Ceramic Capacitors Research Articles

Effect of Reaction Layers on Internal Stresses in Co‐Fired Multilayers of Calcium Manganate and Calcium Cobaltite

A widespread recovery of waste heat requires a cost‐effective production of thermoelectric generators. Thermoelectric oxides are predestined for use at high temperatures. For manufacturing reasons, a multilayer generator design will be easily scalable and cost‐effective. To evaluate the potential of ceramic multilayer technology for that purpose, a multilayer of the promising thermoelectric oxides calcium cobaltite (Ca3Co4O9), calcium manganate (CMO, CaMnO3), and glass–ceramic insulation layers is fabricated. Cracks and reaction layers at the interfaces are observed in the microstructure. The compositions of these reaction layers are identified by energy‐dispersive X‐ray spectroscopy and X‐ray diffraction. Mechanical and thermal properties of all layers are compiled from literature or determined by purposeful sample preparation and testing. Based on this data set, the internal stresses in the multilayer after co‐firing are calculated numerically. It is shown that tensile stresses in the range of 50 MPa occur in the CMO layers. The reaction layers have only a minor influence on the level of these residual stresses. Herein, it is proven that the material system is basically suitable for multilayer generator production, but that the co‐firing process and the layer structure must be adapted to improve densification and reduce the tensile stresses in the CMO.

Ceramic-Based Dielectric Materials for Energy Storage Capacitor Applications.

Materials offering high energy density are currently desired to meet the increasing demand for energy storage applications, such as pulsed power devices, electric vehicles, high-frequency inverters, and so on. Particularly, ceramic-based dielectric materials have received significant attention for energy storage capacitor applications due to their outstanding properties of high power density, fast charge-discharge capabilities, and excellent temperature stability relative to batteries, electrochemical capacitors, and dielectric polymers. In this paper, we present fundamental concepts for energy storage in dielectrics, key parameters, and influence factors to enhance the energy storage performance, and we also summarize the recent progress of dielectrics, such as bulk ceramics (linear dielectrics, ferroelectrics, relaxor ferroelectrics, and anti-ferroelectrics), ceramic films, and multilayer ceramic capacitors. In addition, various strategies, such as chemical modification, grain refinement/microstructure, defect engineering, phase, local structure, domain evolution, layer thickness, stability, and electrical homogeneity, are focused on the structure-property relationship on the multiscale, which has been thoroughly addressed. Moreover, this review addresses the challenges and opportunities for future dielectric materials in energy storage capacitor applications. Overall, this review provides readers with a deeper understanding of the chemical composition, physical properties, and energy storage performance in this field of energy storage ceramic materials.

Effect of A/B ratio on the dielectric properties and insulation resistance of barium titanate sintered in a reducing atmosphere

The effect of the A/B ratio on the dielectric properties and insulation resistance of barium titanate (BaTiO3) sintered in a reducing atmosphere was investigated in this study. The increased demand for high capacitance, miniaturized, and reliable base metal electrode multilayer ceramic capacitors (BME MLCCs) has emphasized improving insulation properties. This study added Y2O3, MgO, Mn2O3, and SiO2 to tailor the barium titanate properties. We investigated how changes in the A/B ratio affect the microstructure, defect chemistry, and Y3+ ion occupation in BaTiO3, affecting dielectric properties and insulation resistance. It was observed that the activation energies for grain and grain boundary conductivity are dominated by oxygen vacancy and (VBa″−VO··) defect pair, respectively. The Ti3+ and oxygen vacancy concentrations were directly proportional to the room and high-temperature resistivities, respectively. The sample with an A/B ratio of 1.002 had the lowest oxygen vacancy and Ti3+ ratio, resulting in a higher resistance and lower thermally stimulated depolarization current (TSDC).

Strong Local Polarization Fluctuations Enabled High Electrostatic Energy Storage in Pb-Free Relaxors.

