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Grain-orientation-engineered multilayer ceramic capacitors for energy storage applications

Nature Materials volume 19, pages 999–1005 (2020)Cite this article

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Abstract

Dielectric ceramics are highly desired for electronic systems owing to their fast discharge speed and excellent fatigue resistance. However, the low energy density resulting from the low breakdown electric field leads to inferior volumetric efficiency, which is the main challenge for practical applications of dielectric ceramics. Here, we propose a strategy to increase the breakdown electric field and thus enhance the energy storage density of polycrystalline ceramics by controlling grain orientation. We fabricated high-quality <111>-textured Na0.5Bi0.5TiO3–Sr0.7Bi0.2TiO3 (NBT-SBT) ceramics, in which the strain induced by the electric field is substantially lowered, leading to a reduced failure probability and improved Weibull breakdown strength, on the order of 103 MV m−1, an ~65% enhancement compared to their randomly oriented counterparts. The recoverable energy density of <111>-textured NBT-SBT multilayer ceramics is up to 21.5 J cm−3, outperforming state-of-the-art dielectric ceramics. The present research offers a route for designing dielectric ceramics with enhanced breakdown strength, which is expected to benefit a wide range of applications of dielectric ceramics for which high breakdown strength is required, such as high-voltage capacitors and electrocaloric solid-state cooling devices.

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Fig. 1: Finite-element simulations for the distribution of strains and elastic energies in a single layer of an MLCC.
Fig. 2: Fabrication process of <111>-oriented SrTiO3 templates.
Fig. 3: Texture quality of NBT-SBT multilayer ceramics.
Fig. 4: Comprehensive comparison of electric-field-induced strain, breakdown strength and energy storage performance for <111>-textured and nontextured NBT-SBT multilayer ceramics.
Fig. 5: Charge–discharge performance of <111>-textured NBT-SBT multilayer ceramics as functions of temperature and electric field cycle.

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Data availability

The data that support the findings of this study are included with the manuscript as Extended Data and Supplementary Information. Any other relevant data are also available upon request from F.L.

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Acknowledgements

J.L., Z.X. and F.L. thank the National Natural Science Foundation of China (grant nos 51922083, 51831010 and 51802182), the development programme of Shaanxi province (grant no. 2019ZDLGY04-09) and the 111 Project (B14040). S.Z. thanks ARC (FT140100698). Y.C. thanks the National Natural Science Foundation of China (11572103) and the Natural Science Foundation of Heilongjiang Province (YQ2019E026). We thank Z. Ren at Instrument Analysis Center of Xi’an Jiaotong University for his assistence with SEM-EBSD analysis.

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Authors and Affiliations

  1. Electronic Materials Research Laboratory (Key Lab of Education Ministry), State Key Laboratory for Mechanical Behavior of Materials and School of Electronic Science and Engineering, Xi’an Jiaotong University, Xi’an, China

    Jinglei Li, Shuai Yang, Wenlong Zhou, Mingwen Wang, Linghang Wang, Zhuo Xu & Fei Li

  2. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Center for Smart Materials and Device Integration, International School of Material Science and Engineering, Wuhan University of Technology, Wuhan, China

    Zhonghui Shen

  3. State Key Laboratory for Strength and Vibration of Mechanical Structures, School of Aerospace Engineering, Xi’an Jiaotong University, Xi’an, China

    Xianghua Chen & Qun Li

  4. Condensed Matter Science and Technology Institute, School of Instrumentation Science and Engineering, Harbin Institute of Technology, Harbin, China

    Qiangwei Kou, Yingchun Liu & Yunfei Chang

  5. Institute for Superconducting and Electronic Materials, AIIM, University of Wollongong, Wollongong, NSW, Australia

    Shujun Zhang

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Contributions

The work was conceived and designed by J.L., S.Z. and F.L.; J.L. fabricated the capacitors and performed microstructure and dielectric experiments; Z.S., X.C. and Q.L. performed finite-element simulations; and S.Y., W.Z., M.W., L.W., Y.L., Q.K. and Y.C. assisted in the fabrication of templates and textured ceramics. F.L., S.Z., Y.C. and Z.X. supervised the fabrication and test of the samples. F.L. and J.L. drafted the manuscript; S.Z. revised the manuscript; and all authors discussed the results.

