In this study, we notice on Alkali metal complex. They are composites from alkali metal salt and ether molecules. These complexes are very fascinate materials because they are one of the functional material. They have ion transportation ability and low vapor pressure etc. Many researches were reported, for example, Li+/Glyme as solvation ionic liquid and Li+/PEG as solid or gel electrolyte for Li+ ion batteries. They form complex between oxygen atom and Li+. However, electronic states about the complex which should reflect strength of coordinate bonding in them did not get clear in detail. We have investigated about changes in electronic transitions of these composite from PEG and Li by forming complex. Using Attenuated total reflectance spectroscopic in Far Ultra-violet region (ATR-FUV), electronic transitions in 140-200nm (FUV) can be observed easily. Electronic states of PEG were already studied by ATR-FUV. PEGs have 3 transitions about n – Rydberg transitions, 153nm, 163nm and 175nm were assigned to n (OH) – 3p Ryd, n (COC) – 3p and n (COC) – 3s Ryd respectively3. In this study, PEG and Lithium Bis (trifluoromethane sulfonyl) imide (LiTFSI) were investigated in wide range of concentration and also used various samples, for example cations (Li+, Na+, K+) and anions (BF4, PF6, NO3-, and trifluoromethane sulfonyl family etc.). Furthermore, simulation spectra from quantum calculation spectra by time dependent-density function theory (TD-DFT, cam-b3lyp/6-311++g (2d, p)) were investigated. Experimental and calculation results were compared to discuss changes in electronic states and these result.
Far-ultraviolet (FUV) spectroscopy gives rich information about changes in the electronic states of molecules from interactions in condensed phase. We are investigated electronic states of molecules in the condensed ionic environment such as gel electrolytes, ionic liquids, and deep eutectic solvents. To measure the FUV spectra for liquid and solid nondestructively and feasibly, attenuate total reflectance (ATR) spectroscopy were developed to measure spectra of liquid, gel and solid samples in the 140-300 nm region. In this paper, we discuss about changes by interaction due to ionic environment in the electronic state of poly (ethylene glycol) (PEG) in gel electrolytes with Li salts, and deep eutectic solvents composed of acetamide and Li salts.
The wavelength region shorter than 200 nm, far-ultraviolet (FUV) region, is very rich in information about the electronic states and structure of a molecule. We have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140–280 nm region. This paper shows the studies by the attenuated total reflection far-ultraviolet (ATR-FUV) spectroscopy. Intermolecular interactions between alkyl chains such as CH---HC should be reflected in the phase behavior of organic compounds. We measured the attenuated total reflectance spectra in the far-UV region (145–300 nm) of n-tetradecane (Tm = 5.9 °C) from 15 to -38 °C to determine its temperature dependency. With decreasing temperature, the absorption band at 153 nm in the liquid phase becomes weaker and new bands appear at around 200 and 230 nm. These results suggest that an unusually compressed structure might be generated at the surface at low temperatures, and this phase change, which is reversible, is responsible for the unusual absorption observed in the ATR-FUV spectra. We have also investigated composite polymer electrolytes (CPE). ATR-FUV spectra of CPEs composed of Poly(ethylene oxide) (PEO) and Li salt were observed and its variation of anions for the CPEs are studied.
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