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Ionic Conduction and Solution Structure in LiPF6 and LiBF4 Propylene Carbonate Electrolytes

Title
Ionic Conduction and Solution Structure in LiPF6 and LiBF4 Propylene Carbonate Electrolytes
Author(s)
Hwang, SunwookKim, Dong-HuiShin, Jeong HeeJang, Jae EunAhn, Kyoung HoLee, ChulhaengLee, Hochun
Issued Date
2018-08
Citation
Journal of Physical Chemistry C, v.122, no.34, pp.19438 - 19446
Type
Article
Keywords
MICROWAVE DIELECTRIC-RELAXATIONLITHIUM-IONETHYLENE CARBONATELIQUID ELECTROLYTESDIMETHYL CARBONATEELECTRICAL CONDUCTANCEULTRASONIC RELAXATIONORGANIC ELECTROLYTESGAMMA-BUTYROLACTONESELF-DIFFUSION
ISSN
1932-7447
Abstract
Expanding the performance limit of current Li-ion batteries requires ion-ion and ion-solvent interaction, which governs the ion transport behavior of the electrolytes, to be fully understood as a matter of crucial importance. We herein examine the ionic speciation and conduction behavior of propylene carbonate (PC) electrolytes of 0.1-3.0 M LiPF6 and LiBF4 using Raman spectroscopy, dielectric relaxation spectroscopy (DRS), and pulsed-field gradient NMR (PFG-NMR) spectroscopy. In both LiPF6-PC and LiBF4-PC, free ions and a solvent-shared ion pair (SIP) are dominant species at dilute salt concentrations (<0.8 M), and SIP becomes dominant at intermediate concentrations (0.8-1.5 M). At higher concentrations (1.5-3.0 M), the solvent-shared dimer (SSD) and contact dimer (CD) are dominant in LiPF6-PC, whereas the contact ion pair (CIP), CD, and agglomerate (AGG) prevail in LiBF4-PC. Ionic conduction in 0.1-1.5 M LiPF6-PC and LiBF4-PC is governed by the migration of free ions and SIP. Notably, above 1.5 M of the two PC electrolytes, SSD participates in ionic conduction via the migration mode as well. Furthermore, it is suggested that the large number of CIPs present in LiBF4-PC may contribute to ionic conduction via a Grotthuss-type mechanism. © 2018 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/9350
DOI
10.1021/acs.jpcc.8b06035
Publisher
American Chemical Society
Related Researcher
  • 장재은 Jang, Jae Eun
  • Research Interests Nanoelectroinc device; 생체 신호 센싱 시스템 및 생체 모방 디바이스; 나노 통신 디바이스
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Appears in Collections:
Department of Electrical Engineering and Computer Science Advanced Electronic Devices Research Group(AEDRG) - Jang Lab. 1. Journal Articles
Department of Energy Science and Engineering Electrochemistry Laboratory for Sustainable Energy(ELSE) 1. Journal Articles

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