Abstract
Lithium-aluminum layered double hydroxides (LDHs) selectively sorb lithium from brines, concentrating and purifying this critical element for subsequent conversion to active battery components. Lithium ion partitioning into lattice vacancies within the LDH structure is selectively enhanced with iron doping. However, this process leads to a highly coupled set of intercalation interactions whose mechanisms are challenging to assess in situ. Here, we show that iron modulates the size- and shape-dependent composition of LDHs and imposes a powerful control on lithium sorption processes in complex fluids. We observe fundamental units of LDH layers and aluminum ferrihydrite nanoclusters that (dis)assemble to form at least five distinct particle types that influence LDH lithium capacity and cyclability. Importantly, lithium sorption is controlled by feedbacks arising from the dynamic interconversion of planar stacks and scrolls of LDH layers, which exchange lithium, water, and other species in the process of (un)rolling due to similar energy scales of hydration, sorption, and deformation. Under appropriate iron redox conditions, the cycling efficiency and stability of lithium sorption can be optimized for the range of lithium concentrations found in many natural brines.
| Original language | English |
|---|---|
| Pages (from-to) | 3931-3940 |
| Number of pages | 10 |
| Journal | Chemistry of Materials |
| Volume | 35 |
| Issue number | 10 |
| DOIs | |
| State | Published - May 23 2023 |
Funding
We thank Dan Toso for technical assistance with the FEI Titan Krios. We also thank Stephen Harrison for assistance with ICP analysis. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, through its Geoscience program at LBNL under Contract DE-AC02-05CH11231. Synthesis of LDH and Fe-doped LDH sorbents was supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Office of Geothermal Technologies Office through a Technology Commercialization Fund. Bench-scale column extraction research was supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Materials and Manufacturing Technologies Office. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).
| Funders | Funder number |
|---|---|
| Critical Materials Institute | |
| Office of Geothermal Technologies Office | |
| U.S. Department of Energy | |
| Office of Science | |
| Office of Energy Efficiency and Renewable Energy | |
| Basic Energy Sciences | |
| Lawrence Berkeley National Laboratory | DE-AC02-05CH11231 |
| Chemical Sciences, Geosciences, and Biosciences Division | |
| Advanced Materials and Manufacturing Technologies Office | DE-AC05-00OR22725 |
