TY - JOUR
T1 - Soft X-ray Emission Studies on Hydrate-Melt Electrolytes
AU - Shimada, Tatau
AU - Takenaka, Norio
AU - Watanabe, Eriko
AU - Yamada, Yuki
AU - Cui, Yi Tao
AU - Harada, Yoshihisa
AU - Okubo, Masashi
AU - Yamada, Atsuo
N1 - Funding Information:
This work was supported by JSPS KAKENHI Specially Promoted Research (no. 15H05701) and by the Elements Strategy Initiative for Catalysts and Batteries (ESICB) of the Ministry of Education Culture, Sports, Science and Technology (MEXT) (no. JPMXP0112101003). The X-ray emission spectroscopy was performed by the joint research in Synchrotron Radiation Research Organization and the Institute for Solid State Physics, the University of Tokyo (proposal no. 2017B7548). Calculations were executed using the SGI Rackable C2112-4GP3/C1102-GP8 (Reedbush-U/H/L) in the Information Technology Center, the University of Tokyo, and the facilities of the Supercomputer Center, the Institute for Solid State Physics, the University of Tokyo.
Funding Information:
This work was supported by JSPS KAKENHI Specially Promoted Research (no. 15H05701) and by the Elements Strategy Initiative for Catalysts and Batteries (ESICB) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) (no. JPMXP0112101003). The X-ray emission spectroscopy was performed by the joint research in Synchrotron Radiation Research Organization and the Institute for Solid State Physics, the University of Tokyo (proposal no. 2017B7548). Calculations were executed using the SGI Rackable C2112-4GP3/C1102-GP8 (Reedbush-U/H/L) in the Information Technology Center, the University of Tokyo, and the facilities of the Supercomputer Center, the Institute for Solid State Physics, the University of Tokyo.
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/10/21
Y1 - 2021/10/21
N2 - Highly salt-concentrated aqueous solutions are a new class of electrolytes, which provide a wide potential window exceeding 3 V and, hence, realize possibly inexpensive, safe, and high-energy-density storage devices. Herein, we investigate the evolution of the coordination structure and electronic state depending on the salt concentration through soft X-ray emission spectroscopy and first-principles molecular dynamics calculations. Close to the concentration limit, categorized as a "hydrate melt,"a long-range hydrogen-bond network of water molecules disappears with emerging localized electronic states that resemble those in the gas phase. Such localized electronic states are attributed not only to their geometrically isolated nature but also to their dominant electrostatic interaction with Li+ cations. Therefore, the electrical properties of water in the hydrate melt can be more gaslike than liquidlike.
AB - Highly salt-concentrated aqueous solutions are a new class of electrolytes, which provide a wide potential window exceeding 3 V and, hence, realize possibly inexpensive, safe, and high-energy-density storage devices. Herein, we investigate the evolution of the coordination structure and electronic state depending on the salt concentration through soft X-ray emission spectroscopy and first-principles molecular dynamics calculations. Close to the concentration limit, categorized as a "hydrate melt,"a long-range hydrogen-bond network of water molecules disappears with emerging localized electronic states that resemble those in the gas phase. Such localized electronic states are attributed not only to their geometrically isolated nature but also to their dominant electrostatic interaction with Li+ cations. Therefore, the electrical properties of water in the hydrate melt can be more gaslike than liquidlike.
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U2 - 10.1021/acs.jpcb.1c07246
DO - 10.1021/acs.jpcb.1c07246
M3 - Article
C2 - 34617749
AN - SCOPUS:85117509188
SN - 1089-5647
VL - 125
SP - 11534
EP - 11539
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 41
ER -