Electrostatic energy-storage ceramic capacitors are essential components of modern electrified power systems. However, improving their energy-storage density while maintaining high efficiency to facilitate cutting-edge miniaturized and integrated applications remains an ongoing challenge. Herein, we report a record-high energy-storage density of 20.3 J cm-3 together with a high efficiency of 89.3% achieved by constructing a relaxor ferroelectric state with strongly enhanced local polarization fluctuations. This is realized by incorporating highly polarizable, heterovalent, and large-sized Zn and Nb ions into a Bi0.5Na0.5TiO3-BaTiO3 ferroelectric matrix with very strong tetragonal distortion. Element-specific local structure analysis revealed that the foreign ions strengthen the magnitude of the unit-cell polarization vectors while simultaneously reducing their orientation anisotropy and forming strong fluctuations in both magnitude and orientation within 1-3 nm polar clusters. This leads to a particularly high polarization variation (ΔP) of 72 μC cm-2, low hysteresis, and a high effective polarization coefficient at a high breakdown strength of 80 kV mm-1. This work has surpassed the current energy density limit of 20 J cm-3 in bulk Pb-free ceramics and has demonstrated that controlling the local structure via the chemical composition design can open up new possibilities for exploring relaxors with high energy-storage performance.

Direct Observation of Trace Elements in Barium Titanate of Multilayer Ceramic Capacitors Using Atom Probe Tomography.

Accurately controlling trace additives in dielectric barium titanate (BaTiO3) layers is important for optimizing the performance of multilayer ceramic capacitors (MLCCs). However, characterizing the spatial distribution and local concentration of the additives, which strongly influence the MLCC performance, poses a significant challenge. Atom probe tomography (APT) is an ideal technique for obtaining this information, but the extremely low electrical conductivity and piezoelectricity of BaTiO3 render its analysis with existing sample preparation approaches difficult. In this study, we developed a new APT sample preparation method involving W coating and heat treatment to investigate the trace additives in the BaTiO3 layer of MLCCs. This method enables determination of the local concentration and distribution of all trace elements in the BaTiO3 layer, including additives and undesired impurities. The developed method is expected to pave the way for the further optimization and advancement of MLCC technology.

Achieving high energy storage density and efficiency in (Na0.5Bi0.5)TiO3-based lead-free ceramics

Due to the demands of miniaturization, weight reduction and green development for electronic devices, development of lead-free dielectric ceramic capacitors with high recoverable energy density (Wrec) and energy storage efficiency (η) attracts much attention. To this end, (1-x)[0.75(Na0.5Bi0.5)TiO3-0.25SrTiO3]-xNdNbO4 (abbreviated as: NBST-xNN) ceramics were fabricated through a solid-state reaction method. After adding NN, the non-perovskite phase of Bi2Ti2O7 (BTO) with low dielectric constant (εr) and loss (tan δ) is generated. Finite element software (COMSOL) was used to explore the influence of the BTO phase on breakdown strength (Eb). The simulation result indicates that the BTO phase with a low εr concentrates a larger local electric field (LEF), and thus weakens the LEF loading in the main perovskite phase, which is beneficial for enhancing Eb. Moreover, NN doping significantly decreases the oxygen vacancy concentration in NBST ceramics, which plays a key role in improving Eb. On the other hand, as NN content increases, the hysteresis of the polarization (P)-electric field (E) loops is substantially suppressed, and the polarization saturation is delayed, which can be ascribed to the appearance of the BTO phase having a linear dielectric characteristic and to the enhanced fluctuations of composition and charge by NN doping. Benefitting from the above factors, the optimal energy storage performance (ESP) with a Wrec of 4.14 J/cm3 and an η of 90 % is obtained in NBST-0.08NN ceramics. Meanwhile, the ESP of NBST-0.08NN ceramics shows good charge-discharge properties and thermal stability. In conclusion, these results demonstrate that NBST-0.08NN ceramics are promising candidates as environment-friendly dielectric capacitor materials.

