高电压复合固态电解质的原位设计合成与界面调控

随着当前社会对于储能设备能量密度的要求越来越高，而石墨负极已经接近其理论能量密度，开发一种新型的负极材料十分必要。锂金属作为负极材料有着极大的优势，它的电势达-3.04V（vs.SHE），以及具备十倍石墨负极的能量密度。目前，对锂金属负极的研究正受到广泛关注，成为学术界热门的研究领域。但是对于锂金属负极的产业化还存在许多问题，例如枝晶生长导致的安全问题和循环过程中界面不稳定等问题。这些问题限制了锂金属电池的进一步发展。聚合物固态电解质由于具有良好的机械强度，是一种很好提升电池安全性的材料，然而较差的离子电导率限制了它的实际应用。无机固态电解质有着较高的离子电导率、较好的机械强度，但是它与电极之间的界面接触较差。复合固态电解质是一种既有较强的机械性能，又具备较高离子电导率的电解质，是下一代电解质的候选材料。因此，本论文开发出了一种耐高电压，对锂金属稳定的复合固态电解质。

主要内容如下所示：

（1）将粒径大约为420nm的磷酸钛铝锂（LATP）双面涂覆在Celgard2500隔膜上，然后使用乙二醇二甲醚（DME）和1,3,5-三氧六环（TXE）在一定浓度二氟草酸硼酸锂（LiDFOB）的引发下于LATP改性隔膜上原位聚合，制备出了一种复合固态电解质。这款电解质的电化学窗口达5.3V，浮充测试也证明该电解质对高镍钴锰酸锂（NCM811）更稳定，匹配锂金属时，在1mAhcm-2的负载下可以稳定循环200圈。锂对称电池在0.5mAcm-2，0.5mAhcm-2的测试条件下能够稳定循环500圈，其性能远优于未加入TXE的电解质和未引入LATP的电解液。

（2）为了进一步提升电解质的循环稳定性，将双氟磺酰亚胺锂（LiFSI）替换LiDFOB作为主盐，将三氟甲磺酸铝（Al(OTf)3）作为引发剂引发1,3-二氧六环（DOX）聚合，匹配LATP改性隔膜，形成一种新型的聚醚类复合固态电解质，克服了电解液机械强度不足和不耐高电压的问题。该电解质在锂对称电池中能够稳定循环800圈，在NCM811||Li电池中稳定循环250圈后，仍然具有72%的容量保持率。

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