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1.
Phys Chem Chem Phys ; 17(5): 3749-60, 2015 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-25557948

RESUMEN

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O(2-) ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O(2-) (plateau) while Fe seems to retain its 3+ state.


Asunto(s)
Hierro/química , Litio/química , Manganeso/química , Oxígeno/química , Compuestos de Rutenio/química , Técnicas Electroquímicas , Iones/química , Magnetismo , Oxidación-Reducción , Óxidos/química , Espectroscopía de Fotoelectrones
2.
Dalton Trans ; 43(37): 14099-108, 2014 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-25124048

RESUMEN

Aliovalent substitution of Nb(5+) by Ti(4+) in Sr2LuNbO6 is limited to 10% of Nb atoms. A full structural determination by NPD confirms this and reveals that the structure is better described as a superstructure of the simple cubic perovskite (as previously reported) with the monoclinic cell 2(1/2)ap× 2(1/2)ap× 2ap and ß≈ 90° (S.G. P21/n). The substituted materials present both oxygen-vacancies induced by charge compensation and Sr-deficiency. Therefore, their formula should be given as Sr2-yLuNb1-xTixO6-δ. Electrical properties can be fully understood considering these compositional defects. The parent compound Sr2LuNbO6 presents low electrical conductivity in air, which improves by more than one order of magnitude upon Ti substitution. In any case, the title oxides show low electrical conductivity in a wide oxygen partial pressure (pO2) range (10(-25) atm ≤pO2≤ 10(-1) atm). At high pO2 the conductivity increases with pO2 due to oxygen-vacancy annihilation and hole creation, according to a general p-type semiconducting mechanism; A-site substoichiometry and Ti-substitution are the origin of this behaviour. In the low pO2 region, the conductivity increases as the oxygen partial pressure decreases. Reduction of cations, Nb(5+) or Ti(4+), supports n-type conduction by electrons and oxygen vacancy creation. For the intermediate pO2 range a low ionic conduction contribution is observed. Although the estimated ionic conductivity is not high in the substituted compounds, the strategy seems to be valid since a significant enhancement of ionic conduction is observed upon aliovalent substitution.

3.
Phys Chem Chem Phys ; 14(8): 2892-9, 2012 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-22258437

RESUMEN

A detailed structural and electrochemical study of the ion exchanged Li(2)Ti(6)O(13) titanate as a new anode for Li-ion batteries is presented. Subtle structural differences between the parent Na(2)Ti(6)O(13), where Na is in an eightfold coordinated site, and the Li-derivative, where Li is fourfold coordinated, determine important differences in the electrochemical behaviour. While the Li insertion in Na(2)Ti(6)O(13) proceeds reversibly the reaction of lithium with Li(2)Ti(6)O(13) is accompanied by an irreversible phase transformation after the first discharge. Interestingly, this new phase undergoes reversible Li insertion reaction developing a capacity of 170 mAh g(-1) at an average voltage of 1.7 V vs. Li(+)/Li. Compared with other titanates this result is promising to develop a new anode material for lithium ion rechargeable batteries. Neutron powder diffraction revealed that Na in Na(2)Ti(6)O(13) and Li in Li(2)Ti(6)O(13) obtained by Na/Li ion exchange at 325 °C occupy different tunnel sites within the basically same (Ti(6)O(13))(2-) framework. On the other hand, electrochemical performance of Li(2)Ti(6)O(13) itself and the phase released after the first full discharge is strongly affected by the synthesis temperature. For example, heating Li(2)Ti(6)O(13) at 350 °C produces a drastic decrease of the reversible capacity of the phase obtained after full discharge, from 170 mAh g(-1) to ca. 90 mAh g(-1). This latter value has been reported for Li(2)Ti(6)O(13) prepared by ion exchange at higher temperature.

4.
J Infect ; 35(2): 192-4, 1997 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-9354359

RESUMEN

We report the case of a patient with Brucella melitensis osteomyelitis involving non-joint prosthetic implant of the femur. This is the first case published of osteomyelitis by Brucella sp. in a patient with prosthetic implant in bone and the second one with both intra- or extra-articular prosthetic bone implant. Brucella melitensis is a rare organism which causes osteomyelitis in patients with prosthetic hardware, and should be added to the list of suspected organisms responsible for this disease, especially in endemic areas of brucellosis.


Asunto(s)
Brucella melitensis , Brucelosis/microbiología , Fijadores Internos/efectos adversos , Osteomielitis/microbiología , Infecciones Relacionadas con Prótesis/microbiología , Brucelosis/diagnóstico , Humanos , Imagen por Resonancia Magnética , Masculino , Persona de Mediana Edad , Osteomielitis/diagnóstico , Infecciones Relacionadas con Prótesis/diagnóstico
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