有机碱改性的聚丙烯酸系硅基负极粘结剂的合成与应用

硅基材料因其超高的理论比容量（3572 mAh g-1）、对锂电位相对较低， 成本低廉，储量庞大，被认为是最具潜力的下一代商用负极材料。然而， 硅基材料本身在循环过程中所产生的巨大的体积变化，制约了其商业化应 用。本文从电极粘结剂的角度出发，针对硅基材料的膨胀特性以及传统聚 丙烯酸粘结剂柔韧性差的特点重新设计了粘结剂的分子结构，制备了一系 列改性共聚高分子粘结剂，研究了分子结构对粘结剂以及其电极性能的影 响。主要研究内容如下： 本文通过将丙烯酸（AA）与柔性单体丙烯酸二甲氨基乙酯（DMAEA） 在有机弱碱（OB）1-乙基咪唑存在下共聚，制备了一种新型的聚丙烯酸系 粘结剂，并研究了各组分的不同摩尔配比对粘结剂力学性能以及相应硅氧 负 极 的 电 化 学 性 能 的 影 响 。 发 现 当 各 组 分 的 投 料 摩 尔 比 为 OB : AA : DMAEA=2 : 2 : 1时，粘结剂综合性能最佳。其剥离力为3.5 N，弹性模量为 8.2 GPa，柔韧性有较大提升。所制备的粘结剂在抑制电极膨胀方面有明显 效果，120次循环后电极厚度较循环前膨胀了55%，而PAA粘结剂对应电极 膨胀了89%。改性后的粘结剂可以改善电极的循环性能，在0.2 C下循环120 次后仍然可以保持1044 mAh g-1的可逆比容量，容量保持率67%，较改性前 有大幅提升。 为了进一步提升电池电化学性能，本文探究了不同结构OB对粘结剂性 能的影响。通过使用脂肪胺、脂环胺以及芳香胺类OB对前述1-乙基咪唑进 行替换，合成了一系列具有固定投料摩尔比的聚丙烯酸改性粘结剂。发现 在粘结剂的力学性能以及对应电极的电化学性能上，表现出了使用芳香胺 OB改性的粘结剂性能优于使用脂肪胺OB改性的粘结剂，后者的综合性能 又优于含脂环胺OB的粘结剂的规律。同时也优选出以4-二甲氨基吡啶改性 的粘结剂，其综合性能略优于上述使用1-乙基咪唑改性的实验样。

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