Citation: BIAN Pei-Wen, NULI Yan-Na, YANG Jun, WANG Jiu-Lin. Benzenethiolate-Based Solutions for Rechargeable Magnesium Battery Electrolytes[J]. Acta Physico-Chimica Sinica, ;2014, 30(2): 311-317. doi: 10.3866/PKU.WHXB201312201 shu

Benzenethiolate-Based Solutions for Rechargeable Magnesium Battery Electrolytes

1.
School of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Received Date: 24 September 2013
Available Online: 20 December 2013
Fund Project: 国家自然科学基金(21273147) (21273147)上海市科委(11JC1405700)资助项目 (11JC1405700)

The benzenethiolate-based solutions (RSMgCl)_n-AlCl₃/tetrahydrofuran (THF) (R=4-methylbenzene, 4-isopropylbenzene, 4-methoxybenzene; n=1, 1.5, 2, respectively) were obtained by the simple reaction of benzenethiol compounds with the Grignard reagent C₂H₅MgCl/THF and AlCl₃ in THF, and the electrochemical performance as the rechargeable magnesium battery electrolytes are reported. First, 4-methyl-benzenethiolate magnesium chloride (MBMC)/THF, 4- isopropylbenzenethiolate magnesium chloride (IPBMC)/THF, and 4- methoxybenzenethiolate magnesium chloride (MOBMC)/THF solutions (termed as RSMgCl/THF) were synthesized by the reaction of 4-methylbenzenethiol, 4- isopropylbenzenethiol, and 4- methoxybenzenethiol compounds, respectively, with C₂H₅MgCl/THF via a hydrogen metal-radical exchange with rapid evolution of ethane gas. Furthermore, (RSMgCl)_n-AlCl₃/THF solutions were obtained by the reaction of RSMgCl/THF with AlCl₃/THF at different molar ratios of RSMgCl:AlCl₃. The benzenethiolate-based solutions as electrolytes for rechargeable magnesium batteries were characterized in term of anodic stability and reversibility of magnesium deposition-dissolution using cyclic voltammetry and galvanostatic charge/discharge techniques. Furthermore, the compatibility of the solutions with Mo₆S₈ cathode material was verified using coin cells with a Mo₆S₈ cathode, Mg anode, and benzenethiolate-based electrolyte. It is concluded that both the substituents on benzenethiol and the ratio of RSMgCl:AlCl₃ have an effect on the electrochemical performance. 0.5 mol·L^-1 (IPBMC)_1.5-AlCl₃/ THF shows the best electrochemical performance with 2.4 V (vs Mg/Mg²⁺ ) anodic stability, a low voltage for magnesium deposition-dissolution, a high cycling reversibility, and od compatibility with the Mo₆S₈ cathode. Moreover, the air insensitive character and easy preparation make it a promising candidate for rechargeable battery electrolytes.
- Rechargeable magnesium battery,
- Electrolyte,
- Electrochemical performance,
- Air insensitive character,
- Compatibility
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