Ultrahigh Energy Storage Research Articles

Vapor-phase conversion of waste silicon powders to silicon nanowires for ultrahigh and ultra-stable energy storage performanc

Vapor-phase conversion of waste silicon powders to silicon nanowires for ultrahigh and ultra-stable energy storage performanc

Ultra-high energy storage efficiency achieved through the construction of interlocking microstructure and excitation of depressor effects

Ultra-high energy storage efficiency achieved through the construction of interlocking microstructure and excitation of depressor effects

Fluorinated Polyimides incorporated with heterogeneous ZrO2@KNbO3 as multiple carrier transport barriers for Ultra-High energy storage

Advanced electronic devices and electrical power systems require high capacitor energy storage, fast charge–discharge speed and high temperature stability. Inorganic and organic nanocomposite film can achieve this great goal, but the major obstacle is the easy failure of breakdown in harsh environments. Here, we report a seires of inorganic–organic composite films prepared by blending a novel core–shell heterogeneous ZrO2@KNbO3 with fluorinated polyimide (FPI). The ZrO2@KNbO3 forms a distinctive sandwich-like microstructure, which delivers the p-n-p heterojunction interfaces. Multiple energy barriers, arisen at the interfaces, block the charge carrier transport. As a result, the 0.3 ZrO2@KN/FPI nanocomposite film achieves ultrahigh energy densities of 11.62 J cm−3 and 7.9 J cm−3 under electric fields of 665.6 MV m−1 and 550 MV m−1 at 25 °C and 150 °C, respectively, giving rise to a concurrent enhancement in breakdown strength and electrical displacement. Additionally, the 0.3 ZrO2@KN/FPI composite film exhibits superior charge–discharge cycling stability, enduring up to 100,000 cycles. This research provides a cutting-edge perspective to regulate the charge transport path, especially to inhibit charge transport at the interfaces, demonstrating a great potential for high-temperature dielectric capacitor applications.

Remarkably boosted high-temperature energy storage of a polymer dielectric induced by polymethylsesquioxane microspheres.

Polymer dielectrics are the key materials in next-generation electrical power systems. However, they usually suffer from dramatic deterioration of capacitive performance at high temperatures. In this work, we demonstrate that polymethylsesquioxane (PMSQ) microspheres with a unique organic-inorganic hybrid structure can remarkably enhance the energy storage performance of a typical high-temperature dielectric polymer polyetherimide (PEI). Compared with traditional ceramic fillers, there exists -CH3 on the surface of PMSQ microspheres, which results in good compatibility between PMSQ and PEI. In addition, the PMSQ microspheres with excellent insulating properties can effectively block the charge transport, yielding significantly enhanced breakdown and energy storage performance. Consequently, the PEI based composite film with 5 wt% PMSQ microspheres exhibits ultrahigh energy storage densities of 12.83 J cm-3 and 9.40 J cm-3 with an efficiency (η) above 90% at 150 °C and 200 °C, respectively, which are 10.5 and 50.5 times those of the pure PEI film. This work demonstrates that microspheres with an organic-inorganic hybrid structure are excellent candidates for enhancing the high-temperature performance of polymer dielectrics, and these PMSQ/PEI composite films have huge potential for application in high-temperature film capacitors.

Investigating structural, dielectric and energy storage properties of NaNbO3 based ferroelectric ceramics

Sodium niobate (NaNbO3) based dielectric materials are getting recognition for the electric energy storage applications due to their promising ferroelectric/anti-ferroelectric properties. In the present work, (0.95-x)NaNbO3-0.05SrTiO3-xBi(Fe1/3Zn1/3Ti1/3)O3 (abbreviated as NNSTBFZT, x=0.04, 0.07 and 0.10) lead-free ferroelectric ceramics were synthesized using conventional solid-state reaction technique. A magnificent recoverable energy storage density (Wrec) and an ultrahigh energy storage efficiency (η) have been observed for x4 (∼1.05 J/cm3) and x10 (∼85 %) samples, respectively which reliant on the non-equivalent replacement of ions at the A and B sites of perovskite unit cell. Further, the phase investigation has been studied using X ray diffraction and Raman spectroscopy, which elucidate the effect of incorporation of the substituent ions at host matrix properly. A moderate dielectric constant with ultralow losses has been obtained and all the samples show diffuse phase transition, which is in favor of enhanced energy storage parameters. Moreover, the morphological analysis indicates decrease in grain size ∼ 1 µm, which also reflects the increased breakdown strength responsible for enhancing energy storage capacity. Therefore, proposed sodium niobate based ceramics become favorable for high energy dielectric capacitors applications.

