Abstract
A critical challenge for the application of lead-free antiferroelectrics in energy storage systems is their poor thermal stability and low efficiency when the superior energy storage density is attained, primarily due to the inherent first-order nature and narrow temperature window of antiferroelectric-to-ferroelectric transitions. Here, we elucidate a unique percolating interaction between antipolar regions in antiferroelectrics and engineered defect pairs using density functional theory and phase field calculations. Strategic distribution of the strongly coupled Li-Ta pairs in AgNbO3 fosters a percolating interaction that facilitates antipolar rotations, enabling a pronounced polarization change with minimal hysteresis. Guided by theoretical calculations, a large recoverable energy storage density of 12.8 J/cm3, with a high efficiency of 90%, is achieved at room temperature in Ag0.95Li0.05Nb0.35Ta0.65O3 ceramics. Moreover, the superior energy storage performance can remain stable within a wide temperature range from −70 to 170 °C, which paves the way for application in advanced energy capacitors.
Similar content being viewed by others
Data availability
The data supporting the findings of this study are available within the paper and its Supplementary Information. Relevant additional data can be obtained from the corresponding author upon request.
References
Wang, G. et al. Electroceramics for high-energy density capacitors: current status and future perspectives. Chem. Rev. 121, 6124–6172 (2021).
Zhang, M. et al. Ultrahigh energy storage in high-entropy ceramic capacitors with polymorphic relaxor phase. Science 384, 185–189 (2024).
Shu, L. et al. Partitioning polar-slush strategy in relaxors leads to large energy-storage capability. Science 385, 204–209 (2024).
Pan, H. et al. Ultrahigh-energy density lead-free dielectric films via polymorphic nanodomain design. Science 365, 578–582 (2019).
Liu, Z. et al. Antiferroelectrics for energy storage applications: a review. Adv. Mater. Technol. 3, 1800111 (2018).
Wang, H. et al. Ultrahigh energy-storage density in antiferroelectric ceramics with field-induced multiphase transitions. Adv. Funct. Mater. 29, 1807321 (2019).
Akram, F. et al. Thermally-stable high energy-storage performance over a wide temperature range in relaxor-ferroelectric Bi1/2Na1/2TiO3-based ceramics. Ceram. Int. 47, 23488–23496 (2021).
Hao, X., Zhai, J., Kong, L. B. & Xu, Z. A comprehensive review on the progress of lead zirconate-based antiferroelectric materials. Prog. Mater. Sci. 63, 1–57 (2014).
Zhao, L., Liu, Q., Gao, J., Zhang, S. & Li, J. F. Lead-free antiferroelectric silver niobate tantalate with high energy storage performance. Adv. Mater. 29, 1701824 (2017).
Yang, D. et al. Lead-free antiferroelectric niobates AgNbO3 and NaNbO3 for energy storage applications. J. Mater. Chem. A 8, 23724–23737 (2020).
Tian, Y. et al. Silver niobate perovskites: structure, properties and multifunctional applications. J. Mater. Chem. A 10, 14747–14787 (2022).
Fu, D. et al. Ferroelectricity of Li-doped silver niobate (Ag, Li)NbO3. J. Phys. Condens. Matter 23, 075901 (2011).
Dai, K. et al. Phase diagram with an antiferroelectric/ferroelectric phase boundary in AgNbO3-LiTaO3 energy-storage ceramics by lattice dynamics and electronic transitions. Phys. Rev. B 104, 174104 (2021).
Yang, Y. et al. Excellent energy storage performance of Nd-modified lead-free AgNbO3 ceramics via triple collaborative optimization. Nano Energy 131, 110242 (2024).
Chao, W., Gao, J., Yang, T. & Li, Y. Excellent energy storage performance in La and Ta co-doped AgNbO3 antiferroelectric ceramics. J. Eur. Ceram. Soc. 41, 7670–7677 (2021).
Yuan, H. et al. Simultaneous enhancement of breakdown strength, recoverable energy storage density and efficiency in antiferroelectric AgNbO3 ceramics via multi-scale synergistic design. Chem. Eng. J. 456, 141023 (2023).
Huang, K. et al. Ultralow electrical hysteresis along with high energy-storage density in lead-based antiferroelectric ceramics. Adv. Electron. Mater. 6, 1901366 (2020).
Mohapatra, P. et al. Effect of electric hysteresis on fatigue behavior in antiferroelectric bulk ceramics under bipolar loading. J. Mater. Chem. C 9, 15542 (2021).
