Construction of nitrogen-doped carbon cladding LiMn<sub>2</sub>O<sub>4</sub> film electrode with enhanced stability for electrochemically selective extraction of lithium ions

doi:10.1007/s11705-023-2343-7

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (12) : 2050-2060 https://doi.org/10.1007/s11705-023-2343-7

RESEARCH ARTICLE

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

Jiahui Ren¹, Yongping He², Haidong Sun², Rongzi Zhang², Juan Li², Wenbiao Ma¹, Zhong Liu³, Jun Li³, Xiao Du¹(

), Xiaogang Hao¹(

)

¹. College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
². Academia Sinica, Qinghai Salt Lake Industry Group Company Limited, Golmud 816000, China
³. Qinghai Institute of Salt Lakes Chinese Academy of Sciences, Xining 810008, China

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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.

Keywords LiMn₂O₄ lithium extraction surface coating cyclic stability Mn dissolution

Corresponding Author(s): Xiao Du,Xiaogang Hao

Just Accepted Date: 19 July 2023 Online First Date: 07 October 2023 Issue Date: 30 November 2023

Cite this article:

Jiahui Ren,Yongping He,Haidong Sun, et al. Construction of nitrogen-doped carbon cladding LiMn₂O₄ film electrode with enhanced stability for electrochemically selective extraction of lithium ions[J]. Front. Chem. Sci. Eng., 2023, 17(12): 2050-2060.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2343-7
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I12/2050

Fig.1 Schematic illustration of the synthesis of C-N@LMO.

Fig.2 SEM images of (a) LMO, (b) PPy@LMO, and (c, d) C-N@LMO; (e) TEM image of C-N@LMO and (f) HRTEM image of the square area in (e).

Fig.3 Elemental mapping of C-N@LMO: (a) SEM image, (b) general elements, (c) Mn, (d) O, (e) C, and (f) N.

Fig.4 (a) XRD patterns of LMO and C-N@LMO; (b) FTIR spectra of LMO, PPy, PPy@LMO, and C-N@LMO.

Fig.5 CV curves of LMOE and C-N@LMOE in 0.1 mol?L^?1 LiCl solution at a scan rate of 0.5 mV?s^?1.

Fig.6 Electrical resistivity of LMOE and C-N@LMOE.

Fig.7 The intercalation rate and capacities of Li⁺ ions on the LMOE and C-N@LMOE.

Fig.8 The Mn dissolution ratio of LMOE and C-N@LMOE.

Fig.9 (a) The XPS full spectra of (1) the pristine LMOE, (2) pure LMOE after 10 cycles, and (3) C-N@LMOE after 10 cycles; (b) the high-resolution Mn 2p spectrum.

Fig.10 The mechanism of Li⁺ ions recovery by ESIX and the mitigation of Mn dissolution from LMO by the C-N layer.

Fig.11 (a, b) The intercalation and deintercalation capacities of LMOE and C-N@LMOE for Li⁺ ions in simulated brine and NaCl solution, respectively; (c) the change in normalized ion exchange capacity measured as a function of cycle number in the LiCl aqueous solution; (d) Li⁺ ions intercalation capacities of C-N@LMOE in LiCl solution with different electrode potentials.

Fig.12 (a) CV curves of the C-N@LMOE in 0.1 mol?L^?1 MCl electrolytes (M = Li⁺, Mg²⁺) at a scan rate of 0.5 mV?s^?1; (b) the competitive intercalation capacity of Li⁺ and Mg²⁺ ions on the C-N@LMOE.

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[1]	Chang WANG,Yanlong ZHAI,Xi WANG,Ming ZENG. Preparation and characterization of lithium λ-MnO₂ ion-sieves[J]. Front. Chem. Sci. Eng., 2014, 8(4): 471-477.

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