{"title":"拓宽Na+扩散自由度,开启氟磷酸盐阴极快速储钠潜能。","authors":"Hong Yu, Jinjin Wang, Hongbo Jing, Chao Wu, Erhai Hu, Shibo Xi, Xiaomei Wang, Zhiyu Fang, Xing-Long Wu, Qinghua Liang, Weihong Qi, Qingyu Yan, Hongqiang Wang, Cheng-Feng Du","doi":"10.1016/j.scib.2025.06.005","DOIUrl":null,"url":null,"abstract":"<p><p>High safety and high energy-density sodium-ion batteries require the promising polyanionic insertion-type cathode possessing fast dis-/charging capability, yet persistent challenges remain in the kinetic optimization to accelerate their intrinsically low Na<sup>+</sup> diffusivity. Exampled by the representative Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)O<sub>2</sub>F (NVPOF) with considerable theoretical energy density, structural distortion results in a one-dimensional sluggish Na<sup>+</sup> diffusion out of the two-dimensional Na<sup>+</sup> pathway provided structurally. Previous endeavors with Na site or transition-metal site regulation successfully optimize the Na<sup>+</sup> diffusion energy barrier of the available one-dimensional path. However, these substituted elements with non-equivalent valances or sizes further elevate the energy barrier of the other unavailable Na<sup>+</sup> diffusion path. Herein, by defining the independently accessible Na<sup>+</sup> diffusion pathways in the crystallographic structure as Na<sup>+</sup> diffusion degree of freedom (df<sub>[Na+]</sub>), we demonstrate broadening df<sub>[Na+]</sub> to two in NVPOF by a mild perturb at the dangling site can fundamentally revise the Na<sup>+</sup> diffusion behaviour. As demonstrated by in-situ synchrotron, various spectroscopic techniques, and density functional theory (DFT) modeling, this mild perturb equalizes the Na<sup>+</sup> diffusion energy barriers along a and b directions and enables two-dimensional Na<sup>+</sup> transportation. The as-prepared NVPOF depicts an altered solid-solution phase transition, higher disorder in the framework and dramatically enhanced Na<sup>+</sup> diffusivity, which leads to unprecedentedly high sodium storage properties in half cell (68.6 mAh g<sup>-1</sup> at 100 C; 103.3 mAh g<sup>-1</sup> after 1300 cycles at 20 C; 1 C = 130 mA g<sup>-1</sup>) and full cell (313.8 Wh kg<sup>-1</sup>@4063.5 W kg<sup>-1</sup>; 113.9 Wh kg<sup>-1</sup>@16,397.2 W kg<sup>-1</sup>). This study enlightens the valuable role of broadening df<sub>[Na+]</sub> in fundamentally maximizing the polyanionic insertion-type performance.</p>","PeriodicalId":421,"journal":{"name":"Science Bulletin","volume":" ","pages":""},"PeriodicalIF":21.1000,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Broadening the Na<sup>+</sup> diffusion degree of freedom to unlock a rapid sodium storage potential in fluorophosphate cathode.\",\"authors\":\"Hong Yu, Jinjin Wang, Hongbo Jing, Chao Wu, Erhai Hu, Shibo Xi, Xiaomei Wang, Zhiyu Fang, Xing-Long Wu, Qinghua Liang, Weihong Qi, Qingyu Yan, Hongqiang Wang, Cheng-Feng Du\",\"doi\":\"10.1016/j.scib.2025.06.005\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>High safety and high energy-density sodium-ion batteries require the promising polyanionic insertion-type cathode possessing fast dis-/charging capability, yet persistent challenges remain in the kinetic optimization to accelerate their intrinsically low Na<sup>+</sup> diffusivity. Exampled by the representative Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)O<sub>2</sub>F (NVPOF) with considerable theoretical energy density, structural distortion results in a one-dimensional sluggish Na<sup>+</sup> diffusion out of the two-dimensional Na<sup>+</sup> pathway provided structurally. Previous endeavors with Na site or transition-metal site regulation successfully optimize the Na<sup>+</sup> diffusion energy barrier of the available one-dimensional path. However, these substituted elements with non-equivalent valances or sizes further elevate the energy barrier of the other unavailable Na<sup>+</sup> diffusion path. Herein, by defining the independently accessible Na<sup>+</sup> diffusion pathways in the crystallographic structure as Na<sup>+</sup> diffusion degree of freedom (df<sub>[Na+]</sub>), we demonstrate broadening df<sub>[Na+]</sub> to two in NVPOF by a mild perturb at the dangling site can fundamentally revise the Na<sup>+</sup> diffusion behaviour. As demonstrated by in-situ synchrotron, various spectroscopic techniques, and density functional theory (DFT) modeling, this mild perturb equalizes the Na<sup>+</sup> diffusion energy barriers along a and b directions and enables two-dimensional Na<sup>+</sup> transportation. The as-prepared NVPOF depicts an altered solid-solution phase transition, higher disorder in the framework and dramatically enhanced Na<sup>+</sup> diffusivity, which leads to unprecedentedly high sodium storage properties in half cell (68.6 mAh g<sup>-1</sup> at 100 C; 103.3 mAh g<sup>-1</sup> after 1300 cycles at 20 C; 1 C = 130 mA g<sup>-1</sup>) and full cell (313.8 Wh kg<sup>-1</sup>@4063.5 W kg<sup>-1</sup>; 113.9 Wh kg<sup>-1</sup>@16,397.2 W kg<sup>-1</sup>). This study enlightens the valuable role of broadening df<sub>[Na+]</sub> in fundamentally maximizing the polyanionic insertion-type performance.