Feng, Y. et al. Effect of La modifier on the electric hysteresis of lead zirconate stannate titanate compounds. Ceram. Int. 30, 1393–1396 (2004).
Li, F., Zhang, S., Damjanovic, D., Chen, L.-Q. & Shrout, T. R. Local structural heterogeneity and electromechanical responses of ferroelectrics: learning from relaxor ferroelectrics. Adv. Funct. Mater. 28, 1801504 (2018).
Li, J. et al. Grain-orientation-engineered multilayer ceramic capacitors for energy storage applications. Nat. Mater. 19, 999–1005 (2020).
Randall, C. A., Fan, Z., Reaney, I., Chen, L. Q. & Trolier-McKinstry, S. Antiferroelectrics: history, fundamentals, crystal chemistry, crystal structures, size effects, and applications. J. Am. Ceram. Soc. 104, 3775–3810 (2021).
Yang, B. et al. Enhanced energy storage in antiferroelectrics via antipolar frustration. Nature 637, 1104–1110 (2025).
Luo, N. et al. Constructing phase boundary in AgNbO3 antiferroelectrics: pathway simultaneously achieving high energy density and efficiency. Nat. Commun. 11, 4824 (2020).
Chen, L., Zhou, C., Zhu, L., Qi, H. & Chen, J. Compromise optimized superior energy storage performance in lead-free antiferroelectrics by antiferroelectricity modulation and nanodomain engineering. Small 20, 2306486 (2024).
He, L. Q. et al. Superior energy storage properties with thermal stability in lead-free ceramics by constructing an antiferroelectric/relaxor-antiferroelectric crossover. Acta Mater. 249, 118826 (2023).
Li, S. et al. Giant energy density and high efficiency achieved in silver niobate-based lead-free antiferroelectric ceramic capacitors via domain engineering. Energy Storage Mater. 34, 417–426 (2021).
Wu, S. et al. Superb energy storage capability for NaNbO3-based ceramics featuring labyrinthine submicro-domains with clustered lattice distortions. Small 19, 2303915 (2023).
Zhang, L. et al. Glass-glass transitions by means of an acceptor-donor percolating electric-dipole network. Phys. Rev. Appl. 8, 054018 (2017).
He, L. Q. et al. Large electrostrain with nearly-vanished hysteresis in eco-friendly perovskites by building coexistent glasses near quadruple point. Nano Energy 90, 106519 (2021).
Zhang, L. et al. Superior electrostrain with excellent thermal stability by constructing glassy ferroelectric crossover. Acta Mater. 294, 121153 (2025).
Li, F. et al. Ultrahigh piezoelectricity in ferroelectric ceramics by design. Nat. Mater. 17, 349–354 (2018).
Fang, X. et al. Low-field-driven superior energy storage effect with excellent thermal stability by constructing coexistent glasses. ACS Appl. Mater. Interfaces 16, 11497–11505 (2024).
Sun, Y. et al. Ultrahigh energy storage density in glassy ferroelectric thin films under low electric field. Adv. Sci. 9, 2203926 (2022).
Song, A. et al. Antiferroelectricity and ferroelectricity in A-site doped silver niobate lead-free ceramics. J. Eur. Ceram. Soc. 41, 1236–1243 (2021).
Farid, U., Gibbs, A. S. & Kennedy, B. J. Impact of Li doping on the structure and phase stability in AgNbO3. Inorg. Chem. 59, 12595–12607 (2020).
Gopalan, V. & Gupta, M. C. Observation of internal field in LiTaO3 single crystals: Its origin and time-temperature dependence. Appl. Phys. Lett. 68, 888–890 (1996).
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).
Zhang, L. et al. Ultra-weak polarization-strain coupling effect boosts capacitive energy storage. Adv. Mater. 36, 2406219 (2024).
Yang, J. et al. Field-induced strain engineering to optimize antiferroelectric ceramics in breakdown strength and energy storage performance. Acta Mater. 257, 119186 (2023).
Cai, H. et al. Significantly improved energy storage properties and cycling stability in La-doped PbZrO3 antiferroelectric thin films by chemical pressure tailoring. J. Eur. Ceram. Soc. 39, 4761–4769 (2019).
Soon, H. P. et al. Ferroelectricity triggered in the quantum paraeletric AgTaO3 by Li-substitution. Appl. Phys. Lett. 95, 242904 (2009).
