F<sup>−</sup>对熔融NaCl–KCl熔盐中钛离子配位结构的影响

刘姗姗; 李少龙; 刘晨晖; 何季麟; 宋建勋

doi:10.1007/s12613-022-2527-z

Volume 30 Issue 5

May 2023

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文章导航 > 矿物冶金与材料学报（英文） > 2023 > 30(5): 868-876

Shanshan Liu, Shaolong Li, Chenhui Liu, Jilin He, and Jianxun Song, Effect of fluoride ions on coordination structure of titanium inmolten NaCl–KCl, Int. J. Miner. Metall. Mater., 30(2023), No. 5, pp. 868-876. https://doi.org/10.1007/s12613-022-2527-z

Cite this article as:

Shanshan Liu, Shaolong Li, Chenhui Liu, Jilin He, and Jianxun Song, Effect of fluoride ions on coordination structure of titanium inmolten NaCl–KCl, Int. J. Miner. Metall. Mater., 30(2023), No. 5, pp. 868-876. https://doi.org/10.1007/s12613-022-2527-z

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研究论文

F⁻对熔融NaCl–KCl熔盐中钛离子配位结构的影响

1)
郑州大学河南省资源与材料工业技术研究院，郑州450001，中国
2)
郑州大学材料科学与工程学院，郑州450001，中国

通讯作者:
宋建勋 E-mail: songjx00@163.com

文章亮点

(1) 研究了氟离子对钛离子在NaCl–KCl熔盐中的电化学还原机制的影响。

(2) 得到了Ti–F在不同氟离子含量下的配位机理。

(3) 熔盐中F⁻的加入缩短了钛离子的还原步骤，并极大地影响了价态钛离子的比例，为沉积钛过程提供了理论支持。

中文摘要

本文采用电化学、数学分析和光谱分析相结合的方法，研究了氟离子(F⁻)对钛离子(Tiⁿ⁺)的电化学行为和配位性能的影响，以α表示F⁻和Tiⁿ⁺的摩尔浓度比。采用循环伏安法(CV)、方波伏安法(SWV)和开路电位法(OCP)研究了不同α条件下钛离子的电化学行为，并采用原位采样器制备了α = 0、1.0、2.0、3.0、4.0、5.0、6.0、8.0时的熔盐样品，然后用X射线光电子能谱(XPS)和拉曼光谱对样品进行分析。结果表明:熔盐中F⁻的加入缩短了钛离子的还原步骤，并极大地影响了价态钛离子的比例，使高价态钛含量增加且更加稳定，当α大于3.0时，Ti²⁺不再存在于熔盐中，最终转移到价态更高的钛离子中。研究发现，这些现象背后的机制是由于配合物(TiCl_jF_i^m−)的形成，这对揭示钛还原过程机理和电解质的选择具有重要意义。

关键词:

Research Article

Effect of fluoride ions on coordination structure of titanium inmolten NaCl–KCl

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Abstract

Abstract

The effects of fluoride ions (F⁻) on the electrochemical behavior and coordination properties of titanium ions (Tiⁿ⁺) were studied in this work, by combining electrochemical and mathematical analysis as well as spectral techniques. The α was taken as a factor to indicate the molar concentration ratio of F⁻ and Tiⁿ⁺. Cyclic voltammetry (CV), square wave voltammetry (SWV), and open circuit potential method (OCP) were used to study the electrochemical behavior of titanium ions under conditions of various α, and in-situ sampler was used to prepare molten salt samples when α equal to 0.0, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, and 8.0. And then, samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results showed that F⁻ in molten salt can reduce the reduction steps of titanium ions and greatly affects the proportion of valence titanium ions which making the high-valence titanium content increased and more stable. Ti²⁺ cannot be detected in the molten salt when α is higher than 3.0 and finally transferred to titanium ions with higher valence state. Investigation revealed that the mechanism behind those phenomenon is the coordination compounds ($\text{TiCl}_{j}\text{F}_{i}^{m-}$) forming.
- molten salt;
- sodium chloride–potassium chloride;
- ratio of fluoride and titanium ions;
- coordination mechanism

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F⁻对熔融NaCl–KCl熔盐中钛离子配位结构的影响

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Effect of fluoride ions on coordination structure of titanium inmolten NaCl–KCl

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F−对熔融NaCl–KCl熔盐中钛离子配位结构的影响

文章亮点

中文摘要

Effect of fluoride ions on coordination structure of titanium inmolten NaCl–KCl

Abstract

References

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F⁻对熔融NaCl–KCl熔盐中钛离子配位结构的影响