NN-NBT ceramics through compositional modification." Journal of Alloys and Compounds 989 (2024): 174276. Lu, Xiang, et al. "Effect of analogue nucleating agent on the interface polarization and energy-storage performance of NaNbO 3 -based glass-ceramics." Ceramics International 50.21 (2024): 44503-44510. Patela, Satyanarayan, et al. "Enhanced energy storage performance of glass added 0.715 Bi 0.5 Na 0.5 TiO 3 -0.065 BaTiO3-0.22 SrTiO 3 ferroelectric ceramics." (2015). Li, Y. Q., et al. "The Effect of ZnO–B 2 O 3 –SiO 2 Additive on Sintering and Dielectric Properties of Ba 0. 3 Sr 0. 7 TiO 3 Ceramics." Ferroelectrics 403.1 (2010): 45-53. Wang, Xiangrong, et al. "Glass additive in barium titanate ceramics and its influence on electrical breakdown strength in relation with energy storage properties." Journal of the European Ceramic Society 32.3 (2012): 559-567. Ouaha, Ahmed, et al. "Exploring structural compatibility and energy storage performances enhancement in lead-free BNT dielectric ceramics with NBTP glass integration." Ceramics International 50.13 (2024): 24648-24661. Song, Zhe, et al. "Effect of grain size on the energy storage properties of (Ba 0.4 Sr 0.6 ) TiO 3 paraelectric ceramics." Journal of the European Ceramic Society 34.5 (2014): 1209-1217. Yang, Bingbing, et al. "High-entropy enhanced capacitive energy storage." Nature Materials 21.9 (2022): 1074-1080. Shannon, Robert D. "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides." Foundations of Crystallography 32.5 (1976): 751-767. Patel, Satyanarayan, et al. "Enhanced energy storage performance of glass added 0.715 Bi 0.5 Na 0.5 TiO 3 -0.065 BaTiO 3 -0.22 SrTiO 3 ferroelectric ceramics." Journal of Asian Ceramic Societies 3.4 (2015): 383-389. Zhao, Lei, et al. "Lead-free AgNbO 3 anti-ferroelectric ceramics with an enhanced energy storage performance using MnO 2 modification." Journal of Materials Chemistry C 4.36 (2016): 8380-8384. Sun, Zixiong, et al. "Ultrahigh Energy Storage Performance of Lead-Free Oxide Multilayer Film Capacitors via Interface Engineering." Advanced Materials (Deerfield Beach, Fla.) 29.5 (2016). Kamal, Amira A, et al. "Enhancement of entropy induced suppression of interfacial polarization to bolster breakdown strength in (Na 0.5 Bi 0.5 ) TiO 3 -Based ceramics." Ceramics International (2025). Patel, Satyanarayan, et al. "Enhanced energy storage performance of glass added 0.715 Bi 0.5 Na 0.5 TiO 3 -0.065 BaTiO 3 -0.22 SrTiO 3 ferroelectric ceramics." Journal of Asian Ceramic Societies 3.4 (2015): 383-389. Liu, Gang, et al. "Enhanced electrical properties and energy storage performances of NBT-ST Pb-free ceramics through glass modification." Journal of Alloys and Compounds 836 (2020): 154961. Babeer, Afaf M., et al. "A-site disorder induced ferroelectric to relaxor phase transition of Na(Nb 0.75 Ti 0.25 ) O 3 ceramics by Bi 3+ for ultra-high energy storage properties." Materialia 33 (2024): 102009. Wang, Changyuan, et al. "Equimolar high-entropy for excellent energy storage performance in Bi 0.5 Na 0.5 TiO 3 -based ceramics." Energy Storage Materials 70 (2024): 103534. Qi, He, et al. "Ultrahigh energy‐storage density in NaNbO 3 ‐based lead‐free relaxor antiferroelectric ceramics with nanoscale domains." Advanced Functional Materials 29.35 (2019): 1903877. Qi, He, et al. "Emerging antiferroelectric phases with fascinating dielectric, polarization and strain response in NaNbO 3 -(Bi 0.5 Na 0.5 )TiO 3 lead-free binary system." Acta Materialia 208 (2021): 116710. Zhang, Lan, et al. "Effect of Bi-B-Si-Zn-Al glass additive on the properties of low-temperature sintered silicon carbide ceramics." Frontiers in Physics 10 (2023): 1090437. Li, Xinheng, et al. "Enhancing energy storage density of BNT-ST-based ceramics by a stepwise optimization strategy on the breakdown strength." Journal of the European Ceramic Society 44.11 (2024): 6422-6429. Zheng, Yuanyuan, et al. "Enhancing energy storage performance of BT-based ceramics by doping modification." Materials Science in Semiconductor Processing 196 (2025): 109656. Li, Hongtian, et al. "Remarkable energy storage performance of BiFeO 3 -based high-entropy lead-free ceramics and multilayers." Chemical Engineering Journal 499 (2024): 156112. Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9295258","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":620620171,"identity":"6e043fdb-5982-46f7-9cbf-84526157e36e","order_by":0,"name":"Anwar Farag Ali","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABC0lEQVRIiWNgGAWjYNACGxDBfOBA4j8gS4IoLWkggi3xwQO2NJK08BgbPmA7TFgL/+wew88VCXb5/P0LzCQSeM4n9s9uPviAocYmGpcWiTtnjCXPJCRbzrjxIE0iQeJ24ow7x5INGI6l5Tbg0nMjd4Nk4w9mA4YbB45JJBjcTmy4kWMmwdhwGKcW+Ru5m382JNQbyN842CaRkHAucT4hLQY3crdJNiQcNjA438xskAAM5w2EtBjeyP9m2ZBw3MDwBhvjg8SGZOONN9KSDRLw+EUOqOBmQ0K1gdz58x8O/mywk513I/nggw81Nri9DwcSCWDKEawygaByEOA/AKbsiVI8CkbBKBgFIwoAABFiZr4cnPVWAAAAAElFTkSuQmCC","orcid":"","institution":"The High Institute of Engineering and Technology","correspondingAuthor":true,"prefix":"","firstName":"Anwar","middleName":"Farag","lastName":"Ali","suffix":""},{"id":620620172,"identity":"0e730e29-573c-4f5f-adea-eda88ee2ff1a","order_by":1,"name":"A.A. Ebnalwaled","email":"","orcid":"","institution":"Electronics \u0026 Nano Devices (END) lab, Physics Department, Faculty of Science, South Valley University, Qena 83523, Egypt","correspondingAuthor":false,"prefix":"","firstName":"A.A.","middleName":"","lastName":"Ebnalwaled","suffix":""},{"id":620620173,"identity":"b4b86678-a0f9-46a4-a679-ff4f97e51764","order_by":2,"name":"Moukhtar A. Hassan","email":"","orcid":"","institution":"Al-Azhar University","correspondingAuthor":false,"prefix":"","firstName":"Moukhtar","middleName":"A.","lastName":"Hassan","suffix":""},{"id":620620174,"identity":"82a2fe20-fa1e-41d5-b56c-fe98847a0eab","order_by":3,"name":"Abd El-razek Mahmoud","email":"","orcid":"","institution":"South Valley University","correspondingAuthor":false,"prefix":"","firstName":"Abd","middleName":"El-razek","lastName":"Mahmoud","suffix":""}],"badges":[],"createdAt":"2026-04-01 18:39:08","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9295258/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9295258/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":107000490,"identity":"bff30c17-eb63-434c-b8ec-933dbde62628","added_by":"auto","created_at":"2026-04-15 15:43:06","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":336534,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eA schematic diagram of a strategy used in this paper\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/5b63a440785d3a273fbe9c41.png"},{"id":107000499,"identity":"b0a9f91c-cb16-43bf-8e53-d452dc4e1a2d","added_by":"auto","created_at":"2026-04-15 15:43:07","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":126426,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)XRD pattern of BNT, BNT -NN, and BNT-NN-2.5% glass ceramics sintered at 1130º C, (inset: XRD of BBCZT glass powder), (b) enlarged (200) peak for the present ceramic.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/77103e7c1e55a7281542048e.png"},{"id":107000685,"identity":"3b62c57a-eacf-4a84-8c64-e45233cdcd36","added_by":"auto","created_at":"2026-04-15 15:43:24","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":863057,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSEM micrographs of BNT, BNT -NN, and BNT-NN-2.5% glass ceramics.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/55c44ee4f1a8fc056e3d4111.png"},{"id":107000521,"identity":"129aae3e-d812-4d31-9f08-0b84644530a4","added_by":"auto","created_at":"2026-04-15 15:43:10","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":74829,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a,b,c): The temperature dependence of the dielectric permittivity and dielectric loss, (d) Temperature versus\u003c/strong\u003e \u003cstrong\u003econductivity and (e) the activation energy for BNT, BNT -NN, and BNT-NN-2.5% glass ceramics .\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/f19c5171f8ad59a284d7383a.png"},{"id":107000727,"identity":"dc4cd865-92ec-4b08-aa7e-5c5627d8aade","added_by":"auto","created_at":"2026-04-15 15:43:25","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":90306,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a–c) The Neqyest plot of impedance for the samples at temperature degrees (550 ◦C, 650 ◦C), (d–f) the variation of \u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eZ\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e″ and \u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eM\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e″ at 650 ◦C with frequency.