Interface reaction between lithium (Li) and materials at the anode is not well understood in an all-solid environment. This paper unveils a new phenomenon of constriction susceptibility for materials at such an interface, the utilization of which helps facilitate the design of an active three-dimensional scaffold to host rapid plating and stripping of a significant amount of a thick Li metal layer. Here we focus on the well-known anode material silicon (Si) to demonstrate that, rather than strong Li–Si alloying at the conventional solid–liquid interface, the lithiation reaction of micrometre-sized Si can be significantly constricted at the solid–solid interface so that it occurs only at thin surface sites of Si particles due to a reaction-induced, diffusion-limiting process. The dynamic interaction between surface lithiation and Li plating of a family of anode materials, as predicted by our constrained ensemble computational approach and represented by Si, silver (Ag) and alloys of magnesium (Mg), can thus more homogeneously distribute current densities for the rapid cycling of Li metal at high areal capacity, which is important in regard to solid-state battery application.

在全固体环境中，锂 (Li) 与阳极材料之间的界面反应尚不清楚。本文揭示了材料在这种界面处的收缩敏感性的新现象，利用该现象有助于促进活性三维支架的设计，以快速电镀和剥离大量厚的锂金属层。在这里，我们重点关注众所周知的阳极材料硅（Si），以证明微米级硅的锂化反应可以在固-固界面上显着限制，而不是在传统的固-液界面处发生强Li-Si合金化。由于反应引发的扩散限制过程，它仅发生在硅颗粒的薄表面位置。正如我们的约束系综计算方法所预测的那样，一系列阳极材料的表面锂化和锂镀层之间的动态相互作用，并以硅、银 (Ag) 和镁合金 (Mg) 为代表，因此可以更均匀地分布电流密度锂金属在高面积容量下的快速循环，这对于固态电池应用非常重要。