</p>\",\"PeriodicalId\":421,\"journal\":{\"name\":\"Science Bulletin\",\"volume\":\" \",\"pages\":\"\"},\"PeriodicalIF\":21.1000,\"publicationDate\":\"2025-06-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science Bulletin\",\"FirstCategoryId\":\"103\",\"ListUrlMain\":\"https://doi.org/10.1016/j.scib.2025.06.005\",\"RegionNum\":1,\"RegionCategory\":\"综合性期刊\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MULTIDISCIPLINARY SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science Bulletin","FirstCategoryId":"103","ListUrlMain":"https://doi.org/10.1016/j.scib.2025.06.005","RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MULTIDISCIPLINARY SCIENCES","Score":null,"Total":0}
引用次数: 0
摘要
高安全和高能量密度的钠离子电池需要具有快速放电能力的聚阴离子插入型阴极,但在动力学优化方面仍然存在持续的挑战,以加速其固有的低Na+扩散率。以具有相当理论能量密度的Na3V2(PO4)O2F (NVPOF)为例,结构畸变导致Na+从结构提供的二维Na+途径中一维缓慢扩散。先前对Na位点或过渡金属位点调控的研究成功地优化了可用的一维路径的Na+扩散能垒。然而,这些具有非等效价或尺寸的取代元素进一步提高了其他不可用Na+扩散路径的能垒。本文通过将晶体结构中独立可达的Na+扩散路径定义为Na+扩散自由度(df[Na+]),证明了在NVPOF中通过在悬空位置进行轻微扰动将df[Na+]扩展到2可以从根本上改变Na+的扩散行为。原位同步加速器、各种光谱技术和密度泛函数理论(DFT)模型表明,这种轻微的扰动使Na+沿a和b方向的扩散能垒均衡,并使二维Na+输运成为可能。制备的NVPOF具有改变的固溶相变,更高的框架无序性和显著增强的Na+扩散率,从而在半电池中具有前所未有的高钠存储性能(100℃时68.6 mAh g-1;103.3 mAh g-1,在20℃下循环1300次;1 C = 130 mA g-1)和满电池(313.8 Wh kg-1@4063.5 W kg-1;113.9 Wh kg-1@16,397.2 W kg-1)。该研究揭示了拓宽df[Na+]在从根本上最大化聚阴离子插入型性能方面的重要作用。
Broadening the Na+ diffusion degree of freedom to unlock a rapid sodium storage potential in fluorophosphate cathode.
High safety and high energy-density sodium-ion batteries require the promising polyanionic insertion-type cathode possessing fast dis-/charging capability, yet persistent challenges remain in the kinetic optimization to accelerate their intrinsically low Na+ diffusivity. Exampled by the representative Na3V2(PO4)O2F (NVPOF) with considerable theoretical energy density, structural distortion results in a one-dimensional sluggish Na+ diffusion out of the two-dimensional Na+ pathway provided structurally. Previous endeavors with Na site or transition-metal site regulation successfully optimize the Na+ diffusion energy barrier of the available one-dimensional path. However, these substituted elements with non-equivalent valances or sizes further elevate the energy barrier of the other unavailable Na+ diffusion path. Herein, by defining the independently accessible Na+ diffusion pathways in the crystallographic structure as Na+ diffusion degree of freedom (df[Na+]), we demonstrate broadening df[Na+] to two in NVPOF by a mild perturb at the dangling site can fundamentally revise the Na+ diffusion behaviour. As demonstrated by in-situ synchrotron, various spectroscopic techniques, and density functional theory (DFT) modeling, this mild perturb equalizes the Na+ diffusion energy barriers along a and b directions and enables two-dimensional Na+ transportation. The as-prepared NVPOF depicts an altered solid-solution phase transition, higher disorder in the framework and dramatically enhanced Na+ diffusivity, which leads to unprecedentedly high sodium storage properties in half cell (68.6 mAh g-1 at 100 C; 103.3 mAh g-1 after 1300 cycles at 20 C; 1 C = 130 mA g-1) and full cell (313.8 Wh kg-1@4063.5 W kg-1; 113.9 Wh kg-1@16,397.2 W kg-1). This study enlightens the valuable role of broadening df[Na+] in fundamentally maximizing the polyanionic insertion-type performance.
期刊介绍:
Science Bulletin (Sci. Bull., formerly known as Chinese Science Bulletin) is a multidisciplinary academic journal supervised by the Chinese Academy of Sciences (CAS) and co-sponsored by the CAS and the National Natural Science Foundation of China (NSFC). Sci. Bull. is a semi-monthly international journal publishing high-caliber peer-reviewed research on a broad range of natural sciences and high-tech fields on the basis of its originality, scientific significance and whether it is of general interest. In addition, we are committed to serving the scientific community with immediate, authoritative news and valuable insights into upcoming trends around the globe.