Chemo-mechanics of Li-ion batteries: in-situ and operando studies

Electrochemical energy storage devices play an integral role in the energy transition from fossil fuels to renewable. Still, technological breakthroughs are warranted to expand this progress and enable their use where hydrocarbons are still the dominant option. The requirements restricting further adoption of electrochemical devices are related to energy density, hampering costs of raw materials with the increased global demand, and safety in large scale operations. Furthermore, new applications in flexible electronics add new requisites to this list. Pushing these limits involves multidisciplinary efforts where the mechanics are a crucial part.

This thesis explores the mechanical and kinetic behaviors of batteries at the nano to micro-meter scale through operando mechanical and optical characterization during ongoing electrochemical reactions. A unique experimental platform that enables simultaneous nanoindentation and electrochemical testing of active materials is developed. The validity of mechanical testing during operation in the customized liquid cell is systematically addressed. The evolution of the mechanical properties of electrodes as a function of lithium concentration is probed in real-time. This functional dependence between mechanical properties and composition is then used to introduce the concept of mechanics-informed chemical profiling. This new capability enables characterizing transport kinetics in a detailed and quantitative way, including the role of pressure gradients on diffusion. Pairing these experiments with multi-physics modeling led to a new understanding of the mechanisms regulating charging-rate capability and capacity loss in Li-ion batteries. Experiments on composite electrodes showed that liquid electrolytes change the mechanical properties of both conductive matrix and secondary particles. These observations help understand the interactions between the different components of a battery and demonstrate the need for in-situ mechanical characterization capabilities.