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The propensity of Li to form irregular and nonplanar electrodeposits has become a fundamental barrier for fabricating Li metal batteries. Here, a planar, dendrite‐free Li metal growth on 2D Ti3C2Tx MXene is reported. Ab initio calculations suggest that Li forms a hexagonal close‐packed (hcp) layer on the surface of Ti3C2Tx via ionic bonding and the lattice confinement. The ionic bonding weakens gradually...