Understanding the Mechanical Behaviors of Lithium-Based Battery Anodes─Silicon and Lithium Metal

This dissertation will investigate two of the most promising high-capacity anode

materials for lithium-based batteries: silicon (Si) and metal lithium (Li). It will focus on

studying the mechanical behaviors of the two materials during charge and discharge and

understanding how these mechanical behaviors may affect their electrochemical

performance.

In the first part, amorphous Si anode will be studied. Despite many existing studies

on silicon (Si) anodes for lithium ion batteries (LIBs), many essential questions still exist

on compound formation, composition, and properties. Here it is shown that some

previously accepted findings do not truthfully reflect the actual lithiation mechanisms in

realistic battery configurations. Furthermore the correlation between structure and

mechanical properties in these materials has not been properly established. Here, a rigorous

and thorough study is performed to comprehensively understand the electrochemical

reaction mechanisms of amorphous-Si (a-Si) in a realistic LIB configuration. In-depth

microstructural characterization was performed and correlations were established between

Li-Si composition, volumetric expansion, and modulus/hardness. It is found that the

lithiation process of a-Si in a real battery setup is a single-phase reaction rather than the

accepted two-phase reaction obtained from in-situ TEM experiments. The findings in this

dissertation establish a reference to quantitatively explain many key metrics for lithiated a

Si as anodes in real LIBs, and can be used to rationally design a-Si based high-performance

LIBs guided by high-fidelity modeling and simulations.

In the second part, Li metal anode will be investigated. Problems related to dendrite

growth on lithium metal anodes such as capacity loss and short circuit present major

barriers to the next-generation high-energy-density batteries. The development of

successful mitigation strategies is impeded by the incomplete understanding of the Li

dendrite growth mechanisms. Here the enabling role of plating residual stress in dendrite

initiation through novel experiments of Li electrodeposition on soft substrates is confirmed,

and the observations is explained with a stress-driven dendrite growth model. Dendrite

growth is mitigated on such soft substrates through surface-wrinkling-induced stress

relaxation in deposited Li film. It is demonstrated that this new dendrite mitigation

mechanism can be utilized synergistically with other existing approaches in the form of

three-dimensional (3D) soft scaffolds for Li plating, which achieves superior coulombic

efficiency over conventional hard copper current collectors under large current density.