Construction of nitrogen-doped carbon cladding LiMn₂O₄ film electrode with enhanced stability for electrochemically selective extraction of lithium ions

Abstract

Reducing the dissolution of Mn from LiMn₂O₄ (LMO) and enhancing the stability of film electrodes are critical and challenging for Li⁺ ions selective extraction via electrochemically switched ion exchange technology. In this work, we prepared a nitrogen-doped carbon cladding LMO (C-N@LMO) by polymerization of polypyrrole and high-temperature annealing in the N₂ gas to achieve the above purpose. The modified C-N@LMO film electrode exhibited lower Mn dissolution and better cyclic stability than the LMO film electrode. The dissolution ratio of Mn from the C-N@LMO film electrode decreased by 42% compared to the LMO film electrode after 10 cycles. The cladding layer not only acted as a protective layer but also functioned as a conductive shell, accelerating the migration rate of Li⁺ ions. The intercalation equilibrium time of the C-N@LMO film electrode reached within an hour during the extraction of Li⁺ ions, which was 33% less compared to the pure LMO film electrode. Meanwhile, the C-N@LMO film electrode retained evident selectivity toward Li⁺ ions, and the separation factor was 118.38 for Li⁺ toward Mg²⁺ in simulated brine. Therefore, the C-N@LMO film electrode would be a promising candidate for the recovery of Li⁺ ions from salt lakes.

Key words： LiMn₂O₄; lithium extraction; surface coating; cyclic stability; Mn dissolution

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. U21A20303, 22078217 and U20A20141).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2343-7 and is accessible for authorized users.

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