Dendrite‐Free Li‐Metal Anode Enabled by Dendritic Structure

Abstract The practical application of Li‐metal anode in high‐energy rechargeable Li batteries is still hindered by the uncontrollable formation of Li dendrites. Here, a facile way is reported to stabilize Li‐metal anode by building dendrite‐like Li 3 Mg 7 alloys enriched with Li‐containing polymers as the physical protecting layer and LiH as the Li‐ion conductor. This unique dendritic structure effectively reduces local current density and accommodates volume change during the repeated Li plating/stripping process. More importantly, lithiophilic Li 3 Mg 7 alloys not only guide the uniform Li deposition down into the below Li metal upon Li deposition, but also thermodynamically promote the extraction of Li during the reverse Li stripping process, which suppresses the parasitic reactions occurring on the surface of Li metal and hence inhibits the formation of Li dendrites. Moreover, the facile diffusion of Mg from Li 3 Mg 7 alloys toward Li metal below is thermodynamically permitted, which leads to a uniform distribution of LiMg alloys inside the whole electrode and thus benefits long‐term deep cycling stability. As a result, the protected Li‐metal anode delivers stable and dendrite‐free cycling performance at 10 mA h cm −2 for over 900 h. When coupling this anode with LiFePO 4 and S cathodes, the thus‐assembled full cells exhibit superior cycling stability.