Synthesis and properties of bisoxalatoborate spiro cyclic quaternary ammonium salt in supercapacitors

doi:10.11949/j.issn.0438-1157.20151170

Abstract

Abstract:

Synthesis of bisoxalatoborate spiro cyclic quaternary ammonium salt (BSQA) from 8-oxa-5-azonia- spiro[4,5]decane bromide(ASB), oxalate dihydrate(OD) and boric acid (BA) was by means of ion exchange. Its structure was verified by ¹³C NMR and LC-MS. Synthesis of BSQA was optimized by using orthogonal test. The optimized conditions were as follows: molar ratio of n_ASB:n_BA was 2.8:1, reaction time was 4 h and reaction temperature was 90℃. Finally, the conversion rate of ASB was 90.2% in this optimized condition. Two kinds of electrolyte that made from BSQA, ET₄NBF₄ with acetonitrile separately were applied in simulated supercapacitor to test the electrochemical performance. The result showed that the operating voltage can be 3.0V with charge/ discharge efficiency of 94.89% and the energy density of 11.63 W·h·kg^-1. The product was better than ET₄NBF₄ which was usually used as organic electrolyte in the electrochemical performance with a higher operating voltage.

Key words: supercapacitor, synthesis, electrochemistry, electrolytes, quaternary ammonium salt

摘要：

以溴代8-氧杂-螺[4,5]季铵盐(ASB)、二水草酸(OD)、硼酸(BA)为原料,通过离子交换法制备电解质双草酸硼酸螺环季铵盐(BSQA),通过核磁共振(¹³C NMR)和液相色谱-质谱联用(LC-MS)分析对其进行表征,验证了其结构。采用正交实验对合成工艺进行优化,优化工艺条件为n_ASB:n_BA 2.8:1,反应时间4 h,反应温度90℃,溴代螺环季铵盐的转化率为90.2%。将BSQA、市售四氟硼酸四乙基铵(ET₄NBF₄)分别与乙腈配制成电解液并模拟组装成超级电容器并测试电化学性能。结果表明,BSQA电解液工作电压达3.0 V,充放电效率达94.89%,能量密度达11.63 W·h·kg^-1,产品电化学性能优于常用的有机电解质ET₄NBF₄,适用于更高的工作电压。

关键词: 超级电容器, 合成, 电化学, 电解质, 季铵盐

CLC Number:

TQ150.4

ZHANG Qing, YU Xinwei, CHEN Yao, ZHENG Wenzhi, YU Ziwen, ZHENG Cheng, CHEN Shengzhou, LIU Hui. Synthesis and properties of bisoxalatoborate spiro cyclic quaternary ammonium salt in supercapacitors[J]. CIESC Journal, 2016, 67(4): 1594-1600.

张庆, 于欣伟, 陈姚, 郑文芝, 余子文, 郑成, 陈胜洲, 刘慧. 超级电容器用双草酸硼酸螺环季铵盐的合成及性能[J]. 化工学报, 2016, 67(4): 1594-1600.

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