Aqueous zinc ion storage system has been deemed as one of the most promising alternatives due to its high capacity of zinc metal anode, low cost, and high safety characteristics. Recently, significant attempts have been made to produce highperformance aqueous Zn batteries. (AZBs) and great progress has been achieved. Yet there are a lot of issues still exist and need to be further optimized. In this thesis, we proposed several strategies to tackle these challenges and finally optimize the overall battery performance, including metal anode protection, cathode structural engineering, and rational electrolyte design. In the present thesis, we first developed the ZnF2 layer coated Zn metal anode via a simple plasma treatment method. The plasma treated Zn anode leads to dendrite-free Zn electrodeposition with lower overpotential. Density function theory calculation results demonstrate that the Zn diffusion energy barrier can be greatly reduced on the ZnF2 surface. Benefiting from these merits, the symmetric cell and full cell exhibited much improved electrolchemical performance and stability. Afterthen, We synthesised a layered Mg2+-intercalated V2O5 as the cathode material for AZBs. The large interlayer spacing reachs up to 13.4 A, allowing for efficient Zn2+ (de)insertion. As a result, the porous Mg0.34V2O5・nH2O cathodes can provide high capacities as well as long-term durability. We then recongnized that most of the parasitic side reactions are related to the aqueous electrolyte. We therefore further designed a hybrid electrolyte to realize the anode-free Zn metal batteries. It is demonstrated that in the presence of propylene carbonate, triflate anions are involved in the Zn2+ solvation sheath structure. The unique solvation structure results in the reduction of anions, thus forming a hydrophobic solid electrolyte interphase. Consequently, in the hybrid electrolyte, both Zn anodes and cathodes show excellent stability and reversibility. More importantly, we design an anode-free Zn metal battery, which exhibits good cycling stability (80% capacity retention after 275 cycles at 0.5 mA cm–2).