Holomb Roman, Xu Wu, Markusson Henrik, Johansson Patrik, Jacobsson Per
Department of Applied Physics, Chalmers University of Technology, Göteborg, SE-412 96, Sweden.
J Phys Chem A. 2006 Oct 12;110(40):11467-72. doi: 10.1021/jp0626824.
The effect of lithium ion coordination with the bis(oxalato)borate (BOB-) [B(C2O4)2]- anion in DMSO, PEG, PPG, and d-PPG has been studied in detail by IR and Raman spectroscopy. Ab initio calculations were performed to allow a consistent analysis of the experimental data. The main features observed in the IR and Raman spectra correspond to the presence of "free", un-coordinated, BOB- anions. Only with use of d-PPG as solvent a small amount of Li+...BOB- ion pairs were detected. The Raman spectra and the calculations together indicate that Li+ coordinates bidentately with two end-oxygen atoms of the BOB- anion. The identification of ion pairs can be used to reveal limitations of LiBOB based electrolytes. The results for LiBOB are compared with literature on other Li salts.
通过红外光谱和拉曼光谱详细研究了锂离子与双（草酸根）硼酸根（BOB-）[B(C₂O₄)₂]-阴离子在二甲基亚砜（DMSO）、聚乙二醇（PEG）、聚丙二醇（PPG）和d-聚丙二醇（d-PPG）中的配位作用。进行了从头算计算以便对实验数据进行连贯分析。在红外光谱和拉曼光谱中观察到的主要特征对应于“游离”、未配位的BOB-阴离子的存在。仅使用d-PPG作为溶剂时，检测到少量的Li⁺...BOB-离子对。拉曼光谱和计算结果共同表明，Li⁺与BOB-阴离子的两个端氧原子双齿配位。离子对的鉴定可用于揭示基于LiBOB的电解质的局限性。将LiBOB的结果与其他锂盐的文献进行了比较。
