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The capacity loss and power fade of a Li-ion battery during cycling and storage, known as Li-ion battery ageing, is a key problem to be solved before the Li-ion battery can be widely applied in vehicle electrification. Also, lithium battery safety plays a pivotal role in battery-powered vehicles. In this work we describe our modeling and diagnostic efforts for high-energy Li-ion cells that employ thick electrodes with high coating density.  We shall elucidate chemical degradation, such as SEI layer growth, and mechanical degradation, such as active material pulverization. We will discuss various ageing behaviours under different driving cycles. Finally we will discuss modeling and simulation of battery safety as well as present a new technique to measure reaction temperature at the electrochemical interface in operating Li-ion cells. The reaction temperature sensor (RTS) technology provides early detection and protection for automotive battery systems.