Li Song, Wang Xian-Shu, Han Bing, Lai Chen, Shi Pei-Ran, Ma Jia-Bin, Wang Shu-Wei, Zhang Li-Han, Liu Qi, Deng Yong-Hong, He Yan-Bing, Yang Quan-Hong
Shenzhen Geim Graphene Center, Tsinghua Shenzhen International Graduate School, Shenzhen, 518055, China.
Laboratory of Advanced Materials, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China.
Small. 2022 Feb;18(8):e2106427. doi: 10.1002/smll.202106427. Epub 2021 Dec 9.
Lithium (Li) metal batteries (LMBs) face huge challenges to achieve long cycling life at wide temperature range owing to the severe dendrite growth at subambient temperature and the intense side reactions with electrolyte at high temperature. Herein, an ultrathin LiBO layer with an extremely high Young's modulus of 8.0 GPa is constructed on Li anode via an in situ reaction between Li metal and 4,4,5,5-tetramethyl-1,3,2-dioxa-borolane (TDB) to form LiBO @Li anode, which presents two times higher exchange current density than pristine Li anode. The LiBO layer presents a strong absorption to Li ions and greatly improves the interfacial dynamics of Li-ion migration, which induces homogenous lithium nucleation and deposition to form a dense lithium layer. Consequently, the Li dendrite growth during cycling at subambient temperature and the side reactions with electrolyte at high temperature are simultaneously suppressed. The LiBO @Li/LiNi Co Mn O (NCM811) full batteries with limited Li capacity and high cathode mass loading of 9.9 mg cm can steadily cycle for 300 cycles with a capacity retention of 86.6%. The LiBO @Li/NCM811 full batteries and LiBO @Li/LiBO @Li symmetric batteries also present excellent cycling performance at both -20 and 60 °C. This work develops a strategy to achieve outstanding performance of LMBs at wide working temperature-range.
锂（Li）金属电池（LMBs）在宽温度范围内实现长循环寿命面临巨大挑战，这是由于在低于环境温度下严重的枝晶生长以及在高温下与电解质的剧烈副反应。在此，通过锂金属与4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷（TDB）之间的原位反应，在锂阳极上构建了具有8.0 GPa极高杨氏模量的超薄LiBO层，形成LiBO@Li阳极，其交换电流密度比原始锂阳极高出两倍。LiBO层对锂离子具有强烈的吸附作用，并极大地改善了锂离子迁移的界面动力学，从而诱导均匀的锂成核和沉积，形成致密的锂层。因此，在低于环境温度下循环过程中的锂枝晶生长以及在高温下与电解质的副反应同时得到抑制。具有有限锂容量和9.9 mg cm高阴极质量负载的LiBO@Li/LiNiCoMnO（NCM811）全电池能够稳定循环300次，容量保持率为86.6%。LiBO@Li/NCM811全电池和LiBO@Li/LiBO@Li对称电池在-20和60°C时也表现出优异的循环性能。这项工作开发了一种在宽工作温度范围内实现LMBs优异性能的策略。
