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Journal of Energy Storage · 2022 · IF 8.907

Thermodynamic optimization of lithium chloride-potassium chloride-zinc chloride and lithium chloride-potassium chloride-magnesium chloride for thermal energy storage

Zeyang Kang,Yaohui Shi,Hui Liu,Xiangyang Liu,Maogang He

Electrical generators transducing and concentrating solar power to heat and then to electricity require a material with good thermophysical properties to store heat when there is no sunlight. Here, LiCl-KCl-ZnCl 2 and LiCl-KCl-MgCl 2 were observed for their capacity to store energy by the change in sensible heat content as a function of temperature. The ternary phase diagrams of the two salts were predicted using a thermodynamic model . Three eutectic points for LiCl-KCl-ZnCl 2 and four eutectic points for LiCl-KCl-MgCl 2 were predicted and experimentally verified. The heat capacity and thermal stability of the seven eutectic mixtures were measured to evaluate their heat storage capacity and operating temperature range. LiCl-KCl-ZnCl 2 (13.86 % mol-40.63 % mol-45.51 % mol) and LiCl-KCl-MgCl 2 (47.29 % mol-44.33 % mol-8.38 % mol) were found to be the best choices for heat storage materials, which have low melting points of 451.8 K and 612.8 K, large heat capacity of 1.25 J/g·K and 1.80 J/g·K, and wide operating temperature range from room temperature to higher than 823 K, respectively.

研究领域: 材料科学 · 热力学 · 能源工程
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2022 ·Vol. 331 ·期 12 ·5641-5648 · IF 1.754

Electrochemical separation of uranium from dysprosium on liquid Ga and liquid Cd electrodes in molten LiCl–KCl–CsCl eutectic at recycling of high-level waste

Smolenski Valeri,Novoselova Alena,Yan Yongde,Xue Yun,Ma Fuqiu

The equilibrium potentials of Me(III)/Me (Me = Dy, U) couples and the double Me–Ga, Me–Cd alloys vs. Cl − /Cl 2 reference electrode were measured at the temperature range 673–973 K in molten LiCl–KCl–CsCl eutectic by open-circuit potentiometry. The apparent standard potential and the base thermodynamic properties of alloys were determined. Separation factor for Dy/U couple was calculated on gallium and cadmium electrodes. In addition, it was found that the application of gallium electrodes has a significant advantage over cadmium electrodes in the process of electrochemical separation of uranium and dysprosium.

研究领域: 材料科学 · 核能工程 · 电化学
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GEOCHIMICA ET COSMOCHIMICA ACTA · 2023 · IF 5

Isotopic fractionation of chlorine and potassium during chloride sublimation under lunar conditions

Ziyan Han,Hejiu Hui,Haizhen Wei,Weiqiang Li

The Moon is depleted in volatile elements and compounds, and lunar samples exhibit a wide range of Cl isotopic compositions , which is believed to result from the volatilization of metal chlorides (e.g., NaCl, KCl, and FeCl 2 ). However, the Cl isotopic fractionation behavior during volatilization is not well constrained, particularly for metal chlorides. Furthermore, the effect of metal chloride evaporation on metal isotopes is poorly known. In the present study, we performed NaCl and KCl sublimation experiments to study Cl and K isotopic fractionations at temperatures ranging from 923 K to 1061 K and at pressures of 7×10 –5 bar to 1 bar in an N 2 atmosphere. The isotope fractionation factors of 37/35 Cl( α gas–solid ) from NaCl sublimation experiments are 0.9985±0.0002, 0.9958±0.0004, and 0.99807±0.00004 at 1, 10 –2 , and 7×10 –5 bar, respectively. Those of 41/39 K( α gas–solid ) and 37/35 Cl( α gas–solid ) from KCl sublimation experiments are 0.99884±0.00004 and 0.9988±0.0003 at 1 bar, 0.9977±0.0002 and 0.9972±0.0003 at 10 –2 bar, and 0.9989±0.0002 and 0.9989±0.0001 at 7×10 –5 bar, respectively. Chlorine and K isotopes fractionate more at 10 –2 bar than at 7×10 –5 bar and 1 bar. The saturation index in all the sublimation experiments was >95%, which resulted in near-equilibrium isotopic fractionation at the sublimation interface. Therefore, the isotopic fractionation was controlled by mass transfer processes in the gas and solid phases. The isotopic fractionation at 10 –2 bar was controlled by the chemical diffusion of sublimated gas in an N 2 atmosphere with almost no convection effect, (i.e., Pe number close to zero), whereas the isotopic fractionation at 1 bar was suppressed by atmospheric convection with a turbulence factor of 0.4±0.1 (i.e., Pe number >1). The extremely high sublimation rate and the very slow diffusion in the sublimating solid at 7×10 –5 bar suppressed isotopic fractionations. Based on our experimental results, calculations using Cl/K and Na/K in lunar materials reveal that degassing of KCl contributed very little (<0.2‰) to the K isotopic fractionation (>0.58‰) during lunar magma ocean degassing. The Cl isotopic fractionation factor from lunar samples is similar to our results at 10 –2 bar. This similarity of Cl isotope fractionation indicates that there may have been a transient atmosphere above the lunar magma ocean.

