Phase Chemistry for Hydration Sensitive (De)intercalation of Lithium Aluminum Layered Double Hydroxide Chlorides.

Abstract

Lithium aluminum layered double hydroxide chlorides (LADH-Cl) have been widely used for lithium extraction from brine. Elevation of the performances of LADH-Cl sorbents urgently requires knowledge of the composition-structure-property relationship of LADH-Cl in lithium extraction applications, but these are still unclear. Herein, combining the phase equilibrium experiments, advanced solid characterization methods, and theoretical calculations, we constructed a cyclic work diagram of LADH-Cl for lithium capture from aqueous solution, where the reversible (de)hydration and (de)intercalation induced phase evolution of LADH-Cl dominates the apparent lithium "adsorption-desorption" behavior. It is found that the real active ingredient in LADH-Cl type lithium sorbents is a dihydrated LADH-Cl with an Al:Li molar ratio varying from 2 to 3. This reversible process indicates an ultimate reversible lithium (de)intercalation capacity of ∼10 mg of Li per g of LADH-Cl. Excessive lithium deintercalation results in the phase structure collapse of dihydrated LADH-Cl to form gibbsite. When interacting with a concentrated LiCl aqueous solution, gibbsite is easily converted into lithium saturated intercalated LADH-Cl phases. By further hydration with a diluted LiCl aqueous solution, this phase again converts to the active dihydrated LADH-Cl. In the whole cyclic progress, lithium ions thermodynamically favor staying in the Al-OH octahedral cavities, but the (de)intercalation of lithium has kinetic factors deriving from the variation of the Al-OH hydroxyl orientation. The present results provide fundamental knowledge for the rational design and application of LADH-Cl type lithium sorbents.