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Solvation Structure around Li+ Ions in Organic Carbonate Electrolytes: Spacer-Free Thin Cell IR Spectroscopy

Authors
Lim, ChaihoKim, Joo HyunChae, YeongseokLee, Kyung-KooKwak, KyungwonCho, Minhaeng
Issue Date
21-9월-2021
Publisher
AMER CHEMICAL SOC
Citation
ANALYTICAL CHEMISTRY, v.93, no.37, pp.12594 - 12601
Indexed
SCIE
SCOPUS
Journal Title
ANALYTICAL CHEMISTRY
Volume
93
Number
37
Start Page
12594
End Page
12601
URI
https://scholar.korea.ac.kr/handle/2021.sw.korea/136322
DOI
10.1021/acs.analchem.1c02127
ISSN
0003-2700
Abstract
Organic carbonate electrolytes are widely used materials for lithium-ion batteries. However, detailed solvation structures and solvent coordination numbers (CNs) of lithium cations in such solutions have not been accurately described nor determined yet. Because transmission-type IR spectroscopy is not of use for measuring the carbonyl stretch modes of electrolytes due to their absorption saturation problem, we here show that simple spacer-free thin cell IR spectroscopy can provide quantitative information on the number of solvating carbonate molecules around each lithium ion. We could estimate the solvent (carbonate) CNs of lithium ions in dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, and butylene carbonate over a wide range of lithium salt concentrations accurately, and they are compared with the previous results obtained with attenuated total reflection IR spectroscopy technique. We anticipate that our spacer-free thin cell approach will potentially be used to investigate the solvation dynamics, chemical exchange process, and vibrational energy transfers between solvating carbonate molecules in lithium salt electrolytes when combined with time-resolved IR spectroscopy.
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