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Vol. 17 (2025)

Heteroatoms Synergistic Anchoring Vacancies in Phosphorus-Doped CoSe2 Enable Ultrahigh Activity and Stability in Li–S Batteries

https://doi.org/10.1007/s40820-025-01806-0
Xiaoya Zhou
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China
Wei Mao
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China
Chengwei Ye
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China
Qi Liang
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China
Peng Wang
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China
Xuebin Wang
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China
Shaochun Tang
Key National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, People’s Republic of China

Corresponding Author: Shaochun Tang

tangsc@nju.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 308

Abstract

Electrocatalyst activity and stability demonstrate a “seesaw” relationship. Introducing vacancies (Vo) enhances the activity by improving reactant affinity and increasing accessible active sites. However, deficient or excessive Vo reduces polysulfide adsorption and lowers catalytic stability. Herein, a novel “heteroatoms synergistic anchoring vacancies” strategy is proposed to address the trade-off between high activity and stability. Phosphorus-doped CoSe2 with remained rich selenium vacancies (P-CS-Vo-0.5) was synthesized by producing abundant selenium Vo followed by controlled P atom doping. Atomic-scale microstructure analysis elucidated a dynamic process of surface vacancy generation and the subsequent partial occupation of these vacancies by P atoms. Density functional theory simulations and in situ Raman tests revealed that the Se vacancies provide highly active catalytic sites, accelerating polysulfide conversion, while P incorporation effectively reduces the surface energy of Se vacancies and suppresses their inward migration, enhancing structural robustness. The battery with the optimal P-CS-Vo-0.5 separator delivers an initial discharge capacity of 1306.7 mAh g−1 at 0.2C, and maintain 5.04 mAh cm−2 at a high sulfur loading (5.7 mg cm−2, 5.0 μL mg−1), achieving 95.1% capacity retention after 80 cycles. This strategy of modifying local atomic environments offers a new route to designing highly active and stable catalysts.


Highlights:
1 A volcano-type relationship between catalytic activity and vacancy concentration is revealed based on systematic investigation on selenium-vacancy-rich CoSe2.
2 A novel “heteroatoms synergistic anchoring vacancies” tactic is firstly proposed to achieve P-doped CoSe2 with remained rich selenium vacancies (P-CS-Vo-0.5).
3 It has been demonstrated that P doping lowers Se vacancy surface energy and effectively “pins” active sites, markedly suppressing dynamic migration of vacancies.

Keywords

Vacancy Heteroatomic anchoring Vacancy migration Activity/stability trade-off Electrocatalysts
Zhou, Xiaoya, Wei Mao, Chengwei Ye, Qi Liang, Peng Wang, Xuebin Wang, and Shaochun Tang. 2025. “Heteroatoms Synergistic Anchoring Vacancies in Phosphorus-Doped CoSe2 Enable Ultrahigh Activity and Stability in Li–S Batteries”. Nano-Micro Letters 17 (June):308. https://doi.org/10.1007/s40820-025-01806-0.
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