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Chin. Phys. B, 2016, Vol. 25(6): 066102    DOI: 10.1088/1674-1056/25/6/066102

Thermodynamic and transport properties of spiro-(1,1')-bipyrrolidinium tetrafluoroborate and acetonitrile mixtures: A molecular dynamics study

Qing-Yin Zhang(张庆印)1,2,3, Peng Xie(谢鹏)1, Xin Wang(王欣)2, Xue-Wen Yu(于学文)3, Zhi-Qiang Shi(时志强)3, Shi-Huai Zhao(赵世怀)1
1 The State Key Laboratory of Separation Membranes and Membrane Processes, Department of Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China;
2 Laboratory of Chemical Engineering Thermodynamics, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China;
3 Laboratory of Fiber Modification and Functional Fiber, College of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China

Organic salts such as spiro-(1,1')-bipyrrolidinium tetrafluoroborate ([SBP][BF4]) dissolved in liquid acetonitrile (ACN) are a new kind of organic salt solution, which is expected to be used as an electrolyte in electrical double layer capacitors (EDLCs). To explore the physicochemical properties of the solution, an all-atom force field is established on the basis of AMBER parameter values and quantum mechanical calculations. Molecular dynamics (MD) simulations are carried out to explore the liquid structure and physicochemical properties of [SBP][BF4] electrolyte at room temperature. The computed thermodynamic and transport properties match the available experimental results very well. The microscopic structures of [SBP][BF4] salt solution are also discussed in detail. The method used in this work provides an efficient way of predicting the properties of organic salt solvent as an electrolyte in EDLCs.

Keywords:  electrolyte      self-diffusion      viscosity      molecular dynamics  
Received:  19 October 2015      Revised:  26 January 2016      Accepted manuscript online: 
PACS:  61.20.Qg (Structure of associated liquids: electrolytes, molten salts, etc.)  
  61.20.Ja (Computer simulation of liquid structure)  
  66.20.-d (Viscosity of liquids; diffusive momentum transport)  
  31.15.ap (Polarizabilities and other atomic and molecular properties)  

Project supported by the National Natural Science Foundation of China (Grant Nos. 21476172 and 51172160), the National High Technology Research and Development Program of China (Grant No. 2013AA050905), and the Natural Science Foundation of Tianjin, China (Grant Nos. 12JCZDJC28400, 14RCHZGX00859, 14JCTPJC00484, and 14JCQNJC07200).

Corresponding Authors:  Qing-Yin Zhang, Zhi-Qiang Shi     E-mail:;

Cite this article: 

Qing-Yin Zhang(张庆印), Peng Xie(谢鹏), Xin Wang(王欣), Xue-Wen Yu(于学文), Zhi-Qiang Shi(时志强), Shi-Huai Zhao(赵世怀) Thermodynamic and transport properties of spiro-(1,1')-bipyrrolidinium tetrafluoroborate and acetonitrile mixtures: A molecular dynamics study 2016 Chin. Phys. B 25 066102

