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Abstract:

We report on the surface and bulk chemistry of LixMn2O4 (0 ≤ x ≤ 1) spinel oxide electrode for the selective extraction of LiCl from natural salt lake brines using an electrochemical method based on LiMn2O4 (LMO) lithium intercalation electrode and polypyrrole (PPy) reversible chloride electrode. Both the surface composition and insertion/release of Li ions into/from the crystal structure have been studied with pulsed laser deposited (PLD) thin LixMn2O4 films and composite LMO/carbon black electrodes. Cyclic voltammetry (CV), XPS/UPS, XRD, chrono-amperometry, and galvanostatic intermittent titration technique (GITT) experiments in model LiNO3 solutions and natural brines from Salar de Olaroz (Jujuy, Argentina) have been used. Repetitive CV and GITT experiments showed reversible extraction/intercalation of Li ions in LMO with high selectivity and electrode stability in natural brine, while PPy is reversible to chloride ions. Chronoamperometry for time-bound diffusion in small nanocrystals with interference of concentration profiles yielded DLi + ∼ 10-10 cm2·s-1. Photoelectron spectroscopy showed Mn/O surface stoichiometry close to 1:2 and initial 1:1 MnIV/MnIII ratio with MnIII depletion during oxidation at 1.1 V vs Ag/AgCl and recovery of surface MnIII after reduction at 0.4 V. Coadsorption of Na+ was detected which resulted in slower ion exchange of Li ions, but there was no evidence of Na+ intercalation in the Mn oxide electrode. © 2016 American Chemical Society.

Registro:

Documento: Artículo
Título:Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines
Autor:Marchini, F.; Rubi, D.; Del Pozo, M.; Williams, F.J.; Calvo, E.J.
Filiación:INQUIMAE, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Pabellón 2, Buenos Aires, AR-1428, Argentina
Comisión Nacional de Energía Atómica. Physics. Condensed Matter, Centro Atómico Constituyentes, Gral. Paz 1499 (1650), San Martin, Provincia de Buenos Aires, AR, 1450, Argentina
Palabras clave:Brines; Chlorine compounds; Chronoamperometry; Composite films; Crystal structure; Cyclic voltammetry; Electrodes; Extraction; Intercalation; Ion exchange; Ions; Lakes; Lithium; Lithium alloys; Manganese; Photoelectron spectroscopy; Polypyrroles; Pulsed laser deposition; Surface chemistry; Concentration profiles; ELectrochemical methods; Electrode stability; Galvanostatic Intermittent Titration Techniques; Lithium Intercalation; Lithium ion exchange; Selective extraction; Surface stoichiometry; Electrochemical electrodes
Año:2016
Volumen:120
Número:29
Página de inicio:15875
Página de fin:15883
DOI: http://dx.doi.org/10.1021/acs.jpcc.5b11722
Título revista:Journal of Physical Chemistry C
Título revista abreviado:J. Phys. Chem. C
ISSN:19327447
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_19327447_v120_n29_p15875_Marchini

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Citas:

---------- APA ----------
Marchini, F., Rubi, D., Del Pozo, M., Williams, F.J. & Calvo, E.J. (2016) . Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines. Journal of Physical Chemistry C, 120(29), 15875-15883.
http://dx.doi.org/10.1021/acs.jpcc.5b11722
---------- CHICAGO ----------
Marchini, F., Rubi, D., Del Pozo, M., Williams, F.J., Calvo, E.J. "Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines" . Journal of Physical Chemistry C 120, no. 29 (2016) : 15875-15883.
http://dx.doi.org/10.1021/acs.jpcc.5b11722
---------- MLA ----------
Marchini, F., Rubi, D., Del Pozo, M., Williams, F.J., Calvo, E.J. "Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines" . Journal of Physical Chemistry C, vol. 120, no. 29, 2016, pp. 15875-15883.
http://dx.doi.org/10.1021/acs.jpcc.5b11722
---------- VANCOUVER ----------
Marchini, F., Rubi, D., Del Pozo, M., Williams, F.J., Calvo, E.J. Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines. J. Phys. Chem. C. 2016;120(29):15875-15883.
http://dx.doi.org/10.1021/acs.jpcc.5b11722