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.

Graphical abstract

Keywords

LiMn₂O₄ / lithium extraction / surface coating / cyclic stability / Mn dissolution

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