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
1. [1]
  
  (1) Genders, J. D.; Pletcher, D. J. Electroanal. Chem. Interfa. Electrochem. 1986, 199, 93. doi: 10.1016/0022-0728(86)87044-9
2. [2]
  (2) Liebenow, C. J. J. Appl. Electrochem. 1997, 27, 221. doi: 10.1023/A:1018464210084
3. [3]
  (3) Lu, Z.; Schechter, A.; Moshkovich, M.; Aurbach, D.J. Electroanal. Chem. 1999, 466, 203. doi: 10.1016/S0022-0728(99)00146-1
4. [4]
  (4) Aurbach, D.; Moshkovich, M.; Schechter, A.; Turgeman, R.Electrochem. Solid-State Lett. 2000, 3, 31.
5. [5]
  (5) Gre ry, T. D.; Hoffman, R. J.;Winterton, R. C. J. Electrochem. Soc. 1990, 137, 775. doi: 10.1149/1.2086553
6. [6]
  (6) Liebenow, C.; Yang, Z.; Lobitz, P. Electrochem. Commun. 2000,2, 641. doi: 10.1016/S1388-2481(00)00094-1
7. [7]
  (7) Muldoon, J.; Bucur, C. B.; Oliver, A. G.; Sugimoto, T.; Matsui,M.; Kim, H. S.; Allred, G. D.; Zajicek, J.; Kotani, Y. Energy Environ. Sci. 2012, 5, 5941. doi: 10.1039/c2ee03029b
8. [8]
  (8) Aurbach, D.; Lu, Z.; Schechter, A.; fer, Y.; Gizbar, H.;Turgeman, R.; Cohen, Y.; Moshkovich, M.; Levi, E. Nature2000, 407, 724. doi: 10.1038/35037553
9. [9]
  (9) Aurbach, D.; Schechter, A.; Moshkovich, M.; Cohen, Y.J. Electrochem. Soc. 2001, 148, A1004.
10. [10]
  (10) Aurbach, D.; Gizbar, H.; Schechter, A.; Chusid, O.; ttlieb, H.E.; fer, Y.; ldberg, I. J. Electrochem. Soc. 2002, 149, A115.
11. [11]
  (11) Gizbar, H.; Vestfrid, Y.; Chusid, O.; fer, Y.; ttlieb, H. E.;Marks, V.; Aurbach, D. Organometallics 2004, 23, 3826. doi: 10.1021/om049949a
12. [12]
  (12) Vestfried, Y.; Chusid, O.; fer, Y.; Aped, P.; Aurbach, D.Organometallics 2007, 26, 3130. doi: 10.1021/om061076s
13. [13]
  (13) Viestfried, Y.; Levi, M. D.; fer, Y.; Aurbach, D.J. Electroanal. Chem. 2005, 576, 183. doi: 10.1016/j.jelechem.2004.09.034
14. [14]
  (14) Chen, Q.; Nuli, Y. N.; Yang, J.; Kailibinuer, K.;Wang, J. L. Acta Phys. -Chim. Sin. 2012, 28, 2625. [陈强, 努丽燕娜,杨军, 凯丽比努尔?克日木, 王久林. 物理化学学报, 2012,28, 2625.] doi: 10.3866/PKU.WHXB201208032
15. [15]
  (15) Aurbach, D.; Suresh, G. S.; Levi, E.; Mitelman, A.; Mizrahi, O.;Chusid, O.; Brunelli, M. Adv. Mater. 2007, 19, 4260.
16. [16]
  (16) Mizrahi, O.; Amir, N.; Pollak, E.; Chusid, O.; Marks, V.; ttlieb, H.; Larush, L.; Zinigrad, E.;Aurbach, D. J. Electrochem. Soc. 2008, 155, A103.
17. [17]
  (17) Pour, N.; fer, Y.; Major, D. T.; Aurbach, D. J. Am. Chem. Soc.2011, 133, 6270. doi: 10.1021/ja1098512
18. [18]
  (18) Kim, H. S.; Arthur, T. S.; Allred, G. D.; Zajicek, J.; Newman, J.G.; Rodnyansky, A. E.; Oliver, A. G.; Boggess,W. C.; Muldoon,J. Nat. Commun. 2011, 2, 427. doi: 10.1038/ncomms1435
19. [19]
  (19) Guo, Y. S.; Zhang, F.; Yang, J.;Wang, F. F. Electrochem. Commun. 2012, 18, 24. doi: 10.1016/j.elecom.2012.01.026
20. [20]
  (20) Guo, Y. S.; Zhang, F.; Yang, J.;Wang, F. F.; Nuli, Y. N.; Hirano,S. I. Energy Environ. Sci. 2012, 5, 9100. doi: 10.1039/c2ee22509c
21. [21]
  (21) Zhao, Q. S.; Nuli, Y. N.; Guo, Y. S.; Yang, J.;Wang, J. L.Electrochim. Acta 2011, 56, 6530. doi: 10.1016/j.electacta.2011.04.114
22. [22]
  (22) Wang, F. F.; Guo, Y. S.; Yang, J.; Nuli, Y. N.; Hirano, S. I.Chem. Commun. 2012, 48, 10763. doi: 10.1039/c2cc35857c
23. [23]
  (23) Bian, P.W.; Nuli, Y. N.; Chen, Q.; Yang, J.;Wang, J. L.Electrochemistry 2014, 20, 1. [卞沛文, 努丽燕娜, 陈强,杨军, 王久林. 电化学, 2014, 20, 1.]
24. [24]
  (24) Lancry, E.; Levi, E.; Mitelman, A.; Malovany, S.; Aurbach, D.J. Solid State Chem. 2006, 179, 1879. doi: 10.1016/j.jssc.2006.02.032
25. [25]
  (25) Lancry, E.; Levi, E.; fer, Y.; Levi, M.; Salitra, G.; Aurbach,D. Chem. Mater. 2004, 16, 2832. doi: 10.1021/cm034944+
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沈阳化工大学材料科学与工程学院沈阳 110142