电化学提锂技术中电极材料和电极体系的研究进展

doi:10.16085/j.issn.1000-6613.2020-0108

化工进展 ›› 2020, Vol. 39 ›› Issue (6): 2294-2303.DOI: 10.16085/j.issn.1000-6613.2020-0108

电化学提锂技术中电极材料和电极体系的研究进展

郭志远¹^,²^,³(), 纪志永¹^,²^,³(), 陈华艳⁴, 时雅滨³^,⁵, 张帆¹^,²^,³, 赵颖颖¹^,²^,³, 刘杰¹^,²^,³, 袁俊生¹^,²^,³

^1.河北工业大学化工学院/化工节能过程集成与资源利用国家-地方联合工程实验室，天津 300130
^2.河北工业大学化工学院/海水资源高效利用化工技术教育部工程研究中心，天津 300130
^3.河北省现代海洋化工技术协同创新中心，天津 300130
^4.天津工业大学分离膜与膜过程国家重点实验室，天津 300387
^5.北京交通大学海滨学院，河北黄骅 061199

出版日期:2020-06-05 发布日期:2020-06-16
通讯作者: 纪志永
作者简介:郭志远（1992—），男，博士研究生，研究方向为海水/卤水综合利用。E-mail：guozhiyuan1027@gmail.com。
基金资助:
国家自然科学基金(21978064);河北省自然科学基金(B2019202423);天津市自然科学基金(19JCYBJC20400);省部共建分离膜与膜过程国家重点实验室（天津工业大学）开放课题(M2-201708)

Progress of electrode materials and electrode systems in electrochemical lithium extraction process

Zhiyuan GUO¹^,²^,³(), Zhiyong JI¹^,²^,³(), Huayan CHEN⁴, Yabin SHI³^,⁵, Fan ZHANG¹^,²^,³, Yingying ZHAO¹^,²^,³, Jie LIU¹^,²^,³, Junsheng YUAN¹^,²^,³

^1.National-Local Joint Engineering Laboratory of Chemical Energy Saving Process Integration and Resource Utilization, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
^2.Engineering Research Center of Seawater Utilization of Ministry of Education, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
^3.Hebei Collaborative Innovation Center of Modern Marine Chemical Technology, Tianjin 300130, China
^4.State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China
^5.Beijing Jiaotong University Haibin College, Huanghua 061199, Hebei, China

Online:2020-06-05 Published:2020-06-16
Contact: Zhiyong JI

摘要/Abstract

摘要：

锂及其化合物具有广泛的应用前景，锂资源需求越来越大，因此，开发能实现高储量、低品位的（浓）海水/卤水锂资源高效提取的方法具有重要意义。近年来，电化学提锂技术因其高选择性、低能耗和环境友好等特点而成为研究热点。本文针对电化学提锂技术中锂吸附电极材料的选择/制备和电极体系构建两方面的研究进展进行了归纳分析。在锂吸附电极材料的选择/制备上，基于高锂离子选择性的LiFePO₄、LiMn₂O₄和LiNi_1/3Co_1/3Mn_1/3O₂电极被逐渐开发应用。在电极体系构建上，与具有阴离子可逆交换性能的AgCl、ZnCl₂和聚吡咯对电极所构成的电极体系可避免副反应发生，能耗较低；不含其他对电极材料的“摇椅式”结构电极体系可降低电极成本，提高提锂效率。此外，指出了目前电化学提锂技术尚存在的不足，未来可从电极材料制备、提锂过程优化、装备设计三方面进行研究，以推进电化学提锂技术的发展与应用。

关键词: 锂, 电化学, 电极材料, 电极体系, 选择性, 分离

Abstract:

Lithium and its derivatives have wide application prospects, leading to an increasing demand of lithium resource. Therefore, it is of great significance to develop a method that can extract lithium from (concentrated) seawater/brine with high reserves of low-grade lithium. In recent years, electrochemical lithium extraction technology has become a research focus due to its high selectivity, low energy consumption, and environmental friendliness. This paper reviewed the progress on the selection and preparation of electrode materials for lithium adsorption and the construction of electrode systems in electrochemical lithium extraction technology. In the selection and preparation of lithium adsorption electrode materials, LiFePO₄, LiMn₂O₄ and LiNi_1/3Co_1/3Mn_1/3O₂with high lithium selectivity were developed gradually. In the construction of the electrode structure system, the system with counter electrode of AgCl, ZnCl₂ and polypyrrole, which have the anion reversible exchange performance, can avoid side reactions and reduce energy consumption for lithium extraction. The “rocking chair” system without other counter electrode materials can reduce the cost of the electrode and improve the efficiency of lithium extraction. Furthermore, the current shortcomings of electrochemical lithium extraction technology were pointed out, and its development and application could be promoted by the researches on the electrode material preparation, lithium extraction process optimization and equipment design in future.

