TY - JOUR
T1 - Structural Variation in Carbonate Electrolytes by the Addition of Li Salts Studied by X-Ray Total Scattering
AU - Kimura, Koji
AU - Hayashi, Kouichi
AU - Kiuchi, Hisao
AU - Morita, Masahito
AU - Haruyama, Jun
AU - Otani, Minoru
AU - Sakaebe, Hikari
AU - Fujisaki, Fumika
AU - Mori, Kazuhiro
AU - Yonemura, Masao
AU - Takabayashi, Yasuhiro
AU - Nakatani, Tomotaka
AU - Fujinami, So
AU - Fukunaga, Toshiharu
AU - Matsubara, Eiichiro
N1 - Funding Information:
The authors thank Mr. Kohei Harada, Mr. Akito Asano, and Mr. Haruki Yoshikawa for their great contributions. The authors are also grateful to Dr. Satoshi Uchida for helping us with the sample preparation. This article is based on results obtained from a project, “Research and Development Initiative for Scientific Innovation of New Generation Batteries (RISING2)”, JPNP16001, commissioned by the New Energy and Industrial Technology Development Organization (NEDO). X-ray total scattering experiment was conducted at BL28XU (proposal no. 2018B7611) and BL32B2 in the SPring-8. Neutron total scattering experiment was conducted at MLF of J-PARC with the approval of the Neutron Scattering Program Advisory Committee of IMSS, KEK (proposal no. 2014S10).
Publisher Copyright:
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/11
Y1 - 2020/11
N2 - X-ray total scattering measurements are carried out for the typical electrolyte used in lithium-ion batteries, that is, the mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) electrolyte with LiPF6 salt. The obtained pair distribution function is compared with that of the EC/EMC solvent without LiPF6, to investigate the effect of the Li+ cation on the intramolecular structure. It is found that the peak shift corresponding to the shrinking of the CO bonds is induced by dissolving LiPF6. Also, the peak height becomes lower by the addition of LiPF6. These behaviors are also observed by the X-ray total scattering measurements for the mixture of EC and dimethyl carbonate (DMC) with and without LiPF6. Also, it is ascertained that such a shrinking is present in EC/DMC electrolytes by means of neutron total scattering. First-principles calculations on the basis of the density functional theory for isolated EC, EMC, and DMC molecules with the Li+ cation confirm that the shrinking of the CO bond is accompanied by the formation of the solvation structure. The observed structural variations induced by adding LiPF6 will be a good indicator for the formation of the solvation structure.
AB - X-ray total scattering measurements are carried out for the typical electrolyte used in lithium-ion batteries, that is, the mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) electrolyte with LiPF6 salt. The obtained pair distribution function is compared with that of the EC/EMC solvent without LiPF6, to investigate the effect of the Li+ cation on the intramolecular structure. It is found that the peak shift corresponding to the shrinking of the CO bonds is induced by dissolving LiPF6. Also, the peak height becomes lower by the addition of LiPF6. These behaviors are also observed by the X-ray total scattering measurements for the mixture of EC and dimethyl carbonate (DMC) with and without LiPF6. Also, it is ascertained that such a shrinking is present in EC/DMC electrolytes by means of neutron total scattering. First-principles calculations on the basis of the density functional theory for isolated EC, EMC, and DMC molecules with the Li+ cation confirm that the shrinking of the CO bond is accompanied by the formation of the solvation structure. The observed structural variations induced by adding LiPF6 will be a good indicator for the formation of the solvation structure.
UR - http://www.scopus.com/inward/record.url?scp=85088694505&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85088694505&partnerID=8YFLogxK
U2 - 10.1002/pssb.202000100
DO - 10.1002/pssb.202000100
M3 - Article
AN - SCOPUS:85088694505
SN - 0370-1972
VL - 257
JO - Physica Status Solidi (B) Basic Research
JF - Physica Status Solidi (B) Basic Research
IS - 11
M1 - 2000100
ER -
