Aging Patterns of Silicon-Containing High Energy Cylindrical Li-Ion Cells – Effects of Cell Design and Silicon Usage
The transformation toward climate-neutral mobility (road, air and water transportation) and stationary energy storage systems is a fundamental task of the current generation. In some fields, such as electromobility or stationary storage, Li-ion cell technology has emerged as a potential enabler of this transformation. Nevertheless, research is ongoing regarding Li-ion cells to meet both technical and customer requirements, particularly in terms of range (energy and power density) and safety. In addition to novel cell formats, such as large-format cylindrical cells 21700 or 47xx with tabless design, current research is focusing on new active materials with high specific capacity such as silicon. The challenge resulting from the use of these materials is the high volumetric expansion caused by lithiation. This causes mechanical aging phenomena such as the Loss of Active Material (LAM), which can have a significant negative impact on the service life. This leads to a tradeoff between maximizing the energy density and longevity of the battery system. In addition to optimizing the electrode design, such as the use of nano-silicon or silicon oxide or additives that buffer the mechanical load, the operating strategy of cells in the application can be adapted to minimize degradation. The purpose of this work is to gain a deeper understanding of the (mechanical) aging behavior of cylindrical cells with silicon-containing electrodes and to experimentally investigate the dependence of aging rate on operating conditions.The Samsung 50S Li-Ion cell, which has a 21700 format with a capacity of 5 Ah, was selected for testing. This cell utilizes a blend of Graphite (Gr) and Silicon Oxide (SiOx) as negative electrode, paired with a nickel-rich Lithium-Nickel-Cobalt-Aluminum-Oxide (NCA) as positive electrode. The cell was initially characterized physically, chemically and electrochemically at full and half-cell level. After that, the cycle stability was evaluated under different operating conditions. For this purpose, a cell was disassembled, electrode material was removed and laboratory cells were constructed. The laboratory cells were used to measure the potential and the change of thickness during (de)lithiation using a dilatometer. The morphology and chemical composition were determined using SEM, EDX and Glow Discharge Optical Emission Spectroscopy (GDOES) measurements.In the subsequent aging studies, terminal discharge voltages and current rates were systematically varied to investigate the influence of silicon utilization. To evaluate the aging behavior, check-up routines were performed every 100 Equivalent Full Cycles (EFC) and at the beginning of the test, which included a discharge and charge pulse at 50 % SoC as well as a pseudo Open Circuit Voltage (pOCV) measurement at 1/20C in the charge and discharge directions. These data were used to determine aging mechanisms such as Loss of Lithium Inventory (LLI) and LAM using Differential Voltage Analysis (DVA) and OCV-fitting. These analyses provide important insights into a better understanding of aging processes taking place inside the cell. Selected cells were disassembled after cycling in a glovebox and aging effects were validated visually and with the help of SEM and GDOES. The characterization of the cell shows a typical tab design with one tab per current collector (1x1) and a capacity share of silicon of 25 % (1.25 Ah) based on DVA. The dilatometer measurements resulted in a change in thickness of the negative electrode of 14.3 % with a very pronounced hysteresis and a significantly lower expansion with an expansion of 3 % and hysteresis of the positive electrode. In the aging study, accelerated aging of the cells was observed above a certain Depth of Discharge (DoD). While the cells with a lower utilization of the available capacity (DoD=55 %, SoC range: 40 % - 95 %) still showed a State of Health (SoH) of 0.82 after 1,500 EFC (subsequently referred to as slow-aged), the cells with full utilization of the capacity (DoD=100) showed sudden death after 300-400 EFC (subsequently referred to as fast-aged). The post-mortem analysis highlighted aging patterns across the jelly roll of the negative electrode for the fast-aged cells, which can be divided into four areas: At the core of the jelly roll there was a clear detachment of active material, the adjacent area showed Li-plating stripes, which are in the same phi-coordinate of the tab. In the area of the tab (center of the jelly roll), imprints of the tab in the jelly roll were clearly visible, which underlines the mechanical influence of the tab. The outer area showed no noticeable abnormalities. With the help of GDOES measurements, it was confirmed that the strips were Li-plating. The slow-aged cells showed neither these characteristics nor Li plating in these areas. Figure 1
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