CAS / MDL: 7647-14-5 7447-40-7
研究领域: 地球化学 · 行星科学
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ELECTROCHIMICA ACTA · 2016 · IF 4.803

The electrochemical formation of Al-Cu alloys in a LiCl-KCl-AlCl3 molten salt

Wei Li,Zeng Chen,Chaochao Wei,Wenping Kong,Binghua Xu,Xiyang Jia,Chunli Diao,Shengjun Li

An electrochemical method was developed for the formation of Al-Cu alloys. The electrodeposition of aluminum on Mo and Cu substrates was studied using cyclic voltammetry in molten LiCl-KCl-AlCl 3 (2   wt.%). During the cathodic scan of the cyclic voltammograms, three different Al-Cu alloys were observed before pure Al formed on the Cu substrate. The electrochemical formation processes were studied using square wave voltammetry and open circuit chronopotentiometry. The products of the different reduction processes were identified using XRD. The XRD results indicated that three different Al-Cu intermetallic compounds, Al 4 Cu 9 , AlCu, and Al 2 Cu, were obtained using electrochemical deposition in the molten salt system.

研究领域: 材料科学 · 电化学
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IONICS · 2020 ·Vol. 26 ·期 8 ·3901-3909 · IF 2.394

Electrode reaction of Pr(III) and coreduction of Pr(III) and Pb(II) on W electrode in eutectic LiCl-KCl

Li Mei,Sun Zhongxuan,Guo Dan,Han Wei,Sun Yang,Yang Xiaoguang,Zhang Milin

The electrode reaction of Pr(III) and coreduction of Pb(II) and Pr(III) were studied on an inert W electrode in eutectic LiCl-KCl to extract Pr from molten salt. The electrode process kinetic of Pr(III) on W electrode was firstly explored employing cyclic voltammetry (CV) and Tafel technique, such as the diffusion coefficient of Pr(III) in eutectic LiCl-KCl and the exchange current density ( j 0 ) for Pr(III)/Pr(0) couple and the electrode reaction activation energy. Then, various electrochemical techniques were used to investigate the coreduction of Pb(II) and Pr(III). Four cathode current peaks ascribed to the formation of Pr x Pb y intermetallic compounds were detected, which indicated that the Pr could deposit on pre-deposited Pb film, react with Pb, and form Pr x Pb y intermetallic compounds. Furthermore, the electrolytic products formed by galvanostatic electrolysis were characterized by scanning electron microscopy coupled with energy dispersive X-ray diffraction, which illustrated the formation of PrPb 3 intermetallic compound in LiCl-KCl-PbCl 2 -PrCl 3 melt.

CAS / MDL: 7447-41-8 7447-40-7
研究领域: 化学 · 材料科学
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FUEL · 2021 · IF 6.609

Inhibition discrimination of different chloride salts on coal functional groups

Chunhua Zhang,Jiahui Shen,Ji Li,Mei Wan

To study the inhibition characteristics of different chloride salts on the spontaneous combustion of coal and to further reveal why magnesium chloride shows a different inhibitory effect, coal samples from FuSheng Coal Mine No. 15 in Shanxi Province were selected. Based on the characteristics of functional group absorption peak at different temperature, the composition changes and reactivity ranking of the functional groups in oxidized coal samples were tested by thermal oxidation experiments and infrared spectroscopy and analyzed to obtain the chain thermal reactions of different active groups. The weight-loss process and heat release characteristics of raw coal and three chloride salt-containing coal samples (sodium chloride, potassium chloride, and magnesium chloride) were compared and analyzed by synchronous thermal analysis experiments, and their inhibition reaction mechanism were studied. The results showed that different functional groups reacted at different low-temperature stages, and the active groups containing C–H, O–H, C-O, and C = O bonds were important during the spontaneous combustion of coal. In the chain thermal reactions with different active groups, heat and oxidative cleavage of the C-O and O–H bonds determined the chain development of different functional groups, and the R·, RO·, H·, and ·OH, chain thermal reaction products again acted as reactants that promoted further development of the reaction. Sodium chloride and potassium chloride played inhibitory roles in the dehydration-desorption stage and dynamic equilibrium stage through water evaporation and heat absorption, while magnesium chloride participated in the whole coal-oxygen reaction process. The inhibitory mechanism included dehydration and heat absorption by MgCl 2 ·6H 2 O, the complex dehydration of active groups containing O–H, the precipitation and oxygen insulation of [(SH·) n ]Mg and Mg(OH) 2 , the nucleophilic substitution of α-H for RCH 3 and RCH 2 OH groups, and the formation of H…Cl…H bonds.

