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Chin. Phys. B, 2020, Vol. 29(4): 048202    DOI: 10.1088/1674-1056/ab75cc
Special Issue: SPECIAL TOPIC — Advanced calculation & characterization of energy storage materials & devices at multiple scale
SPECIAL TOPIC—Advanced calculation & characterization of energy storage materials & devices at multiple scale Prev   Next  

Comparative calculation on Li+ solvation in common organic electrolyte solvents for lithium ion batteries

Qi Liu(刘琦), Feng Wu(吴锋), Daobin Mu(穆道斌), Borong Wu(吴伯荣)
Beijing Key Laboratory of Environment Science and Engineering, School of Material Science and Engineering, Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing Institute of Technology, Beijing 100081, China
Abstract  It is important for the electrolytes to maintain and enhance the lithium ion battery electrochemical performance, and solvation of Li+ is a key parameter for the property of the electrolytes. The comparative study on Li+ solvation structures, energy, enthalpy, Gibbs free energy, infrared and Raman spectra in common organic electrolyte solvents is completed by density functional theory (DFT) method. The solvation reaction energy results suggest that the Li+ solvation priority order is propylene carbonate (PC) > ethylene carbonate (EC) > ethyl methyl carbonate (EMC) > diethyl carbonate (DEC) > tetrahydrofuran (THF) > dimethyl carbonate (DMC) > 1,3-dioxolane (DOL) > dimethoxyethane (DME) to form 5sol-Li+. It is also indicated that the most innermost solvation shell compounds formations by stepwise spontaneous solvation reaction are four cyclic solvent molecules and three linear solvent molecules combining one Li+ forming 4sol-Li+ and 3sol-Li+, respectively, at room temperature. Besides, the vibration peaks for C=O and C-O bonds in carbonate ester solvents-Li+ compounds shift to lower frequency and higher frequency, respectively, when the Li+ concentration increases in the solvation compounds. All Li-O stretching vibration peaks shift to higher frequency until forming 2solvent-Li+ complexes, and C-H stretching also shifts to higher frequency except for nDME-Li+ solvation compounds. The Raman spectrum is more agile to characterize C-H vibrations and IR is agile to C=O, C-O, and Li-O vibrations for Li+ solvation compounds.
Keywords:  Li+ solvation      frequency shift      infrared spectra      Raman spectra  
Received:  06 October 2019      Revised:  08 February 2020      Published:  05 April 2020
PACS:  82.45.-h (Electrochemistry and electrophoresis)  
  78.30.-j (Infrared and Raman spectra)  
Fund: Project supported by International Science & Technology Cooperation of China (Grant No. 2019YFE0100200), the National Natural Science Foundation of China (Grant No. 51902024), the National Postdoctoral Program for Innovative Talents of China (Grant No. BX20180038), China Postdoctoral Science Foundation (Grant No. 2019M650014), NASF, China (Grant No. U1930113), and Beijing Natural Science Foundation, China (Grant No. L182022).
Corresponding Authors:  Feng Wu, Daobin Mu     E-mail:;

Cite this article: 

Qi Liu(刘琦), Feng Wu(吴锋), Daobin Mu(穆道斌), Borong Wu(吴伯荣) Comparative calculation on Li+ solvation in common organic electrolyte solvents for lithium ion batteries 2020 Chin. Phys. B 29 048202

