Enhancing Cyclic Performance of Lithium–Aluminum Layered Double Hydroxides Type Adsorbents via Vanadium Anions Intercalation for Li⁺ Extraction from Sulfate-Type Brines

Abstract

Owing to its excellent eco-friendliness and facile water elution properties, aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li⁺ from Salt Lake brines, which account for more than 60% of the global lithium resources. However, structural collapse, facile deactivation during desorption process, and ultra-low actual adsorption capacity limit its further large-scale application, particularly in low-grade sulfate-type brines. Herein, considering its advantages, limitations, and structural features, the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO₃⁻ and V₂O₇⁴⁻ into the interlayer of [LiAl₂(OH)₆]⁺. Evidently, the initial adsorption capacity and {\text{α}}_{\text{Mg}}^{\text{Li}} of as-configured adsorbents powder are 14.96 mg g⁻¹ and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L⁻¹ Li⁺ and 9.56 g L⁻¹ SO₄²⁻. Furthermore, the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g⁻¹, respectively, which are almost 10 times higher than those of industrially utilized products. Based on experiments and density functional theory calculations, the process and mechanism of anion intercalation control were preliminarily elucidated. Furthermore, research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents. This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents, thereby enabling the high-efficiency and stable extraction of Li⁺ from low-grade brines, including sulfate-type brines.

Keywords

adsorption capacity / formation mechanism / lithium–aluminum layered double hydroxide / Salt Lake brines / structure stability

References

[1] S. Yang, Y. Wang, H. Pan, P. He, H. Zhou, Nature 2024, 636, 309.

[2] S. Zhang, X. Wei, X. Cao, M. Peng, M. Wang, L. Jiang, J. Jin, Nat. Commun. 2024, 15, 238.

[3] B. Li, L. Jiang, N. Xiao, S. Liu, Y. Lu, H. Zhang, Z. Zhang, F. Liu, Adv. Funct. Mater. 2025, 35, 2425353.

[4] R. Zhang, S. Liu, C. Lian, J. Yu, S. Lin, Angew. Chem. Int. Ed. 2025, 64, e202503644.

[5] T. Wulandari, D. Fawcett, S. B. Majumder, G. E. J. Poinern, Battery Energy 2023, 2, 20230030.

[6] D. Yang, Y. Yang, T. Wong, S. Iguodala, A. Wang, L. Lovell, F. Foglia, P. Fouquet, C. Breakwell, Z. Fan, Y. Wang, M. M. Britton, D. R. Williams, N. Shah, T. Xu, N. B. McKeown, M.-M. Titirici, K. E. Jelfs, Q. Song, Nat. Water 2025, 3, 319.

[7] C. Grosjean, P. H. Miranda, M. Perrin, P. Poggi, Renew. Sustain. Energy Rev. 2012, 16, 1735.

[8] Y. Guo, Y. Ying, Y. Mao, X. Peng, B. Chen, Angew. Chem. Int. Ed. 2016, 128, 15344.

[9] A. Razmjou, M. Asadnia, E. Hosseini, A. Habibnejad Korayem, V. Chen, Nat. Commun. 2019, 10, 5793.

[10] J. C. Kelly, M. Wang, Q. Dai, O. Winjobi, Resour. Conserv. Recycl. 2021, 174, 105762.

[11] B. K. Biswal, B. Zhang, P. Thi Minh Tran, J. Zhang, R. Balasubramanian, Chem. Soc. Rev. 2024, 53, 5552.

[12] J.-L. Yang, X.-X. Zhao, M.-Y. Ma, Y. Liu, J.-P. Zhang, X.-L. Wu, Carbon Neutraliz. 2022, 1, 247.

[13] Q. Sun, H. Chen, J. Yu, Ind. Eng. Chem. Res. 2022, 61, 4672.

[14] J. Cadotte, R. Forester, M. Kim, R. Petersen, T. Stocker, Desalination 1988, 70, 77.

