Degradation models are important tools for understanding and mitigating lithium-ion battery aging, yet a universal model that can predict degradation under all operating conditions remains elusive. One challenge is the coupled influence of calendar and cycle aging phases on degradation mechanisms, such as solid electrolyte interphase (SEI) formation. In this work, we identify and systematically compare three different SEI interaction theories found in the literature, and apply them to experimental degradation data from a commercial lithium-ion cell. In a step-by-step process, and after careful data selection, we show that SEI delamination without any cracking of the active particles, and SEI microcracking, where cycling only affects SEI growth during the cycle itself, are both unlikely candidates. Instead, the results indicate that upon cycling, both the SEI and the active particle crack, and we provide a simple, 4-parameter equation that can predict the particle crack rate. Contrary to the widely-accepted Paris’ law, the particle crack rate decreases with increasing cycles, potentially due to changing intercalation dynamics resulting from the increasing surface-to-volume ratio of the active particles. The proposed model predicts SEI formation accurately at different storage conditions, while simply adding the degradation from pure calendar and cycle aging underestimates the total degradation.

Constraining lithium-ion cells increases the cyclic lifetime. However, depending on an expected volume expansion during charge and discharge cycling, defining the optimal constraining pressure range is not straightforward. In this study, we investigate a lithium iron phosphate/graphite pouch cell at four initial constraining pressure levels. As a function of C-Rate, the thermodynamic principle of the non-monotonic pressure curve during full charge and discharge cycles is evaluated. Using the rubber balloon model to calculate the chemical potential of lithium iron phosphate and discussing the relationship between the chemical potential and pressure, we illustrate the pressure curve qualitatively. By applying differential pressure analysis, we evaluate the resulting pressure curves of a single graphite stage. Approaching a fundamental understanding of reduced cycling lifetime of full cells with unknown material composition, we allocate the stages and stage transitions of graphite as well as the phase transition of lithium iron phosphate. Local extreme values in the differential pressure analysis indicate phase and stage transitions. These values can identify critical operating conditions that should be considered for defining the optimum initial constraining pressure range.

Testing of improved battery components and new electrochemical energy storage materials in a coin cell format as a test cell is becoming the state of the art. The pressure on the electrode surfaces inside an electrochemical cell is one of the important parameters for high ionic/electronic conductivity and the cyclic lifetime. A self-designed pressure monitoring cell allows both applying an adjustable pressure and monitoring the state of charge-dependent cell pressure during cycling. The load cell shows a reciprocal behavior of the temperature sensitivity dependent on the ambient temperature and requires constant temperature conditions while monitoring the cell pressure. Further, dependent on the initial cell pressure, the relaxation time of the assembled pressure monitoring cell must be considered. The present paper describes the setup, the influence of the environment temperature and the mechanical relaxation of the pressure monitoring cell. The first cycling results, using an NCM/graphite coin cell, demonstrate the functionality of the pressure monitoring cell measuring the cell’s pressure as a function of the C-rate.