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Microstructures 2023;3:2023002. 10.20517/microstructures.2022.21 © The Author(s) 2023.
Open Access Research Article

BaTiO3-NaNbO3 energy storage ceramics with an ultrafast charge-discharge rate and temperature-stable power density

State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China.

Correspondence to: Prof. Xiaohui Wang, State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China. E-mail:

    This article belongs to the Special Issue Dielectric Energy Storage
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    Academic Editors: Shiqing Deng, Ruzhong Zuo, Shujun Zhang | Copy Editor: Fangling Lan | Production Editor: Fangling Lan

    © The Author(s) 2023. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License (, which permits unrestricted use, sharing, adaptation, distribution and reproduction in any medium or format, for any purpose, even commercially, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.


    Dielectric capacitors with ultrafast charge-discharge rates are extensively used in electrical and electronic systems. To meet the growing demand for energy storage applications, researchers have devoted significant attention to dielectric ceramics with excellent energy storage properties. As a result, the awareness of the importance of the pulsed discharge behavior of dielectric ceramics and conducting characterization studies has been raised. However, the temperature stability of pulsed discharge behavior, which is significant for pulsed power applications, is still not given the necessary consideration. Here, we systematically investigate the microstructures, energy storage properties and discharge behaviors of nanograined (1-x)BaTiO3-xNaNbO3 ceramics prepared by a two-step sintering method. The 0.60BaTiO3-0.40NaNbO3 ceramics with relaxor ferroelectric characteristics possess an optimal discharge energy density of 3.07 J cm-3, a high energy efficiency of 92.6%, an ultrafast discharge rate of 39 ns and a high power density of 100 MW cm-3. In addition to stable energy storage properties in terms of frequency, fatigue and temperature, the 0.60BaTiO3-0.40NaNbO3 ceramics exhibit temperature-stable power density, thereby illustrating their significant potential for power electronics and pulsed power applications.


    Dielectric capacitors, as fundamental components in high-power energy storage and pulsed power systems, play an important role in many applications, including hybrid electric vehicles, portable electronics, medical devices and electromagnetic weapons, due to their high power density, ultrafast charge-discharge rates and long lifetimes[1-6]. However, most current commercial polymer dielectric capacitors and multilayer ceramic capacitors (MLCCs) possess somewhat low energy densities of < 1-2 J cm-3, which results in them occupying relatively large volumes and/or weights in devices[7-10]. The development of third-generation semiconductors and the need for device miniaturization have resulted in an urgent demand for high-energy-density dielectric capacitors[1,11].

    Under an applied voltage, the dielectric materials in dielectric capacitors polarize to store energy[1,12,13]. Their energy storage properties can be calculated through polarization-electric field (P-E) loops, namely, , and η = Wd/Wc, where Wc and Wd are the charge and discharge energy density, respectively, Pmax and Pr are the maximum and remnant polarization, respectively, and η is the energy efficiency[14-16]. Among all dielectric materials, relaxor ferroelectrics with high Pmax, low Pr, high breakdown strength (Eb) and slim P-E loops have been investigated extensively for their excellent energy storage properties[17-22]. The polar nanoregions in relaxor ferroelectrics can switch rapidly under an applied electric field, which significantly reduces loss and results in high η[23-28]. In addition, the excellent fatigue and temperature stability of the pulsed discharge behavior and energy storage properties are highly desirable for dielectric capacitors operating in harsh environments, i.e., aerospace fields and oil-well drilling[29-32]. Many strategies have been utilized to enhance the temperature stability of dielectric materials in recent years, including multiscale optimization[27], composite strategy design[28], unmatched temperature range design[33] and special sintering methods[34]. However, the temperature stability of pulsed discharge behavior is not given sufficient attention in current research into dielectric materials.

    In this study, we prepare nanograined (1-x)BaTiO3-xNaNbO3 ceramics, which possess relaxor ferroelectric characteristics with a good P-E relationship (high Pmax, low Pr and slim P-E loops) and high Eb, using a solid-state reaction method. The 0.60BaTiO3-0.40NaNbO3 ceramics exhibit an optimal Wd of 3.07 J cm-3 and a high η of 92.6% under 38.1 MV m-1 at ambient temperature. Stable energy storage properties in terms of frequency (0.1-100 Hz), fatigue (106 cycles) and temperature (25-120 °C) are also achieved. Moreover, the ceramics possess an ultrafast discharge rate of 39 ns and a high power density of 100 MW cm-3. The variation of the power density is less than 15% from 25 to 140 °C. All these results suggest that 0.60BaTiO3-0.40NaNbO3 ceramics are ideal candidates for energy storage applications in pulsed power systems.


