In this study, the calendar aging of lithium-ion batteries is investigated at different temperatures for 16 states of charge (SoCs) from 0 to 100%. Three types of 18650 lithium-ion cells, containing different cathode materials, have been examined. Our study demonstrates that calendar aging does not increase steadily with the SoC. Instead, plateau regions, covering SoC intervals of more than 20%-30% of the cell capacity, are observed wherein the capacity fade is similar. Differential voltage analyses confirm that the capacity fade is mainly caused by a shift in the electrode balancing. Furthermore, our study reveals the high impact of the graphite electrode on calendar aging. Lower anode potentials, which aggravate electrolyte reduction and thus promote solid electrolyte interphase growth, have been identified as the main driver of capacity fade during storage. In the high SoC regime where the graphite anode is lithiated more than 50%, the low anode potential accelerates the loss of cyclable lithium, which in turn distorts the electrode balancing. Aging mechanisms induced by high cell potential, such as electrolyte oxidation or transition-metal dissolution, seem to play only a minor role. To maximize battery life, high storage SoCs corresponding to low anode potential should be avoided.

Single-layered pouch-type cells were exposed to quasi-isothermal external short circuit tests to study the influence of electrode loading and tab configuration on the short circuit characteristics. Additionally, test conditions such as initial cell temperature, cell voltage and external short circuit resistance were varied. Keeping the cell's temperature increase below 1 • C whilst using a calibrated calorimetric setup, a direct correlation between the electrical and thermal behavior could be shown without occurring exothermal side reactions. Previously studied step-like characteristics in the transient current profile could be confirmed for all cells and test conditions, showing differing durations and magnitudes of the observed plateaus based on ohmic resistances, transport processes and reaction kinetics. Lower electrode loadings, counter-tab configurations homogenizing the current density distribution and higher initial cell temperatures accelerate the short circuit by increasing the cell current due to a reduced effective cell resistance. Whilst the chosen initial cell voltages and external short circuit resistances showed a minor impact on the short circuit dynamics, the initial state of charge revealed a noticeable influence defining the discharged capacity and the amount of generated heat. By post mortem analysis, the observed over-discharge could be correlated to an anodic dissolution of the negative electrode's copper current collector.

Measurement data gained from quasi-isothermal external short circuit tests on single-layered pouch-type Li-ion cells presented in the first part of this combined work was used to validate a well-known homogenized physical-chemical model for different electrode loadings, cell temperatures, initial cell voltages, and external short circuit resistances. Accounting for diffusion-limited reaction kinetics, effective solid phase diffusion coefficients, and one representative active material particle size within each electrode, the model is capable of describing the experimentally observed characteristic change in magnitudes of current and heat generation rate throughout the short circuit. Underlying mechanisms for the observed characteristics are studied by evaluating the predicted concentration distribution across the electrodes and separator and by calculating the cell polarization due to ohmic losses, diffusion processes, and reaction kinetics. The importance of mass transport in the solid and liquid phase limiting reaction kinetics is discussed and evaluated in the context of a sensitivity analysis. Concentration dependent transport properties, electrode tortuosity, particle size, and electrode energy density are affecting different stages of a short circuit. Simulation results suggest a strong impact of electrode design on the short circuit dynamics allowing for an optimization regarding a cell's energy and power characteristics whilst guaranteeing a high short circuit tolerance.

Multi-dimensional modeling is a powerful approach to get access to internal variables such as current density or temperature distribution. In this work, an effective coupling approach is developed to describe the behavior of a modified commercial LFP/graphite cell during discharge. The model is based on a geometrical decomposition of the cell’s features followed by a re-assembly by means of a scaled volume averaging method (SVAM). Following this approach, mass and charge transport within the porous electrode and separator domain, charge transport within the current collector domain and heat transport within the cell domain can be described in detail whereby the effective coupling method allows for precise spatially resolved simulation results within minutes. Simulated cell voltage profiles and internal temperature agree well with measurements which are performed and discussed in Part I. By addressing local potentials and internal temperature the model is validated more precisely than by measuring surface temperature and terminal voltage only. Additionally, a study on current density distribution, internal temperature and local state of charge is performed.

