The kinetics of hydrogen absorption/desorption within nanostructured composite Ni<inf>79.1</inf>Co<inf>18.6</inf>Cu<inf>2.3</inf> alloy using resistometry

Abstract

Ni79.1Co18.6Cu2.3 powder was obtained by electrochemical deposition from an ammonium sulfate bath. The structure and surface morphology of the powder were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemically obtained Ni79.1Co18.6Cu2.3 alloy contained an amorphous phase and nanocrystals with an average size of 6.8 nm of FCC phase of the solid solution of cobalt and copper in nickel. Nanocrystals were characterized by a high average microstrain value and high minimum density of chaotically distributed dislocations. X-ray analysis also showed that powder hydrogenation at an elevated temperature of up to 200 °C did not change unit cell parameters and mean crystallite size value. SEM images show the formation of two shapes of powder particles: large cauliflower-like particles and small dendritic ones. Powder pressing at 10 MPa and at 25 °C gave samples that were analyzed for hydrogen absorption/desorption within the temperature range of 160-200 °C. Changes in electrical resistivity during absorption/desorption were monitored. The reciprocal value of resistivity (electrical conductivity) was found to increase linearly with increasing amount of absorbed hydrogen. The experimental results were used to propose an absorption/desorption mechanism. The adsorbed hydrogen molecule dissociates on alloy surface, forming adsorbed atoms. Adatoms penetrate and diffuse into the bulk of the alloy, simultaneously donating their electrons to the conduction band of the alloy. The increase in the concentration of free electrons induces a decrease in electrical resistivity. The overall absorption rate during initial absorption is determined by the dissociation of adsorbed hydrogen molecules. At a later stage, the diffusion of H+ ions into the alloy bulk was found to be the rate determining step. The rate of the desorption reaction during the initial stage is governed by the recombination of adsorbed hydrogen atoms. Over time, H + diffusion becomes the slowest step in the mechanism, hence determining the desorption rate. © 2012 Elsevier B.V. All rights reserved.