    (1-x)BaTiO3-xNaNbO3 ((1-x)BT-xNN) dielectric ceramics with x = 0.35, 0.40, 0.45 and 0.50 were prepared through a conventional solid-state method. According to the stoichiometric ratio of (1-x)BT-xNN ceramics, BaCO3, TiO2, Na2CO3 and Nb2O5 powders with analytical grade, as the raw materials, were weighed and ball milled with ethanol for 24 h. The mixed powders were then dried at 80 °C and calcined at 950-1030 °C for 5 h in the closed alumina crucibles to avoid the volatilization of Na. Afterward, the calcined (1-x)BT-xNN powders were ground with a polyvinyl butyraldehyde solution (PVB, 10 wt.%) and uniaxially pressed into cylinders with a diameter of 8 mm and a thickness of 0.5 mm under a pressure of 2 MPa. The cylinders were heated at 600 °C for 5 h to remove the PVB binder and then sintered with a two-step sintering method[35,36] (all samples were heated to 1250-1350 °C for 1-10 min and then cooled down to 1100-1150 °C for 3-5 h).

    The ambient-temperature X-ray diffraction profiles of the (1-x)BT-xNN ceramics were obtained using a Rigaku 2500 X-ray diffractometer (Rigaku, Tokyo, Japan) with Cu Kα radiation and λ = 1.5418 Å. The surface microstructures of the ceramics after thermally etching at 1050 °C for 0.5 h were characterized using scanning electron microscopy (SEM, MERLIN VP Compact, Zeiss Ltd., Germany) at 15 kV. To measure the ferroelectric properties and pulsed discharge behaviors, the compact ceramics were polished down to 180-200 µm in thickness and then gold electrodes with a radius of 1.5 mm were sputtered on both surfaces. The P-E loops were measured using a TF ANALYZER 2000E ferroelectric measurement system (aixACCT Systems GmbH, Aachen, Germany) under different frequencies (0.1-100 Hz) and various temperatures (25-140 °C). The dielectric properties were measured under a frequency range of 1 kHz to 1 MHz and a temperature range of -150 to 300 °C using an impedance analyzer (E4980A, Agilent Technologies, USA). The overdamped and underdamped pulsed discharge behavior was measured using a charge-discharge platform (CFD-001, Gogo Instruments Technology, Shanghai, China) with a resistor-capacitance load circuit. More details regarding the resistor-capacitance circuit measurement system are given in Supplementary Figure 1.


    The ambient-temperature X-ray diffraction profiles of the (1-x)BT-xNN ceramics are displayed in Figure 1. All samples exhibit typical perovskite structures with traces of a Ba6Ti7Nb9O42 secondary phase (PDF#47-0522). The approximate amounts of Ba6Ti7Nb9O42 phases are displayed in Supplementary Table 1 and are less than 5% in all (1-x)BT-xNN ceramics. The (200) peaks between 45° and 46° without splitting suggest that all samples are mainly pseudocubic phases at room temperature. The cell parameters of (1-x)BT-xNN ceramics decrease with increasing NN content [Supplementary Table 2], which is mainly because the radius of Na+ (1.39 Å) is smaller than that of Ba2+ (1.61 Å). The SEM images of the surface and cross-section microstructures of the (1-x)BT-xNN ceramics are displayed in Figure 2 and Supplementary Figure 2. There are no obvious pores in the (1-x)BT-xNN ceramics, suggesting that all samples possess high relative density. The grain size distributions [Supplementary Figure 3] are counted by the Feret diameters of more than 250 grains from the SEM images, and they show that all the ceramics possess nanograins with average grain sizes of 180-280 nm. The grain size tends to increase with NN content and the distribution moves toward larger sizes. Generally, fine grains are conducive to achieving high Eb and η. The elemental distribution results of the 0.60BT-0.40NN ceramics are shown in Supplementary Figure 4, where it can be seen that all the elements are uniformly distributed in the ceramics.

    Figure 1. X-ray diffraction profiles of (1-x)BT-xNN ceramics.

    Figure 2. Surface microstructure images of (A) 0.65BT-0.35NN; (B) 0.60BT-0.40NN; (C) 0.55BT-0.45NN; and (D) 0.50BT-0.50NN.