[1] Zhang Y, Yu C, Yang M, Zhang L R, He Y C, Zhang J Y and Yan H 2017 Chin. Phys. Lett. 34 038101
[2] Wang J M, Chen K, Xie W G, Shi T T, Liu P Y, Zheng Y F and Zhu R 2019 Acta Phys. Sin. 68 158806 (in Chinese)
[3] Yang Z G, Zhang J L, Kintner-Meyer M C W, Lu X C, Choi D W, Lemmon J P and Liu J 2011 Chem. Rev. 111 3577
[4] Etacheri V, Marom R, Elazari R, Salitra G and Energ. D 2011 Energ. Environ Sci. 4 3243
[5] Armand M and Tarascon J M 2008 Nature 451 652
[6] Alias N and Mohamad A A 2015 J. Power Sources 274 237
[7] Freire M, Kosova N V, Jordy C, Chateigner D, Lebedev O I, Maignan A and Pralong V 2016 Nat. Mater. 15 173
[8] Goodenough J B 2018 Nat. Electron. 1 204
[9] Wu B, Bi J, Liu Q, Mu D, Wang L, Fu J and Wu F 2019 Electrochim. Acta 298 609
[10] Urbonaite S, Poux T and Novák P 2015 Adv. Energ. Mater. 5 1500118
[11] Wang Z, Dong Y, Li H, Zhao Z, Wu H B, Hao C and Lou X W D 2014 Nat. Commun. 5 5002
[12] Chung S H, Chang C H and Manthiram A 2016 Energ. Environ. Sci. 9 3188
[13] Yin Y X, Xin S, Guo Y G and Wan L J 2013 Angew. Chem. Int. Edit. 52 13186
[14] Lu Y, Gu S, Hong X, Rui K, Huang X, Jin J and Wen Z 2018 Energ. Storage Mater. 11 16
[15] Xu K 2004 Chem. Rev. 104 4303
[16] Xu K 2014 Chem. Rev. 114 11503
[17] Liu Q, Zhao Z, Wu F, Mu D, Wang L and Wu B 2019 Solid State Ionics 337 107
[18] An S J, Li J, Daniel C, Mohanty D, Nagpure S and Wood III D L 2016 Carbon 105 52
[19] Edström K, Gustafsson T and Thomas J O 2004 Electrochim. Acta 50 397
[20] Liu Q, Mu D, Wu B, Xu H, Wang L, Gai L and Wu F 2017 J. Electrochem. Soc. 164 A3144-A3153
[21] Patel M U, Demir-Cakan R, Morcrette M, Tarascon J M, Gaberscek M and Dominko R 2013 ChemSusChem. 6 1177
[22] Zhang S S 2012 Electrochim. Acta 70 344
[23] Liu Q, Mu D, Wu B, Wang L, Gai L and Wu F 2017 RSC Adv. 7 33373
[24] See K A, Leskes M, Griffin J M, Britto S, Matthews P D, Emly A and Seshadri R 2014 J. Am. Chem. Soc. 136 16368
[25] Matsuda Y, Fukushima T, Hashimoto H and Arakawa R 2002 J. Electrochem. Soc. 149 A1045-A1048
[26] Borodin O and Smith G D 2006 J. Phys. Chem. B 110 4971
[27] Yamada Y, Koyama Y, Abe T and Ogumi Z 2009 J. Phys. Chem. C 113 8948
[28] Bhatt M D, Cho M and Cho K 2010 Appl. Sur. Sci. 257 1463
[29] Yang L, Xiao A and Lucht B L 2010 J. Mol. Liq. 154 131
[30] Bogle X, Vazquez R, Greenbaum S, Cresce A V W and Xu K 2013 J. Phys. Chem. Lett. 4 1664
[31] Okoshi M, Yamada Y, Yamada A and Nakai H 2013 J. Electrochem. Soc. 160 A2160-A2165
[32] Bhatt M D and O'Dwyer C 2014 Curr. Appl. Phys. 14 349
[33] Suo L, Hu Y S, Li H, Armand M and Chen L 2013 Nat. Commun. 4 1481
[34] Wu B, Liu Q, Mu D, Ren Y, Li Y, Wang L and Wu F 2014 J. Phys. Chem. C 118 28369
[35] Doi T, Masuhara R, Hashinokuchi M, Shimizu Y and Inaba M 2016 Electrochim. Acta 209 219
[36] Wang J, Yamada Y, Sodeyama K, Chiang C H, Tateyama Y and Yamada A 2016 Nat. Commun. 7 12032
[37] Ong M T, Verners O, Draeger E W, Van Duin A C, Lordi V and Pask J E 2015 J. Phys. Chem. B 119 1535
[38] Seo D M, Reininger S, Kutcher M, Redmond K, Euler W B and Lucht B L 2015 J. Phys. Chem. C 119 14038
[39] Logan E R, Tonita E M, Gering K L, Li J, Ma X, Beaulieu L Y and Dahn J R 2018 J. Electrochem. Soc. 165 A21
[40] Liu Q, Cresce A, Schroeder M, Xu K, Mu D, Wu B and Wu F 2019 Energ. Storage Mater. 17 366
[41] Shi S, Gao J, Liu Y, Zhao Y, Wu Q, Ju W, Ouyang C and Xiao R 2016 Chin. Phys. B 25 018212
[42] Skarmoutsos I, Ponnuchamy V, Vetere V and Mossa S 2015 J. Phys. Chem. C 119 4502
[43] Bhatt M D, Cho M and Cho K 2012 J. Solid State Electr. 16 435
[44] Bhatt M D, Cho M and Cho K 2012 Model. Simul. Mater. Sci. 20 065004
[45] Li Z, Smith G D and Bedrov D 2012 J. Phys. Chem. B 116 12801
[46] Cui W, Lansac Y, Lee H, Hong S T and Jang Y H 2016 Phys. Chem. Chem. Phys. 18 23607
[47] Borodin O, Olguin M, Ganesh P, Kent P R, Allen J L and Henderson W A 2016 Phys. Chem. Chem. Phys. 18 164
[48] Chaban V 2015 Chem. Phys. Lett. 631-632 1
[49] Hou B, Gan Z, et al. 2019 Acta Phys. Sin. 68 128801 (in Chinese)
[50] Frisch M J, Trucks G W, Schlegel H B, et al. 2010 Gaussian 09 Gaussian, Inc., Wallingford, CT
[51] Liu Q, Xu H, Wu F, Mu D, Shi L, Wang L, Bi J and Wu B 2019 ACS Appl. Energy Mater. 2 8878
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