Raić, Matea; Magdić Košiček, Katja; Kvastek, Krešimir (2025) Improving Reliability of EIS in Nonstationary Conditions: Applications to dynamic behavior of Magnesium Rechargeable Batteries. Journal of The Electrochemical Society, 172 (7). ISSN 1945-7111
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Abstract
Rechargeable magnesium batteries suffer a significant overpotential response during galvanostatic cycling often associated with processes at the magnesium/electrolyte interface. These changes cause the system instability, making it difficult to interpret measurements accurately, especially when obtained under uncontrolled conditions, as is often the case in testing of commercial cells. To solve this problem, in this study, we utilized operando electrochemical impedance spectroscopy to investigate the magnesium electrode under nonstationary conditions using the 4D analysis method. This approach enables generation of instant impedance spectra by establishing a mathematical relationship between iso-frequency impedance values and operating time, enabling extrapolation or interpolation of the spectra at any specific moment. Unlike lithium-based systems, where similar corrections have been successfully applied, magnesium systems face unique challenges, primarily due to the divalent nature of Mg ions. These include stronger ion-solvent interactions, sluggish mass transport, and low cation transfer numbers. These factors contribute to potential shifts and instabilities when using Mg metal as a reference electrode. This research focuses on the analysis of the symmetric Mg/Mg cell under galvanostatic and potentiostatic polarization, conditions where nonstationarity is prominent. Continuous impedance measurements taken during these polarizations were used to generate instant spectra through the 4D method. Our goal was to improve the reliability of spectra obtained under nonstationary conditions, paving the way for more accurate online monitoring of battery systems. This, in turn, enhances understanding of electrode/electrolyte processes and supports the development of more stable and efficient rechargeable magnesium batteries.
| Item Type: | Article | ||||||||
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| Uncontrolled Keywords: | electrochemical impedance spectroscopy; nonstationarity; 4-dimensional analysis; magnesium batteries | ||||||||
| Subjects: | NATURAL SCIENCES > Chemistry > Physical Chemistry | ||||||||
| Divisions: | Division for Marine and Enviromental Research Division of Materials Physics |
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| Depositing User: | Katja Magdić Košiček | ||||||||
| Date Deposited: | 03 Dec 2025 13:58 | ||||||||
| URI: | http://fulir.irb.hr/id/eprint/10272 | ||||||||
| DOI: | 10.1149/1945-7111/adf09d |
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