    The temperature-dependent (150-300 °C) dielectric properties of the (1-x)BT-xNN ceramics were measured at various frequencies [Figure 3] and indicated prototypical relaxor ferroelectric characteristics. The dielectric constants of all the (1-x)BT-xNN ceramics at room temperature are ~1000-1200 and the Ba6Ti7Nb9O42 phases are considered to have paraelectric characteristics. Hence, the Ba6Ti7Nb9O42 phases may not significantly affect the dielectric characteristics of the ceramics. It can be found that the dielectric constant and the Curie temperature increase with increasing NN content. All the (1-x)BT-xNN ceramics exhibit low dielectric loss of less than 0.012 between -100 and 200 °C. Generally, the modified Curie-Weiss law, 1/ε – 1/εm = (T - Tm)γ/C, is utilized to describe the dielectric characteristics of relaxor ferroelectrics, where ε and εm are the dielectric constant and maximum value of ε, respectively, T and Tm are the corresponding temperatures, C is the Curie constant and γ is used to describe the degree of diffuseness. The γ value varies from one for typical ferroelectrics to two for ideal relaxor ferroelectrics[24,37]. The fitted γ values of all the ceramics are shown in Figure 4 and are between 1.686 and 1.766 at 1 MHz, thereby manifesting strong relaxation behavior. This strong relaxation behavior causes the (1-x)BT-xNN ceramics to respond rapidly under an applied electric field, resulting in high η.

    Figure 3. Temperature-dependent dielectric properties measured at 1 kHz to 1 MHz for (A) 0.65BT-0.35NN; (B) 0.60BT-0.40NN; (C) 0.55BT-0.45NN; and (D) 0.50BT-0.50NN.

    Figure 4. Fitted γ values for (A) 0.65BT-0.35NN; (B) 0.60BT-0.40NN; (C) 0.55BT-0.45NN; and (D) 0.50BT-0.50NN.

    The unipolar P-E loops of all ceramics measured at 25 °C and 20 MV m-1 are shown in Figure 5A, with all ceramics exhibiting slim P-E loops. Among these, the 0.55BT-0.45NN ceramics possess the largest Pmax and Pmax - Pr values [Figure 5B], leading to high Wd. However, due to the lower Pr, relatively larger Pmax - Pr value and the highest Eb [Figure 5B and C], a Wd of 3.07 J cm-3 and a high η of 92.6% are achieved in the 0.60BT-0.40NN ceramics at 38.1 MV m-1, which are the optimum energy storage properties among all the (1-x)BT-xNN ceramics at 25 °C [Figure 5D]. Figure 6 exhibits the energy storage properties as a function of the applied electric field. All BT-NN ceramics possess high Eb between 32.7 and 38.1 MV m-1 and high η between 87.5% and 93.0%. The corresponding current-field curves of the (1-x)BT-xNN ceramics are shown in Supplementary Figure 5, confirming the high η. Noticeably, the η of the 0.60BT-0.40NN ceramics decreases slightly with increasing E and shows a slight variation of < 4% within the whole electric field range tested, which is conducive to high η energy storage applications.

    Figure 5. (A) Unipolar P-E loops for (1-x)BT-xNN ceramics at 25 °C, 20 MV m-1 and 10 Hz. (B) Pmax, Pr and Pmax - Pr as a function of NN content. (C) Unipolar P-E loops at 25 °C, maximum applied electric field and 10 Hz. (D) Energy storage properties as a function of NN content.

    Figure 6. Energy storage properties at 25 °C and 10 Hz for (A) 0.65BT-0.35NN; (B) 0.60BT-0.40NN; (C) 0.55BT-0.45NN; and (D) 0.50BT-0.50NN.

    Given that the stability of the energy storage properties for dielectric materials is crucial in practical applications, the frequency, fatigue and temperature stabilities of the energy storage properties for the 0.60BT-0.40NN ceramics are characterized in Figure 7. The Pmax of the 0.60BT-0.40NN ceramics only decreases from 15.1 to 14.3 µC cm-2 with increasing frequency from 0.1 to 100 Hz, while the Pr remains almost unchanged [Figure 7A]. Hence, the variations in Wd and η are less than 6.0% and 1.2%, respectively [Figure 7B]. The stable frequency-dependent energy storage properties are realized because the polar nanoregions can switch rapidly under the applied electric field[38]. To evaluate the fatigue stability, the unipolar P-E loops under 15 MV m-1 are characterized for 106 cycles [Figure 7C]. Fortunately, the P-E loops have no noticeable change and the variations in Wd and η are less than 0.6% and 0.7%, respectively [Figure 7D]. Figure 7E exhibits the unipolar P-E loops measured under 20 MV m-1 at various temperatures. It can be found that the Pmax of the 0.60BT-0.40NN ceramics is consistent with the trend of the ε and gradually decreases with increasing temperature. The reduction in Pmax results in a decrease in Wd, while the η stays over 90% when the temperature is up to 120 °C. Figure 7F shows the energy storage properties (Wd and η) of the 0.60BT-0.40NN ceramics with increasing temperature from 25 to 120 °C, revealing good temperature stability.

    Figure 7. (A) Unipolar P-E loops of 0.60BT-0.40NN ceramics measured under 19 MV m-1 at various frequencies, (C) under 15 MV m-1 at different cycles and (E) under 20 MV m-1 at various temperatures. Corresponding (B) frequency-dependent, (D) fatigue-dependent and (F) temperature-dependent energy storage properties.