[1] Kotz R and Carlen M 2000 Electrochim. Acta 45 2483
[2] Hall P J, Mirzaeian M, Fletcher S I, Sillars F B, Rennie A J R, Shitta-Bey G O, Wilson G, Cruden A and Carter R 2010 Energy Environ. Sci. 3 1238
[3] Gao Q, Demarconnay L, Raymundo-Pinero E and Beguin F 2012 Energy Environ. Sci. 5 9611
[4] Demarconnay L, Raymundo-Pinero E and Beguin F 2010 Electrochem. Commun. 12 1275
[5] Fic K, Lota G, Meller M and Frackowiak E 2012 Energy Environ. Sci. 5 5842
[6] Burke A 2007 Electrochim. Acta 53 1083
[7] Beguin F, Presser V, Balducci A and Frackowiak E 2014 Adv. Mater. 26 2219
[8] Plechkova N V and Seddon K R 2008 Chem. Soc. Rev. 37 123
[9] Schuetter C, Husch T, Korth M and Balducci A 2015 J. Phys. Chem. C 119 13413
[10] Chmiola J, Yushin G, Gogotsi Y, Portet C, Simon P and Taberna P L 2006 Science 313 1760
[11] Yang L, Fishbine B H, Migliori A and Pratt L R 2009 J. Am. Chem. Soc. 131 12373
[12] Feng G, Huang J, Sumpter B G, Meunier V and Qiao R 2010 Phys. Chem. Chem. Phys. 12 5468
[13] Vatamanu J, Borodin O and Smith G D 2011 J. Phys. Chem. B 115 3073
[14] Shim Y, Jung Y and Kim H J 2011 J. Phys. Chem. C 115 23574
[15] Higashiya S, Devarajan T S, Rane-Fondacaro M V, Dangler C, Snyder J and Haldar P 2009 Helv. Chim. Acta 92 1600
[16] Chiba K, Ueda T and Yamamoto H 2007 Electrochem. 75 664
[17] Perricone E, Chamas M, Lepretre J C, Judeinstein P, Azais P, Raymundo-Pinero E, Beguin F and Alloin F 2013 J. Power Sources 239 217
[18] Zheng C, Gao J, Yoshio M, Qi L and Wang H 2013 J. Power Sources 231 29
[19] Yu X, Ruan D, Wu C, Wang J and Shi Z 2014 J. Power Sources 265 309
[20] Shi Z, Yu X, Wang J, Hu H and Wu C 2015 Electrochim. Acta 174 215
[21] Perdew J P, Burke K and Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[22] Delley B 1996 J. Phys. Chem. 100 6107
[23] Delley B 2000 J. Chem. Phys. 113 7756
[24] Yu Y X 2013 J. Mater. Chem. A 1 13559
[25] Yu Y X 2014 ACS Appl. Mater. Interfaces 6 16267
[26] Mulliken R S 1955 J. Chem. Phys. 23 1833
[27] Yu Y X 2013 Phys. Chem. Chem. Phys. 15 16819
[28] Weiner S J, Kollman P A, Case D A, Singh U C, Ghio C, Alagona G, Profeta S and Weiner P 1984 J. Am. Chem. Soc. 106 765
[29] Yu Y X and Fujinoto S 2013 Sci. China: Chem. 56 1735
[30] Soolo E, Brandell D, Liivat A, Kasemagi H, Tamm T and Aabloo A 2012 J. Mol. Model. 18 1541
[31] De Andrade J, Boes E S and Stassen H 2002 J. Phys. Chem. B 106 13344
[32] Wu X, Liu Z, Huang S and Wang W 2005 Phys. Chem. Chem. Phys. 7 2771
[33] Plimpton S 1995 J. Comput. Phys. 117 1
[34] Nose S 1984 J. Chem. Phys. 81 511
[35] Hoover W G 1985 Phys. Rev. A 31 1695
[36] Humphrey W, Dalke A and Schulten K 1996 J. Molec. Graphics 14 33
[37] Zeng J, Zhang Y, Sun R and Chen S 2014 Electrochim. Acta 134 193
[38] Fan Y S, Chen X, Zhou W, Shi S P and Li Y 2011 Acta Phys. Sin. 60 032802 (in Chinese)
[39] Farhadian N and Malek K 2014 Solid State Ionics 268 162
[40] Ju Y Y, Zhang Q M, Gong Z Z and Ji G F 2013 Chin. Phys. B 22 083101
[41] Morrow T I and Maginn E J 2003 J. Phys. Chem. B 106 12807
[42] Allen M P and Tildesley D J 1987 Computer Simulation of Liquids (Oxford: Clarendon Press) pp. 64-64
[43] Noda A, Hayamizu K and Watanabe M 2001 J. Phys. Chem. B 105 4603
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