Determination of Leakage Currents Via Voltage Hold and Voltage Relaxation Method Using High Precision Coulometry - a Comparison and Optimization Study

Parasitic side reactions on the surface of the anode and the cathode of lithium-ion batteries contribute significantly to calendar and cyclic aging [1, 2]. In order to investigate these parasitic side reactions, such as solid electrolyte interface growth, this study focuses on two methods broadly utilized to determine leakage currents: the voltage hold and the voltage relaxation method. Regarding the voltage relaxation method, the open circuit voltage (OCV) decay is observed over weeks without allowing active electrode de-/lithiation [3] and subsequently, a small pulse is performed to calculate the leakage current [4]. For the voltage hold method, a defined voltage is kept constant, which compensates the parasitic side effects and allows active electrode de-/lithiation to maintain the state of charge (SoC) [5, 6]. To compare these methods, different results are found in literature. On the one hand, both methods were reported to deliver individual results [3, 7], while other research activities [8] found the variance only at 100% SoC. Therefore, voltage hold and voltage relaxation were compared in this study, utilizing high precision coulometry (HPC). The measurements were conducted on 16 commercial LGChem INR18650MJ1 cylindrical cells at 25 °C, 40 °C and 55 °C and different SoCs of 10%, 50%, 90%, and 100% SoC, respectively. The cells were preconditioned to each SoC and were subsequently stored for 30 days to minimize relaxation and anode overhang effects. Afterwards, voltage hold and voltage relaxation measurements were carried out for 21 days at each temperature and SoC. In addition to the discharge pulse, an incremental capacity analysis (ICA) was conducted for all three temperatures through the whole voltage range to compare and validate the results obtained. The measurements of this study delivered similar results for the voltage hold and the voltage relaxation method, especially at 10% SoC and 50% SoC. Consequently, the voltage hold did not contribute to additional parasitic side reactions from allowing active de-/lithiation of the electrode. Minor deviations were found for 90% SoC and 100% SoC, for which one possible explanation may be the flat shape of the OCV curve, among others. In addition, the results show a strong dependency on the pulse length and strength. This study was part of the project ExZellTUM III, funded by the German Federal Ministry of Education and Research (BMBF) under grant number 03XP0255, supervised by Project Management Jülich (PTJ). Literature [1] Smith, A.; Burns, J.; Dahn, J.: A high precision study of the coulombic efficiency of Li-ion batteries, In: Electrochemical and Solid-State Letters 13, p. A177, 2010 [2] Birkl, C. R.; Roberts, M. R.; McTurk, E.; Bruce, P. G.; Howey, D. A.: Degradation diagnostics for lithium ion cells, In: Journal of Power Sources 341, p. 373-386, 2017 [3] Zilberman, I.; Sturm, J.; Jossen, A.: Reversible self-discharge and calendar aging of 18650 nickel-rich, silicon-graphite lithium-ion cells, In: Journal of Power Sources 425 (9), p. 217-226, 2019 [4] Schmidt, J. P.; Weber, A.; Ivers-Tiffée, E.: A novel and fast method of characterizing the self-discharge behaviour of lithium-ion cells using a pulse-measurements technique, In: Journal of Power Sources 274, p.1231-1238, 2015 [5] Lewerenz, M.; Käbitz, S.; Knips, M.; Münnix, J.; Schmalstieg, J.; Warnecke, A.; Uwe Sauer, D.: New method evaluating currents keeping the voltage constant for fast and highly resolved measurement of Arrhenius relation and capacity fade, In: Journal of Power Sources 353, p.144-151, 2017 [6] Vadivel, N. R.; Ha, S.; He, M.; Dees, D.; Trask, S.; Polzin, B.; Gallagher, K. G.: On leakage current measured at high cell voltages in lithium-ion batteries, In: Journal of The Electrochemical Society, 164 (2), p. 508-A517, 2017 [7] Theiler, M.; Endisch, C.; Lewerenz, M.: Float Current Analysis for Fast Calendar Aging Assessment of 18650 Li(NiCoAl)O2/Graphite Cells, In: Batteries 7 (2), p. 22–22, 2021 [8] Käbitz, S.; Gerschler, J. B.; Ecker, M., Yurdagel, Y.; Emmermacher, B.; André, D.; Mitsch, T.; Uwe Sauer, D.: Cycle and calendar life study of a graphite LiNi1/3Mn1/3Co1/3O2 Li-ion high energy system. Part A: Full cell characterization, In: Journal of Power Sources 239, p. 572-583, 2013