Key words: lithium, electrochemical, electrode materials, electrode system, selectivity, separation

中图分类号:

TQ150.9

郭志远, 纪志永, 陈华艳, 时雅滨, 张帆, 赵颖颖, 刘杰, 袁俊生. 电化学提锂技术中电极材料和电极体系的研究进展[J]. 化工进展, 2020, 39(6): 2294-2303.

Zhiyuan GUO, Zhiyong JI, Huayan CHEN, Yabin SHI, Fan ZHANG, Yingying ZHAO, Jie LIU, Junsheng YUAN. Progress of electrode materials and electrode systems in electrochemical lithium extraction process[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2294-2303.

参考文献

1	GROSJEAN C, MIRANDA P H, PERRIN M, et al. Assessment of world lithium resources and consequences of their geographic distribution on the expected development of the electric vehicle industry[J]. Renewable & Sustainable Energy Reviews, 2012, 16(3): 1735-1744.
2	MATHEW M, KONG Q H, MCGRORY J, et al. Simulation of lithium ion battery replacement in a battery pack for application in electric vehicles[J]. Journal of Power Sources, 2017, 349(1): 94-104.
3	VIKSTR?M H, DAVIDSSON S, H??K M. Lithium availability and future production outlooks[J]. Applied Energy, 2013, 110: 252-266.
4	TSUCHIYA S, NAKATANI Y, IBRAHIM R, et al. Highly efficient separation of lithium chloride from seawater[J]. Journal of the American Chemical Society, 2002, 124(18): 4936-4937.
5	YANG S X, ZHANG F, DING H P, et al. Lithium metal extraction from seawater[J]. Joule, 2018, 2(9): 1648-1651.
6	纪志永, 焦朋朋, 袁俊生, 等. 锂资源的开发利用现状与发展分析[J]. 轻金属, 2013(5): 1-5.
6	JI Z Y, JIAO P P, YUAN J S, et al. The exploitation and utilization of lithium resources and its development[J]. Light Metals, 2013 (5): 1-5.
7	SOMRANI A, HAMZAOUI A H, PONTIE M. Study on lithium separation from salt lake brines by nanofiltration (NF) and low pressure reverse osmosis (LPRO)[J]. Desalination, 2013, 317(15): 184-192.
8	GUO Z Y, JI Z Y, CHEN Q B, et al. Prefractionation of LiCl from concentrated seawater/salt lake brines by electrodialysis with monovalent selective ion exchange membranes[J]. Journal of Cleaner Production, 2018, 193: 338-350.
9	CHEN Q B, JI Z Y, LIU J, et al. Development of recovering lithium from brines by selective-electrodialysis: effect of coexisting cations on the migration of lithium[J]. Journal of Membrane Science, 2018, 548(15): 408-420.
10	JI Z Y, YANG F J, ZHAO Y Y, et al. Preparation of titanium-base lithium ionic sieve with sodium persulfate as eluent and its performance[J]. Chemical Engineering Journal, 2017, 328(15): 768-775.
11	XIAO G P, TONG K F, ZHOU L S, et al. Adsorption and desorption behavior of lithium ion in spherical PVC-MnO₂ ion sieve[J]. Industrial & Engineering Chemistry Research, 2012, 51(33): 10921-10929.
12	GANDOMAN F H, JAGUEMONT J, GOUTAM S, et al. Concept of reliability and safety assessment of lithium-ion batteries in electric vehicles: basics, progress, and challenges[J]. Applied Energy, 2019, 251(1): 113343.
13	MA S, JIANG M D, TAO P, et al. Temperature effect and thermal impact in lithium-ion batteries: a review[J]. Progress in Natural Science: Materials International, 2018, 28(6): 653-666.
14	FERGUS J W. Recent developments in cathode materials for lithium ion batteries[J]. Journal of Power Sources, 2010, 195(4): 939-954.
15	JI Z Y, ZHAO M Y, YUAN J S, et al. Li⁺ extraction from spinel-type LiMn₂O₄ in different eluents and Li⁺ insertion in the aqueous phase[J]. Solvent Extr. Ion Exch. , 2016, 34(6): 549-557.
16	JI Z Y, ZHAO M Y, ZHAO Y Y, et al. Lithium extraction process on spinel-type LiMn₂O₄ and characterization based on the hydrolysis of sodium persulfate[J]. Solid State Ionics, 2017, 301: 116-124.
17	ZHAO L L, WANG R S. Preparation of MnO₂(Li) and its ion exchange kinetics[J]. Acta Physica-Chimica Sinica, 2003, 19(10): 933-937.
18	XU X, CHEN Y M, WAN P Y, et al. Extraction of lithium with functionalized lithium ion-sieves[J]. Progress in Materials Science, 2016, 84: 276-313.
19	OOI K, MIYAI Y, SAKAKIHARA J. Mechanism of Li⁺ insertion in spinel-type manganese oxide. Redox and ion-exchange reactions[J]. Langmuir, 1991, 7(6): 1167-1171.
20	ELIAD L, SALITRA G, SOFFER A, et al. Ion sieving effects in the electrical double layer of porous carbon electrodes: estimating effective ion size in electrolytic solutions[J]. The Journal of Physical Chemistry B, 2001, 105(29): 6880-6887.
21	TARASCON J M, ARMAND M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861): 359-367.
22	ROBINSON D M, GO Y B, GREENBLATT M, et al. Water oxidation by λ-MnO₂: catalysis by the cubical Mn₄O₄ subcluster obtained by delithiation of spinel LiMn₂O₄[J]. J. Am. Chem. Soc., 2010, 41(45): 11467-11469.