A single-layered NMC/graphite pouch cell is investigated by means of differential local potential measurements during various operation scenarios. 44 tabs in total allow for a highly resolved potential measurement along the electrodes whilst the single layer configuration guarantees the absence of superimposed thermal gradients. By applying a multi-dimensional model framework to this cell, the current density and SOC distribution are analyzed quantitatively. The study is performed for four C-rates (0.1C, 0.5C, 1C, 2C) at three temperatures (5 • C, 25 • C, 40 • C). The maximum potential drop as well the corresponding SOC deviation are characterized.The results indicate that cell inhomogeneity is positively coupled to temperature, i.e. the lower the temperature, the more uniform the electrodes will be utilized. Within the past decades, demand for lithium-ion batteries in mobile applications has significantly increased. Due to their well proven performance as well as their stability in long-term usage, lithium-ion batteries became the technology of choice for electrochemical energy storage devices.1,2 Still, the specific energy density as well as cycle life are constantly being optimized by either commercializing new active materials, electrolytes and additives or by reducing the fraction of non-active parts within a battery. Often, this corresponds to thicker electrodes or larger form factors leading to capacities of up to 100 Ah per cell. In these large format cells, severe gradients in current density and temperature distribution can occur along the electrode stack, 3-9 which might provoke a performance loss during operation due to inhomogeneous utilization. Also non-properly adapted thermal conditioning can have a crucial impact on the performance of larger cells. [10][11][12] Modeling of internal distributions of potential and temperature along the electrodes is quite challenging, since even to calculate only a few cycles, a lot of computational resources are required for fully resolved models. In literature, there are many examples for spatially resolved multi-dimensional modeling approaches, 8,9,[13][14][15][16] which aim at representing the cell's internal behavior in terms of potential, current density, state of charge (SOC) and temperature distribution. Unfortunately, all of these examples lack a detailed, i.e. spatially resolved experimental validation, which is capable of tracking internal variables instead of measuring the surface temperature at a few spots and considering the overall battery's terminal voltage. Also, only a few examples of direct measurements of the internal current density distribution were published so far. Zhang et al.6,7 built a specific LFP/graphite prototype cell for this purpose. A segmented cathode was used for analyzing the current distribution during discharge at varying C-rates and temperatures. This setup allows for a precise monitoring of the current of each electrode element individually. Large deviations in SOC of up to several percent were identified during the process...

This work presents a modification approach and first measurements of commercial cylindrical Li-ion cells with multiple local potential probes and an internal temperature sensor. Local potential measurements at low currents show a non-uniform potential distribution along the electrode, dominated by the open circuit voltage (OCV) of the negative electrode. For higher currents, the overpotential along the current collector becomes dominant and instead of a corrugated potential distribution, a significant current dependent voltage gradient can be detected, indicating a highly non-uniform state of charge (SOC) distribution with increasing distance to the current collecting tab. After the discharge operation, a quick potential equalization can be witnessed which results in a non-detectable potential difference between the single electrode sections after 12 min, even though the overall cell voltage relaxation has not reached an equilibrium state yet. The presented modification approach combines the advantages of high quality industrial manufactured cells showing uniform coating thicknesses and packing density with the advantages of special tailor made cells for in situ measurements. Due to the low impact of the modification and its long-term stability, highly reproducible measurements can be conducted at different locations of the electrodes.Li-ion cells show continuing commercial success as a power source in the consumer application market. High energy density, safety and reliability make Li-ion technology the rechargeable battery of choice for portable electronics such as mobile phones and laptop computers. 1,2 In recent years, Li-ion batteries also become increasingly prominent for applications in the field of full and hybrid electric vehicles (FEVs/ HEVs)which demand for power optimized batteries with large capacities. 3 Eventhough an up-scaling of the established Li-ion technology from the consumer electronics market to batteries with feasable capacities of up to 100 Ah, retaining the energy density and reliability of smaller systems is a continuing technological challenge.Designing application oriented large format batteries nowadays is increasingly is supported by simulation tools of varying degree of complexity, ranging from early 1-Dimensional models utilizing porous electrode theory stated by Newman et al., 4 over analytical calculations 5,6 to more recent multi-scale multi-dimensional model frameworks combining various approaches. 7-10 These models can help to predict the spatial distribution and time evolution of single cell's or a battery pack's parameters such as potential, current, state of charge (SOC) and temperature. Yet, little spatially resolved experimental data is available for model validation. Inhomogeneities in the degree of lithiation have been investigated by means of neutron diffraction, 11 colorimetry, 12 X-ray micro-diffraction (μXRD) 13 and Raman spectroscopy. 14 These methods typically rely on custom small scale in-situ cells or ex-situ measurements on materials from disassembled cells. N...

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