Using first principle calculations, we uncover the underlying mechanisms explaining the brittle-to-ductile transition of LixSi electrodes in lithium ion batteries with increasing Li content. We show that plasticity initiates at x = ∼ 0.5 with the formation of a craze-like network of nanopores separated by Si–Si bonds, while subsequent failure is still brittle-like with the breaking of Si–Si bonds. Transition to ductile behavior occurs at x ⩾ 1 due to the increased density of highly stretchable Li–Li bonds, which delays nanopore formation and stabilizes nanopore growth. Collapse of the nanopores during unloading of the LixSi alloys leads to significant strain recovery.
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