CAS / MDL: 7786-30-3
研究领域: 化学工程 · 能源科学 · 材料科学
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2020 ·Vol. 167 ·期 14 ·142505 · IF 3.721

Electrochemical Coreduction of Gd(III) with Pb(II) and Recovery of Gd from LiCl-KCl Eutectic Assisted by Pb Metal

Wei Han,Wenjuan Wang,Mei Li,Yangyang Meng,Wenjing Ji,Yang Sun

To recover Gd from LiCl-KCl eutectic, the coreduction mechanism of Gd(III) with Pb(II) was investigated using electrochemical methods. The formation potentials related to the formation of three Gd-Pb intermetallics were detected by cyclic voltammetry, square wave voltammetry and chronopotentiometry, and the formation mechanism of Gd-Pb compounds could be described as xPb(II) + 2xe− = xPb. Meanwhile, the electroreduction of Gd on liquid Pb electrode was explored. The diffusion coefficient of Gd metal in liquid metallic Pb was determined by anodic chronopotentiometry. The kinetic parameters of Gd(III)/Gd(in Pb) couple in the temperature range from 723 K to 873 K were determined employing linear polarization (LP) method. Based on the relationship of exchange current density and temperature, the reaction activation energy was estimated to be 23.17 kJ mol−1. In addition, the recovery of Gd from molten salts was performed assisted by liquid Pb electrode by constant potential electrolysis (CPE) and constant current electrolysis (CCE). The products characterized using XRD, SEM with EDS are comprised of GdPb3 and Pb phases. The concentration change of Gd during CCE process was monitored by ICP-AES, and the recovery rate was estimated. The results showed that Gd concentration decreased and recovery rate increased with the duration.

研究领域: 材料科学 · 电化学工程
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International Journal of Minerals Metallurgy and Materials · 2025 ·Vol. 32 ·期 4 ·892-901 · IF 7.2

Electrochemical extraction of strontium from molten salts using reactive zinc and aluminum electrodes

Zhang Yongcheng,Yin Taiqi,Zhang Lei,Zhang Xiaochen,Bo Tao,Tan Xiaoli,Li Mei,Han Wei

Herein, the electrochemical behaviors of Sr on inert W electrode and reactive Zn/Al electrodes were systematically investigated in LiCl-KCl-SrCl 2 molten salts at 773 K using various electrochemical methods. The chemical reaction potentials of Li and Sr on reactive Zn/Al electrodes were determined. We observed that Sr could be extracted by decreasing the activity of the deposited metal Sr on the reactive electrode, although the standard reduction potential of Sr(II)/Sr was more negative than that of Li(I)/Li. The electrochemical extraction products of Sr on reactive Zn and Al electrodes were Zn 13 Sr and Al 4 Sr, respectively, with no codeposition of Li observed. Based on the density functional theory calculations, both Zn 13 Sr and Al 4 Sr were identified as stable intermetallic compounds with Zn-/Al-rich phases. In LiCl-KCl molten salt containing 3wt% SrCl 2 , the coulombic efficiency of Sr in the Zn electrode was ∼54%. The depolarization values for Sr on Zn and Al electrodes were 0.864 and 0.485 V, respectively, exhibiting a stronger chemical interaction between Zn and Sr than between Al and Sr. This study suggests that using reactive electrodes can facilitate extraction of Sr accumulated while electrorefining molten salts, thereby enabling the purification and reuse of the salt and decreasing the volume of the nuclear waste.

CAS / MDL: 10025-70-4 10476-85-4
研究领域: 材料科学 · 核能工程 · 电化学
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Journal of Magnesium and Alloys · 2020 · IF 7.115

Study on the electrochemical behavior of Mg and Al ions in LiCl-KCl melt and preparation of Mg-Al alloy

Shaolong Li,Yusi Che,Chenyao Li,Yongchun Shu,Jilin He,Bin Yang,Jianxun Song

The electrochemical behavior of Mg 2+ and Al 3+ in LiCl-KCl (mass 4: 1) melt at 973 K was studied on a Mo electrode systematically by cyclic voltammetry, square wave voltammetry and chronopotentiometry. The results showed that the reductions of Mg 2+ and Al 3+ were reversible processes controlled by the rate of the mass transfer. When Mg 2+ and Al 3+ coexisted in LiCl-KCl melt, they had no significant effect on the reduction potential of each other. The equilibrium potentials of Mg 2+ /Mg and Al 3+ /Al were obtained by open circuit potential method. Their apparent standard potentials were also calculated in this system and the values were −2.52 V vs Cl 2 /Cl − , −1.66 V vs Cl 2 /Cl − , respectively. Correspondingly, the apparent Gibbs free energies of Mg 2+ /Mg and Al 3+ /Al were −485.71 kJ/mol, −480.78 kJ/mol. Finally, potentiostatic electrolysis was performed on a Mo electrode in LiCl-KCl-MgCl 2 -AlCl 3 (the mass ratio of MgCl 2 to AlCl 3 was 10:1) melt at different potentials. The components of the deposits were characterized by scanning electron microscope and energy dispersive spectroscopy. The study revealed that the content of Al in the deposit decreased as the overpotential increased and Al tended to segregate at the grain boundaries.

