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A strategy to avoid solid formation within the reactor during magnesium and calcium electrolytic removal from lithium-rich brines

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Abstract

It is expected that lithium sourcing from aqueous sources in the medium term will account for over half of worldwide production, since reserves in brines are more abundant than in hard rock ores. To produce high purity lithium products, the full abatement of both Mg2+ and Ca2+ cations is fundamental. Current practice involves the use of large volumes of chemicals, NaOH and Na2CO3, leaving behind only residues. We recently proposed to produce brine alkalinization via water reduction using a simple 2 compartment electrolyzer fitted with an anion exchange membrane. Here, we advanced the study of this system by correlating voltage drop, pH, and cation concentrations with the advancement of electrolysis. Results suggest that solids are not formed within the membrane, but only on its surface. We also propose a new strategy to avoid all together solid formation within the electrolyzer, arriving at very similar results regarding Mg2+ abatement and minimal Li+ depletion in the processed brine (average 99.6% Mg2+ depletion). However, Ca2+ concentrations remained at values between 30 and 44% of the original brine content. The voltage drop between electrodes in the new reactor setup was lower than that in the original setup (2 V lower at 200 A m−2). That difference suggests both that the membrane is not degrading at the more alkaline pH and that the electrical consumption for the electrolysis would be lower with the new setup.

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Funding

MLV acknowledges a post-doctoral fellowship from CONICET. CJOP and NAP acknowledge doctoral fellowships from CONICET. CHDN, WRT, and VF are CONICET permanent research fellows. This work was supported by the ERA-MIN2 call, an ERA-NET Cofund scheme under Horizon 2020 (Li + WATER project), and ANPCyT, AR (grant PICT 2019–1939). The natural brine sample was a generous gift from MINERA SANTA RITA (Argentina).

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Author notes

  1. María L. Vera, Camilo J. O. Palacios, and César H. Díaz Nieto contributed equally to this work.

Authors and Affiliations

  1. Centro de Investigación y Desarrollo en Materiales Avanzados y Almacenamiento de Energía de Jujuy-CIDMEJu (CONICET, Universidad Nacional de Jujuy), Av. Martijena S/N, 4612, Palpalá, Argentina

    María L. Vera, Camilo J. O. Palacios, César H. Díaz Nieto, Noelia A. Palacios, Natalia Di Carlantonio, Franco G. Luna, Walter R. Torres & Victoria Flexer

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  1. María L. Vera
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  2. Camilo J. O. Palacios
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Correspondence to Victoria Flexer.

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Personal dedication

Prof. Aurbach has been extremely generous helping with the development of a new public scientific research center in the far northwest of Argentina, located in the vicinity of the richest lithium brine deposits. He insisted that it was of outmost importance that the local people, and particularly the young local talents, could be involved in advancing the frontiers of knowledge in the fields of lithium mining and lithium batteries. Today, several of those young talents are co-authoring this manuscript. I, Victoria Flexer, am personally grateful to Prof. Aurbach, who offered to discuss any of the new topics I was venturing in, when I had just stopped being a post-doctoral fellow and was trying to establish myself as a PI. Prof. Aurbach has already visited our region in three occasions, and in every occasion he gave insightful and clear lectures for our students and young scientists.

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Vera, M.L., Palacios, C.J.O., Díaz Nieto, C.H. et al. A strategy to avoid solid formation within the reactor during magnesium and calcium electrolytic removal from lithium-rich brines. J Solid State Electrochem 26, 1981–1994 (2022). https://doi.org/10.1007/s10008-022-05219-6

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  • DOI: https://doi.org/10.1007/s10008-022-05219-6

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