Preparation of Interlayer Anion Controllable LiAl-LDHs and Lithium Adsorption Performance

doi:10.6023/A24120367

Abstract

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

Cite this article

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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Fig. & Tab. 19

Figure 1. XRD patterns of adsorbents

Figure 2. FT-IR spectra of adsorbents

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

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

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

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

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

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

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

Table 4. Intra-particle diffusion parameters of adsorbents

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

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

Table 6. Freundlich isothermal adsorption fitting model parameters for adsorbents

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

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

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

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

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

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

References 52

[1]	Ahmed, M. A.; Mohamed, A. A. Inorg. Chem. Commun. 2023, 148, 110325.
[2]	Baudino, L.; Santos, C.; Pirri, C. F.; La Mantia, F.; Lamberti, A. Adv. Sci. 2022, 9, 2201380.
[3]	Chen, F.; Chen, C.; Hu, Q.; Xiang, B.; Song, T.; Zou, X.; Li, W.; Xiong, B.; Deng, M. Chem. Eng. J. 2020, 401, 126145.
[4]	Chen, J.; Lin, S.; Yu, J. J. Hazard. Mater. 2020, 388, 122101.
[5]	Chen, T.; Luo, L.; Wu, X.; Zhou, Y.; Yan, W.; Fan, M.; Zhao, W. J. Alloy. Compd. 2021, 859, 158318.
[6]	Ding, Q.; Li, J.; Li, S.; Wang, J.; Huang, W.; Sun, S.; Xu, Y.; Li, H. J. Energy Storage 2023, 67, 107556.
[7]	Dong, M.; Luo, Q.; Li, J.; Wu, Z.; Liu, Z. J. Saudi Chem. Soc. 2022, 26, 101535.
[8]	Farhan, A.; Khalid, A.; Maqsood, N.; Iftekhar, S.; Sharif, H. M. A.; Qi, F.; Sillanpää, M.; Asif, M. B. Sci. Total Environ. 2024, 912, 169160.
[9]	Feng, X.; Shi, Y.; Shi, J.; Hao, L.; Hu, Z. Int. J. Hydrogen Energy 2021, 46, 5169.
[10]	Gao, H.; Cao, Y.; Chen, Y.; Liu, Z.; Guo, M.; Ding, S.; Tu, J.; Qi, J. Appl. Surf. Sci. 2019, 465, 929.
[11]	Heidari, N.; Momeni, P. Environ. Earth Sci. 2017, 76, 551.
