The commercialization of alloy-type anodes has been hindered by rapid capacity degradation due to volume fluctuations. To address this issue, stress-relief engineering is proposed for Si anodes that combines hierarchical nanoporous structures and modified layers, inspired by the phenomenon in which structures with continuous changes in curvature can reduce stress concentration. The N-doped C-modified hierarchical nanoporous Si anode with a microcurved pore wall (N-C@m-HNP Si) is prepared from inexpensive Mg-55Si alloys using a simple chemical etching and heat treatment process. When used as the anode for lithium-ion batteries, the N-C@m-HNP Si anode exhibits initial charge/discharge specific capacities of 1092.93 and 2636.32 mAh g-1 at 0.1 C (1 C = 3579 mA g-1), respectively, and a stable reversible specific capacity of 1071.84 mAh g-1 after 200 cycles. The synergy of the hierarchical porous structure with a microcurved pore wall and the N-doped C-modified layer effectively improves the electrochemical performance of N-C@m-HNP Si, and the effectiveness of stress-relief engineering is quantitatively analyzed through the theory of elastic bending of thin plates. Moreover, the formation process of Li15Si4 crystals, which causes substantial mechanical stress, is investigated using first-principles molecular dynamic simulations to reveal their tendency to occur at different scales. The results demonstrate that the hierarchical nanoporous structure helps to inhibit the transformation of amorphous LixSi into metastable Li15Si4 crystals during lithiation.
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