Electrochemical behavior of a platinum anode for reduction of uranium oxide in a LiCl molten salt

The electrochemical behavior of a platinum anode has been investigated during the electrolysis of uranium oxide in a LiCl molten salt. Pt is oxidized to Pt²⁺ at 2.6 V (vs. Li–Pb reference electrode) in the absence of O²⁻ ion. The platinum dissolution takes place at a more anodic potential with an increase of O²⁻ ion. Although the main anodic process in the electrolysis is the oxygen evolution by oxidation of O²⁻ ion at a higher concentration of Li₂O, a thin film due to the formation of Li₂PtO₃ was coated on the anode surface. The platinum dissolution proceeds with an intergranular corrosion-like behavior at a low concentration of Li₂O.     

熔盐冷冻壁厚度测量方法

熔盐冷冻壁防腐蚀技术是采用凝固熔盐层阻止气液介质与金属器壁直接接触,冷冻壁厚度的准确监测及控制是其成功应用的关键。本文以混合硝酸盐熔盐为实验介质,研究了冷冻壁形成及维持过程中不同在线厚度监测方法,并与机械卡尺的直接测量值进行对比分析。结果表明,温度梯度推算法在非稳态及厚度较小时误差较大,在平衡维持态时则能较准确地判定厚度,但需要设置合适的热电偶组;冷却热量推算法可通过外夹套换热量及换热壁面温度推算冷冻壁厚度,但其稳定性及准确性取决于冷却量的精确衡算,其优点是不需增加额外设备;在线图像处理法能比较直观地反映冷冻壁厚度,但需要配备稳定可靠的高温摄像系统。鉴于未来熔盐冷冻壁应用是在无水无氧密闭容器中,这几种在线监测方法在真实高温熔盐化学体系的适用性还有待于进一步研究和评估。     

Low-temperature synthesis of tungsten diboride powders via a simple molten salt route

WB₂ powders were successfully prepared at 1000°C using NaCl–KCl salts as molten salts. Compared to the conventional solid-state reaction, the introduction of NaCl–KCl salts decreased the synthesis temperature of WB₂ phase, which was related to the faster diffusion rate of particles in the liquid state than in the solid-state. The effect of reaction temperature, time, and the amount of molten salts on the synthesis of WB₂ were studied in detail. The template formation mechanism was considered to have played an essential part in the synthesis process. Transmission electron microscope analysis showed that the as-synthesized WB₂ powders exhibited a hexagonal crystal structure. Furthermore, the oxidation protective performance of as-synthesized WB₂ powders was investigated by TG-DSC measurement.     

有机熔盐LiTFSI/NaTf中锂在铝电极上的电极过程

采用循环伏安、计时电流和恒电流充放电等电化学测试技术考察了LiTFSI/NaTf熔盐电解质中锂在铝电极上的电化学行为。研究结果表明：在该熔盐中,锂在铝电极上的电化学还原过程伴随着锂铝合金的成核过程,且反应生成的LiAl合金只有一种合金相是可逆的;恒电流循环充放电实验发现,首次循环的库仑效率较低,库仑效率随电流密度的增大而有所减小,但随温度的升高而增大。计时电流实验发现,锂原子嵌入铝电极中形成α-LiAl合金的过程受锂在铝基体内扩散步骤控制,且该扩散系数为1.7×10^-10 cm²·s^-1。     

用于熔盐体系的氮化硼隔膜Ag/AgCl参比电极性能

介绍了熔盐中常使用的参比电极的性质和存在的问题,制得可用于高温氟化物盐中的氮化硼隔膜Ag/AgCl的参比电极,并对它的性能做了重点研究。确定了AgCl的物质的量分数为2%时较好,且需确保AgCl均匀地混合在LiCl-KCl熔盐中;该种参比电极在制备过程中应注意在各接口处严格密封,以减缓盐的蒸发和导线的腐蚀。对参比电极的性能做了评价,发现活化温度对活化时间有影响;温度变化对电位影响较小;参比电极的极化可逆性均良好;稳定性良好,但是受AgCl浓度、温度及光线的影响,长期使用电极的重现性较好。最终发现该参比电极性质稳定可长期连续（至少28 d）用于熔盐电化学实验中。     

