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Neutron reflectometry analysis of Li4Ti5O12/organic electrolyte interfaces: characterization of surface structure changes and lithium intercalation properties

Published online by Cambridge University Press:  19 September 2016

Masaaki Hirayama ,
Takumi Shibusawa ,
Ryo Yamaguchi ,
KyungSu Kim ,
Sou Taminato ,
Norifumi L. Yamada ,
Masao Yonemura ,
Kota Suzuki  and
Ryoji Kanno
Masaaki Hirayama*
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
Takumi Shibusawa
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
Ryo Yamaguchi
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
KyungSu Kim
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
Sou Taminato
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
Norifumi L. Yamada
Affiliation:
Neutron Science Division, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tokai, Ibaraki 319-1106, Japan
Masao Yonemura
Affiliation:
Neutron Science Division, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tokai, Ibaraki 319-1106, Japan
Kota Suzuki
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
Ryoji Kanno
Affiliation:
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori-ku, Yokohama 226-8502, Japan
*
a) Address all correspondence to this author. e-mail: hirayama@echem.titech.ac.jp
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Abstract

The structure changes and lithium intercalation properties in the surface region of Li4Ti5O12 were investigated using epitaxial Li4Ti5O12(111) film model electrodes. The discharge–charge measurements, which were conducted with 1 mol/dm3 LiPF6-containing propylene carbonate, revealed that a 23.8 nm-thick film exhibited a small capacity of 115 mA h/g compared to the theoretical value of 175 mA h/g. In situ neutron reflectometry and ex situ x-ray diffractometry and reflectometry indicated that an irreversible phase change had occurred in the 10-nm surface region of Li4Ti5O12 during the initial reaction processes. The level of deterioration of the surface structure was significantly reduced by decreasing the LiPF6 concentration; in addition, side reactions of the cell components with the electrolyte species, and their products, may be associated with the deterioration of the Li4Ti5O12 surface. The surface reactions have a significant impact on the capacity of lithium intercalation in nano-sized Li4Ti5O12.

Keywords

energy storageepitaxyneutron scattering
Type
Invited Paper
Information
Journal of Materials Research , Volume 31 , Issue 20 , 28 October 2016 , pp. 3142 - 3150
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Copyright
Copyright © Materials Research Society 2016 

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