Ultrahigh Energy-Storage in Dual-Phase Relaxor Ferroelectric Ceramics.

High-performance dielectric energy-storage ceramics are beneficial for electrostatic capacitors used in various electronic systems. However, the trade-off between reversible polarizability and breakdown strength poses a significant challenge in simultaneously achieving high energy density and efficiency. Here a strategy is presented to address this issue by constructing a dual-phase structure through in situ phase separation. (Bi0.5Na0.5)TiO3-BaTiO3-based relaxor ferroelectric ceramics are developed, creating a grain-separated dual perovskite phase structure using a facile solid-state reaction method. These ceramics feature two interactive relaxor phases with diversified nanoscale polar structures and heterogeneous grain boundaries, synergistically contributing to high polarization with low hysteresis, substantially increased resistivity, and suppressed electrostrain. Remarkably, a record-high energy density of 23.6Jcm-3 with a high efficiency of 92% under 99kVmm-1 is achieved in the bulk ceramic capacitor. This strategy holds promise for enhancing overall energy-storage performance and related functionalities in ferroelectrics.

Realizing Ultrahigh Energy Storage Density in (Bi0.5Na0.5)0.94Ba0.06TiO3-Based Ceramics via Manipulating the Domain Configuration and Grain Boundary Density.

Dielectric capacitors with a high power density are widely used in various pulsed power electronic systems. However, their low comprehensive energy storage performance severely limits the development of these systems in terms of miniaturization and lightweight design. Herein, we achieved decent energy storage performance in a class of (Bi0.5Na0.5)0.94Ba0.06TiO3 (BNTBT)-based ceramics by synergistically manipulating domain configurations and grain boundary densities. High-resolution transmission electron microscopy and piezoresponse force microscopy confirm that composition-driven refined domain configurations with weak polarity effectively improve the polarization response of BNTBT-based ceramics. The results of experimental and phase-field simulation analysis indicate that the refined grain size contributes to its high breakdown electric strength (Eb). Benefiting from the high polarization difference (ΔP) of 32.62 μC/cm2, delayed saturation polarization behavior, and an ultrahigh Eb of 815.00 kV/cm, BNT-based ceramics simultaneously achieve a high energy storage density (Wrec) of ∼12.25 J/cm3 and an efficiency (η) of ∼86.90%. Because of these structure-induced advantages, the ceramics also exhibit good energy storage temperature stability in the range of 30-150 °C. We believe that the findings of this work may provide practical guidance for the development of high-performance energy storage ceramics.

Optimized energy storage performances via high-entropy design in KNN-based relaxor ferroelectric ceramics

Dielectric capacitors play an irreplaceable role in complex and integrated electronic systems. However, attaining ultrahigh recoverable energy storage density (Wrec) alongside energy storage efficiency (η) poses a formidable challenge, impeding the advance towards the miniaturization and integration of cutting-edge energy storage devices. In this work, a high-entropy strategy with a viscous polymer process is adopted, bringing about ultrafine grains and polar nanoregions (PNRs) accompanied by enhanced electrical homogeneity and polarization relaxation characteristics. As a result, an ultrahigh Wrec ∼ 7.51 J/cm3 is achieved in a high-entropy KNN-based energy storage ceramic with a high η ∼ 88.4% at 750 kV/cm. Moreover, the ceramic capacitor exhibits a colossal power density reaching approximately 420 MW/cm3 and a discharge energy density of approximately 4.85 J/cm3 at 160 ℃. Impressively, it maintains low variation rates of less than 4% across a broad temperature range from 20 ℃ to 160 ℃. The new approach opens avenues for the design and development of superior dielectric materials used in next-generation high-power pulse devices.

