用于半固态锂电池的凝胶电解质设计与性能研究

凝胶聚合物电解质(GPE)同时具有固态电解质和液态电解质的优势， 备受研究学者的关注，因其具有制备工艺简单，良好的界面相容性以及高 安全性等诸多优点。使用液态电解质的商用锂电池，存在泄露、燃烧爆炸 等风险，具有严重的安全隐患。同时，目前的固态电解质由于较低的室温 离子电导率，对于实现商业化应用仍有一定距离。因此，半固态锂离子电 池能综合上述优势，满足人们日益增长的能量需求，而针对凝胶聚合物电 解质的研究是其中的关键。本论文旨在制备具有优异电化学性质的 GPE， 并评估其在高温以及高压情况下的性能表现。本论文主要以聚甲基丙烯酸 甲酯（PMMA）和聚戊烯酮（PEVK）分别作为 GPE 的聚合物基体材料， 制备了两种具有优异电化学性质的聚合物凝胶电解质，并分别探究其在高 温磷酸铁锂正极体系和高压镍钴锰 811 正极体系电池下的性能及相关机理。 在高温磷酸铁锂电池体系中，我们选取了甲基丙烯酸甲酯为单体，六 氟磷酸锂（LiPF6）为锂盐，PEGDA 为交联剂，AIBN 为引发剂，溶解在 液态电解质中，以原位聚合的方式制备了凝胶聚合物电解质。在 30 ℃下， 该凝胶电解质的离子电导率达到 7.7×10−3 S cm-1。并且该电解质表现出优 异的对锂稳定性，60 ℃时在 0.2 mA cm-2 电流下稳定循环 300 h 以上。在 0.5 C 倍率下，该电解质在 LiFePO4 //Graphite 软包电池循环 200 圈后，容 量保持率高达 90%，表现出优异的循环稳定性。 在高压 NCM811 电池体系中，我们以酮类单体 1-戊烯-3 酮作为聚合物 单 体 ， 1,4-丁 二 醇 二 丙 烯 酸 酯 作 为 交 联 剂 ， 锂 盐 使 用 双 氟 磺 酰 亚 胺 锂 （LiFSI），AIBN 作为引发剂，通过原位聚合法制备了新型凝胶聚合物电解 质。该酮类单体有效降低了电解质的 HOMO 能级，将电化学窗口提升到 5.21 V。在 30 ℃和 0.5 mA cm-2 电流密度的条件下，该电解质在 Li//Li 电 池 中 的 稳 定 循 环 时 间 能 够 达 到 650 h 以上。0.5 C 倍 率 下 ， NCM811//SiC450 软包电池也表现优秀的循环稳定性，循环 170 圈后，容 量保持率为 88%。

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