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/6ccc8a67bf1999eba55f9b6c.png"},{"id":107000550,"identity":"7fac22d8-b724-44a1-9914-c31cf7bd6653","added_by":"auto","created_at":"2026-04-15 15:43:11","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":181422,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a,b,c) P-E and I-E loops at 50 kV/cm of the sintered ceramics.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/c3932e1a11d388d77a822bb3.png"},{"id":107000523,"identity":"3c3a17d4-9124-4306-80e8-78a3269c92b3","added_by":"auto","created_at":"2026-04-15 15:43:11","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":42077,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a,b) The unipolar P–E loops of BNT-NN, and BNT-NN-2.5% glass, respectively, sintered ceramics at room temperature under (50-150Kv/cm).\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/24dd0d9c3dc6b45542148613.png"},{"id":107001535,"identity":"a592df3b-ac6a-4564-a9d0-2b8bdf785c06","added_by":"auto","created_at":"2026-04-15 15:46:02","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":43534,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a): The unipolar P-E hysteresis loops of BNT-NN-2.5% glass ceramic at temperatures (25-150\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e0\u003c/strong\u003e\u003c/sup\u003e\u003cstrong\u003eC).\u0026nbsp; (b): W\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003erec \u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eand ƞ at 10Hz and different temperatures at E = 100 kV/cm.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/7ed5f5f44e75b027bc49612c.png"},{"id":107002411,"identity":"a5afc00f-c201-4f30-b4eb-f72bf0a884ae","added_by":"auto","created_at":"2026-04-15 15:49:20","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2821389,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9295258/v1/b11a77f2-5eea-45bd-b987-b70974890a48.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eEffect of glass addition into interfacial polarization and energy storage properties of (Na\u003csub\u003e0.5\u003c/sub\u003eBi\u003csub\u003e 0.5\u003c/sub\u003e )TiO\u003csub\u003e3\u003c/sub\u003e based NaNbO\u003csub\u003e3\u003c/sub\u003e ceramics\u003c/p\u003e","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eNowadays, because of the current global energy crisis caused by the depletion of fossil fuels, the most attention has been paid to research into clean, efficient, and renewable energy sources like water, solar, wind, thermal, and wave energy [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Fuel cells, batteries, and dielectric capacitors are examples of energy storage systems that are becoming more and more necessary because these energies depend on them. Among them, lead-free dielectrics are currently more advantageous for renewable energy storage systems because of their low cost, great power density, and quick charging and discharge times (\u0026lt;\u0026thinsp;100ns), lack of chemical reaction during the charge and discharge processes, and greater mechanical and thermal robustness than the other systems [\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. However, these materials are not appropriate for energy storage applications, because of their lower DBS, lower η, and lower W\u003csub\u003erec\u003c/sub\u003e [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Thus, developing a new ceramic material with remarkable energy storage properties-like high DBS, quick charge-discharge, thermal stability, and recoverable energy storage density is essential.\u003c/p\u003e \u003cp\u003eTheoretically, the depolarization curve can be integrated via the polarization versus electric field (P\u0026ndash;E) hysteresis loop using Eq.\u0026nbsp;(1\u0026ndash;3), to determine the W\u003csub\u003etot\u003c/sub\u003e, W\u003csub\u003erec\u003c/sub\u003e, and η of dielectric materials. respectively\u003c/p\u003e \u003cp\u003e \u003cb\u003eW\u003c/b\u003e \u003csub\u003e \u003cb\u003etot\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e=\u003c/b\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{\\int\\:}_{0}^{\\varvec{P}\\varvec{m}\\varvec{a}\\varvec{x}}\\varvec{E}\\varvec{d}\\varvec{P}\\)\u003c/span\u003e\u003c/span\u003e \u003cb\u003e(1)\u003c/b\u003e\u003c/p\u003e \u003cp\u003e \u003cb\u003eW\u003c/b\u003e \u003csub\u003e \u003cb\u003erec\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e=\u003c/b\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{\\int\\:}_{\\varvec{P}\\varvec{r}}^{\\varvec{P}\\varvec{m}\\varvec{a}\\varvec{x}}\\varvec{E}\\varvec{d}\\varvec{P}\\)\u003c/span\u003e\u003c/span\u003e \u003cb\u003e(2)\u003c/b\u003e\u003c/p\u003e \u003cp\u003e \u003cb\u003eη =\u003c/b\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\frac{\\mathbf{W}\\mathbf{r}\\mathbf{e}\\mathbf{c}}{\\mathbf{W}\\mathbf{t}\\mathbf{o}\\mathbf{t}}\\)\u003c/span\u003e\u003c/span\u003e \u003cb\u003e=\u003c/b\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\frac{\\mathbf{W}\\mathbf{r}\\mathbf{e}\\mathbf{c}}{\\mathbf{W}\\mathbf{r}\\mathbf{e}\\mathbf{c}+\\mathbf{W}\\mathbf{l}\\mathbf{o}\\mathbf{s}\\mathbf{s}}\\)\u003c/span\u003e\u003c/span\u003e \u003cb\u003e(3)\u003c/b\u003e\u003c/p\u003e \u003cp\u003ewhere W\u003csub\u003eloss\u003c/sub\u003e and E stand for the applied electric field and energy loss density, respectively. These equations indicate that in order to attain higher energy performance, dielectric capacitors with big P\u003csub\u003emax\u003c/sub\u003e - P\u003csub\u003er\u003c/sub\u003e (ΔP), high DBS, and high η are essential. Thus far, the energy-storage properties have been applied to four different kinds of dielectric materials: relaxor-ferroelectric materials (RFEs), ferroelectric materials (FEs), anti-ferroelectric materials (AFEs), and linear dielectric materials (LDs) [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. As a result, AFEs and RFEs exhibit considerable promise for energy-storage applications, and several different materials, such as Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e (BNT), K\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eNbO\u003csub\u003e3\u003c/sub\u003e (KNN), NaNbO\u003csub\u003e3\u003c/sub\u003e (NN), Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-BaTiO\u003csub\u003e3\u003c/sub\u003e (BNT-BT) have been investigated [8\u0026ndash;11]. However, because to the significant loss caused by the huge hysteresis between the forward and backward between AFE-FE and FE-AFE phase transitions, AFEs with macro domains often feature typical double P-E hysteresis loops with low η [12]. To overcome these limitations, RFEs materials have emerged as a pivotal class of dielectrics for the next generation of pulse power applications [13]. Unlike standard ferroelectrics, RFEs are characterized by the presence of polar nanoregions (PNRs) instead of long-range ordered domains, which allows for a highly reversible polarization response with minimal hysteresis [14]. The strategic advantage of RFEs lies in their unique ability to maintain a high maximum polarization (P\u003csub\u003emax\u003c/sub\u003e) while simultaneously exhibiting a near-zero remnant polarization (P\u003csub\u003er\u003c/sub\u003e). This \"slimming\" of the P-E hysteresis loop is essential for maximizing the W\u003csub\u003erec\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eBNT material is a conventional lead-free ferroelectric material and one of the most promising energy storage technologies, due to it crystallizes in the rhombohedral symmetry (R, space group: R\u003cb\u003e3\u003c/b\u003ec) with significant anti-phase octahedral rotation and considerable cation displacements along the [111]\u003csub\u003eC\u003c/sub\u003e polar axis [15]. Near T\u003csub\u003ed\u003c/sub\u003e (about 200\u0026deg;C), the tetragonal distortion (T, space group: P4bm) appears, and it subsequently predominates close to T\u003csub\u003em\u003c/sub\u003e (around 320\u0026deg;C). An ideal cubic perovskite structure is seen when the temperature is raised over 540\u0026deg;C. R phase and T phase octahedral tilting are denoted by a\u003csup\u003e\u0026minus;\u003c/sup\u003ea\u003csup\u003e\u0026minus;\u003c/sup\u003ea\u003csup\u003e\u0026minus;\u003c/sup\u003e and a\u003csup\u003e0\u003c/sup\u003ea\u003csup\u003e0\u003c/sup\u003ec\u003csup\u003e+\u003c/sup\u003e, respectively. Therefore, it is proposed that a substantial polarization in BNT (about 43 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e) results from strong hybridization between the Bi\u003csup\u003e3+\u003c/sup\u003e 