Kinetic study on electrochemical intercalation/deintercalation method for lithium extraction from brine

doi:10.11949/0438-1157.20201727

Abstract

Abstract:

The electrochemical intercalation/deintercalation method for lithium extraction from salt lake brine has the advantages of good selectivity, high extraction rate, and environmental friendliness, but the speed of lithium extraction is slow and the efficiency is low. In this paper, the kinetic study of the lithium extraction process is carried out to find out the control steps, and provide theoretical guidance for the optimization of the method. The influence of cell voltage, reaction temperature, lithium concentration, coating density and other factors on the lithium extraction rate was systematically studied, and the kinetic fitting analysis was carried out using the shrinking nucleus model. Compared with other factors, the cell voltage has a significant impact on the rate of lithium extraction. The speed-control step of the lithium extraction reaction showed a transition from chemical reaction control to shrinking nucleus model (the mass transfer of the solution to the inside of the electrode is the reaction limiting step) as the cell voltage increased. When the cell voltage is high (0.1 V), the calculated apparent activation energy of the reaction is 18.9 kJ/mol, the reaction order of lithium concentration is 0.382, the dependence coefficient of coating density is -1.46, and the corresponding reaction kinetic equation is established.

Key words: electrochemical intercalation/deintercalation method, lithium extraction from brine, LiFePO₄, kinetics, electrolysis, separation

摘要：

电化学脱嵌法盐湖提锂技术具有选择性好、提取率高、环境友好等优点，但提锂速度慢、效率较低。通过对提锂过程进行动力学研究来探明其控制步骤，为该方法的优化提供理论指导。通过系统研究槽电压、反应温度、锂浓度以及涂覆密度等因素对锂提取速率的影响规律，采用收缩核模型进行了动力学拟合分析。相较于其他因素，槽电压对提锂速率的影响显著，提锂反应速控步骤随着槽电压的升高呈现出由化学反应控制到内扩散控制（溶液向电极内部的传质为反应限制步骤）的转变。高槽电压（0.1 V）时，计算所得反应表观活化能为18.9 kJ/mol，锂浓度反应级数为 0.382，涂覆密度的依赖系数为-1.46。建立了提锂反应动力学方程。

关键词: 电化学脱嵌法, 盐湖提锂, LiFePO₄, 动力学, 电解, 分离

CLC Number:

TF 826.3

XU Wenhua, LIU Dongfu, HE Lihua, LIU Xuheng, ZHAO Zhongwei. Kinetic study on electrochemical intercalation/deintercalation method for lithium extraction from brine[J]. CIESC Journal, 2021, 72(6): 3105-3115.

徐文华, 刘冬福, 何利华, 刘旭恒, 赵中伟. 电化学脱嵌法盐湖提锂电极反应动力学研究[J]. 化工学报, 2021, 72(6): 3105-3115.

Figures/Tables 13

Fig.1 Sketch of the lithium extraction process(a)， SEM image of the electrode (b)

Fig.2 Spherical shrinking nucleus model (a), flat shrinking nucleus model (b)

Table 1 Kinetic reaction models and kinetic equations

动力学控制

步骤

球形收缩核模型

平板收缩核模型

化学反应

控制

1 - {(1 - x)}^{1 / 3} = \frac{k C_{0}^{n}}{r_{0} ρ} t = K_{1} t

x = \frac{k C_{0}^{n}}{l_{0} ρ} t = K_{4} t

外扩散控制

x = K_{2} t

x = K_{2} t

内扩散

控制

1 - \frac{2}{3} x - {(1 - x)}^{2 / 3} = \frac{2 D_{2} C_{0}}{β r_{0}^{2} ρ} t = K_{3} t

x^{2} = \frac{2 C_{0} D_{1}}{γ l_{0}^{2} ρ} t = K_{5} t

Table 1 Kinetic reaction models and kinetic equations

动力学控制

步骤

球形收缩核模型

平板收缩核模型

化学反应

控制

1 - {(1 - x)}^{1 / 3} = \frac{k C_{0}^{n}}{r_{0} ρ} t = K_{1} t

x = \frac{k C_{0}^{n}}{l_{0} ρ} t = K_{4} t

外扩散控制

x = K_{2} t

x = K_{2} t

内扩散

控制

1 - \frac{2}{3} x - {(1 - x)}^{2 / 3} = \frac{2 D_{2} C_{0}}{β r_{0}^{2} ρ} t = K_{3} t

x^{2} = \frac{2 C_{0} D_{1}}{γ l_{0}^{2} ρ} t = K_{5} t

Fig.3 Effect of cell voltage on the lithium adsorption capacity

Fig.4 Fitting curves of various kinetic equations under different cell voltage

Fig.5 Effect of temperature on the lithium adsorption capacity

Fig.6 Fitting curves of various kinetic equations under different reaction temperature

Fig.7 Effect of lithium concentration on the lithium adsorption capacity

Fig.8 Fitting curves of various kinetic equations under different lithium concentration

Fig.9 Effect of coating density of electrode materials on the lithium adsorption capacity

Fig.10 Fitting curves of various kinetic equations under different coating density

Table 2 Kinetic equations under different temperature, Li+ concentration and coating density

温度/ ℃	动力学方程	锂浓度/ (mol/L)	动力学方程	涂覆密度/ (mg/cm²)	动力学方程
10	x²=1.0×10^-3t	0.1	x²= 0.8×10^-3t	16	x²=3.0×10^-3t
20	x²=1.3×10^-3t	0.2	x²= 1.0×10^-3t	22	x²=1.7×10^-3t
30	x²=1.7×10^-3t	0.4	x²= 1.3×10^-3t	30	x²=1.2×10^-3t
40	x²=2.1×10^-3t	0.6	x²= 1.6×10^-3t
50	x²=2.8×10^-3t

Fig.11 The correction diagrams of kinetic parameters: Arrhenius diagram of electrochemical lithium extraction reaction (a); The relationship between comprehensive rate constant lgK5 and lithium concentration lgCLi (b); The relationship between comprehensive rate constant lgK5 and coating density lg?αLiFePO4 (c); The relationship between x2 and CLi0.382αLiFePO4-1.46exp(-1.89×104/8.314?T)?t (d)

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