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.

Effect of Anions on the Delithiation of [Li–Al] Layered Double Hydroxides: Thermodynamic Insights

“…A higher water content may weaken the interactions, as the anions and water molecules would be more loosely bound in the interlayer space. The recent report by Li et al and Whittaker et al discuss the possibility of phase and morphological changes in the [Li–Al] LDH upon hydration and how it impacts the lithiation and delithiation process . Consequently, the ΔH° f,bc values of Cl-LDH-O, OH-LDH-O, and SO 4 -LDH-O are more exothermic compared to Cl-LDH-A, OH-LDH-A, and SO 4 -LDH-A (Table ).…”