{"title":"A/B-site co-doping strategy driven two-phase proportional equilibrium to optimize energy storage property in Bi0.5Na0.5TiO3","authors":"Zihan Ruan, Bing Li, Jingsong Liu","doi":"10.1111/jace.70132","DOIUrl":null,"url":null,"abstract":"<p>Lead-free perovskite ceramics have emerged as promising candidates for energy storage applications due to their excellent dielectric properties and environmental compatibility. Among them, Bi<sub>0.5</sub>Na<sub>0.5</sub>TiO<sub>3</sub> (BNT)-based ceramics stand out for large spontaneous polarization (<i>P</i><sub>S</sub>) and high Curie temperature (<i>T</i><sub>C</sub>). However, practical applications of BNT are hindered by challenges such as high dielectric loss and low breakdown electric field strength, which limit their energy storage capabilities. To address the limitations, this work proposes a second component solid solution and dual-site doping strategy with Ca<sup>2+</sup> substitution at the A-site and Hf<sup>4+</sup> substitution at the B-site, then the 0.65(Bi<sub>0.5</sub>Na<sub>0.5</sub>)<sub>1-</sub><i><sub>x</sub></i>Ca<i><sub>x</sub></i>Hf<i><sub>y</sub></i>Ti<sub>1-</sub><i><sub>y</sub></i>O<sub>3</sub>-0.35Sr<sub>0.7</sub>Bi<sub>0.2</sub>TiO<sub>3</sub> (BNC<i><sub>x</sub></i>H<i><sub>y</sub></i>T-SBT, <i>x, y</i> = 0, 0.03, 0.05, 0.07, 0.09) ceramics were designed and synthesized. At the optimized composition (<i>x, y</i> = 0.07), BNC<sub>0.07</sub>H<sub>0.07</sub>T-SBT ceramic exhibits a recoverable energy density of 3.45 J/cm<sup>3</sup> under 250 kV/cm electric field, representing more than 30% enhancement in recoverable energy density compared to the undoped BNT–SBT, with an energy efficiency of 83%. Multi-level microstructure characterization and analysis indicates that Ca<sup>2+</sup>/Hf<sup>4+</sup> co-doping stabilizes the TiO<sub>6</sub> octahedral structure, refines grain size and promotes nano-domains formation. In addition, BNC<sub>0.07</sub>H<sub>0.07</sub>T-SBT ceramic achieves a balanced coexistence of <i>P</i>4bm and <i>R</i>3c phases, significantly enhancing polarization dynamics and relaxor behavior, thereby maximizing energy storage performance. This work provides critical insights into phase engineering and offers a viable strategy for developing high-performance energy storage ceramics.</p>","PeriodicalId":200,"journal":{"name":"Journal of the American Ceramic Society","volume":"108 12","pages":""},"PeriodicalIF":3.8000,"publicationDate":"2025-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Ceramic Society","FirstCategoryId":"88","ListUrlMain":"https://ceramics.onlinelibrary.wiley.com/doi/10.1111/jace.70132","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, CERAMICS","Score":null,"Total":0}
引用次数: 0
Abstract
Lead-free perovskite ceramics have emerged as promising candidates for energy storage applications due to their excellent dielectric properties and environmental compatibility. Among them, Bi0.5Na0.5TiO3 (BNT)-based ceramics stand out for large spontaneous polarization (PS) and high Curie temperature (TC). However, practical applications of BNT are hindered by challenges such as high dielectric loss and low breakdown electric field strength, which limit their energy storage capabilities. To address the limitations, this work proposes a second component solid solution and dual-site doping strategy with Ca2+ substitution at the A-site and Hf4+ substitution at the B-site, then the 0.65(Bi0.5Na0.5)1-xCaxHfyTi1-yO3-0.35Sr0.7Bi0.2TiO3 (BNCxHyT-SBT, x, y = 0, 0.03, 0.05, 0.07, 0.09) ceramics were designed and synthesized. At the optimized composition (x, y = 0.07), BNC0.07H0.07T-SBT ceramic exhibits a recoverable energy density of 3.45 J/cm3 under 250 kV/cm electric field, representing more than 30% enhancement in recoverable energy density compared to the undoped BNT–SBT, with an energy efficiency of 83%. Multi-level microstructure characterization and analysis indicates that Ca2+/Hf4+ co-doping stabilizes the TiO6 octahedral structure, refines grain size and promotes nano-domains formation. In addition, BNC0.07H0.07T-SBT ceramic achieves a balanced coexistence of P4bm and R3c phases, significantly enhancing polarization dynamics and relaxor behavior, thereby maximizing energy storage performance. This work provides critical insights into phase engineering and offers a viable strategy for developing high-performance energy storage ceramics.
期刊介绍：
The Journal of the American Ceramic Society contains records of original research that provide insight into or describe the science of ceramic and glass materials and composites based on ceramics and glasses. These papers include reports on discovery, characterization, and analysis of new inorganic, non-metallic materials; synthesis methods; phase relationships; processing approaches; microstructure-property relationships; and functionalities. Of great interest are works that support understanding founded on fundamental principles using experimental, theoretical, or computational methods or combinations of those approaches. All the published papers must be of enduring value and relevant to the science of ceramics and glasses or composites based on those materials.
Papers on fundamental ceramic and glass science are welcome including those in the following areas:
Enabling materials for grand challenges[...]
Materials design, selection, synthesis and processing methods[...]
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Mechanisms, Theory, Modeling, and Simulation[...]
JACerS accepts submissions of full-length Articles reporting original research, in-depth Feature Articles, Reviews of the state-of-the-art with compelling analysis, and Rapid Communications which are short papers with sufficient novelty or impact to justify swift publication.
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