Corresponding Author

Xiao-Zhou Cao(caoxz@smm.neu.edu.cn)


Antimony is a chemically stable metal that has been widely used in industry, military and other fields. The use of electrodeposition to prepare antimony coating has the advantages of simple operation and low cost. The deep eutectic solvent (DES) is a eutectic mixture composed of a hydrogen bond donor and a hydrogen bond acceptor at a fixed molar ratio. It has the advantages of wide electrochemical window, high thermal stability, easy preparation, and low cost. Selecting DES as the electrolyte for electrodeposition can avoid the hydrogen evolution reaction of the aqueous system and the toxicity of ionic liquids. In recent years, there have been more and more researches on the preparation of metal coatings by electrodeposition in DES. In this work, choline chloride (ChCl) and ethylene glycol (EG) were heated and mixed at a molar ratio of 2:1 to form DES, while antimony(III) chloride (SbCl3) was added to form an electrolyte. At room temperature, Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy were used to analyze the structure of the electrolyte. The results show that there were a large number of hydrogen bonds in DES, and that the existence of hydrogen bonds played an important role in the formation of DES. Sb(III) existed in the eutectic solvent in the form of [SbCl4]-. Using a three-electrode system, cyclic voltammetry was used to study the electrochemical behaviors in DES at different sweep speeds (25 ~ 55 mV·s-1), different temperatures (333 ~ 363 K), and different concentrations (0.01 ~ 0.10 mol·L-1) of Sb(III). The results indicate that at 343 K, the reduction of Sb(III) in ChCl-EG became a quasi-reversible reaction controlled by diffusion through one-step three-electron transfer. The diffusion coefficient at 343 K was 3.06×10-9 cm2·s-1. As the temperature and concentration of the electrolyte increased, the overpotential required for the reduction of Sb(III) decreased. The nucleation mode of electrochemical reduction of Sb(III) in ChCl-EG was studied by chronoamperometry. According to the Scharifker-Hills nucleation model, at 343 K, the nucleation of Sb on the tungsten electrode follows three-dimensional instantaneous nucleation. In addition, the electrodeposition products were characterized by SEM and XRD. SEM observations reveal that the applied deposition potential is the main driving force for the reduction of Sb(III). As the deposition potential increased from -0.33 V to -0.41 V, the morphology of the electrodeposition product gradually changed from granular crystals to dendrites. XRD data shows that there was Sb phase in the deposited product obtained at -0.41 V. In addition, the Cu2Sb phase was presented due to the interfacial reaction between the newly deposited Sb and the substrate Cu to form intermetallic compounds. Future research can continually study the influences of such inorganic additives as boric acid (BA), ammonium chloride (NH4Cl), and organic additives includingethylene-diaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) and Idranal VII (HEDTANa3) on Sb electrodeposition.

Graphical Abstract


electrodeposition, deep eutectic solvent, choline chloride-ethylene glycol, antimony, cyclic voltammetry

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[1] Xue F L(薛福连). Antimony with a wide range of uses[J]. Metal World(金属世界), 2007, 5: 67-67.

[2] Diao J J(刁静君), Wang W(王为). Research progress of semi-metals and semi-conductors electrodeposited in ionic liquid[J]. Mater. Prot.(材料保护), 2013, 46(4): 40-43.

[3] Su B(苏波), Li J(李坚), Hua Y X(华一新), Xu C Y(徐存英), Li Y(李艳), Ai G H(艾刚华). Electrochemistry of Sn2+/Sn in choline chloride-glycol deep eutectic solvents[J]. J. S.-Cent. Univ. Natl. (Nat. Sci. Ed.)(中南大学学报(自然科学版)), 2018, 49(9): 2129-2136.

