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郑州大学 & 新加坡国立大学 Advanced Science:Sb@HCF 空心限域结构助力超稳定钠金属负极

  • 2026-04-16 02:49:04
郑州大学 & 新加坡国立大学 Advanced Science:Sb@HCF 空心限域结构助力超稳定钠金属负极

电池时代

文 章 信 息

嵌Sb空心碳纳米纤维协同离子输运与空间限域而实现稳定钠金属负极

第一作者:韩枫**,袁梦环**

通讯作者:王辉*,许婷婷*,杨会颖*

单位:郑州大学,新加坡国立大学

电池时代

研 究 背 景

钠金属电池(SMBs)因钠资源丰富、理论容量高(1166 mAh g-1)、氧化还原电位低,是高能量密度储能系统的理想选择。但钠金属负极(SMA)存在枝晶不可控生长、固体电解质界面(SEI)不稳定、副反应严重等问题,导致库伦效率低、循环寿命短、安全风险高。

传统3D核壳宿主虽能解决枝晶和SEI不稳定的问题,但仍存在离子输运调控不足、合成工艺复杂、亲钠位点仅作为静态成核点等缺陷,亟需设计兼具高效离子输运与空间限域的新型钠金属宿主。

电池时代

文 章 简 介

近日,郑州大学与新加坡国立大学联合团队,通过静电纺丝和湿法刻蚀策略,制备出3D亲钠嵌Sb空心碳纳米纤维(Sb@HCF)宿主材料。结合原位表征与理论模拟,证实原位形成的Na-Sb合金可同步实现均匀钠沉积引导与Na+快速输运,协同抑制枝晶、构建富NaF稳定SEI,大幅提升钠金属负极的循环稳定性与倍率性能,为高能量密度钠金属电池的应用提供新方案。

图1.结构与组成表征。(a)Sb@HCF与HCF的钠沉积行为示意图对比。(b)SEM图像,显示Sb@HCF的三维纤维状结构。(c)TEM图像显示空心腔体及Sb纳米颗粒的均匀分布。(d)Sb晶粒的高分辨透射电子显微镜图像。(e)Sb@HCF的SAED。(f)Sb@HCF中Sb、C和N的EDS元素mapping。(g)Sb@HCF和HCF的XRD图。

电池时代

本 文 要 点

要点一:Na+输运与沉积/剥离机制

原位 TEM/XRD:Sb原位与Na反应生成Na3Sb合金,该合金在钠负极工作电压窗口内稳定存在,既是亲钠成核位点,又是Na⁺快速输运通道。

理论模拟:Na3Sb对Na+吸附能达-2.58 eV(HCF仅-0.03 eV),Na⁺扩散系数(9.43×10-13 cm² s-1)是HCF的近10倍,离子输运动力学显著提升。

缓解应力:空心结构缓冲钠沉积 / 合金化的体积膨胀,维持结构完整性。

要点二:稳定富NaF的SEI构建

深度刻蚀XPS:Sb@HCF表面SEI富无机NaF、Na2O,有机组分(C-O/C=O)显著低于HCF。

TEM表征:循环后电极Sb@HCF表面SEI薄层致密且均匀;HCF表面SEI厚且不均匀。

界面稳定:致密无机SEI阻断副反应,抑制SEI反复破裂重构,提升界面稳定性。

要点三:无枝晶钠沉积行为

原位光学观测:2 mA cm-2下,Sb@HCF表面90 min内始终无枝晶、均匀沉积;铜箔15 min出现枝晶,HCF 30 min出现枝晶。

COMSOL模拟:Sb纳米颗粒提供均匀成核位点,电流密度分布均匀,消除尖端效应。

非原位 SEM:钠沉积/剥离后,Sb@HCF结构完整、无钠残留;HCF 与铜箔出现残留钠与枝晶。

要点四:优异的电化学性能

半电池:4 mA cm-2/4 mAh cm-2下,1400次循环库伦效率99.88%,远优于纯空心碳(HCF)与铜箔。

对称电池:10 mA cm-2/2 mAh cm-2条件下稳定运行1200 h,电压滞后仅58 mV;累计沉积容量达 6 Ah cm-2,交换电流密度2.86 mA cm-2。

