Superior oxygen-resistance and intrinsic mechanisms of coherent Pd/Pd3Zr@ZrCo structure with excellent cycling durability

As a promising candidate for hydrogen isotopes storage, ZrCo alloy suffers tremendously from the poisoning of impurity gases, especially in oxygen-containing atmospheres, but related effective modification method for long cycling durability is still lacking. In this work, the anti-oxygen-poisoning behaviors and mechanisms of virginal ZrCo and palladium-coated ZrCo with different heating evacuation methods were detailly investigated. Notably, the phase transition occurs during traditional heating evacuation (550 °C for 60 min) with the gradual generation of Pd3Zr from original Pd coating and ZrCo substrate. According to absorption behaviors and degeneration state of O πp-orbital peak from theoretical calculations, O2 undergoes spontaneous dissociation and strong hybridization at the surface of ZrCo and Pd3Zr, especially for ZrCo, while much weak surface absorption is recognized on Pd. Considering the superior anti-poisoning properties but weak substrate anchoring strength of Pd, it’s valuable to reconstruct the Pd/ZrCo interface to generate transition Pd3Zr layer that is less susceptible to hydrogen embrittlement. Accordingly, a coherent structure of Pd/Pd3Zr@ZrCo was successfully obtained by high temperature short time pretreatment (550 °C for 10 min), and its cycling capacity retention in O2-containg hydrogen atmosphere is significantly enhanced from initial 74.87 % after 5 cycles to 90.83 % after 10 cycles, which is superior to Pd-plating hydrogen storage alloys ever reported. The interface reconstruction of coherent structure proposed here can function as a promising strategy for construction of protective layer for all related surface engineering.