熔盐法热解液化聚丙烯的研究

以熔融氯化锌作为热载体,对聚丙烯(PP)的热解液化进行研究。考察了热载体用量、热解温度对各组分收率的影响,以及热解温度对反应时间的影响,确定了热载体用量与聚丙烯的质量比为4:1,最佳热解温度范围为420—440℃。分馏液相产物得到汽油、柴油和重油组分,采用红外光谱对液相产物进行表征,并对汽油组分进行色-质分析和辛烷值计算,辛烷值可达86.32。结果表明,熔盐法热解聚丙烯具有速度快、汽油组分收率高、辛烷值高的特点。     

基于有限元方法的CeCl3和NdCl3在LiCl-KCl熔盐中的电极动力学模拟

充分理解锕系元素和镧系元素在熔盐中的行为和性质是实现反应堆乏燃料熔盐电解后处理的关键,然而熔盐电解实验所需的高温环境、腐蚀性熔盐甚至放射性物质等条件限制了实验的广泛开展。为寻求一种低成本且可靠的获取元素在熔盐中性质的途径,采用有限元方法在不同温度下模拟了不同浓度的三氯化铈和三氯化钕在LiCl-KCl熔盐中的循环伏安曲线,并与实验数据做了对比。结果表明,有限元方法能够较为准确地反映实际电化学过程,继而为乏燃料熔盐电解后处理提供数据支持。     

硫酸装置熔盐系统的设计及运行

根据生产实践,论述WSA硫酸装置熔盐系统的设计及在正常操作与开停车期间的控制参数。详细介绍了熔盐性质,提出在熔盐充装、熔盐管道、阀门、泵槽、保温设置等方面应注意的事项和规避的风险,以保证硫酸装置的稳定运行。     

端士伯特拉姆斯公司熔盐加热、降膜蒸发生产片碱技术应用总结

介绍了引进瑞士Bertrams公司三效逆流降膜蒸发生产片碱的成套技术、设备，及在投料试车中出现的问题和解决方法。     

氟化物熔盐的制备及其应用进展

氟化物熔盐具有高温稳定性好、热导率高、比热容大、电化学窗口宽、饱和蒸汽压低和中子吸收截面小等一系列优点,是一种具有广阔应用前景的重要功能材料。本文介绍了氟化物熔盐的典型制备及净化方法（如真空除水法、氟氢化铵法、H₂-HF净化法、电化学净化法、添加还原剂法）,分析了不同方法去除熔盐中杂质离子的作用机制和技术特点。总结了氟化物熔盐在核能、冶金、功能材料制备、先进储能介质、表面处理技术、电子化学品、精细化工及熔盐电池材料等领域的应用及最新进展。突出了氟化物熔盐作为核反应堆冷却剂、熔盐电解质、高温储能材料及反应介质等方面的应用优势。指出了氟化物熔盐在制备及应用过程中存在的问题及发展趋势,并就其发展前景进行了展望。文章指出开展氟化物熔盐制备与纯化机制研究、探索氟化物熔盐净化过程中杂质的存在形式与迁移规律、阐明氟化物熔盐制备与净化机理、发展新的熔盐净化方法以减小熔盐的腐蚀性和降低成本对熔盐的工业化生产和应用至关重要。     

Fabrication and characterization of ternary La1‐xCexB6 by a novel molten salt synthesis route

A novel molten salt synthesis route has been developed to prepare ternary La_1‐xCe_xB₆ (x = 0.2, 0.4, 0.6, 0.8), using LaCl₃, CeCl₃, and NaBH₄ as reactants and eutectic LiCl/KCl salt as molten salt medium. All the synthesized ternary La_1‐xCe_xB₆ are single‐phase solid solution, and their lattice constant decreases linearly with increasing x. Morphology, microstructure, and elements composition of La_0.6Ce_0.4B₆ which is a typical representative of the series of La_1‐xCe_xB₆ are analyzed in detail.     

热电池电解质与隔膜材料研究进展

作为一种在使用时使电解质熔融而激活工作的储备电池,热电池的熔融盐电解质是决定其性能的关键要素之一。近年来,通过组分调控电解质新体系来降低熔点和提高离子电导率成为研究热点,利用基于热力学理论和热力学数据库的相图计算（CALPHAD）进行三元甚至四元熔融盐体系的筛选,为得到性能优异的熔融盐电解质提供便利,从而达到提升热电池性能特别是延长电池寿命的目的。熔融盐功能组分如黏结剂MgO等的加入可以减少电解质熔融盐泄漏,其用量和结构的优化可以提高熔融盐与电解液的亲和性以及减小电池内阻,进而提高热电池电化学性能;无机纤维隔膜的引入可以更大程度地减小或者消除无离子传导MgO的使用,同时无机纤维隔膜的使用提高了电池的安全可靠性,也为热电池的小型化提供了指导方向。     