Barium Strontium Titanate-based multilayer ceramic capacitors with excellent energy storage and charge-discharge performance

Energy storage capacitors for advanced pulse power systems and high-power electric devices is a kind of important electronic components, the demand continues to grow, specifications are constantly being upgraded, and performance boundaries are continuously being pushed. Multilayer ceramic capacitors (MLCCs) for energy storage applications have received increasing attention due to the advantages of ultralow equivalent series inductance, equivalent series resistance, good frequency characteristics, strong voltage overload ability, and stable operability at high temperatures. However, the relatively low energy storage density significantly limits its broader applications. Here, 0.4Ba0.55Sr0.45TiO3-0.4Bi0.5Na0.5TiO3-0.2SrZrO3 (0.4BST-0.4BNT-0.2SZ) relaxor ferroelectric MLCCs are prepared at different heating rates. Excellent recoverable energy storage density of 10.3 J cm−3 and high energy efficiency of 93 % are achieved in fast-fired MLCCs under the electric field of 106.3 V μm−1. The impedance spectroscopy and thermally stimulated depolarization current technologies are employed to investigate the conductance mechanism of MLCCs, and the results can explain the effect of heating rate on the performance of MLCCs. In addition, the charge-discharge performances of fast-fired MLCCs are also thoroughly investigated, exhibiting great thermal and fatigue stability.

Advancements and challenges in BaTiO3-Based materials for enhanced energy storage

Numerous researchers worldwide have been motivated to develop highly effective, environmentally acceptable green energy sources as a result of the recent sharp increase in energy use and the need for low emission levels. The energy generated from various renewable sources can be stored efficiently with a system that has a high energy density and high energy efficiency. Due to their enhanced dielectric, ferroelectric, and breakdown strength characteristics, BaTiO3 based dielectric/ferroelectric ceramic materials have received a lot of interest for energy storage applications in the past tw decades. In the present work, a thorough analysis of recent advancements in composites and single-phase BaTiO3 materials with enhanced energy storage performance. This review's main focus is on the crucial tactics and theoretical frameworks for improving the energy efficiency and recovered energy storage density of various BaTiO3-based materials. A thorough summary has been provided with the most recent developments in BaTiO3 based materials for multi-layered ceramic capacitors (MLCCs), pulse power capacitors, piezoelectric transducers, energy harvesting, electric vehicle batteries, and high-power electronic devices in order to confirm the commercial applications of BaTiO3 based single phase as well as multi-phase layered structures and composites.

Influence of TiO2 addition on the Mg4Nb2O9 ceramic phase and its application in the radiofrequency region

In this work, the dielectric properties of (1-x) Mg4Nb2O9 – (x) TiO2 composite ceramics in radiofrequency and the microwave region were evaluated. X-ray diffraction demonstrated that Mg4Nb2O9 (MNO) reacted with TiO2 resulting in the formation of new crystalline phase Mg5(Nb0.625Ti0.375)4O15. Complex Impedance Spectroscopy (CIS) analysis was realized to analysis the electrical properties of materials, whereas was observed that activation energy (Ea) decrease from 1.64 to 1.37 eV with an increase in TiO2 concentration. Temperature capacitance coefficient (TCC) was obtained and showed that at different frequencies all materials could be used as Class 1 ceramic capacitors according to EIA RS-198. In the Microwave region, MNO – TiO2 demonstrated ε’r between 12.07 (MNO) and 14.08 (MNO18T), tan δ values varying of 2.64 × 10-4 (MNO) up to 5.92 × 10−4 (MNOT14). Regarding the temperature coefficient of resonant frequency (τf) was observed that the values decreased with the increase in TiO2, with the value closest to zero being that of pure MNO (τf = −27 ppm.°C−1). The results presented show that materials evaluated could be utilized in devices that can be act in radio frequency (RF) and microwave (MW) regions.

Prediction of thermal shock induced cracking in multi-material ceramics using a stress-energy criterion

Impact of residual stresses on the thermal shock resistance of alumina–zirconia multi-layer ceramics is investigated within the framework of finite fracture mechanics, using astress-energy criterion. The critical temperature difference (ΔTc) for crack formation is strongly dependent on the magnitude of residual stress and the material’s strength. The predicted minimal spacing between cracks, critical time for crack initiation, and initial depth of the induced cracks are compared and discussed for different designs. An increase of up to ∼40 % in ΔTc is predicted for multi-material ceramics with athin alumina surface layer with compressive stresses, compared to bulk reference alumina.