23	XU X, ZHOU Y, FENG Z W, et al. A self-supported λ-MnO₂ film electrode used for electrochemical lithium recovery from brines[J]. ChemPlusChem, 2018, 83(6): 521-528.
24	WANG L, MA W, LIU R, et al. Correlation between Li⁺ adsorption capacity and the preparation conditions of spinel lithium manganese precursor[J]. Solid State Ionics, 2006, 177(17/18): 1421-1428.
25	ZHENG H, CHEN X, YANG Y, et al. Self-assembled LiNi_1/3Co_1/3Mn_1/3O₂ nanosheet cathode with high electrochemical performance[J]. ACS Applied Materials & Interfaces, 2017, 9(45): 39560-39568.
26	ZHENG J, CHEN J, JIA X, et al. Electrochemical performance of the LiNi_1/3Co_1/3Mn_1/3O₂ in aqueous electrolyte[J]. Journal of the Electrochemical Society, 2010, 157(6): A702-A706.
27	LAWAGON C P, NISOLA G M, CUEVAS R A I, et al. Li_1-_xNi_0.33Co_1/3Mn_1/3O₂/Ag for electrochemical lithium recovery from brine[J]. Chemical Engineering Journal, 2018, 348(15): 1000-1011.
28	ZHAO Z W, SI X F, LIU X H, et al. Li extraction from high Mg/Li ratio brine with LiFePO₄/FePO₄ as electrode materials[J]. Hydrometallurgy, 2013, 133: 75-83.
29	ZHAO M Y, JI Z Y, ZHANG Y G, et al. Study on lithium extraction from brines based on LiMn₂O₄/Li_1-_xMn₂O₄ by electrochemical method[J]. Electrochimica Acta, 2017, 252(20): 350-361.
30	KIM S, LEE J, KIM S, et al. Electrochemical lithium recovery with a LiMn₂O₄-Zinc battery system using zinc as a negative electrode[J]. Energy Technology, 2018, 6(2): 340-344.
31	KANOH H, OOI K, MIYAI Y, et al. Electrochemical recovery of lithium ions in the aqueous phase[J]. Separation Science and Technology, 1993, 28(1/2/3): 643-651.
32	PASTA M, BATTISTEL A, MANTIA F L. Batteries for lithium recovery from brines[J]. Energy & Environmental Science, 2012, 5(11): 9487-9491.
33	JAEHAN L, SEUNG-HO Y, CHOONSOO K, et al. Highly selective lithium recovery from brine using a λ-MnO₂-Ag battery[J]. Physical Chemistry Chemical Physics, 2013, 15(20): 7690-7695.
34	KIM S, LEE J, KANG J S, et al. Lithium recovery from brine using a λ-MnO₂/activated carbon hybrid supercapacitor system[J]. Chemosphere, 2015, 125: 50-56.
35	任丽, 王立新, 赵金玲, 等. 导电聚合物及导电聚吡咯的研究进展[J]. 材料导报, 2002(2): 60-62.
35	REN L, WANG L X, ZHAO J L, et al. Progress in research on conductive polymer and conductive polypyrrole[J]. Materials Review, 2002(2): 60-62.
36	WEIDLICH C, MANGOLD K M, JUTTNER K. Conducting polymers as ion-exchangers for water purification[J]. Electrochimica Acta, 2001, 47(5): 741-745.
37	杜晓. 聚吡咯及其电活性离子印迹功能材料的可控合成与应用[D]. 太原: 太原理工大学, 2015.
37	DU X. Controllable synthesis and application of polypyrrole and its electroactive ion imprinted functional materials[D]. Taiyuan: Taiyuan University of Technology, 2015.
38	MARCHINI F, RUBI D, POZO M DEL, et al. Surface chemistry and lithium-ion exchange in LiMn₂O₄ for the electrochemical selective extraction of LiCl from natural salt lake brines[J]. Journal of Physical Chemistry C, 2016, 120(29): 15875-15883.
39	MISSONI L L, MARCHINI F, POZO M DEL, et al. A LiMn₂O₄-polypyrrole system for the extraction of LiCl from natural brine[J]. Journal of the Electrochemical Society, 2016, 163(9): A1898-A1902.
40	MARCHINI F, WILLIAMS F J, CALVO E J. Sustainable selective extraction of lithium chloride from natural brine using a Li_1-_xMn₂O₄ ion pump[J]. Journal of the Electrochemical Society, 2018, 165(14): A3292-A3298.
41	ZHAO Z W, SI X F, LIANG X X, et al. Electrochemical behavior of Li⁺, Mg²⁺, Na⁺ and K⁺ in LiFePO₄/FePO₄ structures[J]. Transactions of Nonferrous Metals Society of China, 2013, 23(4): 1157-1164.
42	ZHAO Z W, SI X F, LIU X H, et al. Li extraction from high Mg/Li ratio brine with LiFePO₄/FePO₄ as electrode materials[J]. Hydrometallurgy, 2013, 133: 75-83.
43	LIU D F, SUN S Y, YU J G. A new high-efficiency process for Li⁺ recovery from solutions based on LiMn₂O₄/λ-MnO₂ materials[J]. Chemical Engineering Journal, 2019, 377(1): 119825.
44	OKUMURA T, FUKUTSUKA T, MATSUMOTO K, et al. Lithium-ion transfer reaction at the interface between partially fluorinated insertion electrodes and electrolyte solutions[J]. The Journal of Physical Chemistry C, 2011, 115(26): 12990-12994.
45	KOBAYASHI S, UCHIMOTO Y. Lithium ion phase-transfer reaction at the interface between the lithium manganese oxide electrode and the nonaqueous electrolyte[J]. The Journal of Physical Chemistry B, 2005, 109(27): 13322-13326.

