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Based on the unique ubiquity of similar solvate structures found in solvate crystals and superconcentrated electrolytes, we performed a systematic study of four reported solvate crystals which consist of different lithium salts (i.e., LiMPSA, LiTFSI, LiDFOB, and LiBOB) solvated by acetonitrile (MeCN) based on first principles calculations. Based on the calculations, these solvate crystals are predicted to be electronic insulators and are expected to be similar to their insulating liquid counterpart (e.g., 4 M superconcentrated LiTFSI-MeCN electrolyte), which has been confirmed to be a promising electrolyte in lithium batteries. Although the MeCN molecule is highly unstable during the reduction process, it is found that the salt-MeCN solvate molecules (e.g., LiTFSI-(MeCN)2, LiDFOB-(MeCN)2) and their charged counterparts (anions and cations) are both thermodynamically and electrochemically stable, which can be confirmed by Raman vibrational modes through the unique characteristic variation in C≡N bond stretching of MeCN molecules. Therefore, in addition to the development of new solvents or lithium salts, we suggest it is possible to utilize the formation of superconcentrated electrolytes with improved electrochemical stability based on existing known compounds to facilitate the development of novel electrolyte design in advanced lithium batteries.
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Practical and Instructive Approach to Purify Acetonitrile for a Wide Electrochemical Window
Because of its large electrochemical window, acetonitrile (MeCN) is one of the most widely used solvents in electrochemistry. It is a suitable solvent for nonaqueous electrolytes that allows studies of cathodic and anodic processes, but electrolyte purification remains challenging. As received, the high-performance liquid chromatography (HPLC) grade is unsuitable for most electroanalytical applications. We present an approach to optimize the purification of HPLC-grade acetonitrile to yield a tetrabutylammonium perchlorate (TBAP)/MeCN electrolyte for experiments in nonaqueous media. We used cyclic voltammetry (CV) to show the background due to impurities and to guide the experimental design to a background current acceptable for CVs of a 1 mM typical concentration of a redox-active molecule. We use 3A molecular sieves, followed by distillation over CaH2 with a final treatment with Al2O3. The optimized procedure yields CH3CN with small background currents, increasing the signal-to-noise ratio and minimizing chemical complications over a wide potential window. Our approach includes discriminating between impurities in the solvent and electrolyte salts; for TBAP, we recrystallize from ethyl acetate and 95 % ethanol. The process and theoretical guidelines apply to other nonaqueous electrolytes dealing with electroactive impurities, including organic molecules, oxygen, and water.
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- Award ID(s):
- 2108462
- PAR ID:
- 10494560
- Publisher / Repository:
- Mexican Chemical Society
- Date Published:
- Journal Name:
- Journal of the Mexican Chemical Society
- ISSN:
- 1870-249X
- Page Range / eLocation ID:
- 393 to 402
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.29356/jmcs.v67i4.2013
