• A 3D-printed Ti-graphene-Ti (TGT) current collector extends the voltage window of aqueous zinc-ion batteries to 1.0–2.2 V by suppressing electrolyte decomposition via a surface TixOy protective layer.
• The graphene layer in the TGT enhances cation adsorption and insertion/extraction kinetics, achieving a high specific capacity of 307.5 mAh g−1 and prolonged cycling life.
• AZIBs with TGT current collectors exhibit stable charge/discharge performance over 400 cycles at high voltage, demonstrating excellent durability.
• The study reveals that the geometric arrangement of Ti and graphene in 3D printing significantly influences the energy storage mechanism, offering new design insights for high-voltage-resistant composite current collectors.