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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.

References

  1. Pan, H. et al. Ultrahigh-energy density lead-free dielectric films via polymorphic nanodomain design. Science 365, 578–582 (2019).

    CAS  Google Scholar 

  2. Li, Q. et al. Flexible high-temperature dielectric materials from polymer nanocomposites. Nature 523, 576–579 (2015).

    CAS  Google Scholar 

  3. Chu, B. J. et al. A dielectric polymer with high electric energy density and fast discharge speed. Science 313, 334–336 (2006).

    CAS  Google Scholar 

  4. Xu, B., Iniguez, J. & Bellaiche, L. Designing lead-free antiferroelectrics for energy storage. Nat. Commun. 8, 15682 (2017).

    CAS  Google Scholar 

  5. Kumar, N. et al. Multilayer ceramic capacitors based on relaxor BaTiO3-Bi(Zn1/2Ti1/2)O3 for temperature stable and high energy density capacitor applications. Appl. Phys. Lett. 106, 252901 (2015).

    Google Scholar 

  6. Hou, C. M. et al. Ultrahigh energy density in SrTiO3 film capacitors. ACS Appl. Mater. Inter. 9, 20484–20490 (2017).

    CAS  Google Scholar 

  7. Cai, Z. M. et al. Giant dielectric breakdown strength together with ultrahigh energy density in ferroelectric bulk ceramics via layer-by-layer engineering. J. Mater. Chem. A 7, 17283–17291 (2019).

    CAS  Google Scholar 

  8. Palneedi, H., Peddigari, M., Hwang, G. T., Jeong, D. Y. & Ryu, J. High-performance dielectric ceramic films for energy storage capacitors: progress and outlook. Adv. Funct. Mater. 28, 1803665 (2018).

    Google Scholar 

  9. Neusel, C. et al. Thickness-dependence of the breakdown strength: analysis of the dielectric and mechanical failure. J. Eur. Ceram. Soc. 35, 113–123 (2015).

    CAS  Google Scholar 

  10. Li, F. et al. Fine-grain induced outstanding energy storage performance in novel Bi0.5K0.5TiO3-Ba(Mg1/3Nb2/3)O3 ceramics via a hot-pressing strategy. J. Mater. Chem. C 7, 12127–12138 (2019).

    CAS  Google Scholar 

  11. Liu, B. B., Wang, X. H., Zhang, R. X. & Li, L. T. Grain size effect and microstructure influence on the energy storage properties of fine-grained BaTiO3-based ceramics. J. Am. Ceram. Soc. 100, 3599–3607 (2017).

    CAS  Google Scholar 

  12. Kim, C., Pilania, G. & Ramprasad, R. From organized high-throughput data to phenomenological theory using machine learning: the example of dielectric breakdown. Chem. Mater. 28, 1304–1311 (2016).

    CAS  Google Scholar 

  13. Shindo, Y., Yoshida, M., Narita, F. & Horiguchi, K. Electroelastic field concentrations ahead of electrodes in multilayer piezoelectric actuators: experiment and finite element simulation. J. Mech. Phys. Solids 52, 1109–1124 (2004).

    Google Scholar 

  14. Li, F., Wang, L. H., Jin, L., Xu, Z. & Zhang, S. J. Achieving single domain relaxor-PT crystals by high temperature poling. CrystEngComm 16, 2892–2897 (2014).

    CAS  Google Scholar 

  15. Li, F., Jin, L., Xu, Z. & Zhang, S. J. Electrostrictive effect in ferroelectrics: an alternative approach to improve piezoelectricity. Appl. Phys. Rev. 1, 011103 (2014).

    Google Scholar 

  16. Shen, Z. H. et al. Phase-field modeling and machine learning of electric-thermal-mechanical breakdown of polymer-based dielectrics. Nat. Commun. 10, 1843 (2019).

    Google Scholar 

  17. Zhao, X. J., Liu, B. & Fang, D. N. Study on electroelastic field concentration around the electrode tip in multilayer ferroelectric actuators of two designs and their optimizations. Int. J. Plast. 26, 533–548 (2010).

    CAS  Google Scholar 

  18. Ang, C. & Yu, Z. High remnant polarization in (Sr0.7Bi0.2)TiO3-(Na0.5Bi0.5)TiO3 solid solutions. Appl. Phys. Lett. 95, 232908 (2009).