Improved energy storage properties and stability of La modified 0.7Bi0.5Na0.5TiO3-0.3SrTiO3 ceramics

The pursuit of lead-free ceramic capacitors with superior energy storage properties has garnered increasing attention. Herein, 0.7Bi0.5Na0.5TiO3-0.3SrTiO3-xLa (BNT-ST-xLa) ceramics were synthesized via citrate combustion technology. The results show that La doped BNT-ST induces dielectric relaxation behavior and promotes the formation of nanoscale domains, which has been confirmed by PFM and TEM, and slim hysteresis loops are realized as addition of La. The recoverable energy-storage density (Wre of 2.05 J/cm3) and efficiency (η of 82 %) are obtained in 4 mol% La doped ceramic under relatively low electric field of 170 kV/cm. The energy-storage performances of the ceramics show excellent frequency stability (Wre varies <1.9 % and η varies <3.1 % at 5 Hz–100 Hz) and thermal stability (Wre varies <1 % and η varies <6.1 % within 23 °C to 73 °C). It is revealed that the introduction of La results in the formation of nanodomains with currently improved energy storage properties.

High energy storage density in AgNbO3-based lead-free antiferroelectrics using A/B-site co-doping strategy

Lead-free antiferroelectric AgNbO3 ceramics have garnered extensive attention due to their rapid charge/discharge capabilities and environmentally friendly nature, holding immense potential for energy storage applications. However, the practical utilization of AgNbO3 has been hindered by its low energy storage density. This study employed an A/B-site co-doping strategy, which yielded positive effects on the energy performance of AgNbO3 ceramics. By modifying the A/B-sites with equivalent amounts of Bi3+ and Y3+ ions, enhanced maximum polarization, improved breakdown field, and slimmer hysteresis loops were simultaneously achieved, as the combined effects of refined grain size, wider optical bandgap, and randomly distributed antiferroelectric nanodomains, which were verified through the scanning electron microscope, transmission electron microscope, and ultraviolet–visible spectrum. As a consequence, a high energy storage density of 5.40 J/cm3 accompanied by an energy storage efficiency of 56.5% was achieved in the Ag0.97Bi0.01Nb0.994Y0.01O3 ceramic under a relatively low electric field of 190 kV/cm. This study underscores the effectiveness of A/B-site aliovalent co-doping as a viable strategy for developing high-performance ceramic capacitors for energy storage applications.

The study of BMN cubic pyrochlores based multi-layer capacitors

The multi-layer ceramic capacitor (MLCC) is prepared with Bi1.5MgNb1.5O7 (BMN) pyrochlores, which has medium dielectric constant, large dielectric tunability, and especially the very small dielectric loss. The multilayer ceramic capacitors with Bi1.5MgNb1.5O7 as the dielectric material are prepared by a tape-casting method. The dielectric constant of the BMN thick film was observed to be superior to that of the bulk material, indicating its potential application in electronic devices. The increase in dielectric constant during the preparation of multilayer ceramic capacitors was explained by investigating the interdiffusion between the ceramic thick films and the electrodes. The BMN thick films and Ag0.7/Pd0.3 electrodes showed a dense microstructure and serial interfaces when sintering at 1050 °C for 1.5 h. The capacitor exhibited good temperature stability with a dielectric constant temperature coefficient of −249.94 ppm/°C, a relative dielectric constant of 216, and a dielectric loss of 0.00036. Provides insights for the development and optimization of high-performance dielectric tunable electronic device.

