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Lithium isotope fractionation during uptake by gibbsite


The intercalation of lithium from solution into the six-membered μ2-oxo rings on the basal planes of gibbsite is well-constrained chemically. The product is a lithiated layered-double hydroxide solid that forms via in situ phase change. The reaction has well established kinetics and is associated with a distinct swelling of the gibbsite as counter ions enter the interlayer to balance the charge of lithiation. Lithium reacts to fill a fixed and well identifiable crystallographic site and has no solvation waters. Our lithium-isotope data shows that 6Li is favored during this intercalation and that the solid-solution fractionation depends on temperature, electrolyte concentration and counter ion identity (whether Cl-, NO3- or ClO4-). We find that the amount of isotopic fractionation between solid and solution (δLisolid-solution) varies with the amount of lithium taken up into the gibbsite structure, which itself depends upon the extent of conversion and also varies with electrolyte concentration and in the counter ion in the order: ClO4-3--. Higher electrolyte concentrations cause more rapid expansion of the gibbsite interlayer and some counter ions, such as Cl-, are more easily taken up than others, probably because they ease diffusion. The relationship between lithium loading and δLisolid-solution indicates two stages: (1) uptake into the crystallographic sites that favors light lithium, in parallel with adsorption of solvated cations, and (2) continued uptake of solvated cations after all available octahedral vacancies are filled; this second stage has no isotopic preference. The two-step reaction progress is supported by solid-state NMR spectra that clearly resolve a second reservoir of lithium in addition to the expected layered double-hydroxide phase.

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