In the development of new hydrogen absorbing materials for a next generation of metal hydride electrodes for rechargeable batteries, metastable Mg-Ni-based compounds find currently special attention. Amor phous-nanocrystalline and alloys were produced by mechanical alloying and melt-spinning and characterized by means of XRD, TEM and DSC. On basis of mechanically alloyed Mg-Ni-Y powders, complex hydride electrodes were fabricated and their electrochemical behaviour in 6M KOH (pH=14,8) was investigated. The electrodes made from powders, which were prepared under use of a SPEX shaker mill, with a major fraction of nanocrystalline phase reveal a higher electrochemical activity far hydrogen reduction and a higher maximum discharge capacity (247 mAh/g) than the electrodes from alloy powder with predominantly amorphous microstructure (216 mAh/g) obtained when using a Retsch planetary ball mill at low temperatures. Those discharge capacities are higher that those fur nanocrystalline electrodes. However, the cyclic stability of those alloy powder electrodes was low. Therefore, fundamental stability studies were performed on and ribbon samples in the as-quenched state and after cathodic hydrogen charging by means of anodic and cathodic polarisation measurements. Gradual oxidation and dissolution of nickel governs the anodic behaviour before a passive state is attained. A stabilizing effect of higher fractions of yttrium in the alloy on the passivation was detected. During the cathodic hydrogen charging process the alloys exhibit a change in the surface state chemistry, i.e. an enrichment of nickel-species, causing preferential oxidation and dissolution during subsequent anodization. The effect of chemical pre-treatments in 1% HF and in solution on the surface degradation processes was investigated. A HF treatment can improve their anodic passivation behavior by inhibiting a preferential nickel oxidation-dissolution at low polarisation, whereas a treatment has the opposite effect. Both pre-treatment methods lead to an enhancement of cathodically induced surface degradation processes.

• Gebert A.
• Khorkounov B.
• Schultz L.