In situ Moessbauer effect studies of the electrochemical reaction of lithium with mechanically alloyed Sn{sub 2}Fe
- Dalhousie Univ., Halifax, Nova Scotia (Canada)
A convenient cell design for in situ {sup 57}Fe Moessbauer spectroscopy studies of electrodes for Li batteries is described. The reaction of lithium with Sn{sub 2}Fe is studied using this cell. During the first discharge of Li/Sn{sub 2}Fe cells, the cell reaction is 8.8 Li + Sn{sub 2}Fe {r_arrow} 2Li{sub 4.4}Sn + Fe, where the Fe regions which are formed are located at the interfaces between Li-Sn alloy grains, and give a Moessbauer spectrum characterized by a doublet. If the cell is held in the discharged state (0 V vs Li) for 2 weeks, the Fe regions grow in size and a singlet (superparamagnetic) spectrum results. This spectrum splits into the six-line spectrum characteristic of ferromagnetic iron if the sample is cooled below its blocking temperature (less than 30 K) to 4.2 K, indicating Fe grains of at most 3 nm in size. During the first charge (removing Li from the Li-Sn alloys) there is little change in the {sup 57}Fe Moessbauer spectrum until almost all of the Li is removed, at which point the liberated Sn atoms begin to back react with Fe to form Sn{sub 2}Fe again. This back reaction begins at about 0.63 V vs. Li, at which potential there is a two-phase region wherein Li{sub 2}Sn{sub 5} and Sn are present. Not all of the Fe can react with Sn, because the original spectrum of the Sn{sub 2}Fe starting material is not recovered. Instead some Fe atoms, presumably at the centers of larger grains, remain as Fe. As the cell is cycled consecutively, the size of the Fe grains grows and grows, until by cycle five, the six-line Moessbauer spectrum of ferromagnetic iron is observed even at room temperature in both the charged and discharged states, indicating Fe grains of at least 10 nm. Concurrently, the differential capacity and voltage profile of the electrode resemble those of a Li/Sn cell, indicating that the majority of the Fe atoms are not involved in the back reaction during charge after several cycles.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 316279
- Journal Information:
- Journal of the Electrochemical Society, Vol. 145, Issue 12; Other Information: PBD: Dec 1998
- Country of Publication:
- United States
- Language:
- English
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