{"title":"Zirconium Modification Induced Small-Polaron Breakdown in Na4Fe3(PO4)2P2O7 as Superior Cathode in Sodium-Ion Battery","authors":"Hongmei Dai, Zhian Yang, Tingting Xie, Ziheng Zhao, Yongfei Shang, Changchun Ai, Qun Yi","doi":"10.1002/adfm.202505185","DOIUrl":null,"url":null,"abstract":"<p>Na₄Fe₃(PO₄)₂(P₂O₇) (NFPP) is a promising cathode material for sodium-ion batteries (SIBs) due to its low cost, facile synthesis, environmental compatibility, high structural stability, and suitable operating voltage. However, its practical application is hindered by poor cycling stability, limited rate capability, and low electronic/ionic conductivity. Herein, these challenges are addressed by strategically incorporating Zr⁴⁺ ions at the Fe1 site of NFPP (denoted as NZFPP-X, where X represents the Zr/Fe ratio). The optimized NZFPP-0.05 exhibits significantly enhanced thermodynamic stability and electrochemical performance. Zr substitution induces depolarization effects, which promote electron mobility, thereby improving conductivity, cycling stability, and rate performance. Specifically, NZFPP-0.05 delivers an exceptional capacity retention of 86.6% after 6000 cycles at 10 C and a remarkable rate capability of 58.5 mAh g⁻¹ at 50 C. These advancements are attributed to the reduced energy barrier and accelerated kinetics of NZFPP-0.05 compared to pristine NFPP. This work presents a novel Zr-substitution strategy to enhance the performance of NFPP cathodes and introduces NZFPP-0.05 as a cost-effective, ultra-stable, and high-rate cathode material for SIBs.</p>","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"35 40","pages":""},"PeriodicalIF":19.0000,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://advanced.onlinelibrary.wiley.com/doi/10.1002/adfm.202505185","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Na₄Fe₃(PO₄)₂(P₂O₇) (NFPP) is a promising cathode material for sodium-ion batteries (SIBs) due to its low cost, facile synthesis, environmental compatibility, high structural stability, and suitable operating voltage. However, its practical application is hindered by poor cycling stability, limited rate capability, and low electronic/ionic conductivity. Herein, these challenges are addressed by strategically incorporating Zr⁴⁺ ions at the Fe1 site of NFPP (denoted as NZFPP-X, where X represents the Zr/Fe ratio). The optimized NZFPP-0.05 exhibits significantly enhanced thermodynamic stability and electrochemical performance. Zr substitution induces depolarization effects, which promote electron mobility, thereby improving conductivity, cycling stability, and rate performance. Specifically, NZFPP-0.05 delivers an exceptional capacity retention of 86.6% after 6000 cycles at 10 C and a remarkable rate capability of 58.5 mAh g⁻¹ at 50 C. These advancements are attributed to the reduced energy barrier and accelerated kinetics of NZFPP-0.05 compared to pristine NFPP. This work presents a novel Zr-substitution strategy to enhance the performance of NFPP cathodes and introduces NZFPP-0.05 as a cost-effective, ultra-stable, and high-rate cathode material for SIBs.
Na₄Fe₃(PO₄)₂(P₂O₇)(NFPP)具有成本低、合成简单、环境相容性好、结构稳定性高、工作电压合适等优点,是一种很有发展前景的钠离子电池正极材料。然而,它的实际应用受到循环稳定性差、速率能力有限和电子/离子电导率低的阻碍。在这里,通过在NFPP的Fe1位点(表示为NZFPP-X,其中X表示Zr/Fe比率)战略性地结合Zr⁴+离子来解决这些挑战。优化后的NZFPP-0.05表现出明显增强的热力学稳定性和电化学性能。Zr取代引起去极化效应,提高电子迁移率,从而提高电导率、循环稳定性和速率性能。具体来说,NZFPP-0.05在10℃下6000次循环后的容量保持率为86.6%,在50℃下的速率为58.5 mAh g⁻¹。这些进步归功于与原始NFPP相比,NZFPP-0.05降低了能量垒和加速了动力学。这项工作提出了一种新的zr替代策略来提高NFPP阴极的性能,并介绍了NZFPP-0.05作为一种经济高效、超稳定、高速率的sib阴极材料。
期刊介绍:
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