[12]	Hou, C.; Li, T.; Zhang, Z.; Chang, C.; An, L. Mater. Lett. 2022, 309, 131361.
[13]	Lee, Y.; Jung, D.-Y. Appl. Clay Sci. 2022, 228, 106631.
[14]	Zhao, M.; Wang, X.; Liu, Y.; He, Y.; Li, D. Acta Chim. Sinica 2021, 79, 1518 (in Chinese). doi: 10.6023/A21070343
	(赵敏, 王雪, 刘雅楠, 贺宇飞, 李殿卿, 化学学报, 2021, 79, 1518.) doi: 10.6023/A21070343
[15]	Li, M.-H.; Zhao, L.-X.; Xie, M.; Li, N.; Wang, X.-L.; Zhao, R.-S.; Lin, J.-M. Sep. Purif. Technol. 2022, 290, 120898.
[16]	Li, X.; Yu, L.; Wang, G.; Wan, G.; Peng, X.; Wang, K.; Wang, G. Electrochim. Acta 2017, 255, 15.
[17]	Li, Y.; Tang, N.; Zhang, L.; Li, J. Colloid. Surface. A 2023, 658, 130641.
[18]	Li, Y.-H.; Zhao, Z.-W.; Liu, X.-H.; Chen, X.-Y.; Zhong, M.-L. Trans. Nonferrous Met. Soc. China 2015, 25, 3484.
[19]	Liu, Z.; Deng, Z.; He, G.; Wang, H.; Zhang, X.; Lin, J.; Qi, Y.; Liang, X. Nat. Rev. Earth Env. 2021, 3, 141.
[20]	Lv, S.; Zhao, Y.; Zhang, L.; Zhang, T.; Dong, G.; Li, D.; Cheng, S.; Ma, S.; Song, S.; Quintana, M. Chem. Eng. J. 2023, 472, 145026.
[21]	Pan, Y.; Du, J.; Chen, J.; Lian, C.; Lin, S.; Yu, J. Desalination 2022, 539, 115966.
[22]	Shan, X.; Guo, Z.; Qu, Z.; Zou, Y.; Zhao, L.; Chen, P. Mater. Res. Lett. 2022, 10, 593.
[23]	Sun, X.; Ouyang, M.; Hao, H. Joule 2022, 6, 1738.
[24]	Sun, Y.; Guo, X.; Hu, S.; Xiang, X. J. Energy Chem. 2019, 34, 80.
[25]	Tong, H.; Li, L.; Wu, C.; Tao, Z.; Fang, J.; Guan, C.; Zhang, X. ChemSusChem 2024, 17, e202400142.
[26]	Wang, J.; Ding, Q.; Bai, C.; Wang, F.; Sun, S.; Xu, Y.; Li, H. Nanomaterials 2021, 11, 2155.
[27]	Wang, X.; Cheng, Y.; Qiao, X.; Zhang, D.; Xia, Y.; Fan, J.; Huang, C.; Yang, S. J. Energy Storage 2022, 52, 104834.
[28]	Wang, X.; Zhang, D.; Shi, X.; Qiao, X.; Cheng, Y.; Zhao, H.; Chang, L.; Yu, Z.; Huang, C.; Yang, S. Chinese J. Inorg. Chem. 2023, 39, 607 (in Chinese).
	(王晓亮, 张多, 石雪梅, 乔心页, 程焱, 赵浩男, 常雷明, 于振秋, 黄传辉, 杨绍斌, 无机化学学报, 2023, 39, 607.)
[29]	Lv, B.; Kou, M.; Gao, D.; Luo, K. New Chem. Mater. 2023, 51, 46 (in Chiness).
	(吕斌, 寇梦楠, 高党鸽, 雒康, 化工新型材料, 2023, 51, 46.) doi: 10.19817/j.cnki.issn1006-3536.2023.04.008
[30]	Zheng, M.; Mao, F.; Kong, X.; Duan, X. Chem. J. Chin. Univ. 2022, 43, 20220456 (in Chinese).
	(郑美琪, 毛方琪, 孔祥贵, 段雪, 高等学校化学学报, 2022, 43, 20220456.) doi: 10.7503/cjcu20220456
[31]	Wu, X.; Du, N.; Li, H.; Zhang, R.; Hou, W. Acta Chim. Sinica 2014, 72, 963 (in Chinese).
	(兀晓文, 杜娜, 李海平, 张人杰, 侯万国, 化学学报, 2014, 72, 963.) doi: 10.6023/A14030146