三元硝酸熔盐高温热稳定性实验研究与机理分析

通过熔盐质量损失率和试样中NO2-含量变化状况,以及熔盐材料的热重(TG)曲线,研究了三元硝酸熔盐(53%KNO3-40%NaNO2-7%NaNO3)在空气和氮气气氛中高温条件下的热稳定性性能。结果表明,三元硝酸熔盐空气中的上限使用温度为773K,高温时存在劣化现象;而在氮气气氛中三元熔盐的热分解温度为723K。同时,从热力学和动力学角度分析得到,三元硝酸熔盐在773K以下空气中发生的反应为亚硝酸钠的分解和氧化;而在氮气气氛中三元熔盐723K以下时主要发生的是亚硝酸钠的分解反应。在氧气含量一定的情况下,氧气的扩散和亚硝酸盐的分解反应符合一级反应动力学模型。     

Scale-up and optimization of a two-stage molten salt oxidation reactor system for the treatment of cation exchange resins

A prototype two-stage MSO (molten salt oxidation) reactor system with a capacity of 10 kg/h was developed based on the test results of lab-scale and bench-scale MSO systems. This study first discusses the features of the prototype MSO reactor system. The second part of the study attempts to identify the proper conditions of the prototype two-stage MSO reactor system, where each reactor performs different functions. The volatility of radioactive elements doped in the spent resins was first investigated to establish the proper operating conditions of the primary MSO reactor. A parametric model study of the secondary MSO reactor for the oxidation of hydrocarbons from the primary reactor and an experimental validation were then performed to establish the optimum conditions for the two-stage MSO reactor system. The retention of cesium was greatly influenced by the pyrolysis temperature. The highest pyrolysis temperature with cesium retention of ≥99.9% was 790 °C and this was established as the optimum primary reactor temperature. The optimum conditions of secondary MSO reactor for the substantial oxidation of hydrocarbons generated from the primary MSO reactor were determined to be λ (the ratio of actual air feed rate per stoichiometric air rate) of 2, and a temperature of 800 °C.     

Phase evolution and chemical stability of Nd-doped Y3Fe5O12 waste forms synthesized in molten salt at a low temperature

Molten salt provides a fast mass transfer and nucleation process, so the ceramic solid solution for immobilization of high-level nuclear waste (HLW) can be synthesized at lower temperatures. The chemical stability in the process of interaction with groundwater determines the ability of the matrix phase to prevent radionuclides from entering the biosphere. Nd-doped Y₃Fe₅O₁₂ ceramics were prepared by the molten salt method at different sintering temperatures (1000℃, 1100℃, 1200℃) and different m (eutectic salt): m (oxide) ratios (2:1, 3:1, 4:1). The sintered ceramic is Y_3-xNd_xFe₅O₁₂, where x is the solubility of Nd in YIG. The results show that the optimum mass ratio of molten salt to oxide is 3:1. The solubility of Nd in garnet is 33.3 mol% (x = 1.1) and 56.7 mol% (x = 1.6) at 1100℃ and 1200℃, respectively. In the neutral medium, Nd does not transfer to the liquid phase. Acid leaching promotes the strong dissolution of the garnet matrix. In this case, the leaching rate of Nd from ceramics to the liquid phase is two to three orders of magnitude higher than that in a neutral medium. The experimental results suggest that garnet matrices can reliably immobilize actinides in subsurface repositories.     

含钙三元氯化物体系相图计算与熔盐热稳定性

为寻求太阳能热利用高温传热储热材料,以盐湖资源为原料,提出分支/分区相图计算方法,设计NaCl-CaCl₂-KCl和KCl-CaCl₂-MgCl₂熔盐传热储热材料。基于正规溶液模型,以不同分支不同相互作用系数,计算了5个边界体系相图,实现用正规溶液模型计算含化合物体系复杂相图。含化合物KCl-CaCl₂和KCl-MgCl₂体系及3个不含化合物二元体系的计算相图与实验相图十分吻合。以分区域方法计算三元体系相图,预测出5个低共熔点来指导熔盐制备。采用差示扫描量热法测试并验证熔盐最低共熔点,确定其工作温度下限;以质量损失实验,确定其工作温度上限。结果表明,钠钾钙和钾镁钙氯化物熔盐能在550~850℃和480~700℃内稳定运行,可用作高温传热储热流体。     

