物理化学学报 >> 2007, Vol. 23 >> Issue (04): 526-530.doi: 10.3866/PKU.WHXB20070415

研究论文 上一篇    下一篇

胺对锂电池电解液中小分子的稳定作用

张忠; 许旋; 左晓希; 李伟善   

  1. 华南师范大学化学与环境学院, 广州 510631
  • 收稿日期:2006-09-21 修回日期:2006-11-29 发布日期:2007-04-05
  • 通讯作者: 许旋;李伟善 E-mail:xuxuan@scnu.edu.cn; liwsh@scnu.edu.cn

Stabilizing Effect of Amine on SmallMolecules in Electrolyte of LithiumBatteries

ZHANG Zhong; XU Xuan; ZUO Xiao-Xi; LI Wei-Shan   

  1. School of Chemistry and Environment, South China Normal University, Guangzhou 510631, P. R. China
  • Received:2006-09-21 Revised:2006-11-29 Published:2007-04-05
  • Contact: XU Xuan; LI Wei-Shan E-mail:xuxuan@scnu.edu.cn; liwsh@scnu.edu.cn

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摘要： 用密度泛函理论(DFT)方法在PBE0/6-31+G(d, p)水平上对乙胺、乙二胺分别与电解液中的小分子H2O、HF分子间的相互作用进行理论计算, 并在PBE/TZP 水平上利用能量分解分析(EDA)方法对胺与HF、H2O 结合的II-1、II-2、III-1和III-2模型进行计算分析. 结果表明, 胺类物质都能与HF、H2O形成N…H—F(O)、F(O)…H—N或F(O)…H—C的稳定氢键. 但HF与胺类物质形成的氢键比H2O与胺形成的氢键强, 故胺类物质在电解液中优先稳定HF. 乙二胺与HF、H2O结合的稳定性比乙胺强. 乙胺、乙二胺与HF(H2O)形成的最稳定构型均由F(O)—H…N 和F(O)…H—C 氢键结合形成.

关键词: 胺, 分子间相互作用, PBE0, NBO, EDA

Abstract: Intermolecular interactions between ethylamine or ethylenediamine and H2O or HF were studied theoretically using density functional theory (DFT) at the PBE0/6-31+G(d, p) level. Natural bond orbital (NBO) analyses were employed to elucidate the hydrogen bond characteristics in these complexes. Energy decomposition analysis (EDA) method was applied to complexes of II-1, II-2, III-1, and III-2 at the PBE/TZP level. From this study, four important conclusions were drawn as follows: (1) Both HF and H2O can be stabilized by amines through N…H—F(O), F(O)…H—N or F(O)…H—C hydrogen bonds; (2) Amines have the priority to stabilize HF, because the high electronegativies of florine atom results in the intense N—H…F hydrogen bonds; (3) Stability of the ethylenediamine-associated complexes is higher than that of ethylamine-associated complexes; (4) The most stable complexes, formed by amines with HF or H2O, include F(O)—H…N and F(O)…H—C hydrogen bonds.

Key words: Amine, Intermolecular interaction, PBE0, NBO, EDA