6s and O\u003csup\u003e2\u0026minus;\u003c/sup\u003e 2p orbitals [16]. Second, a change in the A-site ionic radius or valence bond type results in more local structural disorder and distortion, which is beneficial for generating high energy storage performances (ESP). However, Because of its high P\u003csub\u003er\u003c/sub\u003e, low breakdown electric field (E\u003csub\u003eb\u003c/sub\u003e), and strong nonlinear polarization response (early saturation polarization), pure BNT cannot be employed directly for energy storage. As previously studies, considerable major improvements have been made in improving the energy storage capacity of BNT-based ceramics; however, further work is still required to achieve ultrahigh W\u003csub\u003erec\u003c/sub\u003e (\u0026ge;\u0026thinsp;8 J/cm\u003csup\u003e3\u003c/sup\u003e) and η (\u0026ge;\u0026thinsp;90%), satisfying the requirements of modern electronic devices' lightweight and miniaturization [17,18]. Additionally, strong temperature stability is essential for dielectrics. It is suggested that adding AFE materials such as NN to BNT ceramics and designing RAFEs can result a stable AFE behavior, large E\u003csub\u003eb\u003c/sub\u003e, increase the degree of relaxor phase, hence obtain better energy storage characteristic of BNT ceramics [19,20]. To design RAFEs and enhance the ESP for BNT, NN ceramic was considered, this material is a promising lead-free AFE material garnered a lot of attention for energy storage [21\u0026ndash;23]. When NN is introduced into BNT, it can promote a transition from a strong ferroelectric state towards a RFE or even an AFE-like behavior, which is very desirable for energy storage applications [24]. For example, studies have shown that incorporating NN into BNT-based ceramics can effectively reduce P\u003csub\u003er\u003c/sub\u003e while maintaining a high maximum polarization (P\u003csub\u003emax\u003c/sub\u003e), thus maximizing the W\u003csub\u003erec\u003c/sub\u003e [25,26]. Furthermore, the introduction of NaNbO\u003csub\u003e3\u003c/sub\u003e can also significantly enhance the BDS of the BNT ceramic. This is often attributed to several factors, including grain refinement and the development of a more compact microstructure, which act as barriers to electrical breakdown [27]. The presence of NN can also create local random fields and induce structural disorder, suppressing large ferroelectric domains and promoting the formation of polar nano-regions (PNRs). These PNRs contribute to a more diffuse phase transition and can further improve the linearity of the P-E loop, leading to higher W\u003csub\u003erec\u003c/sub\u003e [28]. For instance, He Qi, Ruzhong Zuo, et al examined how the 0.24BNT additive affected the energy storage capacity of 0.76 NN, obtaining W\u003csub\u003erec\u003c/sub\u003e value of 12 J/cm\u003csup\u003e3\u003c/sup\u003e at E\u003csub\u003eb\u003c/sub\u003e =700kV/cm, however the system has a low η (69%) [27].\u003c/p\u003e \u003cp\u003eTo further enhance energy density and efficiency, recent research has focused on enhancing these properties through compositional tuning and microstructure engineering, such as the introduction of glass phases or secondary additives. These modifications disrupt the coupling between dipoles, intensifying the relaxor behavior and effectively increasing DBS [29]. Furthermore, the dynamic response of PNRs in these materials enables them to operate efficiently over a wide range of temperatures and frequencies, making them indispensable for modern electronic devices and electric vehicle power modules. Consequently, understanding the transition from ferroelectric to relaxor states is fundamental to achieving the synergistic balance of high W\u003csub\u003erec\u003c/sub\u003e and superior discharge η required for contemporary energy storage technologies. BBCZT as a glass phase was incorporated into NN-NBT to improve antiferro-distortion and relaxor character BNT- NN -2.5% glass. Actually, breakdown field strengths more than 300 kV/cm are the primary determinant of large energy storage densities. It has been stated that glasses when add to ferroelectric ceramics have apparently been enhanced to enable their lowered sintering temperature and influence on the grain size and band gap [30,31], in addition to, a lot of studies have reported that addition of glass can increase their DBS, hence enhance ESP [32,33].\u003c/p\u003e \u003cp\u003eThe motivation of BBCZT glass into BNT material was driven by three considerations;\u003c/p\u003e\n\u003ch3\u003e1- Its low tolerance factor makes ferroelectricity more enhanced.\u003c/h3\u003e\n\u003cp\u003e2Its large to electronegativity contrast and poor polarizability between Ca\u003csup\u003e2+\u003c/sup\u003e and Na\u003csup\u003e+\u003c/sup\u003e/Bi\u003csup\u003e3+\u003c/sup\u003e disturb the long- range order of polarization.\u003c/p\u003e \u003cp\u003e3- The incorporation of BBCZT glass can enhance the E\u003csub\u003eb\u003c/sub\u003e by broad the band gap and optimizing the grain size for the solid solution of BNT-NN ceramic. Where, both internal and exterior ceramic material characteristics, such as the relative dielectric constant (ɛ\u003csub\u003er\u003c/sub\u003e), band gap, grain size (G), sample size, suppression of the interfacial polarization, and test conditions, affect the E\u003csub\u003eb\u003c/sub\u003e of the dielectrics by the following relationships: E\u003csub\u003eb\u003c/sub\u003e α d\u003csup\u003e\u0026minus;\u0026thinsp;0.5\u003c/sup\u003e G\u003csup\u003e\u0026minus;\u0026thinsp;a\u003c/sup\u003e ɛ\u003csup\u003e\u0026minus;0.5\u003c/sup\u003e [34,35]. Herein, we suggest using a synergistic approach (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e(b)) to get a fully optimized W\u003csub\u003erec\u003c/sub\u003e and η in BNT-NN-based ceramics by optimization of chemical composition, existence of PNRs, grain size refinement, suppression of the\u003c/p\u003e \u003cp\u003eInterfacial polarization, and the 2p orbitals of O can hybridize with the lone pair electronic 6s\u003csub\u003e2\u003c/sub\u003e structure in Bi, producing significant saturation polarization in ceramics based on BNT.\u003c/p\u003e \u003cp\u003eBased on this strategy, we demonstrate remarkable enhancements in the W\u003csub\u003erec\u003c/sub\u003e and E\u003csub\u003eb\u003c/sub\u003e for the lead-free ceramics of BNT-NN by incorporation of 2.5% glass. As a result, BNT- NN -2.5% glass ceramic expected to improve the stored energy density by increase the breakdown strength, and maintains a high efficiency. Moreover, excellent temperature and frequency stabilities are expected to be achieved.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Material and methods","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Preparation of BNT and NN ceramic by solid-state reaction method\u003c/h2\u003e \u003cp\u003eInitially, two distinct compositions of BNT and 0.25BNT- 0.75NN were created using a solid solution technique. High purity of Bi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (99.0%), Na\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e (99.8%), Nb\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e (99.5%) and TiO\u003csub\u003e2\u003c/sub\u003e (nanoparticle) as raw materials. Powders were weighed in stoichiometric amounts in accordance with a compositional formula. Powders were measured using a compositional formula and weighed in stoichiometric amounts. The mixture was ball milled for 24 hours in a plastic container using absolute ethyl alcohol as a liquid medium. After drying, the powders were calcined for two hours at 850\u0026deg;C. After that, the calcined powders were crushed into pellets that were about 10 mm in diameter and 1 mm thick after being granulated with 10% polyvinyl alcohol (PVA). The ceramics were sintered for two hours at 1130\u0026deg;C in an alumina crucible following the burning of the PVA.