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Rationalize the High Performance of Lithium Sorbents Derived from Gibbsite Guided by Phase Chemistry

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Abstract

Lithium aluminum layered double hydroxide chlorides (LADH-Cl) are the only industrial-level lithium sorbents. However, as an applied material, the composition-structure-property-performance relation is far from well constrained, leaving the manufacture and application of LADH-Cl lithium sorbents empirical rather than rational. Herein, we studied the phase evolution of gibbsite phase Al(OH)3 in concentrated LiOH aqueous solution, suggesting the formation of lithiated lithium aluminum layered double hydroxide (LADH-OH) with Al:Li molar ratio 2. However, LADH-OH is not an active ingredient as a lithium sorbent. The neutralization of LADH-OH with a dilute HCl aqueous solution resulted in the formation of the active LADH-Cl phase. Unlike the traditional LADH-Cl phase (g-LADH-Cl) generated from direct LiCl intercalation of gibbsite, LADH-OH derived LADH-Cl (b-LADH-Cl) has a topological parent of bayerite instead of gibbsite. This is one of the most important roots for different performances. Another source for the different performance is very likely from variations of the particle size and morphology when the raw gibbsite reacted with LiCl or LiOH aqueous solution. Nevertheless, we found that the limiting-delithiation of b-LADH-Cl is still the same as g-LADH-Cl, that is only maximum 1/3 lithium can be delithiated from the LADH-Cl phase without any decomposition into gibbsite or bayerite. This concluded that b-LADH-Cl and g-LADH-Cl have the same reversible lithium “sorption–desorption” capacity, even through different lithium affinity and sorption kinetics. Also, notably, the “sorption–desorption” performance of the optimal sorbent is very sensitive to the properties of service brines. These results substantially enlarged our knowledge of the LADH-Cl phase and provided a demo of the rational manufacture of lithium sorbent.

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Acknowledgements

D.L. thanks the West Light Foundation of Chinese Academy of Sciences (No. 292022000019), Young Scientist Project of National Key Research and Development Program (No. 2022YFC2906200), and 2023 Kunlun Talents Plan of Qinghai Province for financial support. D.G thanks the Basic Research Project in Qinghai Province (No. 2021-ZJ-747). L.H thanks the 2021 Kunlun Talents Plan of Qinghai Province. We are grateful to Li-Zhi Hong from Shanghai Jiaotong University for ssNMR characterization, and Xiuping Ding from Qinghai Institute of Salt Lakes, CAS for SEM and TEM characterizations.

Funding

This work was financially supported by the West Light Foundation of the Chinese Academy of Sciences (No. 292022000019), Young Scientist Project of the National Key Research and Development Program (No. 2022YFC2906200), 2023 Kunlun Talents Plan of Qinghai Province grant to D. Li, the Basic Research Project in Qinghai Province (No. 2021-ZJ-747) Grant to D. Gao, and 2021 Kunlun Talents Plan of Qinghai Province grant to L. Han.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, People’s Republic of China

    Conglin You, Yanfei Fan & Dewen Zeng

  2. Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining, 810008, People’s Republic of China

    Dongdong Li, Dandan Gao, Li Han & Dewen Zeng

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  1. Conglin You
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  2. Dongdong Li
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Correspondence to Dongdong Li or Dewen Zeng.

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You, C., Li, D., Fan, Y. et al. Rationalize the High Performance of Lithium Sorbents Derived from Gibbsite Guided by Phase Chemistry. J. Sustain. Metall. (2024). https://doi.org/10.1007/s40831-024-00839-w

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