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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
Authors
Hwang, SunwookKim, Dong-HuiShin, Jeong HeeJang, Jae EunAhn, Kyoung HoLee, ChulhaengLee, Hochun
DGIST Authors
Jang, Jae EunLee, Hochun
Issue Date
2018-08
Citation
JOURNAL OF PHYSICAL CHEMISTRY C, 122(34), 19438-19446
Type
Article
Article 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.
URI
http://hdl.handle.net/20.500.11750/9350
DOI
10.1021/acs.jpcc.8b06035
Publisher
AMER CHEMICAL SOC
Related Researcher
  • Author Lee, Hochun Electrochemistry Laboratory for Sustainable Energy(ELSE)
  • Research Interests Lithium-ion batteries; Novel Materials for rechargeable batteries; Novel energy conversion;storage systems; Electrochemistry; 리튬이차전지; 이차전지용 신규 전극 및 전해액; 신규 에너지변환 및 저장 시스템; 전기화학
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Collection:
Department of Energy Science and EngineeringElectrochemistry Laboratory for Sustainable Energy(ELSE)1. Journal Articles
Department of Energy Science and EngineeringElectrochemistry Laboratory for Sustainable Energy(ELSE)1. Journal Articles


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