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Ab Initio Study Of Li2O2 On Noble Metal (Pt, Au, Pd), Pt3M (M=Fe, Co, Ni, Cu) Alloy And Pd3M (M=Fe, Co, Ni, Cu) Alloy Surfaces
This picture of an electrode surface that is covered and does not influence the ORR or influences it by an indirect at-distance mechanism is at odds with experimental evidence that the surface plays a crucial role in the ORR. ORR on Noble metals [1], metal oxide [4], metal alloys [5], and carbon nanotubes [6] has been reported to occur with reduced overpotential and longer cycle life. Also studies of the cathode surface have shown that the Li2O2 nucleates in various 3-D morphologies [6] and even after multiple cycles a significant portion of the surface is bare [6].
The present study addresses the twin challenges of understanding the binding of Li2O2 on active sites and identifying possible candidate materials which would facilitate easy removal of deposited Li2O2 during the charge process. The Li2O2 binding energy (B.ELi2O2) was calculated using DFT on periodic models of noble metal (Pt, Au, Pd), Pt3M (M=Fe, Co, Ni, Cu) alloy and Pd3M (M=Fe, Co, Ni, Cu) alloy surfaces after geometric optimization and by bonding Li2O2 to the surfaces at various orientations and sites. The effect of the various sites on the binding energy and the variation of the binding energy at each site with the change in material were studied. Top and Bridge sites were found to have the lowest B.ELi2O2 in case of the noble metals. Systematic permutation of the first two atomic layers of FCC (111) Pt3M and Pd3Mskin alloys slabs was carried out to find the most stable geometric surface configuration and the influence of the dopant modification of the lattice constant on the B.ELi2O2. Possible guidelines for future alloy design to achieve desired B.ELi2O2 values were formulated and B.ELi2O2 was shown to be a key parameter for screening future Li-O2ORR catalyst candidates
Acknowledgement: Use of the Center for Nanoscale Materials was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
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