层间阴离子可调控LiAl-LDHs的制备及锂吸附性能研究

doi:10.6023/A24120367

摘要/Abstract

锂铝层状双氢氧化物(LiAl-LDHs)是盐湖吸附提锂离子方向中最有前途的吸附剂. 然而, 传统的LiAl-LDHs-Cl易在吸附-脱附过程中失活, 导致吸附容量低、循环稳定性差. 因此本工作提出了一种层间阴离子调控策略, 通过三种表面活性剂十二烷基硫酸钠(SDS)/聚乙烯吡咯烷酮(PVP)/柠檬酸三钠(TSC)的综合调控, 合成了新型LiAl-LDHs类材料, 并用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)、N₂吸脱附等方法对吸附剂的形态结构进行了表征与分析. 结合吸附性能表明, 所合成的LiAl-LDHs-SPT呈现出更好的吸附容量(8.85 mg•g⁻¹)、选择吸附性(Li⁺/Mg²⁺分离系数达53)和循环稳定性(可稳定使用10次以上). 在我国西台吉乃尔盐湖(吸附容量7.36 mg•g⁻¹)与大柴旦盐湖(吸附容量8.96 mg•g⁻¹)的实际应用中也表现优异, 解决了传统材料的缺陷. 该研究为解决传统LiAl-LDHs材料的理论缺陷提供了一种全新的改良策略, 并为盐湖吸附提锂开发提供了一种有应用前景的吸附剂.

关键词: 盐湖吸附提锂, 层状双氢氧化物, 吸附性能, 动力学模拟, 插层

Lithium-aluminum layered double hydroxides (LiAl-LDHs) have emerged as the most promising adsorbents for lithium-ion extraction from salt lakes, owing to their unique lithium-ion memory effect. This property has enabled their commercial-scale application in salt lakes across Qinghai, Xinjiang, Tibet, and other regions of China. However, traditional LiAl-LDHs-Cl materials face significant challenges, including weak interactions between interlayer Cl⁻ and the host layers, as well as electrostatic repulsion between Li⁺ and H⁺. These factors lead to the weakening of interlayer hydrogen bonds, while facilitating the insertion of anions and water molecules, resulting in the desorption of adsorbed Li⁺ back into the solution. Additionally, pore blockage during recycling processes can reduce the number of active adsorption sites, further compromising the material's performance. Consequently, LiAl-LDHs-Cl materials exhibit low adsorption capacity and poor cyclic stability, often becoming inactivated during adsorption-desorption cycles. To address these limitations, recent research has focused on interlayer anion modification as a key strategy to enhance the adsorption performance of LiAl-LDHs. The choice of modifying anions has become a central topic of investigation. In this study, we propose an innovative interlayer anion regulation strategy, utilizing sodium dodecyl sulfate (SDS)/polyvinylpyrrolidone (PVP) association to modulate interlayer anions, expand the material's interlayer spacing, and guide the structure with the assistance of trisodium citrate (TSC) to prevent structural collapse caused by changing in layer spacing. By employing a synergistic approach with three surfactants, we successfully synthesized a new series of LiAl-LDHs materials. These materials were characterized using X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ adsorption-desorption analyses, which revealed significant improvements in interlayer spacing, specific surface area, and pore volume, thereby promoting Li⁺ migration. The adsorption performance of the synthesized LiAl-LDHs-SPT demonstrated remarkable advantages, including an enhanced adsorption capacity of 8.85 mg•g⁻¹, superior selectivity (Li⁺/Mg²⁺ separation coefficient of 53), and excellent cyclic stability (over 10 stable cycles). Moreover, the material exhibited outstanding performance in practical applications, achieving adsorption capacities of 7.36 mg•g⁻¹ in West Taijinar Salt Lake and 8.96 mg•g⁻¹ in Qadim Salt Lake, effectively addressing the shortcomings of traditional materials. This study not only provides a novel and improved strategy to overcome the theoretical limitations of conventional LiAl-LDHs materials but also offers a highly promising adsorbent for advancing lithium extraction technologies in salt lake brines.

Key words: lithium extraction from salt lakes, layered double hydroxide, adsorption property, kinetics simulation, intercalation

引用此文

杨天宇, 代佳楠, 张玉洁, 薛娟琴, 马晶. 层间阴离子可调控LiAl-LDHs的制备及锂吸附性能研究[J]. 化学学报, 2025, 83(6): 569-578.

Tianyu Yang, Jianan Dai, Yujie Zhang, Juanqin Xue, Jing Ma. Preparation of Interlayer Anion Controllable LiAl-LDHs and Lithium Adsorption Performance[J]. Acta Chimica Sinica, 2025, 83(6): 569-578.

