多元醇类凝胶因子的溶剂效应及其在锂硫电池中应用研究-应用化学专业论文.docxVIP

摘 要 本文合成了两种山梨醇单缩醛型低分子量凝胶因子 2,4-(3,4-二氯苯亚甲 基)-D-山梨醇(DCBS)和 2,4-(3,4-二甲基苯亚甲基)-D-山梨醇(DMBS)。 对于凝胶因子 DCBS 的混合溶剂效应的研究发现，DCBS 能溶解在乙醇溶剂 中，而当向体系中加入一定体积分数的甲基环己烷时，能形成稳定的凝胶。SEM 研究表明混合溶剂组成会改变聚集体的微观形貌，并与呈现的宏观凝胶能力变化 相一致。FT-IR 和 XRD 研究结果表明，分子间的氢键作用是分子自组装形成凝 胶的主要驱动力，且不同混合溶剂组成会影响聚集体的堆积方式。Flory-Huggins 溶解度参数进一步解释了单组分凝胶因子的二元混合溶剂效应。基于 DCBS 在其 它不同混合溶剂体系中的凝胶性能，利用 Flory-Huggins 溶解度参数建立了 DCBS 的凝胶化预测模型，实现了 DCBS 在未测试混合溶剂体系中的凝胶行为预测，拓 宽了 Flory-Huggins 参数的应用范围。 利用凝胶因子 DMBS 制备了 1.0mol/L LITFSI/DME:DOL(1:1，v/v)溶液的凝 胶电解质，并尝试将其应用于锂硫电池中。所制备的凝胶电解质较稳定，凝胶- 溶胶相转变温度大于电池的正常使用温度。电化学测试表明凝胶电解质与液态电 解质有相似的电化学行为。凝胶电解质一定程度上能减缓放电过程产生的中间产 多硫化物在液态电解质中的溶解及穿梭，减缓对锂极片的腐蚀，进而提高硫活性 材料的利用率和电池的充放电循环性能。 关键词：山梨醇单缩醛衍生物；低分子量凝胶因子；混合溶剂效应；溶剂参数； 凝胶电解质；锂硫电池 ABSTRACT In this work, sorbitol acetal derivatives 2,4-(3,4-dichlorobenzylidene)-D-sorbitol (DCBS) and 2,4-(3,4-dimethylbenzylidene)-D-sorbitol (DMBS) as low molecular weight gelators were synthesized. Mixed solvent effect on the gelation ability of one-component gelator (DCBS) was evaluated. DCBS was soluble in pure ethanol, but it formed stable gels in a certain volume ratio ethanol-methylcyclohexane mixtures. SEM studies showed that the solvent system changed the morphologies of the aggregates, which was in agreement with the different macroscopic gelation behaviors. According to the FT-IR and XRD, intermolecular hydrogen bonding was the main driving force for the gel formation, and the packing mode also depended on the composition of the solvents. The Flory-Huggins parameter was used to further illustrate the interactions between the gelator and solvents. According to the values of Flory-Huggins parameter and the gelation behaviors of DCBS in other solvent mixtures, a gelation model was established to predict the gelation behavior of DCBS in some untested solvents, which broadened the application of Flory-Huggins parameter. The DMBS was used as a low molecular weight gelator for the gelation of 1.0mol/L LITFSI/DME:DOL(1:1,v/v) solution. The gel electrolyte was stable as the g