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Preparation of BBCZT glass by melt quenching method and BNT-NN-2.5% BBCZT\u003c/h2\u003e \u003cp\u003eIn the second batch, the glass phase was synthesized. The chemical formula BBCZT was used to weight each of them., which included BaCO\u003csub\u003e3\u003c/sub\u003e, CaCO\u003csub\u003e3\u003c/sub\u003e, BH\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, ZrO\u003csub\u003e2\u003c/sub\u003e, and TiO\u003csub\u003e2\u003c/sub\u003e. The conventional melt quenching method was used to create the matching glass phase. In order to create the glass phase, the BBCZT calcined powder was ground into agate mortar, placed in platinum crucibles, and heated in an electric furnace to 1450\u0026deg;C for one hour while the crucibles were constantly stirred to eliminate air bubbles and produce a uniform molten solution. the solution was quenched between two slabs of stainless steel. After that, the molten solution was allowed to cool in air at room temperature. Then The BBCZT glass was ground by agate mortar to obtain the fine powder. After weighing the calcined BNT-NN and BBCZT glass powders using the formula (0.975(BNT-NN)\u0026thinsp;\u0026minus;\u0026thinsp;0.025 BBCZT), they were combined by ball milling in ethanol with zirconia balls for five hours to create a uniform powder, which was then dried and sieved. The dried powder was combined with 5 weight percent polyvinyl alcohols (PVA) as a binder and compressed using a steel die to create pellets that were 10 mm in diameter and around 1 mm thick. this composition was sintered at a 1120 C, where the glass phase reacts as a sintering aid for decreasing the sintering temperature.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Characterizations measurements\u003c/h2\u003e \u003cp\u003ePhase composition was determined by X-ray diffraction (XRD) using a PANalytical X'Pert diffractometer with n (XRD with 0.15 nm of CuKα). The sintered ceramic's morphology was examined using a scanning electron microscope (SEM) (JEOL JSM-840A). The ceramics were polished and silver electrodes were placed on both sides of them to measure their electrical properties. By using an LCR meter (TH2826 LCR Meter 20Hz-5MHz), the temperature dependency of ε\u003csub\u003er\u003c/sub\u003e and loss (tan δ) were measured at four various frequencies in the 1 kHz\u0026ndash;1000 kHz range. In order to assess the energy density properties of manufactured samples, P-E hysteresis loops including bi-polar, mono-polar in addition to piezoelectric were obtained using (RADIANT Precision Premium II Multiferroic Ferroelectric Test System 10kV HVI-SC Model 609B) at various temperatures and electric field intensities.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Crystallization and morphology properties\u003c/h2\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e (a) shows the XRD pattern of BNT, BNT-NN, and BNT-NN-2.5% glass ceramics at ambient temperature. It can be observed that all of the compositions under examination have formed a suitable single phase perovskite structure with no any obvious detection of secondary phases under the detection limit of XRD, suggesting that NN and the glass phases were successfully interacted into BNT lattices during the sintering process resulting in a single-structure solid solution. XRD of as-quenched glass at room temperature is displayed in the inset of Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. It shows that there isn't a peak, confirming that glass is amorphous. For additional crystal structure analysis, the change of the (200) in the 2θ range of 45\u0026thinsp;~\u0026thinsp;48\u0026deg; expanded diffraction peaks were carefully shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b). The patterns revealed that, the peaks moved towards the higher angles compared to pure BNT, indicating a decrease in the lattice volume which might be ascribed to the lower ionic radius of NN. This causes the lattice's volume cell to shrink [36]. Additionally, the enlarging patterns display hump and slight splitting diffraction peaks suggests a typical rhombohedral (R-phase, space group R\u003csub\u003e3c\u003c/sub\u003e) phase for the pure BNT ceramic (x\u0026thinsp;=\u0026thinsp;0). The substitution of NN for BNT makes (200) peak more split and displays a small shoulder at the lower-degree side of (200) diffraction lines, suggesting the phase transition from rhombohedral to rhombohedral- orthorhombic coexistence phases in other samples (R\u0026amp;O phases, with space group R\u003csub\u003e3C\u003c/sub\u003e and Pbma, respectively. An increase in splitting peak of O-phase at 2θ\u0026thinsp;=\u0026thinsp;46 in BNT-NN-2.5% glass show greater compositional fluctuation and cation disorder at room temperature, which may be advantageous for increasing the degree of relaxor phase by adding glass [37].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe microstructural homogeneity and properties of the sintered pellets were examined at the room temperature using a scanning electron microscope (SEM). Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e demonstrates the typical surface microstructure morphologies and the distribution of grains for each sintered ceramics. All samples revealed a very dense microstructure homogenous of grain size, while tiny pores exist among the grain boundaries of the BNT-NN ceramic, due to the high temperature of sintering.\u003c/p\u003e \u003cp\u003eThe presence of the glass phase entirely suppressed the pores, leading to improve the surface morphology. The grain size (G) distribution was determined by Image J software, it dropped from 2.05 \u0026micro;m for pure BNT to 1.63663 \u0026micro;m for BNT-NN and decreased to a sub-micrometer of 0.903\u0026micro;m by adding the glass phase. Furthermore, adding BBCZT glass caused the grain size to decrease because the substitution of different ionic radius may raise the lattice strain energy, which in turn may cause the grain boundary mobility to be disrupted [38]. Ceramics' small grain size helps to increase the breakdown strength via the relationship of E\u003csub\u003eb\u003c/sub\u003e α G\u003csup\u003e\u0026minus;α\u003c/sup\u003e, which raises the energy storage density [39].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Dielectric properties and AC-properties:\u003c/h2\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. (a,b,c) demonstrates the temperature dependence of the ε\u003csub\u003er\u003c/sub\u003e along with dielectric loss (tan δ) for the virgin sintered ceramic at four different frequencies (0.5, 1, 10, and 100 KHz) for BNT, BNT-NN, and BNT-NN-2.5% glass ceramic within the temperature range of (25-300\u003csup\u003eo\u003c/sup\u003e C). As can be seen, each sample exhibits distinct behavior from the others indicates the superior effect of adding of NN and the glass phase into dielectric characteristics of BNT ceramic. In pure BNT, two permittivity peaks were appeared, the first peak was known as the depolarization temperature (T\u003csub\u003ed\u003c/sub\u003e ~ 285\u003csup\u003e◦\u003c/sup\u003eC), at which the crossover of one ferroelectric phase to another with a various crystal structure can be observed, while the second peak is known as curie temperature (T\u003csub\u003ec\u003c/sub\u003e) is ascribed to the phase transition from the ferroelectric to the paraelectric occurred at ~\u0026thinsp;350\u003csup\u003e◦\u003c/sup\u003eC [40]. The observed significant dependence of permittivity values on applied frequency suggests the presence of a microscopic domain structure, large domain size, and LRO of ferroelectricity. In BNT-NN sample, the behavior was completely different, where no discernible phase transition could be seen in temperature range of 25 to 300\u003csup\u003eo\u003c/sup\u003e C, and the ε\u003csub\u003er\u003c/sub\u003e decreased as temperature increased. In BNT-NN-2.5% glass sample, a further decreasing in the permittivity and increasing thermal stability were happened, higher thermal stability was noted across a broad temperature range, and the permittivity is not affected by the frequency, can contribute to the existence of the nano-domain of the relaxor phase and the cation disorder effect resulting from adding the glass phase produced relaxor phase and break the LRO of ferroelectricity for BNT [41,42] a significant reduction in dielectric loss has been accomplished at BNT-NN-2.5% glass sample due to current cation vacancies in the A-site of the lattice caused by the substitution the monovalent Na\u003csup\u003e+\u0026thinsp;1\u003c/sup\u003e ion for the trivalent Bi\u003csup\u003e+\u0026thinsp;3\u003c/sup\u003e ions, which can result in the formation of a relaxor phase and slim hysteresis loop by pinching the remaining polarization. η can be improved by reduced dielectric loss. Because of the conduction process and inadequate electric insulation at high temperatures, values have been seen to slightly increase.\u003c/p\u003e \u003cp\u003eOne of the main factors that is directly connected to interfacial polarization and breakdown strength is the activation energy (Ea), which may be calculated using the Arrhenius equation as follows.