Influence of Cycling in Different State-of Charge Windows on Lifetime and Electrode Expansion of Microscale Silicon-Dominant Lithium-Ion Batteries

Silicon (Si) is a promising active anode material for next-generation lithium-ion batteries due to its high theoretical electrochemical capacity of 3579 mAh/g Si (Li 15 Si 4 ) and low costs using microscale Si particles. 1,2 However, the wide usage of Si as an active anode material is hindered due to its lower lifetime compared to graphite anodes. The degradation in silicon-containing batteries can be suppressed by partial lithiation strategies, 2,3,4 with applications for automotive cells leading to improved lifetime. 5 However, the lifetime problem still exists in partially lithiated microscale Si particles with lower volume expansion 2,3 with ≈200 cycles for one-third silicon utilization, i.e., 1200 mAh/g Si 2 . Moreover, we confirmed in our previous study 6 as reported by Wetjen et al. 4 and Haufe et al. 2 that lower cell discharge cut-off voltages and thus higher silicon delithiation potentials versus Li + /Li led to accerlated aging and should be avoided. Thus, the motivation for this study is to avoid these high anode delithiation potentials by operating the cells in a high full cell state of charge (SoC) and to investigate the influence of different SoC windows on lifetime with laboratory 182.1 ± 0.7 mAh/g NCA Swagelok T-cells comprising a microscale silicon-dominant anode and a NCA cathode. The electrode-specific aging is monitored with the lithium metal reference electrode based on the anode and cathode potentials and pulse tests. To investigate the aging in different SOC regimes, three cycling conditions were chosen in the low (LV), middle (MV) and high voltage (HV) window and compared to cells cycled between 2.8 and 4.2 V as full voltage 6 . The voltage window of LV, MV and HV were chosen to represent cycling between 0-50%, 25-75%, and 50-100% SOC, respectively. Formation and checkups were the same for all cells with 2.80 V to 4.20 V. After reaching the end-of-life criterion of 55% state of health (SoH), the cells were disassembled and anode and cathodes were re-assembled in half-cells for a post-mortem analysis to reveal loss of lithium inventory (LLI) and loss of active material of the anode LAM An , and the cathode LAM Cat of the respective full-cells. Complementary to the electrochemical aging, dilatometer measurements 7 were conducted to quantify the electrode expansion for the different silicon anode SoC windows since particle decoupling is expected to be one of the major aging mechanisms for microscale silicon 2 , which is expected for high electrode expansions. For the electrochemical results, the lifetime can be drastically increased from ≈230 to ≈560 equivalent full cycles (EFCs) for operating the full cell in the HV compared to the FV window, as shown in Fig. 1a. One EFCs is defined as the total charge throughput for charging and discharging one cycle normalized to the capacity of the initial checkup cycle. Over aging, the full cell degradation correlates very well with the end of discharge potential of the silicon anodes. Moreover, the electrode-specific pulse results show strong anode degradation while the cathode remains intact. The post-mortem results reveal LLI as most dominenat aging mode, which was very similar for all voltage windows. The HV cells showed both the highest LAM NE and LAM PE , whereas LAM NE was more dominant compared to LAM PE . The silicon amorphization was the lowest for the LV anodes and the highest for the HV anodes at the same SoH. The dilatometer results show that the silicon electrode expansion is the lowest for the low lithiation, i.e., LV, and the highest for the highest lithiation, i.e., HV. From the dilatometry results, we conclude that the mechanical electrode stability does not limit lifetime. Our results demonstrate that lifetime can be significantly improved by a factor of ≈2.4 based on the EFCs if operating cells with silicon dominant anodes in high SoCs and that low SoCs should be avoided. Acknowledgments: S. F. gratefully acknowledges the financial support from the BMBF (Federal Ministry of Education and Research, Germany) under the auspices of the ExZellTUM III project (grant number 03XP0255). The authors want to thank our student worker, Maximilian Reichl, for the fabrication of the NCA coatings. We also thank Wacker Chemie AG for kindly providing the microscale silicon material. References: 1 Jantke et al. Journal of The Electrochemical Society 2019, 166, A3881–A3885. 2 Haufe et al. Journal of The Electrochemical Society 2021, 168, 080531. 3 Li et al. Electrochiminca Acta 2019, 295, 778-786. 4 Wetjen et al. Journal of The Electrochemical Society 2018, 165, A1503-A1514 5 Mikheenkova et al. Journal of The Electrochemical Society 2023, 170, 080503 6 Friedrich et al. ECS Meeting Abstract 2023 A04-0538. 7 Spingler et al. Journal of The Electrochemical Society 2021, 168, 040515 Figure 1