膜科学与技术

船闸式LMO||PPy双膜系统同步电控提取盐湖卤水中LiCl

作者：高新宇¹，郭欢欢¹，高凤凤¹，²，³，⁵，郝晓刚¹，²，³，简选⁴，仙运昌⁵，赵瑞⁵

单位： 1. 太原理工大学化学与化工学院，太原 030024； 2. 元锂（杭州）分离技术有限公司，杭州 311607； 3. 山西科化技术服务有限公司，太原 030000； 4. 延安大学化学与化工学院陕西省化学反应工程重点实验室，延安 716000；5. 山西阳煤化工机械（集团）有限公司, 太原 030032

关键词： LMO||PPy双膜系统；船闸式电控离子选择渗透；高镁锂比；锂提取；膜分离

DOI号： 10.16159/j.cnki.issn1007-8924.2026.01.002

分类号： TQ150.5

出版年,卷(期):页码： 2026,46(1):11-26

摘要：

针对高镁锂比盐湖卤水中锂资源高效提取的难题，本研究构建了一种非对称异质结构的锰酸锂||聚吡咯（lithium manganate || polypyrrole，LMO||PPy）双膜系统，结合船闸式电控离子选择渗透技术（SL-ESIP），实现了LiCl的高效分离提取。通过调控聚丙烯酸（PAA）含量（55%，质量分数）制备了单面亲水/单面疏水的非对称复合膜，并优化了膜电极导线接口数量（3线连接）和腔室间距（2 mm），显著提升了LiCl渗透通量。实验结果表明，在纯锂溶液中，Li+渗透通量达0.109 mol/(m2·h)；在镁锂比为20∶1(质量比)的模拟卤水中，经10次循环后，Li+通量稳定在0.055 mol/(m2·h)，锂镁分离系数为18.03，展现出优异的循环稳定性和选择性。因此，船闸式LMO||PPy双膜系统可作为LiCl连续同步提取的高效技术方案。

To address the challenge of efficient lithium extraction from salt lake brines with high magnesium-to-lithium ratios, this study constructed an asymmetrically heterostructured lithium manganate||polypyrrole (lithium manganate || polypyrrole，LMO||PPy) dual-membrane system. By combining the ship-lock electrically switched ion permselective (SL-ESIP) technology, achieving highly efficient separation and extraction of LiCl. An asymmetric composite membrane with single-sided hydrophilic/single-sided hydrophobic properties was prepared by adjusting the polyacrylic acid (PAA) content (55%, mass fraction), and the LiCl permeation flux was significantly enhanced by optimizing the number of membrane-electrode wire connection (3-wire connection) and chamber spacing (2 mm). Experimental results demonstrated that in a pure lithium solution, the Li+ permeation flux reached 0.109 mol/(m2·h). In simulated brine with a Mg/Li mass ratio of 20∶1, the Li+ permeation flux stabilized at 0.055 mol/(m2·h) after 10 cycles, with a separation factor of 18.03 for Mg2+/Li+, showcasing excellent cycling stability and selectivity. Therefore, the ship-lock LMO||PPy dual-membrane system presents an efficient technical solution for the continuous and synchronous extraction of LiCl.

基金项目：

国家自然科学基金联合基金重点项目（U23A20119）; 山西省基础研究计划（202403021221039）

作者简介：

高新宇（2002-），女，山西临县人，硕士研究生，主要研究方向为电控离子交换技术及电控膜分离装置.*通讯作者，高凤凤，E-mail：gaofengfeng@tyut.edu.cn；郝晓刚，E-mail：xghao@tyut.edu.cn

