电解质离子尺寸对超级电容器电化学性能的影响
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摘要
为了研究电解质离子尺寸对超级电容器电解液电化学性能的影响,自制了阳离子不同的2种电解质N,N-二甲基吡咯烷四氟硼酸盐(P_(11)-BF_4)和N-乙基-N-甲基吡咯烷四氟硼酸盐(P_(12)-BF_4),并分别配制成以碳酸丙烯酯(PC)为溶剂、浓度为1 mol/L的电解液;通过循环伏安、恒流充放电、交流阻抗谱研究了电解质离子尺寸对活性炭基超级电容器电化学性能的影响。结果表明:电解质离子尺寸和阳离子对称性共同影响着超级电容器的放电比电容,电解质离子尺寸越小,电解液的耐电压特性越好,超级电容器的工作电压越高;电解质离子尺寸的大小和阳离子的对称性共同影响着超级电容器的电化学性能。
In order to study the influence of the size of electrolyte ions on the electrochemical performance of supercapacitor electrolyte, two kinds of electrolytes, N, N-dimethylpyrrolidinium tetrafluoroborate(P_(11)-BF_4), N-ethyl-Nmethylpyrrolidinium tetrafluoroborate(P_(12)-BF_4), are synthesized. The electrolyte salts were arranged into propylene carbonate(PC) with the concentration of 1 mol/L. The influence of the size of electrolyte ion on the electrochemical performance of activated carbon based supercapacitors were investigated by cyclic voltammetry, constant current charge-discharge and AC impedance spectroscopy. The results show that both the electrolyte ion size and cation symmetry affect the discharge specific capacitance of the supercapacitors. The smaller the electrolyte ion size is, the better the voltage withstanding characteristic of the electrolyte is, and the higher the working voltage of the supercapacitor is. The size of the electrolyte ion and the symmetry of the cation affect the electrochemical performance of the supercapacitors.
In order to study the influence of the size of electrolyte ions on the electrochemical performance of supercapacitor electrolyte, two kinds of electrolytes, N, N-dimethylpyrrolidinium tetrafluoroborate(P_(11)-BF_4), N-ethyl-Nmethylpyrrolidinium tetrafluoroborate(P_(12)-BF_4), are synthesized. The electrolyte salts were arranged into propylene carbonate(PC) with the concentration of 1 mol/L. The influence of the size of electrolyte ion on the electrochemical performance of activated carbon based supercapacitors were investigated by cyclic voltammetry, constant current charge-discharge and AC impedance spectroscopy. The results show that both the electrolyte ion size and cation symmetry affect the discharge specific capacitance of the supercapacitors. The smaller the electrolyte ion size is, the better the voltage withstanding characteristic of the electrolyte is, and the higher the working voltage of the supercapacitor is. The size of the electrolyte ion and the symmetry of the cation affect the electrochemical performance of the supercapacitors.
引文
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[2]KOTZ R,CARLEN M.Principles and applications of electrochemical capacitors[J].Electrochimica Acta,2000,45(15/16):2483-2498.
[3]ROUSSE T,BELANGER D,CHIBA K,et al.Materials for electrochemical capacitors[C]//Springer Handbook of Electrochemical Energy.Berlin:Springer Berlin Heidelberg,2017.
[4]MILLER J R,BURKE A F.Electrochemical capacitors:Challenges and opportunities for real-world applications[J].Electrochemical Society Interface,2008,17(1):53-57.
[5]HALL P J,MIRZAEIAN M,FLETCHER S I,et al.Energy storage in electrochemical capacitors:Designing functional materials to improve performance[J].Energy&Environmental Science,2010,3(9):1238-1251.
[6]TIE S F,TAN C W.A review of energy sources and energy management system in electric vehicles[J].Renewable and Sustainable Energy Reviews,2013,20(4):82-102.
[7]BURKE A,LIU Z,ZHAO H.Present and future applications of supercapacitors in electric and hybrid vehicles[C]//Electric Vehicle Conference.[s.l.]:IEEE,2015:1-8.
[8]VOL′FKOVICH Y M,SERDYUK T M.Electrochemical capacitors[J].Russian Journal of Electrochemistry,2002,38(9):935-959.
[9]PORTET C,TABERNA P L,SIMON P,et al.Modification of Al current collector surface by sol-gel deposit for carbon-carbon supercapacitor applications[J].Electrochimica Acta,2004,49(6):905-912.
[10]PERRICONE E,CHAMAS M,LEPR ETRE J C,et al.Safe and performant electrolytes for supercapacitor:Investigation of esters/carbonate mixtures[J].Journal of Power Sources,2013,239(10):217-224.
[11]LEI C,AMINI N,MARKOULIDIS F,et al.Activated carbon from phenolic resin with controlled mesoporosity for an electric double-layer capacitor(EDLC)[J].Journal of Materials Chemistry A,2013(19):6037-6042.
[12]HAN T,PARK M S,KIM J,et al.The smallest quaternary ammonium salts with ether groups for high-performance electrochemical double layer capacitors[J].Chemical Science,2015,7(3):1791-1796.
[13]PARK S,K IM K.Tetramethylammonium tetrafluoroborate:The smallest quaternary ammonium tetrafluoroborate salt for use in electrochemical double layer capacitors[J].Journal of Power Sources,2017,338:129-135.
[14]WANG H,PILON L.Mesoscale modeling of electric double layer capacitors with three-dimensional ordered structures[J].Journal of Power Sources,2013,221(1):252-260.
[15]IOZZO D A B,TONG M,WU G,et al.Numerical analysis of electric double layer capacitors with mesoporous electrodes:Effects of electrode and electrolyte properties[J].Journal of Physical Chemistry C,2015,119(45):25235-25242.
[16]KOH A R,HWANG B,CHULR K,et al.The effect of the ionic size of small quaternary ammonium BF4 salts on electrochemical double layer capacitors[J].Physical Chemistry Chemical Physics Pccp,2014,16(29):15146-15151.
[17]MOUSAVI M P S,WILSON B E,KASHEFOLGHETA S,et al.Ionic liquids as electrolytes for electrochemical double-layer capacitors:Structures that optimize specific energy[J].ACSApplied Materials&Interfaces,2016,8(5):3396-3406.
[18]AZASI P.Manufacturing of industrial supercapacitors[C]//Supercapacitors:Materials,systems,and applications.[s.l.]:Wiley,2013.
[19]李凡群,赖延清,高宏权,等.超级电容器用离子液体电解质的研究进展[J].电池,2008,38(1):63-65.LI F Q,LAI Y Q,GAO H Q,et al.Progress in the research of ionic liquid electrolytes for supercapacitors[J].Battery,2008,38(1):63-65(in Chinese).
[20]LIU W,YAN X,LANG J,et al.Electrochemical behavior of graphene nanosheets in alkylimidazolium tetrafluoroborate ionic liquid electrolytes:Influences of organic solvents and the alkyl chains[J].Journal of Materials Chemistry,2011,21(35):13205-13212.
[21]KANG J,WEN J,JAYARAM S H,et al.Development of an equivalent circuit model for electrochemical double layer capacitors(Supercapacitor)with distinct electrolytes[J].Electrochimica Acta,2014,115(3):587-598.
[22]TONURIST K,THOMBERG T,JANES A,et al.Influence of separator properties on electrochemical performance of electrical double-layer capacitors[J].Journal of Electroanalytical Chemistry,2013,689(2):8-20.