3350 XXXI International Mineral Processing Congress 2024 Proceedings/Washington, DC/Sep 29–Oct 3
Al2O3 – LDH becomes clearly lower than from Al(OH)3 –
LDH, which is a further indication that the latter is losing
mobile species to the environment. On the positive side, as
the different populations of water leave the material, we can
assess different water populations with different degrees of
confinement, which exposes the complexity of the distribu-
tion of water within this sample. For Al2O3 – LDH, a water
population enters the instrumental resolution at 400K and
persists within the dynamic range until 600K, following an
Arrhenius-like behavior with an activation energy of 9.1
± 0.5 kJ.mol–1. Overall, these features guarantee Al2O3 –
LDH the ability to retain a larger amount of highly mobile
species within its structure at high temperatures, as also
highlighted in Figure 8(c), where the comparison between
the elastic fractions of the QENS signals of Al(OH)3 –
LDH and Al2O3 – LDH at 600K is presented. Finally,
Fe-LDH presents remarkably similar dynamics at 300K
and 400K, but it is not clear if such an effect occurs due to
partial elimination of water from the sample (by comparing
Figures 8a and 8b, this sample does present a slight decay in
the elastic contribution, which does not suggest the elimi-
nation of water from the sample).
CONCLUSION
In summary, QENS measurements were used to study
Al(OH)3 and Al2O3 derived Li-Al LDHs, and iron-doped
LDH (Fe-LDH). Through this work, a structural under-
standing of water transport during lithium extraction pro-
cess has emerged. Understanding water interactions from
the bulk, atomic, and structural perspectives has shown
how water contacts and diffuses through these materials in
a variety of conditions. Understanding this allows for the
determination of effective adsorbent deployment depending
on site conditions. Further studies on crystallization kinet-
ics and their influence on proton mobility and microstrain
XRD studies and their influence on particle distribution
will provide valuable information on the reaction condi-
tions needed to produce Li-Al LDHs at scale, providing
another possible source of lithium for electrification.
ACKNOWLEDGMENT
This work was supported by the Critical Materials
Innovation Hub funded by the U.S. Department of
Energy (DOE), Office of Energy Efficiency and Renewable
Energy (EERE), Advanced Materials and Manufacturing
Technologies Office (AMMTO). Neutron scattering stud-
ies was supported by Technology Commercialization Funds,
U.S. DOE, Office of EERE, Geothermal Technologies
Office (GTO). M.P.P. was supported by Office of Science,
Office of Basic Energy Sciences, Materials Sciences and
Engineering Division. Neutron scattering experiment was
performed at ORNL’s Spallation Neutron Source, sup-
ported by the Scientific User Facilities Division, Office of
Basic Energy Sciences, US DOE. S.F.E. is grateful for a
fellowship from the Bredesen Center for Interdisciplinary
Graduate Education.
This manuscript has been authored in part by
UT-Battelle, LLC, under contract DE-AC05-00OR22725
with the US Department of Energy (DOE). The US gov-
ernment retains and the publisher, by accepting the article
for publication, acknowledges that the US government
retains a nonexclusive, paid-up, irrevocable, worldwide
license to publish or reproduce the published form of this
manuscript, or allow others to do so, for US government
purposes. DOE 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).
REFERENCES
Agusdinata, D. B., Liu, W., Eakin, H., Romero, H. 2018.
Socio-environmental impacts of lithium mineral
extraction: towards a research agenda. Environmental
Research Letters 13(12): 123001.
Anantharaj, S., Karthick, K., Kundu, S. 2017. Evolution of
layered double hydroxides (LDH) as high performance
water oxidation electrocatalysts: A review with insights
on structure, activity and mechanism. Materials Today
Energy 6: 1–26.
Cheng, Y., Balachandran, J., Bi, Z., Bridges, C. A.,
Paranthaman, M. P., Daemen, L. L., Ganesh, P.,
Jalarvo, N. 2017. The influence of the local structure
on proton transport in a solid oxide proton conductor
La0.8Ba1.2GaO3.9. Journal of Materials Chemistry A
5(30): 5507–15511.
Crawford, A., Seefeldt, J. L., Kent, R., Helbert, M.,
Guzmán, G. P., González, A., Chen, Z., Abbott,
A. 2021. Lithium: The big picture. One Earth 4(3):
323–326.
Deberdt, R., Le Billon, P. 2021. Conflict minerals and
battery materials supply chains: A mapping review of
responsible sourcing initiatives. The Extractive Industries
and Society 8(4): 100935.
Graham, T. R., Hu, J. Z., Zhang, X., Dembowski, M.,
Jaegers, N. R., Wan, C., Bowden, M., Lipton, A. S.,
Felmy, A. R., Clark, S. B. 2019. Unraveling gibbsite
transformation pathways into LiAl-LDH in concen-
trated lithium hydroxide. Inorganic chemistry 58(18):
12385–12394.
