蛇形流场电控离子交换装置用于选择性提锂

doi:10.11949/0438-1157.20230303

摘要/Abstract

摘要：

通过交替、对称地堆叠带孔的锰酸锂（LiMn₂O₄）基膜电极和导电炭黑（C）基膜电极，组装了单通道的蛇形流场电控离子交换（ESIX）装置，并将其用于从高镁锂比模拟卤水（Mg/Li约500）中选择性提取锂离子。基于这种自下而上的蛇形流场，增加膜组件中腔室的数量可以使模拟卤水中更多的锂离子被捕获。相较于常规的恒电压驱动模式，恒电流-恒电压耦合驱动模式能有效地提升ESIX装置的提锂性能。在0.8 mA·cm^-2-1 V的耦合驱动模式下，该装置在120 min内对锂离子的提取率高达97.6%。此外，X射线衍射（XRD）证明，通过冲洗膜电极表面可以去除大部分吸附的镁离子。因此，这种新型的ESIX装置具有从高镁锂比盐湖卤水中选择性分离锂离子的工业应用潜力。

关键词: 电化学, 蛇形流场, 锂离子提取, 盐湖卤水, 选择性, 分离

Abstract:

An electrochemically switched ion exchange (ESIX) device with single-channel serpentine flow field was assembled by alternately and symmetrically stacking perforated LiMn₂O₄-based and carbon black (C)-based film coated electrodes, and employed for selective extraction of lithium from simulated brine with high Mg/Li ratio (about 500). Based on this bottom-up serpentine flow field, increasing the number of chambers in the membrane module can enable more lithium ions to be trapped in the simulated brine. Compared with the conventional driving mode of constant voltage, the collaborative driving mode of constant current-constant voltage could effectively improve the lithium extraction performance of the ESIX device. The extraction efficiency of Li⁺reached as high as 97.6% in 120 min with a coupled driving mode of 0.8 mA·cm^-2-1 V. In addition, X-ray diffraction (XRD) test demonstrated that most of the adsorbed Mg²⁺ could be removed by rinsing the surface of the film coated electrodes. Therefore, such a novel ESIX device has potential industrial applications for selective separation of lithium from high Mg/Li ratio salt lake brines.

Key words: electrochemistry, serpentine flow field, lithium extraction, salt lake brine, selectivity, separation

中图分类号:

TQ 150.9

张正, 何永平, 孙海东, 张荣子, 孙正平, 陈金兰, 郑一璇, 杜晓, 郝晓刚. 蛇形流场电控离子交换装置用于选择性提锂[J]. 化工学报, 2023, 74(5): 2022-2033.

Zheng ZHANG, Yongping HE, Haidong SUN, Rongzi ZHANG, Zhengping SUN, Jinlan CHEN, Yixuan ZHENG, Xiao DU, Xiaogang HAO. Electrochemically switched ion exchange device with serpentine flow field for selective extraction of lithium[J]. CIESC Journal, 2023, 74(5): 2022-2033.

图/表 12

图1 ESIX装置的光学照片(a)和结构示意图(b)

Fig.1 Photograph (a) and schematic diagram (b) of the ESIX device

图2 ESIX装置的工作机理

Fig.2 Working mechanism of the ESIX device

图3 LiMn2O4/C/PVDF-b-PAA复合物(a)和LiMn2O4/C/PVDF-b-PAA膜电极横截面(b)的SEM图

Fig.3 SEM image of LiMn2O4/C/PVDF-b-PAA composite (a) and cross-sectional SEM image of the film coated electrode (b)

图4 LiMn2O4/C/PVDF-b-PAA复合物及其在氧化电位和还原电位下的XRD谱图

Fig.4 XRD patterns of LiMn2O4/C/PVDF-b-PAA composite and LiMn2O4/C/PVDF-b-PAA composite at oxidation potential and reduction potential

图5 LiMn2O4/C/PVDF-b-PAA膜电极不同溶液中的CV响应（扫描速率：0.1 mV·s-1）

Fig.5 CV responses of the LiMn2O4/C/PVDF-b-PAA film coated electrode in different aqueous solutions

图6 LiMn2O4/C/PVDF-b-PAA膜电极在不同扫描速率下的CV曲线(a)；膜电极的峰电流与扫描速率的平方根（v1/2）之间的关系(b)

Fig.6 CV curves of the LiMn2O4/C/PVDF-b-PAA film coated electrode at different scan rates (a); Relationship between the peak currents and the square root of the scan rate (v1/2) for the film coated electrode (b)

图7 腔室数量对锂离子提取性能的影响

Fig.7 Effect of the number of cells on the extraction performance of Li+

图8 不同驱动模式下电压和电流随时间变化曲线

Fig.8 The plots of voltage and current variation with time at different driving modes

图9 不同驱动模式下的锂离子嵌入量

Fig.9 Li+ intercalation capacity at different driving modes

图10 不同驱动模式下的锂离子提取性能

Fig.10 Extraction performance of Li+ at different driving modes

图11 回收液中锂离子的脱嵌率和镁锂比(a)；LiMn2O4/C/PVDF-b-PAA在电化学预脱嵌锂离子后、电化学捕获测试后及清洗后的XRD谱图(b)

Fig.11 Deintercalation efficiency of Li+ and Mg/Li ratio in the recovery solution (a); XRD patterns of LiMn2O4/C/PVDF-b-PAA after electrochemical deintercalation of Li+, after electrochemical capture test and after rinsing (b)

图12 ESIX装置在10次电化学捕获测试中的锂离子提取率

Fig.12 Lithium extraction efficiency of ESIX device in 10 electrochemical capture tests

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