Abstract

Fracture is the main cause of degradation and capacity fading in lithiated silicon during cycling. Experiments on the fracture of lithiated silicon show conflicting results, and so mechanistic models can help interpret experiments and guide component design. Here, large-scale K-controlled atomistic simulations of crack propagation (R-curve K-I vs Delta a) are performed at LixSi compositions x = 0.5, 1.0, 1.5 for as-quenched/relaxed samples and at x = 0.5, 1.0 for samples created by discharging from higher Li compositions. In all cases, the fracture mechanism is void nucleation, growth, and coalescence. In as-quenched materials, with increasing Li content the plastic flow stress and elastic moduli decrease but void nucleation and growth happen at smaller stress, so that the initial fracture toughness K-Ic approximate to 1.0MPa root m decreases slightly but the initial fracture energy J(Ic) approximate to 10.5J/m(2) is similar. After 10 nm of crack growth, the fracture toughnesses increase and become similar at K-Ic approximate to 1.9MPa root m across all compositions. Plane -strain equi-biaxial expansion simulations of untracked samples provide complementary information on void nucleation and growth. The simulations are interpreted within the framework of Gurson model for ductile fracture, which predicts J(Ic) = alpha sigma D-y where alpha similar or equal to 1 and D is the void spacing, and good agreement is found. In spite of flowing plastically, the fracture toughness of LixSi is low because voids nucleate within nano-sized distances ahead of the crack (D approximate to 1nm). Scaling simulation results to experimental conditions, reasonable agreement with experimentally-estimated fracture toughnesses is obtained. The discharging process facilitates void nucleation but decreases the flow stress (as shown previously), leading to enhanced fracture toughness at all levels of crack growth. Therefore, the fracture behavior of lithiated silicon at a given composition is not a material property but instead depends on the history of charging/discharging. These findings indicate that the mechanical behavior (flow and fracture) of lithiated Si must be interpreted within a fully rate- and history-dependent framework. (C) 2017 Elsevier Ltd. All rights reserved.

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