Ferroelectric tungsten bronze-based ceramics with high-energy storage performance via weakly coupled relaxor design and grain boundary optimization

A multiscale regulation strategy has been demonstrated for synthetic energy storage enhancement in a tetragonal tungsten bronze structure ferroelectric. Grain refining and second-phase precipitation (perovskite phase) are introduced in the BaSrTiNb2-xTaxO9 ceramics by regulating the composition and sintering process. Disordered polarization and distribution, chemical inhomogeneity, and insulating boundary layers are achieved to provide the fundamental structural origin of the relaxation characteristic, high breakdown strength, and superior energy storage performance. Thus, an ultrahigh energy storage density of 12.2 J cm−3 with an low energy consumption was achieved at an electric field of 950 kV cm−1. This is the highest known energy storage performance in tetragonal tungsten bronze-based ferroelectric. Notably, this ceramic shows remarkable stability over frequency, temperature, and cycling electric fields. This work brings new material candidates and structure design for developing of energy storage capacitors apart from the predominant perovskite ferroelectric ceramics.

Achieving ultra-high energy storage performance in simple systems through minimal element substitution

Dielectric capacitors are essential components of modern advanced electronic devices and power systems based on their ultra-fast charging and discharging speeds and supreme power densities. Nevertheless, how to comprehensively boost their energy storage density and storage efficiency is still an insurmountable challenge. Here, we report a simple micro-chemical polarizability modulation strategy that enables SrTiO3-based dielectric materials to achieve excellent energy storage properties. The energy density and energy efficiency are increased to as high as 76 J∙cm−3 and 72 % from 0.4 J∙cm−3 and 46.7 % of pure STO, respectively, which is the largest value in micro-substitution (less than 3 %). Our results show that the introduction of trace amounts of elements with high ionic polarizabilities (Mn, V) facilitates the increase of chemical disorder and the formation of stable and highly dynamic polar nanoregions (PNRs), which reduces the hysteresis of the polarization switching and improves the polarization at the breakdown field strength, synergistically fostering the energy storage performance. The results of X-ray photoelectron spectroscopy and scanning electron microscopy reveal that the micro-substitution of Mn and V promote the reduction of oxygen vacancies and grain size, improving the breakdown resistance and stability of the capacitor. This present approach is expected to be widely used in the development of high-performance dielectrics.

Superior energy storage performance in Bi0.5Na0.5TiO3 based ceramics via synergistic design of multi-size domain construction and multiple phase structures

Lead-free dielectric ceramics, as the crucial materials for the development of eco-friendly high pulse power devices, have faced limitations in achieving energy storage performance comparable to lead-based counterparts. A novel strategy was adopted to enhance the energy storage capability of Bi0.5Na0.5TiO3 based ceramics by constructing multiple phase structures and multi-size domain. An ultrahigh energy storage density of 8.0 J·cm−3 and a large efficiency of 88.9 % were achieved. The superior energy storage properties can be attributed to the synergistic effects of multiple phase structures and multi-size domain construction resulted from a significant polarization intensity difference upon Sr(Zr0.2Ti0.8)O3 doping. Even more surprising, the 0.6Bi0.5Na0.5TiO3-0.4Sr(Zr0.2Ti0.8)O3 ceramic exhibited excellent aging resistance, with variation in discharge energy density (Wd) < ±7% over a temperature range from 20 to 150°C, variations in recoverable energy density (Wrec) < ±8.3 %, and efficiency (η) < ±5.6 % over a frequency range from 1 to 50 Hz and across 105 cycles. The finding in this work not only provides an effective candidate for high power pulse capacitors, but also provides ideas for the study of high energy storage performance of BNT and the related lead-free ceramics.