Deformation and crack growth in multilayered ceramic capacitor during thermal reflow process: numerical and experimental investigation

PurposeThis study aims to investigate the possible defects and their root causes in a soft-termination multilayered ceramic capacitor (MLCC) when subjected to a thermal reflow process.Design/methodology/approachSpecimens of the capacitor assembly were subjected to JEDEC level 1 preconditioning (85 °C/85%RH/168 h) with 5× reflow at 270°C peak temperature. Then, they were inspected using a 2 µm scanning electron microscope to investigate the evidence of defects. The reliability test was also numerically simulated and analyzed using the extended finite element method implemented in ABAQUS.FindingsExcellent agreements were observed between the SEM inspections and the simulation results. The findings showed evidence of discontinuities along the Cu and the Cu-epoxy layers and interfacial delamination crack at the Cu/Cu-epoxy interface. The possible root causes are thermal mismatch between the Cu and Cu-epoxy layers, moisture contamination and weak Cu/Cu-epoxy interface. The maximum crack length observed in the experimentally reflowed capacitor was measured as 75 µm, a 2.59% difference compared to the numerical prediction of 77.2 µm.Practical implicationsThis work's contribution is expected to reduce the additional manufacturing cost and lead time in investigating reliability issues in MLCCs.Originality/valueDespite the significant number of works on the reliability assessment of surface mount capacitors, work on crack growth in soft-termination MLCC is limited. Also, the combined experimental and numerical investigation of reflow-induced reliability issues in soft-termination MLCC is limited. These cited gaps are the novelties of this study.

Superior energy-storage density and ultrahigh efficiency in KNN-based ferroelectric ceramics via high-entropy design

The rapidly advancing energy storage performance of dielectric ceramics capacitors have garnered significant interest for applications in fast charge/discharge and high-power electronic techniques. Simultaneously improving the recoverable energy storage density Wrec and efficiency η becomes more prominent at the present time for their practical applications. Herein, a high-entropy concept is implemented on the (K0·5Na0.5)NbO3 (KNN)-based ferroelectric ceramics to design the high-performance dielectric capacitors. First, the strong lattice distortion can absorb some electric energy during the electrical loading process and result in the delayed polarization saturation. Additionally, the large composition fluctuations induce the weak correlation between polar nanoregions and enhance the η. Finally, the high-entropy design and viscous polymer processing method reduce the grain size and improve the Eb. In consequence, excellent Wrec of 11.14 J/cm3 with high η of 87.1% are achieved under an electric field of 750 kV/cm in the high-entropy component. These results demonstrate that the high-entropy concept is a potential avenue to design the KNN-based high-performance dielectric energy storage capacitors.

Ultrahigh energy storage in high-entropy ceramic capacitors with polymorphic relaxor phase.

Ultrahigh-power-density multilayer ceramic capacitors (MLCCs) are critical components in electrical and electronic systems. However, the realization of a high energy density combined with a high efficiency is a major challenge for practical applications. We propose a high-entropy design in barium titanate (BaTiO3)-based lead-free MLCCs with polymorphic relaxor phase. This strategy effectively minimizes hysteresis loss by lowering the domain-switching barriers and enhances the breakdown strength by the high atomic disorder with lattice distortion and grain refining. Benefiting from the synergistic effects, we achieved a high energy density of 20.8 joules per cubic centimeter with an ultrahigh efficiency of 97.5% in the MLCCs. This approach should be universally applicable to designing high-performance dielectrics for energy storage and other related functionalities.

Simultaneously enhanced of energy storage and energy harvesting performances of [(Bi0.5Na0.5)TiO3–BaTiO3] ceramics by addition of SrTiO3

As is well known, relaxor dielectrics are characterized by high energy storage efficiency (η), while high recoverable energy storage density (Wrec) can be achieved by anti-ferroelectric ceramics. Herein, our approach is to find relaxor- anti-ferroelectric coexistence phases of (Bi0.5Na0.5)TiO3- BaTiO3 ceramics for achieving high performance in energy storage and energy harvesting as well. Therefore, [(0.9-x) ( Bi0.5Na0.5)TiO3-xSrTiO3-0.1BaTiO3] (abbreviation (0.9-x) NBT-0.1BT-xST) (0.0 ≤ x ≤ 0.4) were synthesized via the solid-state reaction route in air. The tolerance factor (τ) increased from 0.9901 to 0.9998 when ST-content increased from 0.0 to 0.4, indicating an increase in crystal lattice symmetry. The FT-IR de-convolution vibration modes shown in the TiO6 octahedra exhibit two peaks at ∼550 and 650 cm−1, which indicate present coexistence phases of the crystal structure. Ferroelectric to relaxor phase crossover has been detected by the addition of ST with the present anti-ferroelectric phase in particular dopant ST = 0.2. The increasing into the diffused phase transition (γ) is signified by enhancement of the relaxor degree of NBT-BT at high content of ST. The rapidly suppressed remnant polarization (Pr) at high content of ST is due to substitute iso-valence (Sr2+) by tri-valence (Bi3+) and mono-valence (Na1+). Ultrahigh Wrec = 1.13 J/ cm3 with excellent η = 92.62% were obtained at ST = 0.3 at low electric field (E = 110 kV cm−1). A remarkable response of the strain with a high converse piezoelectric coefficient ( d33* = 390.47 pm V−1) at ST = 0.2 was obtained due to decreasing the non-revisable 180° domain switching. Based on the obtained results, the addition of ST to NBT-BT ceramics can provide a head start in the implementation of ceramic capacitors for potential effective into energy harvesting and energy storage applications.

