硝基锂钠钾二元及三元盐的相图分析

doi:10.19799/j.cnki.2095-4239.2024.1227

摘要/Abstract

摘要：

熔盐的共晶性能是评估其在储热领域应用潜力的关键指标之一。为了快速、准确地预测混合硝酸盐不同组分之间是否能够形成共晶，并进一步确定其共晶组成和最低熔点，本工作采用FactSage热力学模拟软件对5种常见的硝基盐——硝酸锂(LiNO₃)、硝酸钾(KNO₃)、硝酸钠(NaNO₃)、亚硝酸钾(KNO₂)和亚硝酸钠(NaNO₂)进行了热力学模拟，预测了其二元系和三元系的相图。通过相图预测结果，进一步分析了硝基二元盐和三元盐体系中阴阳离子对共晶性能的影响。研究发现，不同阴阳离子的组合会显著影响共晶的形成温度和共晶组成。为了验证相图预测的准确性，本工作还对具有良好共晶效果的二元盐硝酸Li-K和三元盐硝酸Li-Na-K进行了实验验证，测定了它们的熔点和共晶组成。实验结果表明，二元盐硝酸Li-K和三元盐硝酸Li-Na-K的熔点和共晶组成与相图预测结果一致，进一步证明了FactSage软件在熔盐体系相图预测中的有效性和准确性。与此同时，本工作对几种常见的硝基盐进行了二元系和三元系的相图预测，以分析阳离子和阴离子对混合熔盐储能介质的影响机理。通过这一系列研究，本工作不仅为混合硝酸盐的共晶性能评估提供了新的思路和方法，还为未来储热技术中熔盐的优化与应用提供了重要的理论支持。

关键词: 熔盐, 相图计算, 共晶, 熔点

Abstract:

The eutectic properties of molten salts are key indicators for assessing their potential in thermal storage applications, with broad relevance in efficient thermal storage technologies. To quickly and accurately predict whether a eutectic can form between different components of mixed nitrate salts, and to further determine their eutectic composition and lowest melting point, this study employs FactSage thermodynamic simulation software to simulate five common nitrate salts—lithium nitrate (LiNO₃), potassium nitrate (KNO₃), sodium nitrate (NaNO₃), potassium nitrite (KNO₂), and sodium nitrite (NaNO₂). Phase diagrams of their binary and ternary systems were predicted thermodynamically. Based on the simulation results, the effects of anions and cations on the eutectic properties of binary and ternary nitro salt systems were further analyzed. It was found that different combinations of anions and cations significantly influence the eutectic formation temperature and eutectic composition. To verify the accuracy of the phase diagram predictions, binary salt (Li-K nitrate) and ternary salt (Li-Na-K nitrate) systems with favorable eutectic behavior were experimentally validated by determining their melting points and eutectic compositions. The experimental results showed consistency with the predicted values, further confirming the validity and accuracy of FactSage software in predicting the phase diagrams of molten salt systems. In addition, this study predicts binary and ternary phase diagrams for several common nitro salts to analyze the mechanism by which cations and anions influence mixed molten salt energy storage media. Through this work, new approaches are proposed for evaluating the eutectic behavior of mixed nitrate salts, providing essential theoretical support for optimizing and applying molten salts in future thermal storage technologies.

Key words: molten salt, phase diagram calculation, eutectic, melting point

中图分类号:

TK 02

张金柱, 孟令然, 吴玉庭, 石天庆, 商永强, 智瑞平, 魏雯珍. 硝基锂钠钾二元及三元盐的相图分析[J]. 储能科学与技术, 2025, 14(6): 2515-2523.

Jinzhu ZHANG, Lingran MENG, Yuting WU, Tianqing SHI, Yongqiang SHANG, Ruiping ZHI, Wenzhen WEI. Phase diagram analysis of binary and ternary salts of lithium, sodium and potassium nitroxides[J]. Energy Storage Science and Technology, 2025, 14(6): 2515-2523.

图/表 14

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硝基二元盐种类	共晶温度/℃	共晶组成/%
LiNO₃-KNO₃	124.6	33.89∶66.11
LiNO₃-NaNO₃	196.2	49.17∶50.83
NaNO₃-KNO₃	218.5	43.06∶56.94

硝基二元盐种类	共晶温度/℃	共晶组成/%
LiNO₃-KNO₂	92.31	43.06∶56.94
LiNO₃-NaNO₂	151.5	46.67∶53.33
KNO₃-NaNO₂	136.9	56.94∶43.06

序号	共晶温度/℃	共晶组成(LiNO₃∶KNO₃∶NaNO₃)/%
1	119.16	29.501∶57.224∶13.275
2	119.56	29.573∶57.01∶13.417
3	121.27	31.633∶61.976∶6.391

序号	共晶温度/℃	共晶组成(LiNO₃∶KNO₃∶NaNO₂)/%
1	101.45	26.232∶55.574∶18.194
2	106.13	22.743∶56.848∶20.409
3	112.4	28.119∶45.139∶26.742
4	113.87	27.698∶43.872∶28.43
5	114.7	10.586∶56.776∶32.638
6	115.02	28.706∶42.596∶28.698

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