[32]	Xiao, T.; Wang, S.; Li, J.; Yang, N.; Li, W.; Xiang, P.; Jiang, L.; Tan, X. J. Alloy. Compd. 2018, 768, 635.
[33]	Xu, P.; Hong, J.; Qian, X.; Xu, Z.; Xia, H.; Tao, X.; Xu, Z.; Ni, Q.-Q. J. Mater. Sci. 2020, 56, 16.
[34]	Yang, G.; Takei, T.; Zhu, Y.; Iranmanesh, E.; Liu, B.; Li, Z.; Wang, J.; Hiralal, P.; Amaratunga, G. A. J.; Fontaine, O.; Zhou, H. Electrochim. Acta 2021, 397, 139242.
[35]	Yang, S.; Zhang, F.; Ding, H.; He, P.; Zhou, H. Joule 2018, 2, 1648.
[36]	Yang, Z.; Lin, Y.; Jiao, F.; Li, J.; Wang, J.; Gong, Y. J. Energy Chem. 2020, 49, 189. doi: 10.1016/j.jechem.2020.02.025
[37]	Yu, H.; Naidu, G.; Zhang, C.; Wang, C.; Razmjou, A.; Han, D. S.; He, T.; Shon, H. Desalination 2022, 539, 115951.
[38]	Zhang, L.; Zhang, T.; Zhao, Y.; Dong, G.; Lv, S.; Ma, S.; Song, S.; Quintana, M. Nano Res. 2023, 17, 1646.
[39]	Zhang, P.; Xiang, M.; Li, P.; Ouyang, S.; He, T.; Deng, Q. Environ. Sci. Pollut. Res. 2019, 26, 19320.
[40]	Li, J.; Li, B.; Wang, J.; He, L.; Zhao, Y. Acta Chim. Sinica 2021, 79, 238 (in Chinese).
	(李佳欣, 李蓓, 王纪康, 何蕾, 赵宇飞, 化学学报, 2021, 79, 238.) doi: 10.6023/A20090441
[41]	Zhou, H.; Li, J.; Xu, L.; Li, C.; Lai, X.; Zhang, P.; Huang, Y. Mater. Lett. 2023, 340, 134159.
[42]	Li, L.; Tang, J.; Wang, L.; Li, J.; Quan, H.; Lin, B.; Wang, H.; Li, J.-Q.; Zhou, T. Acta Chim. Sinica 2024, 82, 748 (in Chinese).
	(李雷, 唐鋆磊, 王丽涛, 李江涛, 全洪林, 林冰, 王宏, 李佳奇, 周太刚, 化学学报, 2024, 82, 748.) doi: 10.6023/A24030077
[43]	Zhu, M.; Cai, W.; Wang, H.; He, L.; Wang, Y. J. Alloy. Compd. 2021, 884, 160931.
[44]	Zubair, M.; Daud, M.; McKay, G.; Shehzad, F.; Al-Harthi, M. A. Appl. Clay Sci. 2017, 143, 279.
[45]	Qi, L.; Xu, T.; Wang, Z.; Peng, X. Int. J. Min. Sci. Technol. 2017, 5, 371.
[46]	Ren, B.; Miao, J.; Wang, S.; Xu, Y.; Zhai, Z.; Dong, X.; Liu, Z. Powder Technol 2021, 32, 1774.
[47]	Ma, C.; Wu, J.; Zhu, L.; Han, X.; Ruan, W.; Song, W.; Wang, X.; Zhao, B. Acta Chim. Sinica 2019, 77, 1024 (in Chinese).
	(马超, 武佳炜, 朱琳, 韩晓霞, 阮伟东, 宋薇, 王旭, 赵冰, 化学学报, 2019, 77, 1024.) doi: 10.6023/A19050191
[48]	Sun, S. Y.; Cai, L. J.; Nie, X. Y. J. Water Process Eng. 2015, 7, 210.
[49]	Yu, J.; Zheng, M.; Wu, Q. Solar Energy 2015, 115, 133.
[50]	Sun, Y.; Guo, X. Y.; Hu, S. F. J. Energy Chem. 2019, 34, 80.
[51]	Zhu, Y.; Zhao, X.; Zhong, Y.; Chen, Z.; Yan, H.; Duan, X. Chem. J. Chin. Univ. 2020, 41, 2287 (in Chinese).
	(朱玉荃, 赵晓婕, 钟嫄, 陈子茹, 鄢红, 段雪, 高等学校化学学报, 2020, 41, 2287.) doi: 10.7503/cjcu20200404
[52]	Zhou, G. L.; Chen, L. L.; Chao, Y. H. J. Energy Chem. 2021, 59, 431.

层间阴离子可调控LiAl-LDHs的制备及锂吸附性能研究