Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines

被引：100

作者：

Marchini, Florencia ^{[1
]}

Rubi, Diego ^{[1
,2
]}

del Pozo, Maria ^{[1
]}

Williams, Federcio J. ^{[1
]}

Calvo, Ernesto J. ^{[1
]}

机构：

[1] Fac Ciencias Exactas & Nat Buenos Aires, INQUIMAE, Pabellon 2,Ciudad Univ, AR-1428 Buenos Aires, DF, Argentina

[2] Comis Nacl Energia Atom Phys Condensed Matter, Ctr Atom Constituyentes, Gral Paz 1499 1658, AR-1450 San Martin, Buenos Aires, Argentina

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2016年 / 120卷 / 29期

关键词：

MANGANESE IONS; VALENCE STATE; RECOVERY; CATHODES; MN; SPECTROSCOPY; ELECTRODES; BATTERIES; SPINEL; CELLS;

D O I：

10.1021/acs.jpcc.5b117222

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 D-Li(+) similar to 10(-10) cm(2).s(-1) Photoelectron spectroscopy showed Mn/O surface stoichiometry close to 1:2 and initial 1:1 Mn-IV/Mn-III ratio with Mn-III depletion during oxidation at 1.1 V vs Ag/AgCl and recovery of surface Mn-III 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.

引用

页码：15875 / 15883

页数：9

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