[15] L. Kong, G. Yan, K. Hu, Y. Yu, N. Conte, K. R. McKenzie Jr., M. J. Wagner, S. G. Boyes, H. Chen, C. Liu, X. Liu, Nat. Commun. 2025, 16, 806.

[16] X. Lai, P. Xiong, H. Zhong, Hydrometallurgy 2020, 192, 105252.

[17] H. Li, J. Pan, Y. Ping, J. Su, M. Fang, T. Chen, B. Pan, Z. Lu, Nano Lett. 2023, 23, 10458.

[18] X. Wu, H. Zhang, X. Zhang, Q. Guan, X. Tang, H. Wu, M. Feng, H. Wang, R. Ou, Proc. Natl. Acad. Sci. USA 2024, 121, e2309852121.

[19] Q. Xia, Z. Deng, S. Sun, W. Zhao, J. Ding, B. Xi, G. Gao, C. Wang, Proc. Natl. Acad. Sci. USA 2024, 121, e2400159121.

[20] J. Zhong, S. Lin, J. Yu, Desalination 2021, 505, 114983.

[21] T.-Y. Huang, J. R. Pérez-Cardona, F. Zhao, J. W. Sutherland, M. P. Paranthaman, ACS Sustain. Chem. Eng. 2021, 9, 6551.

[22] L. Zhang, T. Zhang, Y. Zhao, G. Dong, S. Lv, S. Ma, S. Song, M. Quintana, Nano Res. 2024, 17, 1646.

[23] M. P. Paranthaman, L. Li, J. Luo, T. Hoke, H. Ucar, B. A. Moyer, S. Harrison, Environ. Sci. Technol. 2017, 51, 13481.

[24] H. Lin, X. Yu, M. Li, J. Duo, Y. Guo, T. Deng, ACS Appl. Mater. Interfaces 2019, 11, 26364.

[25] R. Chitrakar, H. Kanoh, Y. Miyai, K. Ooi, Ind. Eng. Chem. Res. 2001, 40, 2054.

[26] X. Jiang, L. Zhang, Y. Miao, L. Chen, J. Liu, T. Zhang, S. Cheng, Y. Song, Y. Zhao, Water Res. 2025, 276, 123291.

[27] Y. Gao, J. Wu, Z. Zhang, R. Jin, X. Zhang, X. Yan, A. Umar, Z. Guo, Q. Wang, J. Mater. Chem. A 2013, 1, 9928.

[28] S. Lin, Y. Pan, J. Du, Y. Yang, H. Su, J. Yu, J. Colloid Interface Sci. 2022, 627, 872.

[29] J. P. Thiel, C. K. Chiang, K. R. Poeppelmeier, Chem. Mater. 1993, 5, 297.

[30] S. Kozlova, S. Gabuda, V. Isupov, L. Chupakhina, J. Struct. Chem. 2003, 44, 198.

[31] A. M. Fogg, A. J. Freij, G. M. Parkinson, Chem. Mater. 2002, 14, 232.

[32] H. Yu, G. Naidu, C. Zhang, C. Wang, A. Razmjou, D. S. Han, T. He, H. Shon, Desalination 2022, 539, 115951.

[33] Y. Zhang, J. Liu, Y. Yang, S. Lin, P. Li, Sep. Purif. Technol. 2021, 267, 118613.

[34] L.-R. Bao, J.-Z. Zhang, W.-P. Tang, S.-Y. Sun, Desalination 2023, 546, 116196.

[35] J. Zhong, S. Lin, J. Yu, J. Colloid Interface Sci. 2020, 572, 107.

[36] B. N. S. Al-dhawi, S. R. M. Kutty, L. Baloo, A. M. Alawag, N. M. Y. Almahbashi, G. M. A. Naji, Y. A. A. Alsaeedi, F. A. H. Al-Towayti, A. H. Jagaba, Case Stud. Chem. Environ. Eng. 2023, 7, 100350.

