Amorphous electroless Ni-B coatings were deposited on steel substrates with different surface morphologies and B contents (6.5–8.64 wt.%) that could be changed by altering the temperature and the composition of the baths. The supercapacitive behavior of the coatings was evaluated by cyclic voltammetry and galvanostatic charge–discharge measurements, and it was found that Ni-B coatings had higher capacitance than pure electroless Ni or the bulk Ni plate. A close relationship was identified between the microstructure, the B content, and the capacitive behavior of the coatings. The presence of the B alloying element had the most significant effect in determining the capacitance, while the surface area and particle size also contributed to its increase. A surface-specific capacity of 31 mF/cm² was achieved by the coating containing the highest B content and largest AFM surface area. Furthermore, it was revealed that the particle size of the deposits was determined by the combined effect of the bath temperature and the B content under the applied experimental conditions. The obtained results indicate that Ni-B coatings are promising candidates for supercapacitive applications.

Electroless nickel–phosphorus (Ni–P) coatings were deposited on steel substrates for 20, 40, and 60 min to examine the effect of deposition time on their pseudocapacitive behavior in an alkaline electrolyte. The coatings were characterized by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS). Although coating mass, thickness, and roughness increased monotonically with deposition time, the electrochemical response showed a pronounced maximum at 40 min. The 40 min coating exhibited the highest areal capacitance in both CV and GCD measurements, reaching 33.1 ± 1.8 mF cm⁻² at 10 mV s⁻¹ and 426.5 ± 9.8 mF cm⁻² at 5 mA cm⁻², whereas the 60 min coating showed substantially lower capacitance. SEM and AFM confirmed progressive nodular coarsening and increasing surface roughness with time, but these geometric parameters alone did not explain the non-monotonic capacitance trend. In contrast, XPS revealed that the 40 min coating possessed the highest surface Ni content, while prolonged deposition led to a more P-enriched outermost surface. EIS further showed that the 40 min coating had the most favorable local high-frequency interfacial response, whereas the 60 min coating exhibited the highest local polarization. The results demonstrate that the electrochemical performance of electroless Ni–P coatings is more closely associated with the composition and accessibility of the activated near-surface region than with coating thickness or roughness alone, and that 40 min represents an interfacial optimum under the applied deposition conditions.