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Weiyi Zhang, Jun Gu, Xinyu Liu, Linlin Chen, Haiyan Ji, Yanhong Chao, Yuhong Zhang, Hongping Li, Peiwen Wu, Wenshuai Zhu. Fluorine-Induced Local Electronic Restructuring on LiMn2O4 Surface for Enhanced Selective Lithium Extraction. Green Energy&Environment. doi: 10.1016/j.gee.2026.05.022
Citation: Weiyi Zhang, Jun Gu, Xinyu Liu, Linlin Chen, Haiyan Ji, Yanhong Chao, Yuhong Zhang, Hongping Li, Peiwen Wu, Wenshuai Zhu. Fluorine-Induced Local Electronic Restructuring on LiMn2O4 Surface for Enhanced Selective Lithium Extraction. Green Energy&Environment. doi: 10.1016/j.gee.2026.05.022
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Fluorine-Induced Local Electronic Restructuring on LiMn2O4 Surface for Enhanced Selective Lithium Extraction

doi: 10.1016/j.gee.2026.05.022

  • a. School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013 (PR China);

  • b. School of Materials Science and Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013 (PR China);

  • c. College of Science, State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, (PR China);

  • d. School of Energy, Chemical Engineering and Environment, Sichuan Vocational and Technical College, Suining 629000, (PR China)

Funds:

The authors acknowledge the financial support from the National Natural Science Foundation of China (22278426), supported by Science Foundation of China University of Petroleum, Beijing (ZX20220042, ZX20220044), and supported by the China Postdoctoral Science Foundation (2024M762446). Note: The China Postdoctoral Science Foundation (2024M762446) was obtained through application with Wuxi Jiangnan Cable Co., Ltd. Furthermore, we would like to express our gratitude to Shaojie Ma for his work. He designed the calculation model for the interaction between ions in PAN (based on electrostatic potential).

  • Received date 24 February 2026, Accepted date 18 May 2026, RevRecd date 22 April 2026, Available online 26 May 2026
    Abstract
  • This work targets the long-standing limitations of spinel LiMn2O4 (LMO) in electrochemical lithium extraction from salt-lake brines, including manganese dissolution, surface structural instability, and sluggish Li+ transport kinetics. To address these challenges, a fluorine-induced cooperative surface-electronic engineering strategy is proposed, which enables a distinct reconstruction of the surface electronic structure, characterized by an increased Mn3+ fraction and the generation of oxygen vacancies. The reduced binding energy of the Mn 2p peak in XPS spectra, and the upward shift of the d-band center revealed by PDOS calculations, confirm enhanced surface redox activity and ion-transport capability. Consequently, the fluorine-modified LMO exhibits significantly improved lithium extraction performance in both simulated and real brine environments with 1MF-LMO delivering the optimal performance. In simulated brine, it achieves average Li+ extraction and release rates of 18.16 and 16.45 mg g-1 h-1, representing enhancements of 159% and 229% relative to LMO. Under complex practical conditions, including lithium-rich mother liquor and West Taijinar salt-lake brine, 1MF-LMO maintains high Li+ extraction capacities of 26.51 and 30.21 mg g-1 h-1, respectively, demonstrating excellent adaptability. Furthermore, a trace amount of polyacrylonitrile (PAN) can synergistically optimize interfacial functionality, which combines interfacial electrostatic effects and size-exclusion effects that mainly suppress the co-extraction of Na+ and Mg2+ and thus significantly enhance Li+ selectivity.

     

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