    Google Scholar 

  19. Li, J. L., Li, F., Xu, Z. & Zhang, S. J. Multilayer lead-free ceramic capacitors with ultrahigh energy density and efficiency. Adv. Mater. 30, 1802155 (2018).

    Google Scholar 

  20. Seabaugh, M. M. et al. Development of a templated grain growth system for texturing piezoelectric ceramics. J. Intell. Mater. Syst. Struct. 15, 209–214 (2004).

    CAS  Google Scholar 

  21. Negishi, Y. & Kimura, T. Approaches for preparing <111>-textured Bi0.5Na0.5TiO3-based ceramics by hetero-templated grain growth. Ceram. Int. 38, 5103–5112 (2012).

    CAS  Google Scholar 

  22. Boukheit, N., Karaali, A., Touil, A., Mirouh, K. & Treheux, D. Analogies between the mechanical and dielectric properties in the ceramic material type oxide. Mater. Sci. Eng. A Struct. 502, 144–147 (2009).

    Google Scholar 

  23. Zeller, H. R. & Schneider, W. R. Electrofracture mechanics of dielectric aging. J. Appl. Phys. 56, 455–459 (1984).

    CAS  Google Scholar 

  24. Yang, L. T. et al. Perovskite lead-free dielectrics for energy storage applications. Prog. Mater. Sci. 102, 72–108 (2019).

    CAS  Google Scholar 

  25. Chauhan, A., Patel, S. & Vaish, R. Effect of directional mechanical confinement on the electrical energy storage density in 68Pb(Mn1/3Nb2/3)O3-32PbTiO3 single crystals. Ferroelectrics 478, 40–53 (2015).

    CAS  Google Scholar 

  26. Yuan, Q. B. et al. Simultaneously achieved temperature-insensitive high energy density and efficiency in domain engineered BaTiO3-Bi(Mg0.5Zr0.5)O3 lead-free relaxor ferroelectrics. Nano Energy 52, 203–210 (2018).

    CAS  Google Scholar 

  27. Cai, Z. M. et al. High-temperature lead-free multilayer ceramic capacitors with ultrahigh energy density and efficiency fabricated via two-step sintering. J. Mater. Chem. A 7, 14575–14582 (2019).

    CAS  Google Scholar 

  28. Huang, Y. H. et al. From core-shell Ba0.4Sr0.6TiO3@SiO2 particles to dense ceramics with high energy storage performance by spark plasma sintering. J. Mater. Chem. A 6, 4477–4484 (2018).

    CAS  Google Scholar 

  29. Liu, X. H., Li, Y. & Hao, X. H. Ultra-high energy-storage density and fast discharge speed of (Pb0.98-xLa0.02Srx)(Zr0.9Sn0.1)0.995O3 antiferroelectric ceramics prepared via the tape-casting method. J. Mater. Chem. A 7, 11858–11866 (2019).

    CAS  Google Scholar 

  30. Luo, N. N. et al. Aliovalent A-site engineered AgNbO3 lead-free antiferroelectric ceramics toward superior energy storage density. J. Mater. Chem. A 7, 14118–14128 (2019).

    CAS  Google Scholar 

  31. Qi, H. et al. Ultrahigh energy-storage density in NaNbO3-based lead-free relaxor antiferroelectric ceramics with nanoscale domains. Adv. Funct. Mater. 29, 1903877 (2019).

    Google Scholar 

  32. Shao, T. Q. et al. Potassium-sodium niobate based lead-free ceramics: novel electrical energy storage materials. J. Mater. Chem. A 5, 554–563 (2017).

    CAS  Google Scholar 

  33. Tian, Y. et al. High energy density in silver niobate ceramics. J. Mater. Chem. A 4, 17279–17287 (2016).

    CAS  Google Scholar 

  34. Wang, D. W. et al. Bismuth ferrite-based lead-free ceramics and multilayers with high recoverable energy density. J. Mater. Chem. A 6, 4133–4144 (2018).

    CAS  Google Scholar 

  35. Wang, G. et al. Ultrahigh energy storage density lead-free multilayers by controlled electrical homogeneity. Energy Environ. Sci. 12, 582–588 (2019).

    CAS  Google Scholar 

  36. Wang, H. S., Liu, Y. C., Yang, T. Q. & Zhang, S. J. Ultrahigh energy-storage density in antiferroelectric ceramics with field-induced multiphase transitions. Adv. Funct. Mater. 29, 1807321 (2019).

