齐鲁工业大学顾少楠团队报道了用于超高容量高性能的锂电池稀土单原子催化。相关研究成果于2024年5月18日发表于国际一流学术期刊《德国应用化学》。

锂硫（LiS）电池具有许多优点，但仍面临多硫化物氧化还原动力学和锂枝晶生长迟缓等问题。大多数报道的用于锂离子电池的单原子催化剂（SACs）基于d带过渡金属，其d轨道构成活性价带，这倾向于发生催化剂钝化。基于稀土金属4f内价轨道的SACs由于其极难被激活而具有挑战性。

该文中，研究人员设计并合成了第一个具有富电子4f内轨道的稀土金属Sm-SACs，以促进多硫化物的催化转化和Li的均匀沉积。Sm-SACs通过f-d-p轨道杂化增强了活化4f轨道的催化作用。使用Sm-N3C3改性的隔膜，半电池在2000次循环后提供超过600mAh g^-1的高容量和84.3%的保留率。制备的S/CNT|Sm-N3C3@PP|Sm-N3C3-Li全锂电池在0.2℃下100次循环后，可提供80.6%的保持率的超稳定循环性能，是最好的全锂电池之一。

该项工作为稀土金属单原子催化在锂离子电池，和其他下一代储能电化学系统的电化学反应中的发展提供了新的视角。

附：英文原文

Title: Rare Earth Single-Atom Catalysis for High-Performance Li−S Full Battery with Ultrahigh Capacity

Author: Rong Zhou, Yongqiang Ren, Weixin Li, Meng Guo, Yinan Wang, Haixin Chang, Xin Zhao, Wei Hu, Guowei Zhou, Shaonan Gu

Issue&Volume: 2024-05-18

Abstract: Lithium-sulfur (LiS) batteries have many advantages but still face problems such as retarded polysulfides redox kinetics and Li dendrite growth. Most reported single atom catalysts (SACs) for LiS batteries are based on d-band transition metals whose d orbital constitutes active valence band, which is inclined to occur catalyst passivation. SACs based on 4f inner valence orbital of rare earth metals are challenging for their great difficulty to be activated. In this work, we design and synthesize the first rare earth metal Sm SACs which has electron-rich 4f inner orbital to promote catalytic conversion of polysulfides and uniform deposition of Li. Sm SACs enhance the catalysis by the activated 4f orbital through an f-d-p orbital hybridization. Using Sm-N3C3 modified separators, the half cells deliver a high capacity over 600 mAh g1 and a retention rate of 84.3% after 2000 cycles. The fabricated S/CNTs|Sm-N3C3@PP|Sm-N3C3-Li full batteries can provide an ultra-stable cycling performance of a retention rate of 80.6% at 0.2 C after 100 cycles, one of the best full LiS batteries. This work provides a new perspective for the development of rare earth metal single atom catalysis in electrochemical reactions of LiS batteries and other electrochemical systems for next-generation energy storage.

DOI: 10.1002/anie.202405417

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202405417