[1]	李季桐, 王刚, 熊亚选, 徐钱. 不同工质单效吸收式制冷系统的能量和㶲分析[J]. 化工进展, 2023, 42(S1): 104-112.
[2]	马伊, 曹世伟, 王家骏, 林立群, 邢延, 曹腾良, 卢峰, 赵振伦, 张志军. 低共熔溶剂回收废旧锂离子电池正极材料的研究进展[J]. 化工进展, 2023, 42(S1): 219-232.
[3]	贺美晋. 分子管理在炼油领域分离技术中的应用和发展趋势[J]. 化工进展, 2023, 42(S1): 260-266.
[4]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[5]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[6]	张杰, 白忠波, 冯宝鑫, 彭肖林, 任伟伟, 张菁丽, 刘二勇. PEG及其复合添加剂对电解铜箔后处理的影响[J]. 化工进展, 2023, 42(S1): 374-381.
[7]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[8]	李世霖, 胡景泽, 王毅霖, 王庆吉, 邵磊. 电渗析分离提取高值组分的研究进展[J]. 化工进展, 2023, 42(S1): 420-429.
[9]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[10]	李化全, 王明华, 邱贵宝. 硫酸酸解钙钛矿相精矿的行为[J]. 化工进展, 2023, 42(S1): 536-541.
[11]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[12]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[13]	廖志新, 罗涛, 王红, 孔佳骏, 申海平, 管翠诗, 王翠红, 佘玉成. 溶剂脱沥青技术应用与进展[J]. 化工进展, 2023, 42(9): 4573-4586.
[14]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[15]	雷伟, 姜维佳, 王玉高, 和明豪, 申峻. N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe³⁺检测[J]. 化工进展, 2023, 42(9): 4799-4807.

电化学提锂技术中电极材料和电极体系的研究进展

Progress of electrode materials and electrode systems in electrochemical lithium extraction process

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价