研究领域: 材料科学 · 电化学
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Crystals · 2023 ·Vol. 13 ·期 5 ·817 · IF 2.7

Corrosion Performance of Commercial Alloys and Refractory Metals in Conditions for Electrorefining of Spent Nuclear Fuels

Yanhong Jia,Shuangshuang Chang,Xin Du,Shaoqiang Guo

Molten LiCl-KCl salt and liquid cadmium are proposed as the electrolyte and the reactive cathode for the electrorefining of spent nuclear fuels, but they can be corrosive to the structural alloys. The down-selection of existing materials through corrosion testing is necessary to ensure the longevity of the electrorefiner vessel and electrode assemblies. Haynes C276, Inconel 600, AISI 316L stainless steel, and 42CrMo low-alloy steel were exposed to a LiCl-KCl melt at 500 °C for 500 h in an argon atmosphere. All alloys suffered from dissolution attacks with the presence of oxide islands or a porous oxide layer on the surface. AISI 316L, T91 steel, and tungsten specimens were submitted to corrosion tests in liquid cadmium at 500 °C for 120 h. The corrosion of AISI 316L and T91 stainless steel was predominated by chemical oxidation, with the additional occurrence of severe Ni dealloying and Cd penetration on AISI 316L. Destabilization of the Cr oxide layer by cadmium was discovered, resulting in the formation of CdCrO4. Tungsten only suffered from a dissolution attack at a rate of 0.50 mm/a.Keywords:corrosion;molten salts;liquid cadmium;SEM

CAS / MDL: 7447-41-8 7447-40-7
研究领域: 材料科学 · 核能工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

NH3 Adsorption Performance of Silicon-Supported Metal Chlorides

Cheng Shen,Peng Wang,Laihong Shen,Xianglei Yin,Zhenwu Miao

Alkaline earth metal chlorides (AEMH) are considered to be the key to effectively solving the problem of NH3 storage due to their ability to react with NH3 to form stable ammonia complexes. This study attempted to investigate the NH3 adsorption performance of four metal chlorides (CuCl2, MnCl2, MgCl2, and CaCl2) and silicon-supported composite adsorbents with a fixed bed. The adsorbents were characterized by X-ray diffraction, Brunauer–Emmett–Teller, and scanning electron microscopy to analyze the NH3 adsorption behavior. The experiment found that the NH3 adsorption capacity of four metal chlorides is in order: CuCl2 > MnCl2 > MgCl2 > CaCl2, and the adsorption capacity of metal chlorides decreased with the increase in temperature. In addition, the composite adsorbents of silicon-supported metal chlorides were synthesized by the wet impregnation method. Ammonia adsorption experiments showed that silicon can significantly improve the NH3 adsorption capacity of metal chlorides, and the NH3 adsorption capacity of MnCl2/silicon was 127.5% higher than that of MnCl2. Silicon played the role of the skeleton support in the metal chloride particles, hindering the agglomeration between particles and increasing the number of pores on the surface of the particles, which was conducive to the diffusion of NH3 through the pores into the particles for adsorption.

研究领域: 材料科学 · 化学工程
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JOURNAL OF CHEMICAL THERMODYNAMICS · 2020 · IF 2.888

Thermodynamic properties of stable states cerium compounds in fused 3LiCl-2KCl eutectic

Minghui Xu,Valeri Smolenski,Qi Liu,Alena Novoselova,Kewei Jiang,Jing Yu,Jingyuan Liu,Rongrong Chen,Hongsen Zhang,Milin Zhang,Jun Wang

The interaction of oxygen and cerium-free ions in molten 3LiCl-2KCl eutectic in the temperature range of (723–823) K was studied by the method of potentiometric titration using YZME electrodes. Stable states of cerium compounds in the Ce–O system and the mechanism of interaction of Ce 3+ with O 2− ions have been established. The solubility constants of cerium oxychloride and oxide compounds at different temperatures were determined. Principal thermodynamic data of CeOCl and Ce 2 O 3 were calculated. The Pourbaix (potential-pO 2− ) diagram was drawn and summarizes the properties of stable cerium species in the melt.

研究领域: 化学 · 材料科学
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