物理化学学报 >> 2014, Vol. 30 >> Issue (2): 311-317.doi: 10.3866/PKU.WHXB201312201

电化学和新能源 上一篇    下一篇

苯硫酚盐基溶液的可充镁电池电解液

卞沛文, 努丽燕娜, 再娜甫古丽, 杨军, 王久林   

  1. 上海交通大学化学化工学院, 上海200240
  • 收稿日期:2013-09-24 修回日期:2013-12-20 发布日期:2014-01-23
  • 通讯作者: 努丽燕娜 E-mail:nlyn@sjtu.edu.cn
  • 基金资助:

    国家自然科学基金(21273147)和上海市科委(11JC1405700)资助项目

Benzenethiolate-Based Solutions for Rechargeable Magnesium Battery Electrolytes

BIAN Pei-Wen, NULI Yan-Na, Zainapuguli, YANG Jun, WANG Jiu-Lin   

  1. School of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China
  • Received:2013-09-24 Revised:2013-12-20 Published:2014-01-23
  • Contact: NULI Yan-Na E-mail:nlyn@sjtu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21273147) and Shanghai Municipal Science and Technology Commission, China (11JC1405700).

摘要:

将4-甲基苯硫酚、4-异丙基苯硫酚和4-甲氧基苯硫酚(RSH)分别与格氏试剂C2H5MgCl/THF(四氢呋喃)反应制得的苯硫酚氯化镁(RSMgCl)(分别标记为MBMC、IPBMC和MOBMC)/THF和进一步与Lewis 酸AlCl3反应制得的(RSMgCl)n-AlCl3/THF(n=1,1.5,2)苯硫酚盐基溶液用作可充镁电池电解液,采用循环伏安和恒电流充放电测试研究了电解液的镁沉积-溶出性能和氧化分解电位. 结果表明,苯硫酚上的基团种类和RSMgCl与AlCl3的比例对其电化学性能有影响. 其中,0.5 mol·L-1(IPBMC)1.5-AlCl3/THF 溶液具有最佳的电化学性能,其氧化分解电位适宜(2.4 V(vs Mg/Mg2+)),镁沉积-溶出循环效率稳定,过电位低,电导率较高(2.48 mS·cm-1),与正极材料Mo6S8兼容性良好,且具有一定的空气稳定性,配制方便,有希望应用于实际的可充镁电池体系中.

关键词: 可充镁电池, 电解液, 电化学性能, 空气稳定性, 兼容性

Abstract:

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 good compatibility with the Mo6S8 cathode. Moreover, the air insensitive character and easy preparation make it a promising candidate for rechargeable battery electrolytes.

Key words: Rechargeable magnesium battery, Electrolyte, Electrochemical performance, Air insensitive character, Compatibility

MSC2000: 

  • O646