    In practical applications, dielectric capacitors charge and discharge at the microsecond or nanosecond timescale[1]. The Wd and η calculated by the P-E loops cannot reflect the true energy storage properties[39], so a resistor-capacitance circuit is constructed to evaluate the discharge behavior of the 0.60BT-0.40NN ceramics. Figure 8A displays the overdamped pulsed discharge electric current-time (I-t) curves at various E values. The corresponding Wd can be calculated using , where R and V are the load resistor (here R = 100 Ω) and the effective volume of the sample, respectively[40]. The discharge rate is usually described by the discharge time corresponding to the 90% stored Wd value, which is abbreviated as τ0.9. As the E increases, the current peak and Wd also increase. Finally, the Wd reaches 1.21 J cm-3 at 25 MV m-1 [Figure 8B]. In general, the Wd calculated by the I-t curve is always lower than that calculated by the P-E loop because the characterization mechanisms with different measurement frequencies[1] and dielectric material losses differ[41]. The τ0.9 of the 0.60BT-0.40NN ceramics is ~39 ns [Figure 8B]. The ultrafast discharge rate comes from the low hysteresis polarization response and the relaxor characteristic. This makes the 0.60BT-0.40NN ceramics more competitive in high-power applications[38,42]. Moreover, the undamped pulsed discharge current curves at 25 °C under various E values are displayed in Figure 8C. From the current curves, we can calculate the current density (CD) and power density (PD) from CD = Imax/S and PD = EImax/2S, where Imax and S represent the maximum value of the undamped pulsed discharge current curves and the electrode area, respectively[26]. The CD and PD of the 0.60BT-0.40NN ceramics at 25 MV m-1 are 801 A cm-2 and 100 MW cm-3, respectively [Figure 8D]. More importantly, from the undamped pulsed discharge current curves at 20 MV m-1 under various temperatures [Figure 8E], it can be found that the variations of CD and PD are ~15% from 25 to 140 °C [Figure 8F], which suggests that the 0.60BT-0.40NN ceramics have significant potential for pulsed power system applications.

    Figure 8. (A) Overdamped pulsed discharge current curves under various E values and (B) corresponding Wd as a function of time. Undamped pulsed discharge current curves (C) at 25 °C under various E values and (E) at 20 MV m-1 under various temperatures and (D and F) corresponding CD and PD values.


    In summary, the 0.60BT-0.40NN ceramics with relaxor ferroelectric characteristics have an optimal Wd of 3.07 J cm-3, a high η of 92.6%, a high PD of 100 MW cm-3 and an ultrafast τ0.9 of 39 ns. Moreover, they exhibit stable energy storage properties in terms of frequency (0.1-100 Hz), fatigue (106 cycles) and temperature (25-120 °C), as well as temperature-stable power density (25-140 °C). These ideal energy storage properties and pulsed discharge behavior make the 0.60BT-0.40NN ceramics more promising for high-stability energy storage MLCCs in pulsed power system applications.


    Author’s contributions

    Sample fabrication and characterization: Zhao P

    Data analysis and interpretation: Li L, Wang X

    Preparation of the manuscript and discussion: Zhao P, Li L, Wang X

    Availability of data and materials

    Data can be deposited into data repositories or published as supplementary information in the journal.

    Financial support and sponsorship

    This work was supported by Shuimu Tsinghua Scholar Program, Key-Area Research and Development Program of Guandong Province (No. 2019B090912003), National Natural Science Foundation of China (No. 52032005), High-end MLCC Key Project Supported by Guangdong Fenghua Advanced Technology Holding Co., Ltd.

    Conflicts of interest

    All authors declared that there are no conflicts of interest.

    Ethical approval and consent to participate

    Not applicable.

    Consent for publication

    Not applicable.


    © The Author(s) 2023.

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    Cite This Article

    OAE Style

    Zhao P, Li L, Wang X. BaTiO3-NaNbO3 energy storage ceramics with an ultrafast charge-discharge rate and temperature-stable power density. Microstructures 2023;3:2023002.

    AMA Style

    Zhao P, Li L, Wang X. BaTiO3-NaNbO3 energy storage ceramics with an ultrafast charge-discharge rate and temperature-stable power density. Microstructures. 2023; 3(1):2023002.

    Chicago/Turabian Style

    Zhao, Peiyao, Longtu Li, Xiaohui Wang. 2023. "BaTiO3-NaNbO3 energy storage ceramics with an ultrafast charge-discharge rate and temperature-stable power density" Microstructures. 3, no.1: 2023002.

    ACS Style

    Zhao, P.; Li L.; Wang X. BaTiO3-NaNbO3 energy storage ceramics with an ultrafast charge-discharge rate and temperature-stable power density. Microstructures. 20233, 2023002.




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