The Market Trend Analysis of the MLCC Industry

With the advancement of science and technology, multilayer ceramic capacitors are playing an increasingly important role in electronic products. In this article, we will analyze the market size and competitive landscape of MLCC, as well as their expected development. This article will analyze the growth of the MLCC market by collecting historical and forecast data and identify the major manufacturers and suppliers by surveying the competitive landscape. Finally, the technological innovation advantages of the industry are studied and discussed, and the application scenarios are analyzed. In the fourth part, four MLCC manufacturers will be listed, namely Fenghua Advanced Technology, Sanhuan Group, Murata, and Yageo. Finally, it can be seen that the competition among manufacturers in the MLCC industry is still fierce, and it is developing rapidly in emerging fields. In addition, MLCC products tend to be miniaturized, lightweight, high capacitance, high frequency, and high temperature resistance. Through research, it can help investors better formulate market strategies, provide government regulators with suggestions for the development of the MLCC industry, and serve product development and market expansion, to promote technological innovation and healthy and sustainable development of the industry.

Achieving High Energy Storage Performance under a Low Electric Field in KNbO3-Doped BNT-Based Ceramics.

Ceramic capacitors have great potential for application in power systems due to their fantastic energy storage performance (ESP) and wide operating temperature range. In this study, the (1 - x)Bi0.5Na0.47Li0.03Sn0.01Ti0.99O3-xKNbO3 (BNLST-xKN) energy storage ceramics were synthesized through the solid-phase reaction method. The addition of KN disrupts the long-range ferroelectric order of the BNLST ceramic, inducing the emergence of polar nanoregions (PNRs), which enhances the ESP of the ceramics. The BNLST-0.2KN ceramic demonstrates a high recovered energy density (Wrec ∼ 3.66 J/cm3) and efficiency (η ∼ 85.8%) under a low electric field of 210 kV/cm. Meantime, it exhibits a large current density (CD ∼ 831.74 A/cm2), high power density (PD ∼ 78.86 MW/cm3), and fast discharge rate (t0.9 ∼ 0.1 μs), along with good temperature stability and excellent fatigue stability. These properties make the BNLST-0.2KN ceramic a promising candidate for energy storage applications in low electric fields.

A study on the reduction of microstructural non-uniformity in Ni-multilayer ceramic capacitors via repeated highly accelerated life tests and analyses of degraded local areas

The degree of microstructural non-uniformity and the lifetime extension of multilayer ceramic capacitors (MLCCs) were evaluated by repeating the fabrication of “prebreakdown” MLCCs through highly accelerated life tests (HALTs), the removal of the insulation resistance-degraded layer, and the reformation of the terminal electrode. The total mean time to failure (MTTF) tended to extend and converge as HALTs were repeated. Microstructural analysis in the degraded local area revealed a clear correlation between the shorter lifetime and the minimum number of grains per unit dielectric layer. After HALTs were repeated, the number of grains came close to and converged as much as undegraded areas over a longer lifetime. These results imply that degradation occurs in order from the greatest degree of microstructural non-uniformity and that the weakest-link model can be understood by treating the lifetime as MTTF.