The lead dioxide active mass of positive lead-acid battery plates is a gel-crystal system with proton and electron conductivity of the hydrated gel zones. This paper discusses the influence of Sn2+, Sb3+, Co2+, Mg2+ and Al3+ ions, added to the formation electrolyte, upon the stoichiometry, structure and phase composition of the PbO2 positive active material (PAM) of lead-acid batteries. PAM samples doped with the above metal ions are characterized by: X-ray diffraction (XRD), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and chemical analysis. The obtained results show that different metal ions are incorporated in different quantities in the PbO2 particles. Under the influence of dopants, the stoichiometric coefficient of lead dioxide decreases, i.e. dopants increase the non-stoichiometry of PbO2. The foreign ions in the formation electrolyte exert strong influence on the microstructure of PAM and change the proportion between crystal and hydrated gel zones in the particles.