Résumé
Owing to their high energy density, lithium rechargeable batteries are now considered the technology of choice for electrical energy storage in isolated sites, portable electronic devices and zero emission vehicles. However, in such systems there are often limitations in the energy density of the electrode materials, most commonly caused by weak capacities and limited electrode cycling life. Hence, research is currently underway to find new electrode materials capable of higher performance.
Conversion type materials have recently been considered as a plausible alternative to conventional electrode materials, owing to their strong gravimetric and volumetric energy densities. The ternary alloy TiSnSb was recently proposed as being a suitable negative electrode material in Li-ion batteries owing to its high electrochemical performance. TiSnSb has been shown to reversibly take up more than five lithium per formula unit, leading to reversible capacities of 540 mA h/g or 4070 mA h/cm
3
at a rate of 2C.
Using complementary
in situ
operando X-ray diffraction (XRD) and
in situ
operando
119
Sn Mössbauer spectroscopy, it was determined that during the first discharge, TiSnSb undergoes a conversion process leading to the simultaneous formation of Li-Sb and Li-Sn intermetallic compounds and, as a result, the corresponding electrochemical equation was proposed for Li insertion:
TiSnSb + 6.5Li --> Ti + Li
3
Sb + 0.5Li
7
Sn
2
Some ambiguities however remain: A shifted, group of resonances appears on
7
Li NMR spectra at approx. 20 ppm in addition to a contribution of Li
3
Sb at 3.5 ppm and a resonance at 8.5 ppm, tentatively assigned to Li
7
Sn
2
. The alloy Li
7
Sn
3
has previously been reported at 18 ppm, hence its presence cannot be ruled out. However, this phase has not been detected via
119
Sn Mössbauer spectroscopy in this or any previous studies. Distinct differences in chemical shift have been observed for Li
3
Sb produced at the end of discharge of TiSnSb vs. samples of Li
3
Sb produced via solid state methods and during the discharge of other Sn and/or Sb alloys. It seems that the nature of the other elements present at the end of lithiation plays a key role in changing the
7
Li chemical shift of Li
3
Sb. To confirm whether this is the case, additional model compounds have been studied via NMR, including TiSb
2
and NbSb
2
. Positive NMR shifts are observed, confirming the influence of the“inactive” elements of ternary alloys such as Ti or Nb. The ternary alloy NbSnSb was also investigated as a direct comparison to TiSnSb and to establish the influence of the nature of the inactive metal on the
7
Li NMR shift. The
7
Li NMR spectra obtained for both materials at the end of electrochemical lithiation are very similar, with two groups of resonances at approximately 3 and 20 ppm, respectively. In the Ti-based material, both groups of resonances are clearly shifted towards lower frequencies. This result shows that
7
Li NMR is sensitive to the chemical or electronic environment around the Li
3
Sb phase or clusters and not only to the direct local environment (Li
3
Sb).
The additional study of rough mixtures (not real alloys obtained through ball-milling syntheses) of Ti-Sn-Sb and Sn-Sb indicate that after electrochemical lithiation, the characteristic resonance of Li
3
Sb at −8 ppm is present . This result indicates that the intimate mixing of elements, achieved in the alloys, influences the overall electronic properties of the active material, therefore modifying the observed NMR shift of Li
3
Sb.
In addition, changes in the local environments of Sn and Li nuclei have been detected upon OCV relaxation after the lithiation process, using
119
Sn Mössbauer and
7
Li NMR spectroscopies, respectively. These results suggest an intrinsic instability of the phases formed at the end of the lithiation process and/or the formation of non-stoichiometric phases.
119
Sn Mössbauer spectroscopy and
7
Li MAS NMR have been combined in order to better understand the phases formed upon discharge and subsequent relaxation of a TiSnSb electrode.
Ex situ
7
Li NMR indicates that this evolution is stopped or at least slowed down when the active material is in contact with the electrolyte. Both "
in situ
" and "
ex situ
" type experiments have been completed using the two techniques in order to understand the influence of small changes in composition on Mössbauer signal and
7
Li NMR shifts. A systematic study using both Mössbauer spectroscopy and NMR the phases formed during discharge and subsequent relaxation will be presented and discussed.