Mengyang Li, Guiqiang Cao, Yiming Qi, Chenyang Hou, X Y Song, Ruixian Duan, Huijuan Yang, Yuan Li, Xiaorui Chen, Zongnan Lv, Qinchuan Chen, Yitong Yuan, Guohua Liu, Yi Xu, Jingjing Wang, Wenbin Li, Xifei Li
ABSTRACT Understanding the correlation between spin state and electrocatalytic activity of single‐atom catalysts (SACs) may help us to address the sulfur redox kinetics problems in lithium–sulfur batteries (LSBs). Herein, systematic experiments were carried out to study the catalytic activities of Ni SACs with different spin states via modulating the pyrrolic N/pyridinic N ratio. Ni SACs with high‐spin state show strong catalytic activity toward lithium polysulfides (LPSs), whereas the Ni SACs with low‐spin state have strong adsorption capacity for LPSs. Therefore, the preparation of Ni SACs with an intermediate spin state by controlling pyridinic N and pyrrolic N enables an excellent balance between the adsorption and catalytic. Importantly, the introduction of S atoms can enhance the content of pyrrolic N while ensuring a high total content of pyridinic N and pyrrolic N. Consequently, the sulfur cathode based on Ni‐N pd‐pr ‐SC shows a remarkable battery performance with a high initial capacity of 606 mAh g − 1 at 4.0 C and a capacity retention of 81.3% after 300 cycles. It is believed that this work provides a profound understanding of optimizing the spin state of Ni SACs for LSBs.