Suppression of structural fatigue by doping in spinel electrode probed by in situ bending beam method

The onset of a Jahn-Teller effect at the surface of LiMn2O4 particles during cycling in the 4 V range was previously reported to be one of the causes for the capacity fading. Furthermore, it has been reported that the Jahn-Teller effect in the 4 V range may be suppressed by the substitution of the Mn ions by either Li or other transition metal ions. However, no direct evidence has yet been reported. This study provides evidence for the onset of a Jahn-Teller effect in thin film 4 V LiMn2O4 and its suppression caused by substituting the Mn ions with Co3+ and Ni2+ ions using in situ bending beam method (BBM). The deflectograms are measured simultaneously with galvanostatic charge/discharge or cyclic voltammograms, and the onset of the Jahn-Teller effect is investigated by means of the differential strain peak which is observed at around 3.90-3.95 V during cyclic voltammetry, and the slope variation observed in the strain curves during galvanostatic charge/discharge. The suppression of the Jahn-Teller effect in the doped spinel leads to the magnitude of the differential strain peak resulting from the Jahn-Teller effect being reduced in comparison with the other two pairs of peaks, which correspond to the current peaks of the cyclic voltammogram. (C) 2004 The Electrochemical Society.