[37] J. Chen, K. Huang, J. Du, C. Lian, J. Yu, S. Lin, AICHE J. 2023, 69, e18176.

[38] L. Zhang, T. Zhang, S. Lv, S. Cheng, G. Dong, M. Quintana, S. Song, Y. Zhao, Desalination 2024, 592, 118130.

[39] L. Zhang, T. Zhang, S. Lv, S. Song, O. Galvan, M. Quintana, Y. Zhao, Desalination 2024, 579, 117480.

[40] J. Chen, J. Du, J. Yu, S. Lin, Desalination 2023, 554, 116491.

[41] H. Zhou, J. Li, L. Xu, C. Li, X. Lai, P. Zhang, Y. Huang, Mater. Lett. 2023, 340, 134159.

[42] S. Lv, Y. Zhao, L. Zhang, T. Zhang, G. Dong, D. Li, S. Cheng, S. Ma, S. Song, M. Quintana, Chem. Eng. J. 2023, 472, 145026.

[43] J. Chen, H. Yuan, J. Yu, M. Yan, Y. Yang, S. Lin, J. Colloid Interface Sci. 2023, 649, 694.

[44] A. A. El-sayed, Sci. Rep. 2024, 14, 13017.

[45] S. Bansal, A. Singh, D. Poddar, P. Jain, Ceram. Int. 2023, 49, 8871.

[46] N. M. Amer, P. Lahijani, M. Mohammadi, A. R. Mohamed, S. I. Anthonysamy, Int. J. Environ. Res. 2024, 18, 43.

[47] Z. Wang, Y. Song, J. Wang, Y. Lin, J. Meng, W. Cui, X.-X. Liu, Angew. Chem. Int. Ed. 2023, 62, e202216290.

[48] T. Lv, Y. Peng, G. Zhang, S. Jiang, Z. Yang, S. Yang, H. Pang, Adv. Sci. 2023, 10, 2206907.

[49] Y. Dai, C. Zhang, J. Li, X. Gao, P. Hu, C. Ye, H. He, J. Zhu, W. Zhang, R. Chen, W. Zong, F. Guo, I. P. Parkin, D. J. L. Brett, P. R. Shearing, L. Mai, G. He, Adv. Mater. 2024, 36, 2310645.

[50] T. Wang, Z. Cheng, B. Wang, W. Ma, Chem. Eng. J. 2012, 181–182, 182.

[51] J. Twu, P. K. Dutta, J. Phys. Chem. 1989, 93, 7863.

[52] S. J. Palmer, R. L. Frost, J. Raman Spectrosc. 2011, 42, 224.

[53] C. L. Peacock, D. M. Sherman, Geochim. Cosmochim. Acta 2004, 68, 1723.

[54] K. Prathap, C. Namasivayam, Environ. Chem. Lett. 2010, 8, 363.

[55] P. J. A. Ribeiro-Claro, A. M. Amado, J. J. C. Teixeira-Dias, J. Comput. Chem. 1996, 17, 1183.

[56] Y. Wu, L. Wu, M. L. Zheludkevich, Y. Chen, M. Serdechnova, W. Yao, C. Blawert, A. Atrens, F. Pan, J. Mater. Sci. Technol. 2021, 91, 28.

[57] G. Kresse, J. Furthmuller, Comput. Mater. Sci. 1996, 6, 15.

[58] L. Hou, B. Xing, W. Kang, H. Zeng, H. Guo, S. Cheng, G. Huang, Y. Cao, Z. Chen, C. Zhang, Appl. Clay Sci. 2022, 218, 106418.

[59] X. Pu, X. Du, P. Jing, Y. Wei, G. Wang, C. Xian, K. Wu, H. Wu, Q. Wang, X. Ji, Y. Zhang, Chem. Eng. J. 2021, 425, 130550.

