Silicon-based material is one of the most promising substitutes for commercial graphite anodes for the next generation lithium-ion batteries due to its extremely high theoretical capacity. However, the huge volume changes during the charging and discharging processes will cause rapid capacity decay and a short cycle life. Developing novel silicon-based materials requires a fundamental understanding of their properties. However, in many cases, the present experiments are incapable of completely mimicking real battery-operation conditions, and detailed information about the electrochemical mechanisms and ion and electron kinetic transport at the electrode/electrolyte interface is still ambiguous due to their complexity. First-principles calculations have become an effective method for predicting and interpreting the characteristics of electrode materials, understanding the electrochemical mechanisms at the atomic scale and delivering rational design strategies for electrode materials. In this review, the first-principles calculations of silicon-based anode materials in recent years, based on different modification strategies, are summarized. First, we introduce the diffusion kinetics of lithium ions in silicon and the mechanism of structure changes during the lithiation process. Then, typical examples of novel Si-based anodes, including 2D nanomaterials, silicide materials and coating materials based on theoretical predictions, are presented. Finally, we provide perspectives and future directions of first-principles calculations on Si-based anodes.

由于其极高的理论容量，硅基材料是下一代锂离子电池商业石墨阳极最有前途的替代品之一。然而，充放电过程中巨大的体积变化会导致容量快速衰减和循环寿命短。开发新型硅基材料需要对其特性有基本的了解。然而，在许多情况下，目前的实验无法完全模拟真实的电池工作条件，并且由于其复杂性，有关电极/电解质界面的电化学机制以及离子和电子动力学传输的详细信息仍然不明确。第一性原理计算已成为预测和解释电极材料特性、理解原子尺度电化学机制以及为电极材料提供合理设计策略的有效方法。本文综述了近年来基于不同改性策略的硅基负极材料的第一性原理计算。首先，我们介绍了锂离子在硅中的扩散动力学以及锂化过程中结构变化的机制。然后，介绍了新型硅基阳极的典型例子，包括基于理论预测的二维纳米材料、硅化物材料和涂层材料。最后，我们提供了硅基阳极第一性原理计算的前景和未来方向。