Roll‐to‐Roll Production of High‐Performance All‐Organic Polymer Nanocomposites for High‐Temperature Capacitive Energy Storage

AbstractDielectric materials with significant performance in high temperatures are highly desired, especially in harsh environments. However, the polymer‐based dielectric films have developed so far, the production scale remains at the state of the lab. Here, an all‐organic strategy is proposed by introducing phenyl‐acid‐based polymer nanodots (PAPD) into Polyetherimide (PEI), achieving high capacitive energy storage properties even at 200 °C and mass production by an industrial continuous roll‐to‐roll process. The abundant hydrogen bonding between PAPD and PEI chains ensures uniform distribution for the enhanced interaction between nanofillers and polymer matrix. Under UV irradiation, the electron‐affinity and band gap of the film are further extended, which impede charge transfer and reduction of conductive loss. A low loading (0.3 wt.%) of PAPD renders the membrane significant improvement in breakdown strength and charge–discharge efficiency. An ultrahigh energy storage density of 5.1 J cm−3 with a charge–discharge efficiency of over 90% and charge–discharge cycle stability up to 2 × 104 cycles at 150 °C is observed. Furthermore, a 1000 m long roll of polymeric film is roll‐to‐roll fabricated on an industrial solution‐casting production line and the low cost makes practical commercial scale application possible. Considering the low loading and low cost of nanofiller, this all‐organic design strategy sheds light on the industrial application of high‐temperature dielectric materials.

Ultra-high energy storage characteristics under low electric field in Sm-doped Bi5Mg0.5Ti3.5O15 films through defect dipole engineering

The sol–gel method was used to fabricate lead-free Bi5-xSmxMg0.5Ti3.5O15 (BSxMTO, x = 0.25) relaxor ferroelectric film, which exhibited a recoverable energy storage density of 64 J/cm3 and an energy efficiency of 81.1 % under 1856 kV/cm. The energy storage response specifically reaches as high as 0.1824 J/kV·cm2. Enhancing the ergodic relaxor characteristics, improving the defect dipole driving, and reducing defect concentration are essential factors for BSxMTO (x = 0.25) film to collaboratively achieve enhanced relaxor characteristics and polarization intensity, thereby resulting in excellent medium- and low-field energy storage performances. Furthermore, the BSxMTO (x = 0.25) film also exhibits excellent stability in frequency (1 kHz − 20 kHz) (Ure ∼ (40.95 ± 1.01) J/cm3, η ∼ 85.7 % ± 4.4 %) and temperature (20 °C − 150 °C) (Ure ∼ (40.87 ± 0.30) J/cm3, η ∼ 80.4 % ± 2.2 %) under 1387 kV/cm, offering promising prospects for the application of lead-free dielectric energy storage films in low and medium electric fields.

Ultrahigh Energy Storage in (Ag,Sm)(Nb,Ta)O3 Ceramics with a Stable Antiferroelectric Phase, Low Domain-Switching Barriers, and a High Breakdown Strength.

AgNbO3 (AN) antiferroelectrics (AFEs) are regarded as a promising candidate for high-property dielectric capacitors on account of their high maximum polarization, double polarization-electric field (P-E) loop characteristics, and environmental friendliness. However, high remnant polarization (Pr) and large polarization hysteresis loss from room-temperature ferrielectric behavior of AN and low breakdown strength (Eb) cause small recoverable energy density (Wrec) and efficiency (η). To solve these issues, herein, we have designed Sm3+ and Ta5+ co-doped AgNbO3. The addition of Sm3+ and Ta5+ reduces the tolerance factor, polarizability of B-site cations, and domain-switching barriers, enhancing AFE phase stability and decreasing hysteresis loss. Meanwhile, adding Sm3+ and Ta5+ leads to decreased grain sizes, increased band gap, and reduced leakage current, all contributing to increased Eb. As a benefit from the above synergistic effects, a high Wrec of 7.24 J/cm3, η of 72.55%, power density of 173.73 MW/cm3, and quick discharge rate of 18.4 ns, surpassing those of many lead-free ceramics, are obtained in the (Ag0.91Sm0.03)(Nb0.85Ta0.15)O3 ceramic. Finite element simulations for the breakdown path and transmission electron microscopy measurements of domains verify the rationality of the design strategy.

