Abstract: FeHCF,NiHCF and ZnHCF Prussian blues were synthesized by chemical co-precipitation method,and amorphous a-Si thin film materials were prepared by magnetron sputtering. The chemical performance of the proton batteries constructed by Prussian blue and a-Si electrodes in H₃PO₄ electrolyte was studied. The results show that the synthesized FeHCF and NiHCF have cubic crystal structure,while ZnHCF has hexagonal crystal structure. All three materials possess hierarchical pore structures comprising micropores and mesopores,with a pore size distribution range of 2-50 nm. NiHCF demonstrates good charge-discharge performance in 4 mol/L phosphoric acid solution, with a discharge capacity of 69 mA·h/g. FeHCF, ZnHCF and a-Si electrodes exhibit favorable charge-discharge performance in 8 mol/L H₃PO₄, with maximum discharge capacities of 26.5, 36.6 and 231.3 mA·h/g, respectively. For the constructed a-Si|H₃PO₄(4 mol/L)|NiHCF proton battery,under the condition of a charge and discharge current density of 100 mA/g,the maximum discharge capacity of the battery is 43.4 mA·h/g,and the capacity retention rate is about 49.6% after 200 charge and discharge cycles. At a discharge current density of 1 400 mA/g,the battery discharge capacity reaches 28 mA·h/g,still releasing 62.2% of the initial maximum capacity,showing good high-rate discharge performance. The above work provides certain references for the design and selection of new electrode materials and the optimization of electrolyte for proton batteries.