Enhanced Li+ extraction in ESIP process by LiMn2O4 membrane electrode: The role of Nafion-incorporation

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology Pub Date : 2025-05-30 DOI:10.1016/j.seppur.2025.133821

Zeyu Du , Xiaowei An , Bo Qiao , Peifen Wang , Xuli Ma , Xiao Du , Xiaogang Hao , Guoqing Guan , Abuliti Abudula , Rong Zhang

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Abstract

The poor electrochemical stability of LiMn₂O₄ (LMO) has long limited its application in lithium extraction. In this study, enhanced stability of LMO membrane electrodes is achieved through a simple Nafion-incorporation strategy within a polyvinylidene fluoride (PVDF) binder. The optimized LMO supported on a stainless steel wire mesh (LMO_Nafion/SSWM) membrane electrode was employed in an electrochemically switched ion permselective (ESIP) system for continuous lithium-ion (Li⁺) extraction. Experimental results show that Nafion-incorporation increased the Li⁺ permeability flux of the LMO/SSWM membrane electrode by 64.34 %. More importantly, compared to the unmodified LMO/SSWM membrane electrode, the LMO_Nafiion/SSWM membrane electrode exhibited a significant reduction in Mn leaching rate, dropping from 5.58 % to 1.83 % after 10 adsorption–desorption cycles. Physicochemical characterizations combined with DFT calculations revealed that the hybridization of the p-orbital electrons of the O of the sulfonic acid group in Nafion and the d-orbital electrons of Mn enabled Nafion effectively anchored Mn. This interaction suppressed Mn dissolution and significantly improved the electrochemical performance of the LMO membrane electrode.

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LiMn2O4膜电极强化ESIP工艺中Li+的萃取：钠掺杂的作用

LiMn2O4 （LMO）电化学稳定性差，长期限制了其在锂萃取中的应用。在这项研究中，通过在聚偏氟乙烯（PVDF）粘合剂中加入一种简单的nafion策略，提高了LMO膜电极的稳定性。将优化后的LMO （LMO_Nafion/SSWM）膜电极负载在不锈钢丝网（LMO_Nafion/SSWM）膜电极上，用于电化学开关离子permselective （ESIP）系统中连续提取锂离子（Li+）。实验结果表明，掺入nafion可使LMO/SSWM膜电极的Li+渗透通量提高64.34%。更重要的是，与未修饰的LMO/SSWM膜电极相比，LMO_Nafiion/SSWM膜电极的Mn浸出率显著降低，在10次吸附-解吸循环后，Mn浸出率从5.58%降至1.83%。物理化学表征结合DFT计算表明，Nafion中磺酸基团O的p轨道电子和Mn的d轨道电子的杂化使Nafion有效地锚定Mn。这种相互作用抑制了Mn的溶解，显著提高了LMO膜电极的电化学性能。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Separation and Purification Technology 工程技术-工程：化工

CiteScore

14.00

自引率

12.80%

发文量

2347

审稿时长

43 days

期刊介绍： Separation and Purification Technology is a premier journal committed to sharing innovative methods for separation and purification in chemical and environmental engineering, encompassing both homogeneous solutions and heterogeneous mixtures. Our scope includes the separation and/or purification of liquids, vapors, and gases, as well as carbon capture and separation techniques. However, it's important to note that methods solely intended for analytical purposes are not within the scope of the journal. Additionally, disciplines such as soil science, polymer science, and metallurgy fall outside the purview of Separation and Purification Technology. Join us in advancing the field of separation and purification methods for sustainable solutions in chemical and environmental engineering.