Engineering nanocluster and pyrochlore phase in BiFeO3-based ceramics for electrostatic energy storage

BiFeO3, known for its exceptional spontaneous polarization and high Curie temperature, stands as a pivotal component in power electronics. However, its relatively low breakdown strength has been a bottleneck in improving energy storage performance. Herein, we present an innovative approach to constructing nanoclusters and pyrochlore phases within BiFeO3-based ceramics. Specifically, the integration of the pyrochlore phase and nanoclusters (less than 10 nm) effectively reduces grain size and extends the growth path of electric trees, while imbuing the material with relaxor properties, which contribute to a significant enhancement in breakdown strength. As a result, this method achieves an ultrahigh energy storage density of 7.2 J/cm3 under 800 kV/cm, coupled with remarkable stability of temperature (20–180 °C), frequency (1–500 Hz), and fatigue resistance (over 10, 000 cycles). This work provides a viable pathway for the development of dielectric materials with superior energy storage performance to meet the stringent demands of advanced capacitor applications.

A highly polarizable concentrated dipole glass for ultrahigh energy storage

Relaxor ferroelectrics are highly desired for pulse-power dielectric capacitors, however it has become a bottleneck that substantial enhancements of energy density generally sacrifice energy efficiency under superhigh fields. Here, we demonstrate a novel concept of highly polarizable concentrated dipole glass in delicately-designed high-entropy (Bi1/3Ba1/3Na1/3)(Fe2/9Ti5/9Nb2/9)O3 ceramic achieved via substitution of multiple heterovalent ferroelectric-active principal cation species on equivalent lattice sites. The atomic-scaled polar heterogeneity of dipoles with different polar vectors between adjacent unit cells enables diffuse reorientation process but disables appreciable growth with electric fields. These unique features cause superior recoverable energy density of ~15.9 J cm−3 and efficiency of ~93.3% in bulk ceramics. We also extend the highly polarizable concentrated dipole glass to the prototype multilayer ceramic capacitor, which exhibits record-breaking recoverable energy density of ~26.3 J cm−3 and efficiency of ~92.4% with excellent temperature and cycle stability. This research presents a distinctive approach for designing high-performance energy-storage dielectric capacitors.

Optimizing energy storage performance of lead zirconate-based antiferroelectric ceramics by a phase modulation strategy

Dielectric energy storage has gained considerable significance owing to the high energy requirements of human society. Lead zirconate-based (PZ) antiferroelectric materials have received much attention due to their fast discharge rate, high power density, and low cost. Nevertheless, their low energy storage density seriously limits their practical applications. To overcome this limitation, the phase modulation strategy via chemical modification was adopted to optimize the breakdown strength and phase switching field. Specifically, the antiferroelectric ceramics of (Pb0.97−xGd0.02Srx)(Zr0.87Sn0.12Ti0.01)O3 were prepared by the tape-casting method. An apparent multistage phase transition behavior revealed for x ≥ 0.05 is rarely discussed in reported Sr2+ modified PZ system. This is attributed to the coexistence of the main orthorhombic phase and the tetragonal phase. Although the transition near the lower field reduces the energy storage slightly, the disruption of the long-range order stabilizes the antiferroelectricity of the orthorhombic phase, hence elevating its transition field. In addition, the tetragonal phase with lower polarization suppresses the electrostrain thus improving the breakdown strength. Consequently, an ultrahigh recoverable energy storage density of 14.5 J/cm3 with a high energy efficiency of 81 % is achieved at a high electric field of 717 kV/cm for (Pb0.92Gd0.02Sr0.05)(Zr0.87Sn0.12Ti0.01)O3. Moreover, the fatigue resistance of this composition is excellent within 26,000 fatigue cycles. Besides, it exhibits a high discharge energy density of 9.4 J/cm3 and a great power density of 387 MW/cm3. These results confirm that the energy storage properties of PZ-based antiferroelectric materials can be effectively optimized via a phase modulation strategy.