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图/表 19

图1. 吸附剂的XRD谱图

Figure 1. XRD patterns of adsorbents

图2. 吸附剂的FT-IR谱图

Figure 2. FT-IR spectra of adsorbents

图3. (a) LiAl-LDHs, (b) LiAl-LDHs-SP, (c) LiAl-LDHs-ST和(d) LiAl-LDHs-SPT的SEM图

Figure 3. SEM images of (a) LiAl-LDHs, (b) LiAl-LDHs-SP, (c) LiAl-LDHs-ST and (d) LiAl-LDHs-SPT

图4. LiAl-LDHs-SPT吸附剂的(a, b) TEM图和(c) HRTEM图

Figure 4. (a, b) TEM and (c) HRTEM images of LiAl-LDHs-SPT adsorbents

图5. 吸附剂的N2吸附-脱附等温线及孔径分布图

Figure 5. N2 adsorption-desorption isotherm and pore size distribution of adsorbents

Sample	Surface area/ (m²•g⁻¹)	Pore volume/ (cm³•g⁻¹•nm⁻¹)	Pore diameter/nm
LiAl-LDHs	14.03	0.071	20.141
LiAl-LDHs-ST	15.51	0.107	8.844
LiAl-LDHs-SP	105.03	0.340	28.272
LiAl-LDHs-SPT	130.28	0.637	19.218

表1. 吸附剂的比表面积、孔体积和平均孔径数据

Table 1. Surface area, pore volume and average pore diameter data of adsorbents

图6. 吸附剂的(a)吸附动力学, (b)准一级动力学拟合模型, (c)准二级动力学拟合模型和(d)颗粒内扩散模型

Figure 6. (a) Adsorption curves, (b) quasi-first-order kinetic model, (c) quasi-second-order kinetic model, and (d) intra-particle diffusion model of adsorbents

Sample	Q_e/(mg•g⁻¹)	$Q_{e}^{*}$/(mg•g⁻¹)	k₁/min⁻¹	R²
LiAl-LDHs-ST	5.902	5.558	0.00418	0.986
LiAl-LDHs-SP	4.918	4.678	0.00427	0.990
LiAl-LDHs-SPT	8.852	7.883	0.00494	0.992

表2. 吸附剂的准一级动力学拟合模型参数

Table 2. Quasi-first-order kinetic parameters of adsorbents

Sample	Q_e/(mg•g⁻¹)	$Q_{e}^{*}$/(mg•g⁻¹)	k₂/(g•mg⁻¹•min⁻¹)	R²
LiAl-LDHs-ST	5.902	6.887	0.00188	0.994
LiAl-LDHs-SP	4.918	5.848	0.00206	0.995
LiAl-LDHs-SPT	8.852	9.855	0.00203	0.998

表3. 吸附剂的准二级动力学拟合模型参数

Table 3. Quasi-second-order kinetic parameters of adsorbents

Sample	K₁^a	K₂^a	K₃^a	$R_{1}^{2}$	$R_{2}^{2}$	$R_{3}^{2}$
LiAl-LDHs-ST	0.417	0.336	0.064	0.983	0.986	0.393
LiAl-LDHs-SP	0.417	0.250	0.064	0.983	0.922	0.393
LiAl-LDHs-SPT	0.827	0.379	0.064	0.986	0.976	0.393

表4. 吸附剂的颗粒内扩散拟合模型参数

Table 4. Intra-particle diffusion parameters of adsorbents

图7. 吸附剂的(a)等温吸附线, (b) Langmuir等温吸附拟合模型和(c) Freundlich等温吸附拟合模型

Figure 7. (a) Isothermal adsorption line, (b) Langmuir isothermal adsorption fitting model and (c) Freundlich isothermal adsorption fitting model of adsorbents

Sample	Q_m/(mg•g⁻¹)	K_L/min⁻¹	R²
LiAl-LDHs-ST	6.796	0.055	0.716
LiAl-LDHs-SP	5.947	0.045	0.815
LiAl-LDHs-SPT	9.281	0.139	0.850

表5. 吸附剂的Langmuir等温吸附拟合模型参数

Table 5. Langmuir isothermal adsorption fitting model parameters for adsorbents

Sample	K_F/min⁻¹	n	R²
LiAl-LDHs-ST	3.352	13.93	0.914
LiAl-LDHs-SP	2.834	9.14	0.909
LiAl-LDHs-SPT	5.941	8.88	0.937

表6. 吸附剂的Freundlich等温吸附拟合模型参数

Table 6. Freundlich isothermal adsorption fitting model parameters for adsorbents

图8. 溶液初始pH对吸附容量的影响

Figure 8. Effect of the initial pH of the solution on the adsorption capacity

图9. 吸附剂的选择吸附分离系数(a)与选择吸附性对照实验(b)

Figure 9. Select adsorption-separation parameters (a), and select adsorption test (b) of adsorbents

图10. LiAl-LDHs与LiAl-LDHs-SPT循环稳定性对比图

Figure 10. Comparison of the cyclic stability of LiAl-LDHs and LiAl-LDHs-SPT

图11. LiAl-LDHs-SPT吸附-脱附机理

Figure 11. Adsorption-desorption mechanism of LiAl-LDHs-SPT

图12. LiAl-LDHs-SPT在西台吉乃尔与大柴旦盐湖中的吸附曲线

Figure 12. Adsorption curves of LiAl-LDHs-SPT in West Taijiner salt lake and Qaidam salt lake

图13. 不同LiAl-LDHs材料对Li+吸附性能的比较

Figure 13. Comparison of Li+ adsorption properties of different LiAl-LDHs materials

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