全电池:匹配Na3V2(PO4)3@C正极,100 mA g-1 下1000 次循环容量保持84.10mAh g-1,库伦效率 98.05%。

柔性软包电池:弯折180°仍稳定工作,200 次循环平均库伦效率 98.51%。

电池时代

文 章 链 接

Synergistic lon Transport and Spatial Confinement in Sb-Embedded Hollow Carbon Nanofibers for Stable Na MetalAnodes

https://doi.org/10.1002/advs.202521115

电池时代

通 讯 作 者 简 介

杨会颖(Hui Ying Yang)教授新加坡国立大学材料科学与工程系教授、博士生导师,国际知名储能材料专家。2011年在麻省理工学院机械工程系工作一年,并于2016年升任终身副教授,2022年升任终身教授。现任东盟工程院院士Fellow of ASEAN Academy of Engineering and Technology (FAAET),英国皇家化学学会会士 (Fellow of royal society of chemistry (FRSC)) ,新加坡工程师学会会士 (Fellow of Institution of Engineering Singapore (FIES)) ,美国材料学会,美国工程学会,新加坡物理学会,新加坡化学学会及材料学会会员。她荣获多项国际科技奖项,其中包括2013年获新加坡杰出青年工程成就奖、2013年获陈嘉庚青年发明家奖、2014年获美国工程学会杰出青年奖及 2018年获新加坡物理学会纳米科技奖,2023年新加坡杰出女化学家奖等。主持多个国际及新加坡国家重大项目研究课题工作。迄今为止,在Nat. Commun., Sci. Adv., Chem, Matter, Adv. Mater, Energy Environ. Sci等期刊上发表 SCI论文 400 余篇,她引超过31000 次,H指数突破100。

许婷婷,郑州大学副教授,近年来聚焦钠金属负极的界面失效机制与性能强化策略,开展了从理论模拟、材料创新到原位表征的系统研究。以第一/通讯作者在Angewandte Chemie International Edition,Advanced Functional Materials,Advanced Science等国际权威期刊上已发表SCI学术论文30余篇,主持并完成国家自然科学基金和省自然科学基金。

王辉,郑州大学物理学院副教授,以第一/通讯作者在Advanced Energy Materials, Advanced Functional Materials, Advanced Science, ACS Nano, Energy Storage Materials, Small, Small Methods, Chemical Engineering Journal,Journal of Materials Chemistry A上发表文章20余篇,被引3000余次,参与和主持多项国家自然科学基金和省级自然科学基金,获授权发明专利多项。

电池时代

第 一 作 者 简 介

韩枫,郑州大学硕士研究生,仪器仪表工程专业

袁梦环,郑州大学硕士研究生,电子信息专业

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  1. CONNECT:[ UseTime:0.000834s ] mysql:host=127.0.0.1;port=3306;dbname=i460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001427s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000577s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000568s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.001241s ]
  6. SELECT * FROM `set` [ RunTime:0.000439s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.001298s ]
  8. SELECT * FROM `article` WHERE `id` = 513248 LIMIT 1 [ RunTime:0.011454s ]
  9. UPDATE `article` SET `lasttime` = 1777437963 WHERE `id` = 513248 [ RunTime:0.028085s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.001058s ]
  11. SELECT * FROM `article` WHERE `id` < 513248 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.001640s ]
  12. SELECT * FROM `article` WHERE `id` > 513248 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.001380s ]
  13. SELECT * FROM `article` WHERE `id` < 513248 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.002443s ]
  14. SELECT * FROM `article` WHERE `id` < 513248 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.011428s ]
  15. SELECT * FROM `article` WHERE `id` < 513248 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.017072s ]
0.224448s