Electrochemical Studies of Aging in Lithium-Ion Batteries

Abstract: Lithium-ion batteries are today finding use in automobiles aiming at reducing fuel consumption and emissions within transportation. The requirements on batteries used in vehicles are high regarding performance and lifetime, and a better understanding of the interior processes that dictate energy and power capabilities is a key to strategic development. This thesis concerns aging in lithium-ion cells using electrochemical tools to characterize electrode and electrolyte properties that affect performance and performance loss in the cells. A central difficulty regarding battery aging is to manage the coupled effects of temperature and cycling conditions on the various degradation processes that determine the lifetime of a cell. In this thesis, post-mortem analyses on harvested electrode samples from small pouch cells and larger cylindrical cells aged under different conditions form the basis of aging evaluation. The characterization is focused on electrochemical impedance spectroscopy (EIS) measurements and physics-based EIS modeling supported by several material characterization techniques to investigate degradation in terms of properties that directly affect performance. The results suggest that increased temperature alter electrode degradation and limitations relate in several cases to electrolyte transport. Variations in electrode properties sampled from different locations in the cylindrical cells show that temperature and current distributions from cycling cause uneven material utilization and aging, in several dimensions. The correlation between cell performance and localized utilization/degradation is an important aspect in meeting the challenges of battery aging in vehicle applications. The use of in-situ nuclear magnetic resonance (NMR) imaging to directly capture the development of concentration gradients in a battery electrolyte during operation is successfully demonstrated. The salt diffusion coefficient and transport number for a sample electrolyte are obtained from Li+ concentration profiles using a physics-based mass-transport model. The method allows visualization of performance limitations and can be a useful tool in the study of electrochemical systems.