参考文献：

[1]赵龙. 新型钒基锂离子电池电极材料的制备及电化学性能研究[D]. 广州: 华南理工大学, 2019.
[2]Hu Y, Su H, Zhu T, et al. Environmentally benign techniques of lithium extraction from salt lakes: a review[J]. Environ Chem Lett, 2024, 22(1): 105-120.
[3]Xu X, Chen Y, Wan P, et al. Extraction of lithium with functionalized lithium ion-sieves[J]. Prog Mater Sci, 2016, 84: 276-313.
[4]蒋晨啸, 陈秉伦, 张东钰, 等. 我国盐湖锂资源分离提取进展[J]. 化工学报, 2022, 73(2): 23.
[5]Xu S, Song J, Bi Q, et al. Extraction of lithium from Chinese salt-lake brines by membranes: Design and practice[J]. J Membr Sci, 2021, 635: 119441.
[6]乜贞, 伍倩, 丁涛, 等. 中国盐湖卤水提锂产业化技术研究进展[J]. 无机盐工业, 2022, 54(10): 1-12.
[7]Zhang L, Li L, Rui H, et al. Lithium recovery from effluent of spent lithium battery recycling process using solvent extraction[J]. J Hazard Mater, 2020, 398: 122840.
[8]Xiao W, Xin C, Li S, et al. Insight into fast Li diffusion in Li-excess spinel lithium manganese oxide[J]. J Mater Chem, 2018, 6(21): 9893-9898.
[9]Zhang Y N, Yu D H, Jia C Y, et al. Advances and promotion strategies of membrane-based methods for extracting lithium from brine[J]. Desalination, 2023, 566(15): 116891.
[10]Arrua E C, Bedogni G, Salomon C J, et al. Selective lithium extraction employing lithium manganese oxide-loaded polymeric membranes at natural brine pH and room temperature[J]. Desalination, 2024, 584: 117741.
[11]Gu J, Chen L, Li X, et al. Multifunctional AlPO4 reconstructed LiMn2O4 surface for electrochemical lithium extraction from brine[J]. J Energy Chem, 2024, 89: 410-421.
[12]葛涛, 徐亮, 孟金伟, 等. 盐湖卤水提锂工艺技术研究进展[J]. 有色金属工程, 2021, 11(2): 55-62.
[13]唐力君, 郑绵平, 刘建华. 碳酸盐型盐湖卤水的模拟太阳池结晶试验[J]. 地球学报, 2009, 30(2): 249-255.
[14]孔令杰, 李光壁, 谢佳豪, 等. 盐湖卤水锂提取技术研究进展[J]. 无机盐工业, 2025, 57(1): 14-26.
[15]马效农. 盐湖铝系提锂吸附剂成型条件的影响研究[J]. 化工设计通讯, 2024, 50(8): 148-150.
[16]Li R, Wang W, Wang Y, et al. Novel ionic liquid as co-extractant for selective extraction of lithium ions from salt lake brines with high Mg/Li ratio[J]. Sep Purif Technol, 2021, 277: 119471.
[17]Gong L, Ouyang W, Li Z, et al. Direct numerical simulation of continuous lithium extraction from high Mg2+/Li+ ratio brines using microfluidic channels with ion concentration polarization[J]. J Membr Sci, 2018, 556: 34-41.
[18]康为清. 纳滤法应用于盐湖卤水镁锂分离的研究[D]. 西宁: 中国科学院青海盐湖研究所, 2014.
[19]计超,张杰,张志君,等.DK纳滤膜对高镁锂比卤水的分离性能研究[J].膜科学与技术,2014,34(3):79-85.
[20]王金燕,王曼曼,李鸽,等.盐湖提锂用退役纳滤膜的污染分析[J].膜科学与技术,2023,43(5):83-88.
[21]Zhao W, Zhou M, Yan B, et al. Waste conversion and resource recovery from wastewater by ion exchange membranes: State-of-the-art and perspective[J]. Ind Eng Chem Res, 2018, 57(18): 6025-6039.
[22]Guo L, Yao Y, Xu J, et al. Strategies for lithium extraction from salt lakes by nanofiltration and selective-electrodialysis and analysis of differences between the two methods[J]. Desalination, 2024, 586: 117749.
[23]王守合. 冠醚功能化纳滤膜制备及其锂镁分离性能研究[D]. 天津: 天津工业大学, 2021.
[24]郭志远,张帆,纪志永,等.选择性电渗析提锂技术的研究进展[J].河北工业大学学报,2022,51(6):1-9.
[25]张俊义, 董生德, 贺欣, 等. 电化学法提锂技术的研究进展[J]. 化学通报, 2023, 86(9): 1044-1052.
[26]Xu W, He L, Zhao Z. Lithium extraction from high Mg/Li brine via electrochemical intercalation/de-intercalation system using LiMn2O4 materials[J]. Desalination, 2021, 503: 114935.