Jin, L., Li, F. & Zhang, S. Decoding the fingerprint of ferroelectric loops: comprehension of the material properties and structures. J. Am. Ceram. Soc. 97, 1–27 (2014).
Valant, M., Axelsson, A.-K. & Alford, N. Review of Ag(Nb, Ta)O3 as a functional material. J. Eur. Ceram. Soc. 27, 2549–2560 (2007).
Gao, S. et al. Ultrahigh energy density and excellent discharge properties in Ce4+ and Ta5+ co-modified AgNbO3 relaxor antiferroelectric ceramics via multiple design strategies. Acta Mater. 246, 118730 (2023).
Lu, Z. et al. Mechanism of enhanced energy storage density in AgNbO3-based lead-free antiferroelectrics. Nano Energy 79, 105423 (2021).
Liao, Q. et al. Ultrahigh energy storage performance in AN-based superparaelectric ceramics. Chem. Eng. J. 488, 150901 (2024).
Chen, H. et al. Excellent energy storage properties and stability of NaNbO3-Bi(Mg0.5Ta0.5)O3 ceramics by introducing (Bi0.5Na0.5)0.7Sr0.3TiO3. J. Mater. Chem. A 9, 4789–4799 (2021).
Jiang, J. et al. Enhanced energy storage properties of lead-free NaNbO3-based ceramics via A/B-site substitution. Chem. Eng. J. 422, 130130 (2021).
Wang, Z. et al. Ultra-high energy storage in lead-free NaNbO3-based relaxor ceramics with directional slush-like polar structures design. Nat. Commun. 16, 2892 (2025).
Wang, X. et al. Lead-free high permittivity quasi-linear dielectrics for giant energy storage multilayer ceramic capacitors with broad temperature stability. Adv. Energy Mater. 14, 2400821 (2024).
Palneedi, H. et al. High-performance dielectric ceramic films for energy storage capacitors: progress and outlook. Adv. Funct. Mater. 28, 1803665 (2018).
Li, D. et al. A high-temperature performing and near-zero energy loss lead-free ceramic capacitor. Energy Environ. Sci. 16, 4511–4521 (2023).
Wang, W. et al. Effective strategy to improve energy storage properties in lead-free (Ba0.8Sr0.2)TiO3-Bi(Mg0.5Zr0.5)O3 relaxor ferroelectric ceramics. Chem. Eng. J. 446, 137389 (2022).
Qi, H. & Zuo, R. Linear-like lead-free relaxor antiferroelectric (Bi0.5Na0.5)TiO3-NaNbO3 with giant energy-storage density/efficiency and super stability against temperature and frequency. J. Mater. Chem. A 7, 3971–3978 (2019).
Zhu, X. et al. Ultrahigh energy storage density in (Bi0.5Na0.5)0.65Sr0.35TiO3-based lead-free relaxor ceramics with excellent temperature stability. Nano Energy 98, 107276 (2022).
Chen, L. et al. Outstanding energy storage performance in high-hardness (Bi0.5K0.5)TiO3-based lead-free relaxors via multi-scale synergistic design. Adv. Funct. Mater. 32, 2110478 (2021).
Hu, Q. et al. Achieve ultrahigh energy storage performance in BaTiO3-Bi(Mg1/2Ti1/2)O3 relaxor ferroelectric ceramics via nano-scale polarization mismatch and reconstruction. Nano Energy 67, 104264 (2020).
Luo, 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).
Chen, L. et al. Giant energy-storage density with ultrahigh efficiency in lead-free relaxors via high-entropy design. Nat. Commun. 13, 3089 (2022).
Tian, Y. et al. Phase transitions in tantalum-modified silver niobate ceramics for high power energy storage. J. Mater. Chem. A 7, 834–842 (2019).
Li, D. et al. Improved energy storage properties achieved in (K, Na)NbO3-based relaxor ferroelectric ceramics via a combinatorial optimization strategy. Adv. Funct. Mater. 32, 2111776 (2021).
Kong, X. et al. High-entropy engineered BaTiO3-based ceramic capacitors with greatly enhanced high-temperature energy storage performance. Nat. Commun. 16, 885 (2025).
Yu, H. et al. Design of polymorphic heterogeneous shell in relaxor antiferroelectrics for ultrahigh capacitive energy storage. Nat. Commun. 16, 886 (2025).
Zhao, W. et al. Broad-high operating temperature range and enhanced energy storage performances in lead-free ferroelectrics. Nat. Commun. 14, 5725 (2023).
