添加高氯酸锂对硝酸锂-硝酸钾共晶的影响

IF 2.4 4区 化学 Q3 CHEMISTRY, PHYSICAL
Ionics Pub Date : 2024-07-23 DOI:10.1007/s11581-024-05715-x
A. M. Amirov, M. A. Akhmedov, Z. Yu. Kubataev, M. M. Gafurov, K. Sh. Rabadanov, M. V. Kadiev
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引用次数: 0

摘要

我们的研究通过差示扫描量热法和拉曼光谱对硝酸锂-硝酸钾二元共晶体系中掺杂高氯酸锂 LiClO4 的硝酸根离子和高氯酸根离子的热性质、相变和分子弛豫过程进行了研究。此外,还获得了硝酸锂-KNO3 共晶和硝酸锂-KNO3-LiClO4 三元盐体系的比电导率值。研究发现,在 LiNO3-KNO3 二元共晶中加入高氯酸锂 LiClO4 会提高三元盐体系的比离子电导率。高氯酸锂作为一种活性添加剂,在阴阳离子相互作用的竞争机制下促进了离子迁移率的提高。当加入 0.2 摩尔高氯酸锂时,体系中的比离子电导率值达到最大值。实验证明,随着硝酸盐共晶中高氯酸锂添加量的增加,LiNO3-KNO3 共晶的熔峰降低。在初始含量为 0.5LiClO4 的成分中,LiNO3-KNO3 共晶没有发生相变。很明显,在该体系中,硝酸钾和高氯酸锂发生了交换反应,生成了 KClO4 和 LiNO3。拉曼散射光谱数据也证实了这一结论,该光谱显示,随着 LiClO4 添加量的增加,完全对称伸缩振动 ν1(KNO3)的峰值减小,并出现了 ν1(KClO4)的峰值。加入 0.5 摩尔的 LiClO4 会导致 ν1(KNO3)峰完全消失。盐体系中的离子间相互作用导致了 NO3ˉ 离子局部对称性的变化,这反映在它们的迁移和热力学性质中。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Effect of lithium perchlorate addition on LiNO3–KNO3 nitrate eutectic

Effect of lithium perchlorate addition on LiNO3–KNO3 nitrate eutectic

In our work, thermal properties, phase transitions, and processes of molecular relaxation of nitrate and perchlorate ions in the lithium nitrate–potassium nitrate binary eutectic system doped with lithium perchlorate LiClO4 were studied by differential scanning calorimetry and Raman spectroscopy. The values of specific electrical conductivity of the LiNO3–KNO3 nitrate eutectic and the LiNO3–KNO3–LiClO4 ternary salt system were also obtained. The electrical conductivity was investigated up to melting temperatures and it was found that the addition of lithium perchlorate LiClO4 to the LiNO3–KNO3 binary eutectic leads to an increase in the specific ionic conductivity of the ternary salt system. Lithium perchlorate functions as an active additive that promotes the increase of ion mobility due to competing mechanisms of anion-cation interactions. The value of specific ionic conductivity reaches a maximum in the system when 0.2 mol of lithium perchlorate is added. It has been established that with the increasing addition of lithium perchlorate to the nitrate eutectic, the melting peak of the LiNO3–KNO3 eutectic decreases. For the composition with an initial content of 0.5LiClO4, a phase transition of the LiNO3–KNO3 eutectic is not registered. It is obvious that in the system take place an exchange reaction between potassium nitrate and lithium perchlorate with the formation of KClO4 and LiNO3. This conclusion is also confirmed by the data of Raman scattering spectra, which show that with increasing addition of LiClO4, the peak of fully symmetric stretching vibration ν1(KNO3) decreases and the peak of ν1(KClO4) is observed. The addition of 0.5 mol of LiClO4 leads to the total disappearance of the peak of ν1(KNO3). Interionic interactions in the salt systems, leading to changes in the local symmetry of the NO3ˉ-ion, are reflected in their transport and thermodynamic properties.

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来源期刊
Ionics
Ionics 化学-电化学
CiteScore
5.30
自引率
7.10%
发文量
427
审稿时长
2.2 months
期刊介绍: Ionics is publishing original results in the fields of science and technology of ionic motion. This includes theoretical, experimental and practical work on electrolytes, electrode, ionic/electronic interfaces, ionic transport aspects of corrosion, galvanic cells, e.g. for thermodynamic and kinetic studies, batteries, fuel cells, sensors and electrochromics. Fast solid ionic conductors are presently providing new opportunities in view of several advantages, in addition to conventional liquid electrolytes.
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