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Correspondence to Yunfei Chang, Shujun Zhang or Fei Li.

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Extended data

Extended Data Fig. 1 Finite element simulation of the distributions of strains and electric fields for a dielectric material with a pore under an applied electric field of 70 MV m−1 along X-direction.

a-d, The strains along X direction, the Von Mises equivalent strain (Total-strain), the magnitude of electric field along X direction and total electric field, respectively, for <001>-oriented perovskite dielectric. e-h, The strains along X direction, the Von Mises equivalent strain, the magnitude of electric field along x direction and total electric field, respectively, for <111>-oriented perovskite dielectric.

Extended Data Fig. 2 SEM and EDX images for <111>-oriented SrTiO3 templates.

a, SEM image of <111> SrTiO3 templates. b–e, the EDX images of the Ti, Sr, Ba, and O elements, respectively.

Extended Data Fig. 3 Analysis of the size of <111> SrTiO3 templates used for textured-ceramics fabrication.

a,b, the distributions of the thickness and the length of <111>-oriented SrTiO3 templates, respectively.

Extended Data Fig. 4 Enlarged SEM images for <111>-textured and nontextured NBT-0.35SBT MLCCs.

a,b, <111>-textured samples; c,d, nontextured samples.

Extended Data Fig. 5 Polarization-vs-Electric field (PE) loops for <111>-textured and nontextured NBT-0.35SBT MLCCs.

a-c, <111>-textured samples; d-f, nontextured samples.

Extended Data Fig. 6 Finite-element simulations for the distribution of electric fields for textured NBT-SBT.

a, Distribution of electric fields in the textured NBT-SBT with SrTiO3 templates. b, An enlarged part around a SrTiO3 template. c, The averaged electric fields (along y-direction) on SrTiO3 templates and NBT-SBT matrix. In the simulation, the effective dielectric constantof NBT-SBT is set to 1500, while the dielectric constant of SrTiO3 is set to 300 from the reference; the thicknesses of NBT-SBT dielectric layer and SrTiO3 templates are set to 20 μm and 1 μm, respectively. To simulate the distribution of electric fields, we applied 1400 V on the sample, which means that the electric field should be 70 MV m−1 on the dielectric layer if there are no templates.

Extended Data Fig. 7 Microstructures and properties of <100>-textured NBT-0.35SBT multilayer ceramics.

a, XRD patterns of the main surface of the <100>-textured sample (red line) and nontextured sample (black line). b, Grain orientations for the <100>-textured sample, measured by SEM-EBSD technique. c, Electric-field-induced strains for <111>-textured, <100>-textured and nontextured samples. d, Weibull distribution of the breakdown electric field for <100>-textured samples, comparing to <111>-textured and nontextured counterparts. e, Polarization-vs-electric field (PE) curve of the <100>-textured sample. Five samples were used for measuring the PE curves, while the one with the highest energy density is given here.

Extended Data Fig. 8 Relative dielectric permittivity with respect to the d.c. bias electric field for <111>-textured NBT-0.35SBT ceramics.

a-d, The dielectric permittivity vs d.c. bias electric field at room temperature under the frequencies of 1k, 10k, 100k, and 1 M Hz, respectively.

Extended Data Fig. 9 Polarization-vs-electric field curves for five <111>-textured NBT-0.35SBT multilayer ceramic samples.

a-e, the PE curves of samples 1-5, respectively; f, the energy density and efficiency of the five samples.

Supplementary information

Supplementary Information

Supplementary Figs. 1–6, Tables 1–2 and refs. 1–37.

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Li, J., Shen, Z., Chen, X. et al. Grain-orientation-engineered multilayer ceramic capacitors for energy storage applications. Nat. Mater. 19, 999–1005 (2020). https://doi.org/10.1038/s41563-020-0704-x

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