\u003c/p\u003e \u003cp\u003e \u003cb\u003eδ\u003c/b\u003e \u003csub\u003e \u003cb\u003edc\u003c/b\u003e \u003c/sub\u003e\u0026thinsp;\u003cb\u003e=\u0026thinsp;δ\u003c/b\u003e\u003csub\u003e\u003cb\u003eo\u003c/b\u003e\u003c/sub\u003e \u003cb\u003ee\u003c/b\u003e \u003csup\u003e\u003cb\u003e\u0026ndash;Ea /KBT\u003c/b\u003e\u003c/sup\u003e \u003cb\u003e(4)\u003c/b\u003e\u003c/p\u003e \u003cp\u003eWhere, δo refers to the pre-exponential factor, T represents the kelvin temperature, and K\u003csub\u003eB\u003c/sub\u003e refers to Boltzmann constant. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(d, e) illustrated the variation of Lnδ with T and the activation energy values for the current ceramics, the results verified that Ea increases as adding NN and the glass phase, with a maximum value of 0.075 in BNT-NN-2.5% glass sample.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eImpedance spectroscopy is a technique used to investigating the electrical characteristics of materials. The interface polarization can be suppressed by increasing the resistance of grain (R\u003csub\u003eg\u003c/sub\u003e) until the difference between R\u003csub\u003eg\u003c/sub\u003e and resistance of grain boundary (R\u003csub\u003egb\u003c/sub\u003e) is mismatched, Thus, in addition to the real impedance Z' and imagined impedance Z\u0026Prime; we examined the imagined part of modules M analysis examined. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e (a,b,c) shows the data of Neqyest plot of impedance (Zʹ \u0026amp; Z\u0026Prime;) of the present ceramics in the frequency range (20Hz -5MHz with 20000Hz as frequency step) at various temperatures (550 and 650 \u003csup\u003e◦\u003c/sup\u003eC). As can be seen, all sintered ceramics produced semicircles in the cole-cole plots, indicating that the graphs are influenced by both the grain and the grain boundary. Additionally, the BNT-NN-2.5% glass sample has the biggest radius of the impedance spectrum arc, indicating the highest R\u003csub\u003eg\u003c/sub\u003e. It is possible to interpret the increased R\u003csub\u003eg\u003c/sub\u003e that suppresses the oxygen vacancies effect lead to enhancing E\u003csub\u003eb\u003c/sub\u003e and ESP.\u003c/p\u003e \u003cp\u003eFor studying the suppression of interfacial polarization and determining how the values of R\u003csub\u003eg\u003c/sub\u003e and R\u003csub\u003egb\u003c/sub\u003e changed. The comparing the Z''\u0026minus; f and M\"\u0026minus; f spectra of the samples recorded at 650 \u003csup\u003e◦\u003c/sup\u003eC was displayed in Fig .5 (d,e,f) to unequivocally support this claim, where the value of R\u003csub\u003eg\u003c/sub\u003e is gave by the variation of Z''\u0026minus; f, while R\u003csub\u003egb\u003c/sub\u003e is reflected by M\"\u0026minus; f variation [43]. In all samples the present Z\u0026Prime; and M\u0026Prime; peaks is observed, indicate the present of R\u003csub\u003eg\u003c/sub\u003e and R\u003csub\u003egb\u003c/sub\u003e effect. When peaks overlapping between Z'' and M'' decrease, the interfacial polarization of ceramics is reduced where R\u003csub\u003eg\u003c/sub\u003e and R\u003csub\u003egb\u003c/sub\u003e values would be near one another. According to a number of earlier researches, the interfacial polarization can be determined by the value of frequency gab (Δf) or the difference between the R\u003csub\u003eg\u003c/sub\u003e and R\u003csub\u003egb\u003c/sub\u003e values [40]. The BNT-NN-2.5% glass ceramic has the lowest Δf, indicating the grain's elevation resistance and, consequently, a smaller R\u003csub\u003eg\u003c/sub\u003e-R\u003csub\u003egb\u003c/sub\u003e difference at this sample. Stated differently, interfacial polarization and oxygen vacancy effects can be suppressed by high grain resistance. The current findings clearly show that high-entropy materials with high grain resistance can simultaneously improve ESP, synergistic DBS, and the interfacial polarization effect.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e\u003cem\u003e3.3. Ferroelectric and piezoelectric properties\u003c/em\u003e:\u003c/h2\u003e \u003cp\u003eThe bipolar P-E and I-E loops of BNT, BNT-NN, and BNT-NN-2.5% glass sintered ceramics at RT, applied electric field (E\u0026thinsp;=\u0026thinsp;50 kV/cm), and 10Hz are displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. A strong normal ferroelectric P-E loop was seen in pure BNT, with a large value of P\u003csub\u003emax\u003c/sub\u003e =37\u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e and P\u003csub\u003er\u003c/sub\u003e =32\u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e. This is due to the perovskite's rhombohedral structure [42]. High P\u003csub\u003er\u003c/sub\u003e is attributed to a high degree of domain wall displacement caused by external influences, whereas high P\u003csub\u003emax\u003c/sub\u003e was attributed to high hybridization between Bi\u003csup\u003e3+\u003c/sup\u003e 6P and O\u003csub\u003e2\u003c/sub\u003e\u0026minus; 2P.. In NBT-NN ceramic, the pinched double-like \u003cem\u003eP-E\u003c/em\u003e loops is observed and both P\u003csub\u003emax\u003c/sub\u003e and P\u003csub\u003er\u003c/sub\u003e decrease with adding NN phase, where the values of P\u003csub\u003emax\u003c/sub\u003e decreased from 37 to 7.52 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e. While P\u003csub\u003er\u003c/sub\u003e drops dramatically from approximately 32 to 0.65 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e reveal the AFE characteristic of this ceramics [44]. By adding the glass phase, the shape of \u003cem\u003eP\u003c/em\u003e\u0026ndash;\u003cem\u003eE\u003c/em\u003e loops tend to be slimmer with P\u003csub\u003emax\u003c/sub\u003e 7 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e and a decreasing can be observed in P\u003csub\u003er\u003c/sub\u003e to 0.38 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e, indicating the improvement of relaxation behavior. As shown, despite a drop of P\u003csub\u003emax\u003c/sub\u003e, the attenuation of about 90% in P\u003csub\u003er\u003c/sub\u003e eventually dominates the energy-storage performances of NBT-NN-2.5% glass ceramic because of the resulting slim P-E loop with greatly reduced electric hysteresis loss. Meanwhile, P\u003csub\u003emax\u003c/sub\u003e and P\u003csub\u003er\u003c/sub\u003e of BNT-NN and BNT-NN-2.5% glass ceramics would decrease as a result of the local random field created due to the variable valence and ionic radius, which the long-range dipole alignment would be broken into short-range polar clusters [45]. The relaxor phase can also be confirmed by the current loop, which shows a definite increase in current values as E increases and reaches its maximum values (E\u003csub\u003emax\u003c/sub\u003e). At BNT, there was just one sharp current peak; this behavior confirms the presence of the ferroelectric phase. However, a weak current peak with a rectangular I-E loop form was seen in the BNT-NN sample, which was attributed to a phase change from ferroelectric to relaxor due to the domain switching effect. While, the current peak at BNT-NN-2.5% glass sample dropped and was entirely disappeared with the rectangular I-E loop shape, indicating an enhanced relaxor degree.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cdiv id=\"Sec11\" class=\"Section3\"\u003e \u003ch2\u003e3.4.2. Energy Storage Properties\u003c/h2\u003e \u003cp\u003eThe energy storage performance of the BNT-NN, and BNT-NN-2.5% glass sintered ceramics dependent electric fields (50-150kV/cm) was systematically investigated through the analysis of the unipolar P-E loops illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(a,b) respectively. The outstanding energy storage characterization of these compositions can be understood as follow: In the BNT-NN sample (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e (a)), the curves exhibit a relatively wider curve with a noticeable P\u003csub\u003er\u003c/sub\u003e =1.14 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e. However, as observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e (b), the 2.5% glass-modified ceramic exhibits a slender and delayed ferroelectric hysteresis loop, which is a characteristic feature of RFE. At an applied electric field of 150 kV/cm, the ceramic reaches a P\u003csub\u003emax\u003c/sub\u003e of approximately 19.89 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e, while maintaining a remarkably low P\u003csub\u003er\u003c/sub\u003e of nearly 0.5 \u0026micro;C/cm\u003csup\u003e2\u003c/sup\u003e. The reduction in P\u003csub\u003er\u003c/sub\u003e and the maintenance of a high P\u003csub\u003emax\u003c/sub\u003e in the