Three different forms of Cu powder particles obtained by either galvanostatic electrolysis or a non-electrolytic method were analyzed by a scanning electron microscope (SEM), X-ray diffraction (XRD) and particle size distribution (PSD). Electrolytic procedures were performed under different hydrogen evolution conditions, leading to the formation of either 3D branched dendrites or disperse cauliflower-like particles. The third type of particles were compact agglomerates of the Cu grains, whose structural characteristics indicated that they were formed by a non-electrolytic method. Unlike the sharp tips that characterize the usual form of Cu dendrites, the ends of both the trunk and branches were globules in the formed dendrites, indicating that a novel type of Cu dendrites was formed in this investigation. Although the macro structures of the particles were extremely varied, they had very similar micro structures because they were constructed by spherical grains. The Cu crystallites were randomly oriented in the dendrites and compact agglomerates of the Cu grains, while the disperse cauliflower-like particles showed (220) and (311) preferred orientation. This indicates that the applied current density affects not only the morphology of the particles, but also their crystal structure. The best performance, defined by the largest specific surface area and the smallest particle size, was by the galvanostatically produced powder consisting of disperse cauliflower-like particles.

In this review paper, morphologies of metal powders produced by the constant (potentiostatic and galvanostatic) regimes of electrolysis from aqueous electrolytes are correlated with their crystal structure at the semiquantitative level. The main parameters affecting the shape of powder particles are the exchange current density (rate of electrochemical process) and overpotential for hydrogen evolution reaction. Depending on them, various shapes of dendrites (the needles, the two-dimensional (2D) fern-like, and the three-dimensional (3D) pine-like dendrites), and the particles formed under vigorous hydrogen evolution (cauliflower-like and spongy-like particles) are produced by these regimes of electrolysis. By decreasing the exchange current density value, the crystal structure of the powder particles is changed from the strong (111) preferred orientation obtained for the needle-like (silver) and the 2D (lead) dendrites to the randomly orientated crystallites in particles with the spherical morphology (the 3D dendrites and the cauliflower-like and the spongy-like particles). The formation of metal powders by molten salt electrolysis and by electrolysis in deep eutectic solvents (DESs) and the crystallographic aspects of dendritic growth are also mentioned in this review.

Silver powders chemically synthesized by reduction with hydrazine and those produced by electrolysis from the basic (nitrate) and complex (ammonium) electrolytes were examined by X-ray diffraction (XRD) and scanning electron microscopic (SEM) analysis of the produced particles. Morphologies of the obtained particles were very different at the macro level. The needle-like dendrites, as well as the mixture of irregular and regular crystals, were formed from the nitrate electrolyte, while the highly-branched pine-like dendrites with clearly noticeable spherical grains were formed from the ammonium electrolyte. The agglomerates of spherical grains were formed by reduction with hydrazine. In the particles obtained from the nitrate electrolyte, Ag crystallites were strongly oriented in the (111) plane. Although morphologies of Ag particles were very different at the macro level, the similarity at the micro level was observed between chemically-synthesized particles and those obtained by electrolysis from the ammonium electrolyte. Both types of particles were constructed from the spherical grains. This similarity at the micro level was accompanied by the similar XRD patterns, which were very close to the Ag standard with a random orientation of Ag crystallites. For the first time, morphologies of powder particles were correlated with their crystal structure.