Al2O3 – LDH becomes clearly lower than from Al(OH)3 –
LDH, which is a further indication that the latter is losing
mobile species to the environment. On the positive side, as
the different populations of water leave the material, we can
assess different water populations with different degrees of
confinement, which exposes the complexity of the distribu-
tion of water within this sample. For Al2O3 – LDH, a water
population enters the instrumental resolution at 400K and
persists within the dynamic range until 600K, following an
Arrhenius-like behavior with an activation energy of 9.1
± 0.5 kJ.mol–1. Overall, these features guarantee Al2O3 –
LDH the ability to retain a larger amount of highly mobile
species within its structure at high temperatures, as also
highlighted in Figure 8(c), where the comparison between
the elastic fractions of the QENS signals of Al(OH)3 –
LDH and Al2O3 – LDH at 600K is presented. Finally,
Fe-LDH presents remarkably similar dynamics at 300K
and 400K, but it is not clear if such an effect occurs due to
partial elimination of water from the sample (by comparing
Figures 8a and 8b, this sample does present a slight decay in
the elastic contribution, which does not suggest the elimi-
nation of water from the sample).
CONCLUSION
In summary, QENS measurements were used to study
Al(OH)3 and Al2O3 derived Li-Al LDHs, and iron-doped
LDH (Fe-LDH). Through this work, a structural under-
standing of water transport during lithium extraction pro-
cess has emerged. Understanding water interactions from
the bulk, atomic, and structural perspectives has shown
how water contacts and diffuses through these materials in
a variety of conditions. Understanding this allows for the
determination of effective adsorbent deployment depending
on site conditions. Further studies on crystallization kinet-
ics and their influence on proton mobility and microstrain
XRD studies and their influence on particle distribution
will provide valuable information on the reaction condi-
tions needed to produce Li-Al LDHs at scale, providing
another possible source of lithium for electrification.
ACKNOWLEDGMENT
This work was supported by the Critical Materials
Innovation Hub funded by the U.S. Department of
Energy (DOE), Office of Energy Efficiency and Renewable
Energy (EERE), Advanced Materials and Manufacturing
Technologies Office (AMMTO). Neutron scattering stud-
ies was supported by Technology Commercialization Funds,
U.S. DOE, Office of EERE, Geothermal Technologies
Office (GTO). M.P.P. was supported by Office of Science,
Office of Basic Energy Sciences, Materials Sciences and
Engineering Division. Neutron scattering experiment was
performed at ORNL’s Spallation Neutron Source, sup-
ported by the Scientific User Facilities Division, Office of
Basic Energy Sciences, US DOE. S.F.E. is grateful for a
fellowship from the Bredesen Center for Interdisciplinary
Graduate Education.
This manuscript has been authored in part by
UT-Battelle, LLC, under contract DE-AC05-00OR22725
with the US Department of Energy (DOE). The US gov-
ernment retains and the publisher, by accepting the article
for publication, acknowledges that the US government
retains a nonexclusive, paid-up, irrevocable, worldwide
license to publish or reproduce the published form of this
manuscript, or allow others to do so, for US government
purposes. DOE 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).
REFERENCES
Agusdinata, D. B., Liu, W., Eakin, H., Romero, H. 2018.
Socio-environmental impacts of lithium mineral
extraction: towards a research agenda. Environmental
Research Letters 13(12): 123001.
Anantharaj, S., Karthick, K., Kundu, S. 2017. Evolution of
layered double hydroxides (LDH) as high performance
water oxidation electrocatalysts: A review with insights
on structure, activity and mechanism. Materials Today
Energy 6: 1–26.
Cheng, Y., Balachandran, J., Bi, Z., Bridges, C. A.,
Paranthaman, M. P., Daemen, L. L., Ganesh, P.,
Jalarvo, N. 2017. The influence of the local structure
on proton transport in a solid oxide proton conductor
La0.8Ba1.2GaO3.9. Journal of Materials Chemistry A
5(30): 5507–15511.
Crawford, A., Seefeldt, J. L., Kent, R., Helbert, M.,
Guzmán, G. P., González, A., Chen, Z., Abbott,
A. 2021. Lithium: The big picture. One Earth 4(3):
323–326.
Deberdt, R., Le Billon, P. 2021. Conflict minerals and
battery materials supply chains: A mapping review of
responsible sourcing initiatives. The Extractive Industries
and Society 8(4): 100935.
Graham, T. R., Hu, J. Z., Zhang, X., Dembowski, M.,
Jaegers, N. R., Wan, C., Bowden, M., Lipton, A. S.,
Felmy, A. R., Clark, S. B. 2019. Unraveling gibbsite
transformation pathways into LiAl-LDH in concen-
trated lithium hydroxide. Inorganic chemistry 58(18):
12385–12394.