glass-modified sample lead to a substantial enhancement in W\u003csub\u003erec\u003c/sub\u003e. This \"slimming\" of the loop is a hallmark of improved relaxor ferroelectric behavior, where the LRO of ferroelectric is disrupted into PNRs, allowing for rapid polarization switching with minimal energy loss [46]. Based on the numerical integration of the discharge curve, the calculated W\u003csub\u003erec\u003c/sub\u003e is approximately 1.45 J/cm\u003csup\u003e3\u003c/sup\u003e at 150 kV/cm. The narrow gap between the charging and discharging curves indicates minimal W\u003csub\u003eloss\u003c/sub\u003e, resulting in an ultrahigh ɳ = 96.4% is higher than that of unmodified BNT and BNT\u0026ndash;NN ceramic. This dramatic improvement is primarily ascribed to the \"pinning effect\" and the disruption of the LRO of ferroelectric caused by the NN substitution and the glass phase [47]. Consequently, this improvement can be attributed to the optimized interfacial polarization that occurs at the ceramic-glass grain boundaries. As previously noted, the superior interfacial polarization in sample (b) allows for more effective charge trapping and distribution, which prevents local field concentrations and suppresses leakage currents [29]. In the other hand, the liquid-phase sintering aided by the glass additive promotes a dense, pore-free microstructure and glass additive acts as an insulating barrier resulting in a much denser microstructure that can effectively increases the E\u003csub\u003eb\u003c/sub\u003e which, allowing the material to withstand higher E compared to the pure ceramic [48,49]. Moreover, the grain size is reduced which caused by incorporating the glass phase as a sintering aid result in optimizing the DBS, thus induce an ultrahigh W\u003csub\u003erec\u003c/sub\u003e, where the correlation between the grain size and E\u003csub\u003eb\u003c/sub\u003e is explained by the following equation [41]:\u003c/p\u003e \u003cp\u003e \u003cb\u003eE\u003c/b\u003e \u003csub\u003e \u003cb\u003eb\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eα G\u003c/b\u003e\u003csup\u003e\u003cb\u003e\u0026minus;\u0026thinsp;a\u003c/b\u003e\u003c/sup\u003e \u003cb\u003e(5)\u003c/b\u003e\u003c/p\u003e \u003cp\u003eWhere G is the grain size and (a) is constant between 0.2 and 0.4. Also, reducing the grain size leads to raise the density of grain boundary which works as the barrier areas between the grains with a high resistivity leading to enhancing the insulation characteristics and decrease the pores which are beneficial factors in increasing E\u003csub\u003eb\u003c/sub\u003e. Furthermore, the addition of the glass phase plays an essential role in improvement of relaxation property. By introducing structural disorder into the perovskite lattice, the glass phase promotes a faster polarization response and recovery during the field-removal stage, which is essential for high-power pulse applications [14]. This explains why the area inside the hysteresis loop representing the energy loss is drastically reduced in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e (b) compared to the pure sample in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e (a) resulting in a dramatic increase in ɳ, where, the high efficiency is critical for preventing thermal runaway in high-power electronic applications. Ultimately, the integration of 2.5% glass proves to be a decisive factor in achieving a superior balance between moderate W\u003csub\u003erec\u003c/sub\u003e and exceptionally high ɳ, making it an ideal candidate for high-stability pulse power capacitors.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe thermal reliability of the BNT-NN-2.5% glass sintered ceramic was investigated through unipolar hysteresis measurements across a temperature gradient from from RT to 150\u0026deg;C at 10Hz at field of 100 kV/cm is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e (a), and the conducted of W\u003csub\u003erec\u003c/sub\u003e and ƞ were shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e.(b). It's noteworthy that The material maintains a series of exceptionally slender hysteresis loops, exhibiting a high degree of temperature independence. Quantitatively, P\u003csub\u003emax\u003c/sub\u003e showed remarkable consistency, decreasing only slightly from only from 13.6 \u0026#120583;C/cm\u003csup\u003e2\u003c/sup\u003e to at 25\u0026deg;C to 12.9 \u0026#120583;C/cm\u003csup\u003e2\u003c/sup\u003e at 150\u0026deg;C. This decreasing in W\u003csub\u003erec\u003c/sub\u003e may be related to decreasing the ε\u003csub\u003er\u003c/sub\u003e value. The calculated energy storage parameters further confirm this robustness. ƞ also decreased slightly by increasing the applied temperature. This superior stability is primarily attributed to the relaxor phase characterized by a nano-domain structure PNRs. This level of stability is superior to many reported BNT-based systems and highlights the effectiveness of glass-phase engineering in developing high-performance, thermally reliable dielectric capacitors for harsh environments.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"CONCLUSION","content":"\u003cp\u003eIn summary, this work successfully demonstrates a robust strategy to improve the performance of energy storage of 0.25(Na\u003csub\u003e0.5\u003c/sub\u003eBi\u003csub\u003e0.5\u003c/sub\u003e)TiO\u003csub\u003e3\u003c/sub\u003e-0.75NaNbO\u003csub\u003e3\u003c/sub\u003e(0.25BNT-0.75NN) based through the incorporation of a 0.025 (Ba\u003csub\u003e0.8\u003c/sub\u003eB\u003csub\u003e0.1\u003c/sub\u003eCa\u003csub\u003e0.1\u003c/sub\u003e)(Zr\u003csub\u003e0.1\u003c/sub\u003eTi\u003csub\u003e0.9\u003c/sub\u003e)O\u003csub\u003e3\u003c/sub\u003e (2.5% glass) based glass phase. The addition of the glass phase played a pivotal role in disrupting the long-range ferroelectric order (LRO) and promoting a higher degree of relaxor behavior, which is essential for achieving high efficiency (ɳ). One of the most significant findings is the profound impact of the glass phase on the dielectric breakdown strength (DBS) and charge transport mechanisms. By increasing the grain boundary resistance, the interfacial polarization (Maxwell-Wagner-Sillars effect) was effectively suppressed. This was quantitatively confirmed by the substantial rise in activation energy (Ea) from 0.033 eV to 0.075 eV, indicating a higher barrier for ionic and space charge migration. As a result of these synergistic effects, the glass-modified ceramic achieved a remarkable recoverable energy density (W\u003csub\u003erec\u003c/sub\u003e) of 1.45 J/cm\u003csup\u003e3\u003c/sup\u003e and a superior ɳ of 96.4% at 150 kV/cm. Furthermore, the material exhibited exceptional thermal reliability, with a small fluctuations in energy storage parameters up to 150\u0026deg;C. These findings underscore the potential of glass-ceramic composites as a promising materials for high-stability, high-efficiency pulse power capacitors in advanced electronic systems.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eFunding:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research received no external funding.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe datasets used and/or analysed during the current study available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eL. Yang, X. Kong, F. Li, H. Hao, Z. Cheng, H. Liu, J. Li, S. Perovskite lead-free dielectrics for energy storage applications. \u0026rlm;Prog. Mater Sci. 102 (2019) 72\u0026ndash;108.\u003c/li\u003e\n \u003cli\u003eSun, Z., Wang, Z., Tian, Y., Wang, G., Wang, W., Yang, M., ... \u0026amp; Pu, Y. Progress, outlook, and challenges in lead free energy storage ferroelectrics. \u003cem\u003eAdv Elect Mater\u003c/em\u003e, \u003cem\u003e6\u003c/em\u003e(1), 1900698.\u0026rlm;\u003c/li\u003e\n \u003cli\u003eJiang, Jie, et al. \u0026quot;Ultrahigh energy storage density in lead-free relaxor antiferroelectric ceramics via domain engineering.\u0026quot; \u003cem\u003eEnergy Storage Materials\u003c/em\u003e 43 (2021): 383-390.\u003c/li\u003e\n \u003cli\u003ePan, Yue, et al. \u0026quot;Enhanced energy storage properties of Bi (Ni\u003csub\u003e2/3\u003c/sub\u003eNb\u003csub\u003e1/6\u003c/sub\u003eTa\u003csub\u003e1/6\u003c/sub\u003e) O\u003csub\u003e3\u003c/sub\u003e\u0026ndash;NaNbO\u003csub\u003e3\u003c/sub\u003e solid solution lead-free ceramics.\u0026quot; \u003cem\u003eCeramics International\u003c/em\u003e 48.18 (2022): 26466-26475.\u003c/li\u003e\n \u003cli\u003eYan, Fei, et al. \u0026quot;Progress and outlook on lead-free ceramics for energy storage applications.