Experimental verification of increased electronic excitation energy of water in hydrate-melt water by attenuated total reflection-far-ultraviolet spectroscopy

The demand for Li secondary batteries is increasing, with the need for batteries with a higher level of performance and improved safety features. The use of a highly concentrated aqueous electrolyte solution is an effective way to increase the safety of batteries because it is possible to use “water...

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Veröffentlicht in:The Journal of chemical physics 2022-02, Vol.156 (7), p.074705-074705
Hauptverfasser: Ueno, Nami, Takegoshi, Masato, Zaitceva, Anna, Ozaki, Yukihiro, Morisawa, Yusuke
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container_end_page 074705
container_issue 7
container_start_page 074705
container_title The Journal of chemical physics
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creator Ueno, Nami
Takegoshi, Masato
Zaitceva, Anna
Ozaki, Yukihiro
Morisawa, Yusuke
description The demand for Li secondary batteries is increasing, with the need for batteries with a higher level of performance and improved safety features. The use of a highly concentrated aqueous electrolyte solution is an effective way to increase the safety of batteries because it is possible to use “water-in-salt” (WIS) and “hydrate-melt” (HM) electrolytes for practical applications. These electrolytes exhibit a potential window of >3.0 V, which is attributed to the difference between the HOMO and the LUMO energies of the n orbital of the pure water molecules and that of the water molecules in the hydration shells of a metal ion, according to theoretical predictions. Thus, in the present study, the attenuated total reflectance (ATR)-far-ultraviolet (FUV) spectra of water and super-concentrated aqueous solutions, such as WIS and HM using a Li salt, were experimentally investigated. The effects of anions, cations, and deuteriums on the ATR-FUV spectra were examined. The ATR-FUV method is an excellent means of studying highly concentrated aqueous salt solutions. The results suggest that the transition energy of water molecules in an ultrahighly concentrated aqueous electrolyte containing HM and WIS increased by nearly 0.4 eV (corresponding to an energy shift of over 10 nm) compared to an aqueous electrolyte with a typical water concentration. It was also revealed that the transition energy of water changes depending on the environment of the non-bonding electron, which is directly connected with or affected by hydrogen bonding with other water molecules or directly connected with Li+.
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subjects Aqueous electrolytes
Aqueous solutions
Electrolytes
Hydrogen bonding
Meltwater
Molecular orbitals
Safety
Saline solutions
Spectrum analysis
Storage batteries
Ultraviolet reflection
Ultraviolet spectra
Water chemistry
title Experimental verification of increased electronic excitation energy of water in hydrate-melt water by attenuated total reflection-far-ultraviolet spectroscopy
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