Xu, J. et al. Superior energy storage performance in a self-organized trirelaxor-antiferroelectric nanocomposite over a wide temperature range. Adv. Mater. 37, e2502788 (2025).
Ali, S. et al. Mapping the low tolerance factor Bi(Li1/3Zr2/3)O3 end member and MPB composition nexus in Bi1/2Na1/2TiO3-based ceramics. Chem. Eng. J. 485, 150087 (2024).
Dai, K. et al. High pressure phase boundaries of AgNbO3. J. Materiomics 10, 431–439 (2024).
Sheeraz, M. et al. Enhanced ferroelectricity in perovskite oxysulfides. Phys. Rev. Mater. 3, 084405 (2019).
Ding, X. et al. The intermediate phase and low wavenumber phonon modes in antiferroelectric (Pb0.97La0.02)(Zr0.60Sn0.40-yTiy)O3 ceramics discovered from temperature dependent Raman spectra. J. Alloy Compd. 667, 310–316 (2016).
Li, S. et al. Novel AgNbO3-based lead-free ceramics featurig excellent pyroelectric properties for infrared detecting and energy-harvesting applications via antiferroelectric/ferroelectric phase boundary design. J. Mater. Chem. C 7, 4403–4414 (2019).
Viehland, D. et al. Freezing of the polarization fluctuations in lead magnesium niobate relaxors. J. Appl. Phys. 68, 2916 (1990).
Bing, Y.-H., Bokov, A. A. & Ye, Z.-G. Diffuse and sharp ferroelectric phase transitions in relaxors. Curr. Appl. Phys. 11, S14–S21 (2011).
Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).
Perdew, J. P. et al. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B Condens. Matter. 46, 6671–6687 (1992).
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B Condens. Matter. 50, 17953–17979 (1994).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Chen, L.-Q. & Zhao, Y. From classical thermodynamics to phase-field method. Prog. Mater. Sci. 124, 100868 (2022).
Xu, K., Shi, X., Dong, S., Wang, J. & Huang, H. Antiferroelectric phase diagram enhancing energy-storage performance by phase-field simulations. ACS Appl. Mater. Interfaces 14, 25770–25780 (2022).
Liu, Z. & Xu, B.-X. Insight into perovskite antiferroelectric phases: Landau theory and phase field study. Scr. Mater. 186, 136–141 (2020).
Acknowledgements
The work was financially supported by the National Natural Science Foundation of China (52102146, 52171012), National Natural Science Youth Foundation of China (Grant No. 12204393), the National Key Research and Development Program of China (2022YFE0109500), the Key R&D Project of Shaanxi Province (2023GXLH-006), China Postdoctoral Science Foundation (GZC20232067), China Scholarship Council (202306280326), the Young Talent Support Project of Xi’an Jiaotong University (WL6J020), the Research Grant Council of Hong Kong Special Administrative Region China (Project No. PolyU25300022), the GuangDong Basic and Applied Basic Research Foundation of the Department of Science and Technology of Guangdong Province (Grant No. 2024A1515012752), the Outstanding Youth Fund of Shaanxi Province (2024JC-JCQN-45), the Qin Chuangyuan “Scientist + Engineer” Team Building Project (2023KXJ-183), and 111 Project (BP0618008). The authors acknowledge the technical support regarding the simulation from Prof. Junkai Deng of Xi’an Jiaotong University, China. The technical support from the Computing Center in Xi’an is also acknowledged.
Author information
Authors and Affiliations
Contributions
L.Z. and D.W. conceived and designed the experiments. J.G., Z.Z., and Y.R. performed the TEM observations. L.H., Y.L., and C.Z. fabricated the samples and performed the electrical property measurements. L.Z., K.C., and C.B. conducted DFT calculations. L.H., L.Z., and D.W. performed the phase field simulations. S.Z., D.Y.W., S.Y., X.R., and Z.C. revised the manuscript. L.H., L.Z., and D.W. wrote the manuscript and analyzed the data.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks Chang Won Ahn (eRef), who co-reviewed with Muhammad Sheeraz (ECR), and the other anonymous reviewer(s) for their contribution to the peer review of this work. A peer review file is available.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.
About this article
Cite this article
He, L., Zhang, L., Ran, Y. et al. Ultrahigh energy storage density and efficiency in AgNbO3-based ceramics by percolating interaction between antipolar regions and defect pairs. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68297-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-68297-4