\u0026quot; \u003cem\u003eNano Energy\u003c/em\u003e (2024): 109394.\u003c/li\u003e\n \u003cli\u003eang, Z., Du, H., Jin, L., \u0026amp; Poelman, D. (2021). High-performance lead-free bulk ceramics for electrical energy storage applications: design strategies and challenges. \u003cem\u003eJ. of Materials Chemistry A\u003c/em\u003e, \u003cem\u003e9\u003c/em\u003e(34), 18026-18085.\u0026rlm;\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Emerging antiferroelectric phases with fascinating dielectric, polarization and strain response in NaNbO\u003csub\u003e3\u003c/sub\u003e-(Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003e) TiO\u003csub\u003e3\u003c/sub\u003e lead-free binary system.\u0026quot; \u003cem\u003eActa Materialia\u003c/em\u003e 208 (2021): 116710..\u003c/li\u003e\n \u003cli\u003eJiang, Zehua, et al. \u0026quot;Enhanced breakdown strength and energy storage density of lead-free Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-based ceramic by reducing the oxygen vacancy concentration.\u0026quot; \u003cem\u003eChemical Engineering Journal\u003c/em\u003e 414 (2021): 128921..\u003c/li\u003e\n \u003cli\u003eHre\u0026scaron;čak, Jitka, et al. \u0026quot;Donor doping of K\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eNbO\u003csub\u003e3\u003c/sub\u003e ceramics with strontium and its implications to grain size, phase composition and crystal structure.\u0026quot; \u003cem\u003eJournal of the European Ceramic Society\u003c/em\u003e 37.5 (2017): 2073-2082..\u003c/li\u003e\n \u003cli\u003eDong, Xiaoyan, et al. \u0026quot;Effective strategy to realise excellent energy storage performances in lead-free barium titanate-based relaxor ferroelectric.\u0026quot; \u003cem\u003eCeramics International\u003c/em\u003e 47.5 (2021): 6077-6083.\u003c/li\u003e\n \u003cli\u003e] Y. Shen, L. Wu, J. Zhao, J. Liu, L. Tang, X. Chen, Z. Pan, Constructing novel binary Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-based composite ceramics for excellent energy storage performances via defect engineering, Chem. Eng. J. 439 (2022), 135762.\u003c/li\u003e\n \u003cli\u003eTian, Y., Jin, L., Zhang, H., Xu, Z., Wei, X., Politova, E. D., ... \u0026amp; Yan, H. (2016). High energy density in silver niobate ceramics. \u003cem\u003eJ. Mater. Chem. A\u0026nbsp;\u003c/em\u003e\u003cstrong\u003e2016\u003c/strong\u003e, \u003cem\u003e4\u003c/em\u003e, 17279.\u003c/li\u003e\n \u003cli\u003eYang, Letao, et al. \u0026quot;Perovskite lead-free dielectrics for energy storage applications.\u0026quot; \u003cem\u003eProgress in Materials Science\u003c/em\u003e 102 (2019): 72-108.\u003c/li\u003e\n \u003cli\u003eSu, Xiaopo, et al. \u0026quot;Large electrocaloric effect over a wide temperature span in lead-free bismuth sodium titanate-based relaxor ferroelectrics.\u0026quot; \u003cem\u003eJournal of Materiomics\u003c/em\u003e 9.2 (2023): 289-298.\u003c/li\u003e\n \u003cli\u003eHu, Qingyuan, et al. \u0026quot;Achieve ultrahigh energy storage performance in BaTiO3\u0026ndash;Bi (Mg1/2Ti1/2) O3 relaxor ferroelectric ceramics via nano-scale polarization mismatch and reconstruction.\u0026quot; \u003cem\u003eNano Energy\u003c/em\u003e 67 (2020): 104264.\u003c/li\u003e\n \u003cli\u003ei, X. Hou, J. Wang, H. Zeng, B. Shen, J. Zhai, Structure-design strategy of 0\u0026ndash;3 type (Bi0.32Sr0.42Na0.20)TiO3/MgO composite to boost energy storage density, efficiency and charge-discharge performance, J. Eur. Ceram. Soc. 39 (2019: (2889\u0026ndash;2898.\u003c/li\u003e\n \u003cli\u003eWang, Hua, et al. \u0026quot;Enhanced energy density and discharged efficiency of lead-free relaxor (1-x)[(Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003e)0.94Ba\u003csub\u003e0.06\u003c/sub\u003e]0.98La\u003csub\u003e0.02\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-xKNb\u003csub\u003e0.6\u003c/sub\u003eTa\u003csub\u003e0.4\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e ceramic capacitors.\u0026quot; \u003cem\u003eChemical Engineering Journal\u003c/em\u003e 394 (2020): 124879.\u003c/li\u003e\n \u003cli\u003eXi, Jiachen, et al. \u0026quot;Compromise boosted high capacitive energy storage in lead-free (Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003e) TiO\u003csub\u003e3\u003c/sub\u003e\u0026minus; based relaxor ferroelectrics by phase structure modulation and defect engineering.\u0026quot; \u003cem\u003eChemical Engineering Journal\u003c/em\u003e 502 (2024): 157986.\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Ultrahigh energy‐storage density in NaNbO\u003csub\u003e3\u003c/sub\u003e‐based lead‐free relaxor antiferroelectric ceramics with nanoscale domains.\u0026quot; \u003cem\u003eAdvanced Functional Materials\u003c/em\u003e 29.35 (2019): 1903877.\u003c/li\u003e\n \u003cli\u003eMeng, Xiangyu, et al. \u0026quot;Local structural origin of relaxor antiferroelectric behavior in NaNbO\u003csub\u003e3\u003c/sub\u003e-based ceramics.\u0026quot; \u003cem\u003eChemical Engineering Journal\u003c/em\u003e (2025): 163109.\u003c/li\u003e\n \u003cli\u003eShi, Ruike, et al. \u0026quot;A novel lead-free NaNbO\u003csub\u003e3\u003c/sub\u003e\u0026ndash;Bi (Zn\u003csub\u003e0.5\u003c/sub\u003eTi\u003csub\u003e0.5\u003c/sub\u003e)O\u003csub\u003e3\u003c/sub\u003e ceramics system for energy storage application with excellent stability.\u0026quot; \u003cem\u003eJournal of Alloys and Compounds\u003c/em\u003e 815 (2020): 152356.\u003c/li\u003e\n \u003cli\u003eXu, Mingzhao, et al. \u0026quot;Optimize energy storage performance of NaNbO\u003csub\u003e3\u003c/sub\u003e ceramics by multivariable control strategy.\u0026quot; \u003cem\u003eJournal of the European Ceramic Society\u003c/em\u003e 44.11 (2024): 6460-6469.\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Large (anti) Ferro distortive NaNbO\u003csub\u003e3\u003c/sub\u003e-based lead-free relaxors: Polar nanoregions embedded in ordered oxygen octahedral tilt matrix.\u0026quot; \u003cem\u003eMaterials Today\u003c/em\u003e 60 (2022): 91-97.\u003c/li\u003e\n \u003cli\u003eWang, Hua, et al. \u0026quot;Achieving ultrahigh energy storage density and efficiency in 0.90 NaNbO\u003csub\u003e3\u003c/sub\u003e\u0026ndash;0.10 BaTiO\u003csub\u003e3\u003c/sub\u003e ceramics via a composition modification strategy.\u0026quot; \u003cem\u003eDalton Transactions\u003c/em\u003e 51.26 (2022): 10085-10094.\u003c/li\u003e\n \u003cli\u003eWei, Kun, et al. \u0026quot;Achieving ultrahigh energy storage performance for NaNbO\u003csub\u003e3\u003c/sub\u003e-based lead-free antiferroelectric ceramics via the coupling of the stable antiferroelectric R phase and nanodomain engineering.\u0026quot; \u003cem\u003eACS Applied Materials \u0026amp; Interfaces\u003c/em\u003e 15.41 (2023): 48354-48364.\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Emerging antiferroelectric phases with fascinating dielectric, polarization and strain response in NaNbO\u003csub\u003e3\u003c/sub\u003e-(Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003e)TiO\u003csub\u003e3\u003c/sub\u003e lead-free binary system.\u0026quot; \u003cem\u003eActa Materialia\u003c/em\u003e 208 (2021): 116710.\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Ultrahigh energy‐storage density in NaNbO\u003csub\u003e3\u003c/sub\u003e‐based lead‐free relaxor antiferroelectric ceramics with nanoscale domains.\u0026quot; \u003cem\u003eAdvanced Functional Materials\u003c/em\u003e 29.35 (2019): 1903877.\u003c/li\u003e\n \u003cli\u003eHui, Jiejie, et al. \u0026quot;Improving energy storage properties of NN-NBT ceramics through compositional modification.\u0026quot; \u003cem\u003eJournal of Alloys and Compounds\u003c/em\u003e 989 (2024): 174276.\u003c/li\u003e\n \u003cli\u003eLu, Xiang, et al. \u0026quot;Effect of analogue nucleating agent on the interface polarization and energy-storage performance of NaNbO\u003csub\u003e3\u003c/sub\u003e-based glass-ceramics.\u0026quot; \u003cem\u003eCeramics International\u003c/em\u003e 50.21 (2024): 44503-44510.\u003c/li\u003e\n \u003cli\u003ePatela, Satyanarayan, et al. \u0026quot;Enhanced energy storage performance of glass added 0.715 Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-0.065 BaTiO3-0.22 SrTiO\u003csub\u003e3\u003c/sub\u003e ferroelectric ceramics.\u0026quot; (2015).\u003c/li\u003e\n \u003cli\u003eLi, Y. Q., et al. \u0026quot;The Effect of ZnO\u0026ndash;B\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u0026ndash;SiO\u003csub\u003e2\u003c/sub\u003e Additive on Sintering and Dielectric Properties of Ba\u003csub\u003e0. 3\u003c/sub\u003eSr\u003csub\u003e0. 7\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e Ceramics.\u0026quot; \u003cem\u003eFerroelectrics\u003c/em\u003e 403.1 (2010): 45-53.