Zheng Xueying, Li Peng, Cao Zhang, Luo Wei, Sun Fazhe, Wang Zhongqiang, Ding Bing, Wang Guoxiu, Huang Yunhui
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, 201804, China.
College of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, 210006, China.
Small. 2019 Oct;15(41):e1902688. doi: 10.1002/smll.201902688. Epub 2019 Aug 16.
Sodium (Na) metal anodes stand out with their remarkable capacity and natural abundance. However, the dendritic Na growth, infinite dimensional changes, and low Coulombic efficiency (CE) present key bottlenecks plaguing practical applications. Here, heteroatom-doped (nitrogen, sulfur) hollow carbon fibers (D-HCF) are rationally synthesized as a nucleation-assisting host to enable a highly reversible Na metal. The "sodiophilic" functional groups introduced by the heteroatom-doping and large surface area (≈1052 m g ) synchronously contribute to a homogenous plating morphology with dissipated local current density. High "sodiophilicity" of the D-HCF is confirmed by first-principle calculations and experimental results, where strong adsorption energy of -3.52 eV with low Na nucleation overpotential of 3.2 mV at 0.2 mA cm is realized. As such, highly reversible plating/stripping is achieved at 1.0 mA cm with average CE approximating 99.52% over 600 cycles. The as-assembled Na@D-HCF symmetric cells exhibit a prolonged lifetime for 1000 h. A full-cell paired with Na V (PO ) cathode further demonstrates stable electrochemical behavior for 200 cycles at 1 C along with excellent rate performance (102 mAh g at 5 C). The results clearly show the effectiveness of the D-HCF in manipulating Na deposition and thus the significance of nucleation control in realizing dendrite-free metal anodes.
钠(Na)金属阳极因其卓越的容量和丰富的天然储量而备受瞩目。然而,钠枝晶生长、无限的尺寸变化以及低库仑效率(CE)是困扰其实际应用的关键瓶颈。在此,通过合理合成杂原子掺杂(氮、硫)的中空碳纤维(D-HCF)作为成核辅助主体,以实现高度可逆的钠金属。杂原子掺杂引入的“亲钠”官能团和大表面积(≈1052 m g )共同促成了具有分散局部电流密度的均匀镀覆形态。通过第一性原理计算和实验结果证实了D-HCF具有高“亲钠性”,在0.2 mA cm 时实现了-3.52 eV的强吸附能和3.2 mV的低钠成核过电位。因此,在1.0 mA cm 时实现了高度可逆的镀覆/剥离,在600次循环中平均CE约为99.52%。组装好的Na@D-HCF对称电池的寿命延长至1000 h。与Na V (PO ) 阴极配对的全电池在1 C下进一步展示了200次循环的稳定电化学行为以及优异的倍率性能(5 C时为102 mAh g )。结果清楚地表明了D-HCF在控制钠沉积方面的有效性,从而也体现了成核控制在实现无枝晶金属阳极方面的重要性。