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Lithium (Li) deposition behavior plays an important role in dendrite formation and the subsequent performance of lithium metal batteries. This work reveals the impact of the lithiophilic sites of lithium-alloy on the Li plating process via the first-principles calculations. We find that the Li deposition mechanisms on the Li metal and Li22Sn5 surface are different due to the lithiophilic sites. We first propose that Li plating on the Li metal surface goes through the "adsorption-reduction-desorption-heterogeneous nucleation-cluster drop"