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合理的结构设计和单原子掺杂可以明显提高二氧化钛(TiO2)作为钠离子电池负极的储钠性能。然而单原子掺杂在TiO2中较低的掺杂质量分数与单一的功能作用阻碍了TiO2作为钠离子电池负极电化学性能的进一步增强，因此研究了高质量分数掺杂和双原子掺杂对TiO2储钠性能的影响。通过砂纸打磨对钛箔表面进行预处理除去氧化层，在含有0.56 g的NH_4F、5 mL的H_2O和95 mL的乙二醇(EG)溶液中，在20 min内通过施加阳极氧化电压60 V,在室温环境下对钛箔进行阳极氧化，在其表面生长出TiO2纳米管阵列；以CH_4N_2S作为N源和S源，使用退火的方式对TiO2纳米管阵列进行掺杂，得到S, N共掺杂的TiO2纳米管阵列。实验结果表明，S, N共掺杂TiO2的质量分数分别为1.53%和4.76%时，显著提高了TiO2的电导率，加快了钠离子转移动力学。另外，TiO2作为钠离子电池负极表现出强大的倍率性能和长循环性能，在0.1C(1C=335 mA·g-1)的电流密度下，S,N共掺杂TiO2电极保持296.6 mA·h·g-1的可逆电荷比容量，在25.0C的电流密度下保持158.1 mA·h·g-1的可逆电荷比容量，并在约3 500圈循环后的可逆电荷比容量保持率高达94.8%。相较于单掺杂，双掺杂使掺杂质量分数更高并产生协同效应，该策略为制备出优异性能的电极材料提供了参考。
Abstract：Rational structural design and single-atom doping can significantly improve the sodium storage performance of titanium dioxide(TiO2) as the anode of sodium ion batteries. However, the lower doping mass fraction of single atom doping in TiO2 with a single functional role hinders the further enhancement of electrochemical performance of TiO2 as the anode of sodium ion batteries. Therefore, the effect of high mass fraction doping and diatomic doping on the sodium storage properties of TiO2 was investigated. The surface of titanium foil was pretreated by sandpaper grinding to remove the oxide layer, and the titanium foil was anodized in a solution containing 0.56 g of NH_4F, 5 mL of H_2O and 95 mL of ethylene glycol(EG) by applying anodic oxidation voltage of 60 V at room temperature for 20 min. With CH_4N_2S as the N and S sources, the TiO2 nanotube arrays were grown on the surface of the titanium foil. The TiO2 nanotube arrays were doped by annealing to obtain S, N co-doped TiO2 nanotube arrays. The experimental results show that the mass fractions of S and N co-doped TiO2 are 1.53% and 4.76%, respectively, which significantly improves the conductivity of TiO2 and accelerates the sodium ion transfer kinetics. In addition, S and N co-doped TiO2 as anode of the sodium ion battery exhibits strong rate performance and long cycle performance. The S and N co-doped TiO2 electrode maintains the reversible charge specific capacity of 296.6 mA·h·g-1 at a current density of 0.1C(1C=335 mA·g-1), the reversible charge specific capacity of 158.1 mA·h·g-1 at a current density of 25.0C, and the retention rate of the reversible charge specific capacity reaches 94.8% after about 3 500 cycles. Compared with single-doping, double-doping results in higher mass fraction doping and synergistic effect, and the strategy provides the reference for the preparation of electrode materials with excellent performances.
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基本信息:
DOI：10.13250/j.cnki.wndz.2023.08.005
中图分类号:TM912;TB383.1
引用信息:
[1]蒋琦,任姿旭,陈轲,等.S, N共掺杂TiO_2纳米管作为钠离子电池负极的储钠性能[J].微纳电子技术,2023,60(08):1201-1210.DOI:10.13250/j.cnki.wndz.2023.08.005.
基金信息:
国家自然科学基金(21905099); 山西省百人计划创新团队资助项目(DC2000005702); 1331工程骨干创新团队资助项目(DT17100004)
2023-08-15
2023-08-15