Effect of Silicon Crystallite Size on Its Electrochemical Performance for Lithium‐Ion Batteries

It is reported that silicon (Si) anodes with a smaller crystallite size show better electrochemical performance in lithium‐ion batteries (LIBs); Si particles with different diameters are also used. However, it is yet to be clarified whether the better performance is attributed to crystallite size or particle diameter. The effect of Si crystallite size on its anode performance using Si particles having the same diameter and different crystallite sizes is investigated. Longer cycle life is obtained for smaller crystallite size, due to the small amount of the amorphous Li‐rich Li—Si phase formed during charging. The phase is likely to form in a greater amount in Si particles with larger crystallite size, leading to degradation of the Si electrode at an early stage. Furthermore, Si electrodes with larger crystallite size show superior rate performance because of the high Li diffusion rate into the broader grain boundary; on the other hand, Si with smaller crystallite size should limit Li diffusion due to the narrower grain boundary. Therefore, smaller crystallite size helps improve the cycle life but deteriorates the rate performance of LIBs.