ZrO2对提纯粗ZrCl4用NaCl-KCl熔盐体系物化性质影响

工业上采用NaCl-KCl熔盐体系提纯粗四氯化锆过程中,夹杂物在熔盐体系中富集,造成NaCl-KCl熔盐体系的恶化。利用旋转法、拉筒法和阿基米德原理研究了粗四氯化锆中主要夹杂物二氧化锆对NaCl-KCl熔盐体系表面张力、黏度和密度的影响。结果表明,在660~740 ℃,二氧化锆含量一定的熔盐体系的表面张力随温度的增加而减小,黏度受温度影响较大,当二氧化锆质量分数为0%、10%、15%、20%时密度与温度无关,但当二氧化锆质量分数为5%时,密度受温度的影响较大;温度一定时,熔盐表面张力随二氧化锆含量的增加先保持稳定后迅速减小,黏度随二氧化锆含量的增加逐渐增加,密度随二氧化锆含量的增加先增大后减小随后保持稳定不变。     

熔盐单罐释热过程换热器取热方式优选

盘管释热换热器浸没式布置在熔盐单罐蓄热器内可实现低成本的蓄放热。盘管换热器取热方式会直接影响系统的释热性能。通过数值模拟研究了换热器取热方式对单罐蓄热系统释热性能规律的影响，同时分析了释热过程中熔盐侧流场变化。结果表明，换热器上进下出的取热方式能够提高盘管换热器的出口温度、单罐释热功率及释热效率，研究结果为熔盐单罐蓄放热系统设计提供了理论依据。     

In625合金和316L不锈钢在NaCl-CaCl2-MgCl2熔盐中的腐蚀机理

为了解Cr元素对含铬合金在三元NaCl-CaCl₂-MgCl₂氯化物熔盐中腐蚀的影响机理,选择两种含铬合金镍基Inconel 625（In625）和铁基奥氏体316L型不锈钢,采用全浸没法分别研究它们在500~700℃下于三元氯化物NaCl-CaCl₂-MgCl₂低共熔盐中的腐蚀行为,以及接触空气程度与温度对腐蚀的影响。绘制了In625合金和316L不锈钢在熔盐中600℃下浸没21 d的腐蚀速率曲线。采用XRD（X射线衍射仪）、SEM（扫描电镜）和EDX（X射线能谱仪）对In625合金和316L不锈钢的腐蚀产物和截面形貌进行分析。结果表明：两种金属的腐蚀程度随着接触空气的量和腐蚀温度的增加而加大;600℃下腐蚀21 d后金属表面和截面的元素及形貌分析表明,Cr具有优先脱溶性;600℃下腐蚀21 d后在合金截面形成了贫Cr区域;致密的腐蚀层可以降低金属的腐蚀速率;在NaCl-CaCl₂-MgCl₂三元氯化物熔盐中镍基合金In625拥有比奥氏体不锈钢更好的耐腐蚀性能。     

Electrodeposition behavior of nickel and nickel-zinc alloys from the zinc chloride-1-ethyl-3-methylimidazolium chloride low temperature molten salt

The electrodeposition of nickel and nickel-zinc alloys was investigated at polycrystalline tungsten electrode in the zinc chloride-1-ethyl-3-methylimidazolium chloride molten salt. Although nickel(II) chloride dissolved easily into the pure chloride-rich 1-ethyl-3-methylimidazolium chloride ionic melt, metallic nickel could not be obtained by electrochemical reduction of this solution. The addition of zinc chloride to this solution shifted the reduction of nickel(II) to more positive potential making the electrodeposition of nickel possible. The electrodeposition of nickel, however, requires an overpotential driven nucleation process. Dense and compact nickel deposits with good adherence could be prepared by controlling the deposition potential. X-ray powder diffraction measurements indicated the presence of crystalline nickel deposits. Non-anomalous electrodeposition of nickel-zinc alloys was achieved through the underpotential deposition of zinc on the deposited nickel at a potential more negative than that of the deposition of nickel. X-ray powder diffraction and energy-dispersive spectrometry measurements of the electrodeposits indicated that the composition and the phase types of the nickel-zinc alloys are dependent on the deposition potential. For the Ni-Zn alloy deposits prepared by underpotential deposition of Zn on Ni, the Zn content in the Ni-Zn was always less than 50 atom%.