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1.
Dalton Trans ; 43(40): 15013-21, 2014 Oct 28.
Article in English | MEDLINE | ID: mdl-25043460

ABSTRACT

Herein, cobalt orthosilicate (Co2SiO4, CSO) is presented as a new electrode material for rechargeable lithium-ion batteries. Orthorhombic α-Co2SiO4 (space group: Pbnm) was synthesized by a conventional solid-state method and subsequently characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). To study the reversible lithium uptake and release, cyclic voltammetry (CV), in situ XRD, as well as ex situ X-ray photoelectron spectroscopy (XPS) and SEM analysis were performed. Based on these results a new reaction mechanism is proposed including the reversible formation of lithium silicate. In addition, the electrochemical performance of CSO-based electrodes was investigated by galvanostatic cycling, applying varying specific currents. Such electrodes revealed a good high rate capability and a highly reversible cycling behavior, providing a specific capacity exceeding 650 mAh g(-1) after 60 cycles.

2.
Chemphyschem ; 15(10): 2177-85, 2014 Jul 21.
Article in English | MEDLINE | ID: mdl-24723308

ABSTRACT

The electrochemical performance of nano- and micron-sized Co(3)O(4) is investigated, highlighting the substantial influence of the specific surface area on the obtainable specific capacities as well as the cycling stability. In fact, Co(3)O(4) materials with a high surface area (i.e. a small particle size) show superior specific features, which are, however, accompanied by a rapid capacity fading, owing to the increased formation of an insulating polymeric surface film that results from transition-metal-catalyzed electrolyte decomposition. The simultaneous coating with carbon of Co(3)O(4) nanoparticles and in situ reduction of the Co(3)O(4) by a carbothermal route yields a CoO-Co-C nanocomposite. The formation of this material substantially enhances the long-term cycling stability and coulombic efficiency of the lithium-ion active material used. Although the metallic cobalt enhances the electronic conductivity within the electrode and remains electrochemically inactive (as revealed by in situ powder X-ray diffraction analysis), it might have a detrimental effect on the long-term cycling stability by catalytically inducing continuous electrolyte decomposition.

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