[4] Ibrahim R K, Hayyan M, AlSaadi M A, Ibrahim S, Hayyan A, Hashim M A. Physical properties of ethylene glycol-based deep eutectic solvents[J]. J. Mol. Liq., 2019, 276: 794-800.
doi: 10.1016/j.molliq.2018.12.032 URL

[5] Yang H X, Reddy R G. Electrochemical deposition of zinc from zinc oxide in 2: 1 urea/choline chloride ionic liquid[J]. Electrochim. Acta., 2014, 147: 513-519.
doi: 10.1016/j.electacta.2014.09.137 URL

[6] Vieira L, Schennach R, Gollas B. The effect of the electrode material on the electrodeposition of zinc from deep eutectic solvents[J]. Electrochim. Acta., 2016, 197: 344-352.
doi: 10.1016/j.electacta.2015.11.030 URL

[7] Wang H Y(王怀有), Jing Y(景燕), Lv X H(吕学海), Yin G(尹刚), Wang X H(王小华), Yao Y(姚颖), Jia Y Z(贾永忠). Structure and physico-chemical properties of ionic liquid containing magnesium chloride[J]. J. Chem. Ind. Eng.(化工学报), 2011, 62(S2):21-25.

[8] Tenhunen T M, Lewandowska A E, Orelma H, Johansson L S, Virtanen T, Harlin A, Österberg M, Eichhorn S J, Tammelin T. Understanding the interactions of cellulose fibres and deep eutectic solvent of choline chloride and urea[J]. Cellulose, 2018, 25(1): 137-150.
doi: 10.1007/s10570-017-1587-0 URL

[9] Miller M A, Wainright J S, Savinell R F. Iron electrodeposition in a deep eutectic solvent for flow batteries[J]. J. Ele-ctrochem. Soc., 2017, 164(4): A796-A803.

[10] Chang P, Chen Z, Zhang Y H, Liu Y. Direct measurement of aerosol pH in individual malonic acid and citric acid droplets under different relative humidity conditions via Raman spectroscopy[J]. Chemosphere, 2020, 241: 124960.
doi: 10.1016/j.chemosphere.2019.124960 URL

[11] Haight J G P. Polarography of tripositive antimony and arsenic. Cathodic reduction of antimonous in strong hydrochloric acid and anodic oxidation of arsenite and stibnite in strong sodium hydroxide[J]. J. Am. Chem. Soc., 1953, 75 (15): 3848-3851.

[12] Fung K W, Begun G M, Mamantov G. Raman spectra of molten bismuth trichloride and antimony trichloride and of their mixtures with potassium chloride or aluminum trichloride[J]. Inorg. Chem., 1973, 12 (1): 53-57.
doi: 10.1021/ic50119a014 URL

[13] Habboush D A, Osteryoung R A. Electrochemical studies of antimony (III) and antimony (V) in molten mixtures of aluminum chloride and butylpyridinium chloride[J]. Inorg. Chem., 1984, 23(12): 1726-1734.
doi: 10.1021/ic00180a018 URL

[14] Ali M R, Rahman M Z, Sankarsaha S. Electrodeposition of copper from a choline chloride based ionic liquid[J]. J. Electrochem., 2014, 20(2): 139-145.

[15] Catrangiu A S, Sin I, Prioteasa P, Cotarta A, Cojocaru A, Anicai L, Visan T. Studies of antimony telluride and copper telluride films electrodeposition from choline chloride containing ionic liquids[J]. Thin Solid Films, 2016, 611: 88-100.
doi: 10.1016/j.tsf.2016.04.030 URL

[16] Hinatsu J T, Foulkes F R. Electrochemical kinetic parameters for the cathodic deposition of copper from dilute aqueous acid sulfate solutions[J]. Can. J. Chem. Eng., 1991, 69(2): 571-577.
doi: 10.1002/cjce.5450690224 URL

[17] Nagaishi R, Arisaka M, Kimura T, Kitatsuji Y. Spectroscopic and electrochemical properties of europium (III) ion in hydrophobic ionic liquids under controlled condition of water content[J]. J. Alloys. Compd., 2007, 431(1-2): 221-225.
doi: 10.1016/j.jallcom.2006.05.048 URL

[18] Manh T L, Arce-Estrada E M, Romero-Romo M, Mejía-Caballero I, Aldana-González J, Palomar-Pardavé M. On wetting angles and nucleation energies during the electrochemical nucleation of cobalt onto glassy carbon from a deep eutectic solvent[J]. J. Electrochem. Soc., 2017, 164(12): D694-D699.