[60] G. R. Williams, D. O'Hare, J. Mater. Chem. 2006, 16, 3065.

[61] G. Silversmit, D. Depla, H. Poelman, G. B. Marin, R. De Gryse, J. Electron Spectrosc. Relat. Phenom. 2004, 135, 167.

[62] M. C. Biesinger, L. W. M. Lau, A. R. Gerson, R. S. C. Smart, Appl. Surf. Sci. 2010, 257, 887.

[63] F. Wang, P. Zou, Y. Zhang, W. Pan, Y. Li, L. Liang, C. Chen, H. Liu, S. Zheng, Nat. Commun. 2023, 14, 6019.

[64] V. P. Isupov, S. P. Gabuda, S. G. Kozlova, L. Chupakhina, J. Struct. Chem. 1998, 39, 362.

[65] M. Du, Z. Miao, H. Li, F. Zhang, Y. Sang, L. Wei, H. Liu, S. Wang, Nano Energy 2021, 89, 106477.

[66] Y. T. Liu, M. K. Wang, T. Y. Chen, P. N. Chiang, P. M. Huang, J. F. Lee, Environ. Sci. Technol. 2006, 40, 7784.

[67] H. Song, X. Ou, M. Wang, Y. Zhang, Z. Lin, Environ. Sci. Nano 2022, 9, 3407.

[68] L.-J. Zhou, Z. F. Hou, L.-M. Wu, J. Phys. Chem. C 2012, 116, 21780.

[69] K. N. Houk, Acc. Chem. Res. 1975, 8, 361.

[70] P. K. Chattaraj, Chem. A Eur. J. 2001, 105, 511.

[71] J. Chen, Y. Chen, Colloids Surf. A 2010, 363, 56.

[72] M. H. Rahman, J. Yang, Y. Sun, A. Mannodi-Kanakkithodi, Surf. Interfaces 2023, 39, 102960.

[73] B. Sanyal, O. Eriksson, U. Jansson, H. Grennberg, Phys. Rev. B 2009, 79, 113409.

[74] J. Huo, C. Hai, Y. Sun, S. Dong, L. Ma, X. He, Q. Xu, Y. Zhou, Desalination 2025, 609, 118897.

[75] Z. Fang, H. Suhua, L. Xu, F. Jian, L. Qi, W. Zhiwei, L. Chuanchang, X. Yuanlai, Colloids Surf. A 2021, 627, 127063.

[76] T. Ma, Z. Jin, Z. Jia, W. Peng, Desalination 2025, 594, 118300.

[77] Y. Li, C. Hai, J. Huo, W. Pan, T. Chen, X. Li, X. He, Y. Sun, S. Dong, L. Ma, Q. Xu, Y. Zhou, Chem. Eng. J. 2024, 494, 152919.

[78] A. S. Özcan, A. Özcan, J. Colloid Interface Sci. 2004, 276, 39.

[79] G. Zhang, C. Hai, Y. Zhou, W. Tang, J. Zhang, J. Zeng, Y. Liu, S. Dong, G. Peng, Chem. Eng. J. 2022, 450, 137912.

[80] M. Abbasi, M. M. Sabzehmeidani, M. Ghaedi, R. Jannesar, A. Shokrollahi, Mater. Sci. Eng. B Adv. Funct. Solid State Mater. 2021, 267, 115086.

[81] M. Abbasi, M. M. Sabzehmeidani, M. Ghaedi, R. Jannesar, A. Shokrollahi, Appl. Clay Sci. 2021, 203, 105946.

[82] J.-P. Simonin, Chem. Eng. J. 2016, 300, 254.

[83] G. Kresse, J. Furthmuller, Phys. Rev. B 1996, 54, 11169.

[84] P. E. Blöchl, C. J. Först, J. Schimpl, Bull. Mater. Sci. 2003, 26, 33.

[85] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1997, 78, 1396.

[86] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104.

RIGHTS & PERMISSIONS

2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.