    Google Scholar 

  37. Wu, J. Y. et al. Perovskite Srx(Bi1-xNa0.97-xLi0.03)0.5TiO3 ceramics with polar nano regions for high power energy storage. Nano Energy 50, 723–732 (2018).

    CAS  Google Scholar 

  38. Yan, Z. N. et al. Silver niobate based lead-free ceramics with high energy storage density. J. Mater. Chem. A 7, 10702–10711 (2019).

    CAS  Google Scholar 

  39. Yang, L. T., Kong, X., Cheng, Z. X. & Zhang, S. J. Ultra-high energy storage performance with mitigated polarization saturation in lead-free relaxors. J. Mater. Chem. A 7, 8573–8580 (2019).

    CAS  Google Scholar 

  40. Yang, X. M. et al. High energy storage density and ultrafast discharge in lead lutetium niobate based ceramics. J. Mater. Chem. A 7, 8414–8422 (2019).

    CAS  Google Scholar 

  41. Yang, Z. T. et al. Significantly enhanced recoverable energy storage density in potassium-sodium niobate-based lead free ceramics. J. Mater. Chem. A 4, 13778–13785 (2016).

    CAS  Google Scholar 

  42. Yang, Z. T. et al. Grain size engineered lead-free ceramics with both large energy storage density and ultrahigh mechanical properties. Nano Energy 58, 768–777 (2019).

    CAS  Google Scholar 

  43. Yin, J., Zhang, Y. X., Lv, X. & Wu, J. G. Ultrahigh energy-storage potential under low electric field in bismuth sodium titanate-based perovskite ferroelectrics. J. Mater. Chem. A 6, 9823–9832 (2018).

    CAS  Google Scholar 

  44. Zhao, L., Liu, Q., Gao, J., Zhang, S. J. & Li, J. F. Lead-free antiferroelectric silver niobate tantalate with high energy storage performance. Adv. Mater. 29, 1701824 (2017).

    Google Scholar 

  45. Zhou, M. X., Liang, R. H., Zhou, Z. Y. & Dong, X. L. Superior energy storage properties and excellent stability of novel NaNbO3-based lead-free ceramics with A-site vacancy obtained via a Bi2O3 substitution strategy. J. Mater. Chem. A 6, 17896–17904 (2018).

    CAS  Google Scholar 

  46. Pan, H. et al. Giant energy density and high efficiency achieved in bismuth ferrite-based film capacitors via domain engineering. Nat. Commun. 9, 1813 (2018).

    Google Scholar 

  47. Yadav, A. K. et al. High energy storage density and stable fatigue resistance of Na0.46Bi0.46Ba0.05La0.02Zr0.03Ti0.97-xSnxO3 ceramics. Ceram. Int. 46, 5681–5688 (2020).

    CAS  Google Scholar 

  48. Shi, W. J. et al. The ferroelectric, dielectric and energy storage properties of Pb-free 0.6Na0.5Bi0.5TiO3-0.4SrTiO3 bulk ceramics modified by Fe2O3. Mater. Res. Express 6, 086329 (2019).

    CAS  Google Scholar 

  49. Huang, Y. et al. (Bi0.51Na0.47)TiO3 based lead free ceramics with high energy density and efficiency. J. Materiomics 5, 385–393 (2019).

    Google Scholar 

  50. Lu, S. G. et al. Electrical field dependence of electrocaloric effect in relaxor ferroelectrics. Ceram. Int. 41, S15–S18 (2015).

    CAS  Google Scholar 

  51. Mischenko, A. S., Zhang, Q., Scott, J. F., Whatmore, R. W. & Mathur, N. D. Giant electrocaloric effect in thin-film PbZr0.95Ti0.05O3. Science 311, 1270–1271 (2006).

    CAS  Google Scholar 

  52. Nair, B. et al. Large electrocaloric effects in oxide multilayer capacitors over a wide temperature range. Nature 575, 468–472 (2019).

    CAS  Google Scholar 

  53. Wu, J. et al. Topochemical transformation of single crystalline SrTiO3 microplatelets from Bi4Ti3O12 precursors and their orientation-dependent surface piezoelectricity. CrystEngComm 20, 3084–3095 (2018).

    CAS  Google Scholar 

  54. Chen, L.-Q. in Physics of Ferroelectrics Appendix A, 363–372 (Springer, 2007).

Download references

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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