[27]Guo Z, Ji Z, Wang J, et al. Electrochemical lithium extraction based on “rocking-chair” electrode system with high efficiency: The driving mode of constant current-constant voltage[J]. Desalination, 2022, 533: 115767.
[28]延彩萍. 无机-有机电活性离子交换材料MIL-101@PPy的理论计算及提碘性能研究[D]. 太原: 太原理工大学, 2023.
[29]Ji W, Niu J, Zhang W, et al. An electroactive ion exchange hybrid film with collaboratively-driven ability for electrochemically-mediated selective extraction of chloride ions[J]. Chem Eng J, 2022, 427: 130807.
[30]Wang C, Du X, Gao F, et al. Electrochemically switched ion separation technologies: A review on electroactive ion exchange materials and system architectures[J]. Chem Eng J, 2024, 490: 151708.
[31]郝晓刚. 电控离子交换膜技术:从电控离子交换到电控离子选择渗透膜[C]//第五届全国膜分离技术在冶金工业中应用研讨会论文集. 中国膜工业协会，中南大学, 2016.
[32]高凤凤. 低维碳基电控离子选择渗透膜的制备及重金属离子分离[D]. 太原: 太原理工大学, 2018.
[33]Zhao J, Liu Z, Ji Z, et al. Selective transmembrane transport of iodide based on electrochemically induced iodide-trap BiOI/MWCNTs/PVA composite membrane[J]. J Membr Sci, 2024, 705: 122866.
[34]Gao F, Jiang M, Hao X, et al. A potential-driven NiO/NiCo LDH film electrode for highly efficient extraction of Br- via electrochemical coordination and anion exchange[J]. Chem Eng J, 2023, 475: 146345.
[35]黄琳凯, 黄炳行, 李春霞, 等. 表面改性对锰酸锂电池电化学性能的影响[J]. 中国锰业, 2024, 42(4): 36-41.
[36]Romero V E C, Putrino D S, Tagliazucchi M, et al. Sustainable electrochemical extraction of lithium from natural brine: Part Ⅱ. flow reactor[J]. J Electrochem Soc, 2021, 168(2): 020518.
[37]Chen F, Huang Y, Guo L, et al. Correction: Dual-ions electrochemical deionization: a desalination generator[J]. Energy Environ Sci, 2017, 10(10): 2081-2089.
[38]于学佳, 田思航, 牛俊健, 等. 聚吡咯膜电极电控离子交换技术除氯应用研究[J]. 水处理技术, 2020, 46(3): 96-100.
[39]Guo H, Wang Y, Zhang X, et al.“Sandwich” LiMn2O4||PPy dual membranes coupled with the Ship-lock electrochemically switched ion permselective system for LiCl separation[J]. J Membr Sci, 2025, 727：124126.
[40]Zhang C, Mu Y, Zhao S, et al. Lithium extraction from synthetic brine with high Mg2+/Li+ ratio using the polymer inclusion membrane[J]. Desalination, 2020, 496: 114710.
[41]Peng H, Zhao Q. Heterogeneous membrane for efficient separation of lithium from high magnesium/lithium ratio brine[J]. Adv Funct Mater, 2021, 31(14): 2009430.
[42]Saif H M, Huertas R M, Pawlowski S, et al. Development of highly selective composite polymeric membranes for Li+/Mg2+ separation[J]. J Membr Sci, 2021, 620: 118891.
[43]Pang X, Yu X, He Y, et al. Preparation of monovalent cation perm-selective membranes by controlling surface hydration energy barrier[J]. Sep Purif Technol, 2021, 270: 118768.
[44]Ma W, Han G, Li J, et al. Hierarchical electroactive ion permselective membrane with electrochemical switched ion pump effect for continuous lithium-ion recovery[J]. J Membr Sci, 2024, 700: 122719.
[45]Wang W,Hong G, Zhang Y, et al. Designing an energy-efficient multi-stage selective electrodialysis process based on high-performance materials for lithium extraction[J]. J Memb Sci, 2023, 675: 121534.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com