\u003c/li\u003e\n \u003cli\u003eWang, Xiangrong, et al. \u0026quot;Glass additive in barium titanate ceramics and its influence on electrical breakdown strength in relation with energy storage properties.\u0026quot; \u003cem\u003eJournal of the European Ceramic Society\u003c/em\u003e 32.3 (2012): 559-567.\u003c/li\u003e\n \u003cli\u003eOuaha, Ahmed, et al. \u0026quot;Exploring structural compatibility and energy storage performances enhancement in lead-free BNT dielectric ceramics with NBTP glass integration.\u0026quot; \u003cem\u003eCeramics International\u003c/em\u003e 50.13 (2024): 24648-24661.\u003c/li\u003e\n \u003cli\u003eSong, Zhe, et al. \u0026quot;Effect of grain size on the energy storage properties of (Ba\u003csub\u003e0.4\u003c/sub\u003eSr\u003csub\u003e0.6\u003c/sub\u003e) TiO\u003csub\u003e3\u003c/sub\u003e paraelectric ceramics.\u0026quot; \u003cem\u003eJournal of the European Ceramic Society\u003c/em\u003e 34.5 (2014): 1209-1217.\u003c/li\u003e\n \u003cli\u003eYang, Bingbing, et al. \u0026quot;High-entropy enhanced capacitive energy storage.\u0026quot; \u003cem\u003eNature Materials\u003c/em\u003e 21.9 (2022): 1074-1080.\u003c/li\u003e\n \u003cli\u003eShannon, Robert D. \u0026quot;Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides.\u0026quot; \u003cem\u003eFoundations of Crystallography\u003c/em\u003e 32.5 (1976): 751-767.\u003c/li\u003e\n \u003cli\u003ePatel, Satyanarayan, et al. \u0026quot;Enhanced energy storage performance of glass added 0.715 Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-0.065 BaTiO\u003csub\u003e3\u003c/sub\u003e-0.22 SrTiO\u003csub\u003e3\u003c/sub\u003e ferroelectric ceramics.\u0026quot; \u003cem\u003eJournal of Asian Ceramic Societies\u003c/em\u003e 3.4 (2015): 383-389.\u003c/li\u003e\n \u003cli\u003eZhao, Lei, et al. \u0026quot;Lead-free AgNbO\u003csub\u003e3\u003c/sub\u003e anti-ferroelectric ceramics with an enhanced energy storage performance using MnO\u003csub\u003e2\u003c/sub\u003e modification.\u0026quot; \u003cem\u003eJournal of Materials Chemistry C\u003c/em\u003e 4.36 (2016): 8380-8384.\u003c/li\u003e\n \u003cli\u003eSun, Zixiong, et al. \u0026quot;Ultrahigh Energy Storage Performance of Lead-Free Oxide Multilayer Film Capacitors via Interface Engineering.\u0026quot; \u003cem\u003eAdvanced Materials (Deerfield Beach, Fla.)\u003c/em\u003e 29.5 (2016).\u003c/li\u003e\n \u003cli\u003eKamal, Amira A, et al. \u0026quot;Enhancement of entropy induced suppression of interfacial polarization to bolster breakdown strength in (Na\u003csub\u003e0.5\u003c/sub\u003eBi\u003csub\u003e0.5\u003c/sub\u003e) TiO\u003csub\u003e3\u003c/sub\u003e-Based ceramics.\u0026quot; \u003cem\u003eCeramics International\u003c/em\u003e (2025).\u003c/li\u003e\n \u003cli\u003ePatel, Satyanarayan, et al. \u0026quot;Enhanced energy storage performance of glass added 0.715 Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-0.065 BaTiO\u003csub\u003e3\u003c/sub\u003e-0.22 SrTiO\u003csub\u003e3\u003c/sub\u003e ferroelectric ceramics.\u0026quot; \u003cem\u003eJournal of Asian Ceramic Societies\u003c/em\u003e 3.4 (2015): 383-389.\u003c/li\u003e\n \u003cli\u003eLiu, Gang, et al. \u0026quot;Enhanced electrical properties and energy storage performances of NBT-ST Pb-free ceramics through glass modification.\u0026quot; \u003cem\u003eJournal of Alloys and Compounds\u003c/em\u003e 836 (2020): 154961.\u003c/li\u003e\n \u003cli\u003eBabeer, Afaf M., et al. \u0026quot;A-site disorder induced ferroelectric to relaxor phase transition of Na(Nb\u003csub\u003e0.75\u003c/sub\u003eTi\u003csub\u003e0.25\u003c/sub\u003e) O\u003csub\u003e3\u003c/sub\u003e ceramics by Bi\u003csup\u003e3+\u003c/sup\u003e for ultra-high energy storage properties.\u0026quot; \u003cem\u003eMaterialia\u003c/em\u003e 33 (2024): 102009.\u003c/li\u003e\n \u003cli\u003eWang, Changyuan, et al. \u0026quot;Equimolar high-entropy for excellent energy storage performance in Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003eTiO\u003csub\u003e3\u003c/sub\u003e-based ceramics.\u0026quot; \u003cem\u003eEnergy Storage Materials\u003c/em\u003e 70 (2024): 103534.\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Ultrahigh energy‐storage density in NaNbO\u003csub\u003e3\u003c/sub\u003e‐based lead‐free relaxor antiferroelectric ceramics with nanoscale domains.\u0026quot; \u003cem\u003eAdvanced Functional Materials\u003c/em\u003e 29.35 (2019): 1903877.\u003c/li\u003e\n \u003cli\u003eQi, He, et al. \u0026quot;Emerging antiferroelectric phases with fascinating dielectric, polarization and strain response in NaNbO\u003csub\u003e3\u003c/sub\u003e-(Bi\u003csub\u003e0.5\u003c/sub\u003eNa\u003csub\u003e0.5\u003c/sub\u003e)TiO\u003csub\u003e3\u003c/sub\u003e lead-free binary system.\u0026quot; \u003cem\u003eActa Materialia\u003c/em\u003e 208 (2021): 116710.\u003c/li\u003e\n \u003cli\u003eZhang, Lan, et al. \u0026quot;Effect of Bi-B-Si-Zn-Al glass additive on the properties of low-temperature sintered silicon carbide ceramics.\u0026quot; \u003cem\u003eFrontiers in Physics\u003c/em\u003e 10 (2023): 1090437.\u003c/li\u003e\n \u003cli\u003eLi, Xinheng, et al. \u0026quot;Enhancing energy storage density of BNT-ST-based ceramics by a stepwise optimization strategy on the breakdown strength.\u0026quot; \u003cem\u003eJournal of the European Ceramic Society\u003c/em\u003e 44.11 (2024): 6422-6429.\u003c/li\u003e\n \u003cli\u003eZheng, Yuanyuan, et al. \u0026quot;Enhancing energy storage performance of BT-based ceramics by doping modification.\u0026quot; \u003cem\u003eMaterials Science in Semiconductor Processing\u003c/em\u003e 196 (2025): 109656.\u003c/li\u003e\n \u003cli\u003eLi, Hongtian, et al. \u0026quot;Remarkable energy storage performance of BiFeO\u003csub\u003e3\u003c/sub\u003e-based high-entropy lead-free ceramics and multilayers.\u0026quot; \u003cem\u003eChemical Engineering Journal\u003c/em\u003e 499 (2024): 156112.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Relaxor-antiferroelectric, Breakdown strength, Interfacial polarization, Thermal stability, energy storage density","lastPublishedDoi":"10.21203/rs.3.rs-9295258/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9295258/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study demonstrates a successful strategy for designing 0.25(Na\u003csub\u003e0.5\u003c/sub\u003eBi\u003csub\u003e0.5\u003c/sub\u003e)TiO\u003csub\u003e3\u003c/sub\u003e-0.75NaNbO\u003csub\u003e3\u003c/sub\u003e (0.25BNT-0.75NN) based 0.025 (Ba\u003csub\u003e0.8\u003c/sub\u003eB\u003csub\u003e0.1\u003c/sub\u003eCa\u003csub\u003e0.1\u003c/sub\u003e)(Zr0.\u003csub\u003e1\u003c/sub\u003eTi\u003csub\u003e0.9\u003c/sub\u003e)O\u003csub\u003e3\u003c/sub\u003e (2.5% glass) phase for enhancement their energy storage properties and interfacial polarization suppression. The addition of glass phase foster cations disorder and disrupting long-range ordering (LRO) of BNT-NN ferroelectric phase and enhancement of relaxor degree. Furthermore, the increasing in grain resistance induced inhabitation of interfacial polarization subsequently enhancement of the dielectric breakdown strength (DBS). The activation energy (E\u003csub\u003ea\u003c/sub\u003e) was elevated from 0.033eV in pure BNT-NN to 0.075eV IN BNT-NN-2.5%glass. Remarkable enhancement into energy storage density of (W\u003csub\u003erec\u003c/sub\u003e)\u0026thinsp;=\u0026thinsp;1.45 J/cm\u003csup\u003e3\u003c/sup\u003e and superior energy storage efficiency (η) of 96.4%. Moreover, superior temperature stability across a broad temperature range up to 150\u0026deg;C was achieved in BNT-NN-based glass phase. The variant of W\u003csub\u003erec\u003c/sub\u003e was observed less than 3% within the whole range of applied temperature. This work offers a promising approach for generating high-performance glass-ceramic materials for advanced energy storage applications.\u003c/p\u003e","manuscriptTitle":"Effect of glass addition into interfacial polarization and energy storage properties of (Na0.5Bi 0.5 )TiO3 based NaNbO3 ceramics","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-04-15 15:33:07","doi":"10.21203/rs.3.rs-9295258/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"efd29fb7-96fd-4122-ba86-a870754366b0","owner":[],"postedDate":"April 15th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-04-26T03:38:25+00:00","versionOfRecord":[],"versionCreatedAt":"2026-04-15 15:33:07","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9295258","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9295258","identity":"rs-9295258","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}