Diffusion Coefficients of the \({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\) Anion in the Low-Temperature Chloroaluminate Melt Based on Triethylamine Hydrochloride

IF 0.4 Q4 METALLURGY & METALLURGICAL ENGINEERING Russian Metallurgy (Metally) Pub Date : 2025-01-08 DOI:10.1134/S0036029524701556

A. V. Borozdin, V. A. Elterman

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Abstract—Since the demand for renewable energy sources is still increasing, the main research in the battery industry is focused on the development of safe and high-capacity energy storage systems capable of sustaining high current loads and made of inexpensive and readily available materials. An aluminum-ion battery (AIB) using metallic aluminum as the anode, carbon materials as the cathode, and chloroaluminate ionic liquids as the electrolyte is considered to be among the most promising systems. A low-temperature chloroaluminate melt based on triethylamine hydrochloride (Et₃NHCl) is one of inexpensive electrolytes for AIB. This melt can reversibly precipitate/dissolve metallic aluminum due to the presence of the \({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\) ion in it. However, the diffusion of \({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\) ions in the Et₃NHCl–AlCl₃ system has not been studied previously. In this work, the concentration dependences of the diffusion coefficients of the \({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\) anion are studied using chronopotentiometry in the concentration range N = 1.3–1.95 (where N is the molar ratio of aluminum chloride to organic salt). The diffusion coefficients are shown to increase with an increase in the aluminum chloride content in the melt: from 1.71 × 10^–7 (N = 1.3) to 4.50 × 10^–7 cm² s^–1 (N = 1.95). A similar behavior can be caused by a decrease in the viscosity of the melts with an increase in the \({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\) concentration. The obtained results show that Et₃NHCl–AlCl₃ with N = 1.95 is the most suitable electrolyte for operating in AIB. In addition, the electrochemical reduction of the \({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\) ion on the aluminum electrode surface is found to be complicated by the nucleation process, which has the lowest overvoltage at N = 1.95.

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\({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\)阴离子在盐酸三乙胺低温氯铝酸盐熔体中的扩散系数

摘要：由于对可再生能源的需求仍在不断增加，电池行业的主要研究重点是开发安全、高容量的储能系统，该系统能够承受大电流负载，并且由廉价和易得的材料制成。以金属铝为阳极，碳材料为阴极，氯铝酸盐离子液体为电解质的铝离子电池（AIB）被认为是最有前途的系统之一。基于盐酸三乙胺（Et3NHCl）的低温氯铝酸盐熔体是一种廉价的AIB电解质。由于\({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\)离子的存在，这种熔体可以可逆地沉淀/溶解金属铝。然而，\({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\)离子在Et3NHCl-AlCl3体系中的扩散尚未得到研究。在这项工作中，使用时间电位法研究了\({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\)阴离子在浓度范围N = 1.3-1.95（其中N是氯化铝与有机盐的摩尔比）内扩散系数的浓度依赖性。扩散系数随熔体中氯化铝含量的增加而增加：从1.71 × 10-7 （N = 1.3）增加到4.50 × 10-7 cm2 s-1 （N = 1.95）。随着\({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\)浓度的增加，熔体粘度的降低也会引起类似的现象。结果表明，N = 1.95的Et3NHCl-AlCl3是最适合在AIB中运行的电解质。此外，发现\({\text{A}}{{{\text{l}}}_{{\text{2}}}}{\text{Cl}}_{7}^{ - }\)离子在铝电极表面的电化学还原过程是复杂的成核过程，在N = 1.95时过电压最低。

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来源期刊

Russian Metallurgy (Metally) METALLURGY & METALLURGICAL ENGINEERING-

CiteScore

0.70

自引率

25.00%

发文量

140

期刊介绍： Russian Metallurgy (Metally) publishes results of original experimental and theoretical research in the form of reviews and regular articles devoted to topical problems of metallurgy, physical metallurgy, and treatment of ferrous, nonferrous, rare, and other metals and alloys, intermetallic compounds, and metallic composite materials. The journal focuses on physicochemical properties of metallurgical materials (ores, slags, matters, and melts of metals and alloys); physicochemical processes (thermodynamics and kinetics of pyrometallurgical, hydrometallurgical, electrochemical, and other processes); theoretical metallurgy; metal forming; thermoplastic and thermochemical treatment; computation and experimental determination of phase diagrams and thermokinetic diagrams; mechanisms and kinetics of phase transitions in metallic materials; relations between the chemical composition, phase and structural states of materials and their physicochemical and service properties; interaction between metallic materials and external media; and effects of radiation on these materials.