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.

Calendar aging of lithium-ion cells is investigated by storing commercial 18650 cells with NCA cathode and graphite anode at different states of charge and temperatures. The resulting capacity fades are analyzed by differential voltage analysis (DVA) and coulometry. DVA reveals that the capacity fade results mainly from a shift in the electrode balancing due to a reduced inventory of cyclable lithium. Moreover, DVA confirms that the capacity fade strongly correlates with the anode potential. The observed loss of cyclable lithium is further analyzed by coulomb tracking, which stands for creating a continuous ampere-hour balance from all individual measurements performed with an examined cell and tracking the slippage of charging and discharging endpoints. It reveals the extent of anodic and cathodic side reactions during the storage periods and their effect on the inventory of cyclable lithium. Anodic side reactions, which are related to electrolyte reduction and passivation layer growth, can be identified as the main driver of capacity fade. Coulomb tracking also discloses that increasing cathodic side reactions can reduce the irreversible capacity fade, particularly for storage at very high SoC, which is likely to be misinterpreted as decelerated aging reactions. Evaluating also the reversible capacity fade prevents such a misconception.

In electric vehicles (EVs) and other applications, lithium-ion batteries experience variable load profiles with frequencies up to several kilohertz, as caused by power electronics. It is crucial to know if certain frequencies accelerate battery degradation and should be avoided. This applies in particular for EV batteries with an expected life-time of more than 10 years. The present work investigates the influence of alternating current (AC) profiles on the life-time of lithium-ion batteries. High-energy battery cells were tested for more than 1500 equivalent full cycles to practically check the influence of current ripples. The applied load profiles consisted of a constant current with superimposed AC frequencies. The frequencies were chosen with regards to the impedance spectra and ranged from 30 kHz to 1 Hz. The measurement results are compared to published results and to a second series of experiments conducted with high-power battery cells. The results of the experiments indicate that lithium-ion battery cells cycled with low frequencies experience a 1 to 2% higher impedance increase and capacity fade than battery cells cycled with high AC frequencies. These differences in aging characteristics established within the first 50 cycles of the brand-new battery cells and remained almost constant thereafter. For these experiments, the antithesis is disproved since no accelerated degradation occurred at higher frequencies. So, with regards to battery life-time, high frequencies can be tolerated as long as temperatures are considered as well. This new finding may help to reduce the costs of products with complex battery systems, such as EVs.

This paper presents a lithium-ion battery aging study in which pouch cells comprising a LiCoO₂/LiNi_0.8Co_0.15Al_0.05O₂ blended cathode and a graphite anode are examined. The study focuses on the impact of temperature and discharge rate on the cycle life of the tested cells. Compared to the aging behavior of other lithium-ion cells in the literature, the cells tested here are less sensitive to the discharge rate but more vulnerable to low temperature cycling. The vulnerability to low temperature mainly comes from cathode degradation, especially of the LiCoO₂ component. This is identified by electrochemical impedance spectroscopy, differential voltage analysis and incremental capacity analysis. The cells are able to achieve 3000–5000 cycles before reaching a capacity fade of 20%, also at higher discharge rates up to 5C. All in all, the high discharge rate capability could be a general advantage of pouch cells due to less mechanical and thermal stress in their geometry. Furthermore, more attention should be paid to the cathode health in low temperature applications of lithium-ion cells containing layered oxides. This paper focuses mainly on non-invasive aging detection methods for lithium-ion cells. Post-mortem results will be published in a following paper.