[19] Bu J J, Ru J J, Wang Z W, Hua Y X, Xu C Y, Zhang Y, Wang Y. Controllable preparation of antimony powders by electrodeposition in choline chloride-ethylene glycol[J]. Adv. Powder Technol., 2019, 30(12): 2859-2867.
doi: 10.1016/j.apt.2019.06.027 URL

[20] Hsieh Y T, Chen Y C, Sun I W. 1-Butyl-1-Methylpyrrolidinium dicyanamide room temperature ionic liquid for electrodeposition of antimony[J]. J. Electrochem. Soc., 2016, 163(5): D188-D193.

[21] Hsieh L Y, Fong J D, Hsieh Y Y, Wang S P, Sun I W. Electrodeposition of bismuth in a choline chloride/ethylene glycol deep eutectic solvent under ambient atmosphere[J]. J. Electrochem. Soc., 2018, 165(9): D331-D338.

[22] Jerkiewicz G, Perreault F, Radovic-Hrapovic Z. Effect of temperature variation on the under-potential deposition of copper on Pt(111) in aqueous H2SO4[J]. J. Phys. Chem. C, 2009, 113(28): 12309-12316.
doi: 10.1021/jp900478u URL

[23] Lovric M, Hermes M, Scholz F. The effect of the electrolyte concentration in the solution on the voltammetric response of insertion electrodes[J]. J. Solid State Electr., 1998, 2(6): 401-404.
doi: 10.1007/s100080050117 URL

[24] Kahoul A, Azizi F, Bouaoud M. Effect of citrate additive on the electrodeposition and corrosion behaviour of Zn-Co alloy[J]. Trans. IMF, 2017, 95(2): 106-113.
doi: 10.1080/00202967.2017.1265766 URL

[25] Zhou L P, Dai Y T, Zhang H, Jia Y R, Zhang J, Li C X. Nucleation and growth of bismuth electrodeposition from alkaline electrolyte[J]. B. Korean Chem. Soc., 2012, 33(5): 1541-1546.
doi: 10.5012/bkcs.2012.33.5.1541 URL

[26] Lin Y F, Sun I W. Electrodeposition of zinc from a Lewis acidic zinc chloride-1-ethyl-3-methylimidazolium chloride molten salt[J]. Electrochim. Acta, 1999, 44(16): 2771-2777.
doi: 10.1016/S0013-4686(99)00003-1 URL

[27] Scharifker B, Hills G. Theoretical and experimental studies of multiple nucleation[J]. Electrochim. Acta, 1983, 28(7): 879-889.
doi: 10.1016/0013-4686(83)85163-9 URL

[28] Tamburri E, Angjellari M, Tomellini M, Gay S, Reina G, Lavecchia T, Barbini P, Pasquali M, Orlanducci S. Electrochemical growth of nickel nanoparticles on carbon nanotubes fibers: Kinetic modeling and implications for an easy to handle platform for gas sensing device[J]. Electrochim. Acta, 2015, 157: 115-124.
doi: 10.1016/j.electacta.2015.01.050 URL

[29] Mosby J M, Prieto A L. Direct electrodeposition of Cu2Sb for lithium-ion battery anodes[J]. J. Am. Chem. Soc., 2008, 130(32): 10656-10661.
doi: 10.1021/ja801745n URL

[30] Nam D H, Hong K S, Lim S J, Kwon H S. Electrochemical synthesis of a three-dimensional porous Sb/Cu2Sb anode for Na-ion batteries[J]. J. Power Sources, 2014, 247: 423-427.
doi: 10.1016/j.jpowsour.2013.08.095 URL

[31] Kim R H, Kim K, Lim S J, Nam D H, Han D, Kwon H. Microstructure evolution of novel Sn islands prepared by electrodeposition as anode materials for lithium rechargeable batteries[J]. RSC Adv., 2017, 7(48): 30428-30432.
doi: 10.1039/C7RA04959E URL



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