High‐Entropy Design Toward Ultrahigh Energy Storage Density Under Moderate Electric Field in Bulk Lead‐Free Ceramics

AbstractElectrostatic capacitors with ultrahigh energy‐storage density are crucial for the miniaturization of pulsed power devices. A long‐standing challenge is developing dielectric materials that achieve ultrahigh recoverable energy density Wrec ≥ 10 J cm−3 under moderate electric fields (30 ≤ E ≤ 50 kV mm−1). Herein, a specific high‐entropy strategy is proposed to modulate the phase structure and interfacial polarization of medium‐entropy base materials using linear dielectrics. This strategy ensures a sufficient polar phase and a high enough electric field for complete polarization, thereby achieving ultrahigh Wrec by enhancing polarization strength. The validity of this strategy is demonstrated in the (Na0.282Bi0.282Ba0.036Sr0.28Nd0.08)TiO3‐xCa0.7Bi0.2TiO3 (NBBSNT‐xCBT) (x = 0–0.15) system. The CBT‐modulated samples exhibit a polyphase structure of R3c, P4bm, and Pm‐3m with reduced remnant polarization (Pr). Additionally, the addition of CBT effectively suppresses interfacial polarization, enhancing the maximum polarization (Pmax). These factors significantly improve the value of ∆P = Pmax − Pr. As a result, an ultrahigh Wrec of 10.5 J cm−3 with a high‐efficiency η of 80.3% is obtained in the x = 0.1 sample under a moderate electric field of 45 kV mm−1 for the first time. This work paves the way for achieving superior energy‐storage performance under moderate electric fields.

Polymorphic Localized Heterostructure Design for High-Performance Amorphous/Nanocrystalline Composite Film.

Analogous to linear dielectric, amorphous perovskite dielectrics characterized of high breakdown strength and low remanent polarization possess in-depth application in the sea, land, and air fields. Amorphous engineering is a common approach to balance the inverse relationship between polarization and breakdown strength in dielectric ceramic capacitor, however, the low polarization is the major barrier limiting the improvement of energy storage density. To address this concern, the polymorphic localized heterostructure confirmed by high-resolution transmission electron microscope (HR-TEM) and HADDF images is constructed in BaTiO3-Bi(Ni0.5Zr0.5)O3 amorphous/nanocrystalline composite film with SiO2 addition (BT-BNZ-xS, x = 3, 5, 7, 10 mol%). The stability of nanocrystalline region achieved by Si-rich transition region and the enhancive ultra-short-range ordering in the amorphous region synergistically result in large breakdown strength and nonhysteretic polarized response. This polymorphic localized heterostructure optimizes the thermal stability in a wide temperature range and contributes ultrahigh energy storage density of 149.9 J cm-3 with markedly enhanced efficiency of 79.0%. This study provides a universal strategy to design the polarization behavior in other amorphous perovskite-based dielectrics.

Ultra-high energy storage density in PBSLZS antiferroelectric thick film ceramics

Superior recoverable energy density (Wrec) and efficiency (η) are crucial parameters for capacitors used in pulse-power devices. Here, we achieved an ultrahigh Wrec and high η in (Pb0.95-xBa0.02SrxLa0.02)(Zr0.65Sn0.35)O3 (PBSLZS) antiferroelectric thick film ceramics. All ceramics exhibit an orthorhombic structure, and the forward switching field increases with the increase of Sr2+ ionic content. The PBSLZS (x = 0.03) ceramics exhibit maximum value of total energy density (Wtot) and Wrec of 14.9 J/cm3 and 12.9 J/cm3, respectively, along with a high η of 86.6% at 570 kV/cm. Furthermore, we investigated the impact of multi-field coupling, i.e., the electric field and temperature, on the energy storage performance. An electric field (E) versus temperature (T) phase diagram was also obtained. The outstanding energy storage performance observed in PBSLZS ceramics demonstrates the potential for energy storage capacitors.