Wu Guangxuan, Liu Tongfeng, Lao Zhoujie, Cheng Yihao, Wang Tianshuai, Mao Jing, Zhang Haichang, Liu Enzuo, Shi Chunsheng, Zhou Guangmin, He Chunnian, Hu Wenbin, Zhao Naiqin, Wu Ningning, Chen Biao
School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, People's Republic of China.
Tsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, People's Republic of China.
Angew Chem Int Ed Engl. 2025 Mar 17;64(12):e202422208. doi: 10.1002/anie.202422208. Epub 2025 Jan 9.
P-block metal carbon-supported single-atom catalysts (C-SACs) have emerged as a promising candidate for high-performance room-temperature sodium-sulfur (RT Na-S) batteries, due to their high atom utilization and unique electronic structure. However, the ambiguous electronic-level understanding of Na-dominant s-p hybridization between sodium polysulfides (NaPSs) and p-block C-SACs limits the precise control of coordination environment tuning and electro-catalytic activity manipulation. Here, s-p orbital overlap degree (OOD) between the s orbitals of Na in NaPSs and the p orbitals of p-block C-SACs is proposed as a descriptor for sulfur reduction reaction (SRR) and sulfur oxidation reaction (SOR). Compared to NG and NG-supported InN (NG-InN) SACs, the nitrogen-doped graphene-supported InN (NG-InN) SACs show the largest s-p OOD, demonstrating the weakest shuttle effect and the lowest reaction energy barriers in both SRR and SOR. Accordingly, the designed catalysts allow the Na-S pouch batteries to retain a high capacity of 490.7 mAh g at 2 A g with a Coulombic efficiency of 96 % at a low electrolyte/sulfur (E/S) ratio of 4.5 μl mg. This work offers an s-p orbital overlap descriptor describing the interaction between NaPSs and p-orbital-dominated catalysts for high-performance RT Na-S batteries.
P 区金属碳负载单原子催化剂（C-SACs）因其高原子利用率和独特的电子结构，已成为高性能室温钠硫（RT Na-S）电池的一个有前景的候选材料。然而，对多硫化钠（NaPSs）与 P 区 C-SACs 之间以钠为主的 s-p 杂化的电子层面理解尚不明确，这限制了对配位环境调控和电催化活性操纵的精确控制。在此，提出多硫化钠中钠的 s 轨道与 P 区 C-SACs 的 p 轨道之间的 s-p 轨道重叠度（OOD）作为硫还原反应（SRR）和硫氧化反应（SOR）的描述符。与氮掺杂石墨烯负载的 InN（NG-InN）单原子催化剂和 NG 相比，NG-InN 单原子催化剂表现出最大的 s-p OOD，在 SRR 和 SOR 中均表现出最弱的穿梭效应和最低的反应能垒。因此，所设计的催化剂使钠硫软包电池在 2 A g 的电流密度下，在低电解液/硫（E/S）比为 4.5 μl mg 的情况下，能保持 490.7 mAh g 的高容量，库仑效率为 96%。这项工作提供了一种 s-p 轨道重叠描述符，用于描述多硫化钠与 p 轨道主导的催化剂之间的相互作用，以用于高性能室温钠硫电池。
