Abstract

Silicon, as the next-generation cathode material in lithium-ion batteries, exhibits excellent electrochemical performances compared with traditional cathode material, such as high capacity and cheap price. However, its cycling performances are greatly affected by the volume change of silicon due to the insertion of Li atoms. Lots of work focuses on the analysis of diffusion-induced stresses in electrode, but the convection term is seldom considered in analyzing the diffusion-induced stress in an electrode. In this paper, a mathematical model is established, where the convection term is taken into consideration in the diffusion process. The mechanics equations and diffusion equation are derived based on continuum mechanics and the diffusion theory. Diffusion-induced stress, axial reaction force and the critical buckling time in a hollow cylindrical electrode under galvanostatic charging are calculated. The effects of local velocity, ratio of the outer radius to inner radius, charging rate, material parameters and lithiation induced softening factors on stress field and the critical buckling time are studied. According to the results, it is found that the influence of local velocity on stress distribution increases with the increasing of Li concentration, and the contribution of local velocity to axial reaction force is insignificant. Compared with the results without local velocity, the tensile hoop stress of inner surface is large, and compressive stress at the outer surface is small. The axial reaction force and the critical buckling time are calculated with different ratios of outer radius to inner radius. As the radius ratio increases, the axial reaction force and critical buckling time decrease. The effects of three main material parameters (elastic modulus, diffusion coefficient, partial molar volume) on axial reaction force are discussed. The dimensionless force is independent of elastic modulus due to stress varying linearly with Young's modulus. The critical time is inversely proportional to diffusion coefficient. As the partial molar volume increases, which indicates larger volume change induced by the intercalation of the same quantity of Li-ions, the critical buckling time drops and the effect of local velocity on stress field increases. It takes less time for axial reaction force to reach the critical buckling force at a higher charging rate. The elastic properties of silicon in the lithiation process should be a function of Li concentration due to the formation of Li-Si alloy. The elastic modulus is assumed to be a linear function of Li concentration. The hollow cylindrical electrodes with increasing absolute value of lithiation induced softening factor have lower maximum axial reaction force. However, the lithiation induced softening factor has a limited effect on the critical buckling time due to the fact that the Li concentration at critical buckling time is relatively small.

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