RESUMO
Novel self-organized Ti1/2Sn1/2O2 nanotubes can be produced by the electrochemical anodization of co-sputtered Ti-Sn thin-films. Combined X-ray photoelectron spectroscopy and (119)Sn Mössbauer spectroscopy of pristine samples evidenced the octahedral substitution of Sn(4+) for Ti(4+) in the TiO2 structure. In addition to the improved lithium storage behaviour of the Ti1/2Sn1/2O2 nanotubes, ex situ(119)Sn Mössbauer spectroscopy of cycled electrodes has sufficiently confirmed that no decomposition of the Ti1/2Sn1/2O2 structure occurred, and that no Li-Sn phase was formed during the discharge, corroborating that the electrochemical reaction is due exclusively to Li(+) insertion into the Ti1/2Sn1/2O2 nanotubes in the 1 ≤ U/V ≤ 2.6 voltage range.
RESUMO
Li-ion batteries have empowered consumer electronics and are now seen as the best choice to propel forward the development of eco-friendly (hybrid) electric vehicles. To enhance the energy density, an intensive search has been made for new polyanionic compounds that have a higher potential for the Fe²âº/Fe³âº redox couple. Herein we push this potential to 3.90 V in a new polyanionic material that crystallizes in the triplite structure by substituting as little as 5 atomic per cent of Mn for Fe in Li(Fe(1-δ)Mn(δ))SO4F. Not only is this the highest voltage reported so far for the Fe²âº/Fe³âº redox couple, exceeding that of LiFePO4 by 450 mV, but this new triplite phase is capable of reversibly releasing and reinserting 0.7-0.8 Li ions with a volume change of 0.6% (compared with 7 and 10% for LiFePO4 and LiFeSO4F respectively), to give a capacity of ~125 mA h g⻹.