Bi3+ doped Ti/Sb-SnO2/PbO2 electrode materials were fabricated by electrodeposition to improve their electrochemical performance in zinc electrowinning. The surface morphology, chemical composition, and hydrophilicity of the as-prepared electrodes were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and contact angle. An electrochemical measurement and an accelerated lifetime experiment were also conducted to investigate the electrocatalytic performance and stability of the electrodes. The results show that the Bi3+ modification electrode has an important effect on the coating morphology, the crystal structure, the surface hydrophilicity, the electrocatalytic activity, and the stability. The electrode prepared from the solution containing 2 mmol·L−1 Bi(NO3)3 (marked as the Ti/Sb-SnO2/2Bi-PbO2 electrode) exhibits the best hydrophilicity performance (θ = 21.6°) and the longest service life (1196 h). During the electrochemical characterization analysis, the Ti/Sb-SnO2/2Bi-PbO2 electrode showed the highest oxygen evolution activity, which can be attributed to it having the highest electroactive surface (qT* = 21.20 C·cm−2) and the best charge-transfer efficiency. The DFT calculation demonstrated that the doping of Bi3+ leads to a decrease in the OER reaction barrier and an increase in the DOS of the electrode, which further enhances the catalytic activity and the conductivity of the electrode. Moreover, the simulated zinc electrowinning experiment demonstrated that the Ti/Sb-SnO2/2Bi-PbO2 electrode consumes less energy than other electrodes. Therefore, it is expected that the Bi3+ modified electrode will become a very promising electrode material for zinc electrowinning in the future.
