Lithium-ion batteries on electric vehicles have been increasingly deployed for the enhancement of grid reliability and integration of renewable energy, while users are concerned about extra battery degradation caused by vehicle-to-grid (V2G) operations. This paper details a multi-year cycling study of commercial 24 Ah pouch batteries with Li(NiMnCo)O₂ (NCM) cathode, varying the average state of charge (SOC), depth of discharge (DOD), and charging rate by 33 groups of experiment matrix. Based on the reduced freedom voltage parameter reconstruction (RF-VPR), a more efficient non-intrusive diagnosis is combined with incremental capacity (IC) analysis to evaluate the aging mechanisms including loss of lithium-ion inventory and loss of active material on the cathode and anode. By analyzing the evolution of indicator parameters and the cumulative degradation function (CDF) of the battery capacity, a non-linear degradation model with calendar and cyclic aging is established to evaluate the battery aging cost under different unmanaged charging (V0G) and V2G scenarios. The result shows that, although the extra energy throughput would cause cyclic degradation, discharging from SOC 90 to 65% by V2G will surprisingly alleviate the battery decaying by 0.95% compared to the EV charged within 90–100% SOC, due to the improvement of calendar life. By optimal charging strategies, the connection to the smart grid can potentially extend the EV battery life beyond the scenarios without V2G.

The internal negative electrode potential in lithium-ion batteries (LIBs) is intricately linked to the lithium-ion intercalation and plating reactions occurring within the cell. With the expansion of cell sizes, the internal negative electrode potential distribution gradually becomes inconsistent. However, the existing negative electrode potential estimation models and fast charging strategies have not yet considered the impact of consistency, and the model estimation accuracy will be greatly influenced by different temperatures and charging rates. This study proposes an online lithium-free fast charging equivalent circuit model (OLFEM) for estimating the negative electrode potential terminal voltage and developing fast charging strategies of long-dimensional LIBs in real vehicles. This study employs distributed reference electrodes integrated into long-dimensional LIBs and compares the negative electrode potential measured in the vicinity of both the negative and positive tabs. Subsequently, based on the lowest negative electrode potential point, model parameters were obtained at different temperatures and charging rates. This model is further verified under different operating conditions. Finally, a fast-charging strategy without lithium plating is developed in real-time based on the negative electrode potential estimated by the model. The results demonstrate that long-dimensional cells exhibit a lower negative electrode potential on the positive tab side. Across various temperatures and charging rates, the calibrated model achieves a negative electrode potential estimated error within 25 mV, and the estimation error for terminal voltage is within 5 mV. The proposed fast-charging method prevents lithium plating and charges the cell up to 96.8% within an hour. After 100 cycles, the cell experiences a capacity degradation of less than 2%, and the disassembly results indicate that no lithium precipitation has occurred. The methods outlined in this study provide valuable insights for online fast charging of large-dimensional batteries without lithium plating.