物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2014年
2期
311-317
,共7页
卞沛文%努丽燕娜%再娜甫古丽%杨军%王久林
卞沛文%努麗燕娜%再娜甫古麗%楊軍%王久林
변패문%노려연나%재나보고려%양군%왕구림
可充镁电池%电解液%电化学性能%空气稳定性%兼容性
可充鎂電池%電解液%電化學性能%空氣穩定性%兼容性
가충미전지%전해액%전화학성능%공기은정성%겸용성
Rechargeable magnesium battery%Electrolyte%Electrochemical performance%Air insensitive character%Compatibility
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.
將4-甲基苯硫酚、4-異丙基苯硫酚和4-甲氧基苯硫酚(RSH)分彆與格氏試劑C2H5MgCl/THF(四氫呋喃)反應製得的苯硫酚氯化鎂(RSMgCl)(分彆標記為MBMC、IPBMC和MOBMC)/THF和進一步與Lewis痠AlCl3反應製得的(RSMgCl)n-AlCl3/THF (n=1,1.5,2)苯硫酚鹽基溶液用作可充鎂電池電解液,採用循環伏安和恆電流充放電測試研究瞭電解液的鎂沉積-溶齣性能和氧化分解電位.結果錶明,苯硫酚上的基糰種類和RSMgCl與AlCl3的比例對其電化學性能有影響.其中,0.5 mol?L-1(IPBMC)1.5-AlCl3/THF溶液具有最佳的電化學性能,其氧化分解電位適宜(2.4 V (vs Mg/Mg2+)),鎂沉積-溶齣循環效率穩定,過電位低,電導率較高(2.48 mS?cm-1),與正極材料Mo6S8兼容性良好,且具有一定的空氣穩定性,配製方便,有希望應用于實際的可充鎂電池體繫中.
장4-갑기분류분、4-이병기분류분화4-갑양기분류분(RSH)분별여격씨시제C2H5MgCl/THF(사경부남)반응제득적분류분록화미(RSMgCl)(분별표기위MBMC、IPBMC화MOBMC)/THF화진일보여Lewis산AlCl3반응제득적(RSMgCl)n-AlCl3/THF (n=1,1.5,2)분류분염기용액용작가충미전지전해액,채용순배복안화항전류충방전측시연구료전해액적미침적-용출성능화양화분해전위.결과표명,분류분상적기단충류화RSMgCl여AlCl3적비례대기전화학성능유영향.기중,0.5 mol?L-1(IPBMC)1.5-AlCl3/THF용액구유최가적전화학성능,기양화분해전위괄의(2.4 V (vs Mg/Mg2+)),미침적-용출순배효솔은정,과전위저,전도솔교고(2.48 mS?cm-1),여정겁재료Mo6S8겸용성량호,차구유일정적공기은정성,배제방편,유희망응용우실제적가충미전지체계중.
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.
