Demystifying Activity Origin of M–N–C Single‐Atomic Mediators Toward Expedited Rate‐Determining Step in Li–S Electrochemistry
Jia Jin,
Zhongti Sun,
Tianran Yan,
Zixiong Shi,
Meiyu Wang,
Ting Huang,
Yifan Ding,
Jingsheng Cai,
Peng Wang,
Liang Zhang,
Jingyu Sun
Affiliations
Jia Jin
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS) Light Industry Institute of Electrochemical Power Sources Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies Soochow University Suzhou 215006 P. R. China
Zhongti Sun
School of Materials Science and Engineering Jiangsu University Zhenjiang 212013 P. R. China
Tianran Yan
Institute of Functional Nano & Soft Materials (FUNSOM) Jiangsu Provincial Key Laboratory for Carbon-Based Functional Materials and Devices Soochow University Suzhou 215006 P. R. China
Zixiong Shi
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS) Light Industry Institute of Electrochemical Power Sources Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies Soochow University Suzhou 215006 P. R. China
Meiyu Wang
College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures National Laboratory of Solid-State Microstructures Jiangsu Key Laboratory of Artificial Functional Materials Nanjing University Nanjing 210093 P. R. China
Ting Huang
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS) Light Industry Institute of Electrochemical Power Sources Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies Soochow University Suzhou 215006 P. R. China
Yifan Ding
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS) Light Industry Institute of Electrochemical Power Sources Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies Soochow University Suzhou 215006 P. R. China
Jingsheng Cai
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS) Light Industry Institute of Electrochemical Power Sources Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies Soochow University Suzhou 215006 P. R. China
Peng Wang
College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures National Laboratory of Solid-State Microstructures Jiangsu Key Laboratory of Artificial Functional Materials Nanjing University Nanjing 210093 P. R. China
Liang Zhang
Institute of Functional Nano & Soft Materials (FUNSOM) Jiangsu Provincial Key Laboratory for Carbon-Based Functional Materials and Devices Soochow University Suzhou 215006 P. R. China
Jingyu Sun
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS) Light Industry Institute of Electrochemical Power Sources Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies Soochow University Suzhou 215006 P. R. China
Sluggish sulfur reduction reaction (SRR) kinetics remains a formidable challenge in Li–S electrochemistry. In this sense, the rational design of single‐atom species has become a burgeoning practice to expedite sulfur redox, where the underlying catalytic mechanism otherwise remains elusive. Herein, a class of metal single‐atom modified porous carbon nanofiber films (MSA PCNFs, M = Fe, Co, or Ni), fabricated via a generic synthetic strategy, as mediators to boost SRR kinetics is reported. Throughout electrokinetic measurement and operando instrumental probing, NiSA PCNF is evidenced to harness the catalytic superiority toward the rate‐determining step (i.e., liquid–solid conversion) of the SRR process. Density functional theory (DFT) simulations further reveal that the catalytic features of M–N–C moieties in catalyzing the Li2S precipitation rely heavily upon the coordination environments of adjacent carbon atoms and d‐orbital configurations of metal centers. In response, the thus‐derived S/NiSA PCNF cathode realizes an encouraging areal capacity of 14.12 mAh cm−2 under elevated sulfur loading (10.2 mg cm−2) and lean electrolyte usage (E/S ratio ≈ 5.5 μL mg−1). This work offers insight into the identification of exact catalytic moieties for different transition metal M–N–C single‐atom SRR mediators, showcasing a meaningful guidance and potential impact on Li–S catalysis.