Operando Thermo‐Electrochemical Diagnostics with Au, TiO 2, and LiFePO 4 as Reference Electrodes in Li‐Ion Pouch Cells

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Thermo‐electrochemical monitoring of state‐of‐the‐art rechargeable Li‐ion batteries during operation is critical for safety and reliability, yet it remains quite limited, relying on conventional full cell measurements with in situ techniques lagging behind. Here, the feasibility of incorporating Au, LiFePO4, and TiO2 electrochemical sensors into commercially available pouch cells, in conjunction with thermocouples to track the cell behavior during galvanostatic cycling at varying operating temperatures is demonstrated. It is found that Au provides the best in operando based electrochemical diagnostics for stable thermo‐electrochemical performance via long‐term cyclability (>1000 h), differential capacity curves, and at 25, 40, and 60 °C, followed by TiO2, and LiFePO4. Furthermore, cell temperature changes are analyzed alongside reference electrode readings, demonstrating the advantages of the complementary nature of these techniques for cell thermodynamics. Collectively, these findings offer deep insight into an improved battery management approach for next‐generation lithium‐ion energy storage systems.
Original languageEnglish
Article number2200248
Number of pages8
JournalEnergy Technology
Issue number10
Early online date23 Aug 2022
Publication statusPublished - 6 Oct 2022

Bibliographical note

© 2022 The Authors. Energy Technology published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.


Funding Information: The research work presented in this article is financially supported by the European Union's Horizon 2020 research and innovation project SeNSE (grant agreement No 875548) https://cordis.europa.eu/project/id/875548 and EPSRC project M‐RHEX (EP/R023581/1).


  • LFP
  • Research Article
  • Research Articles
  • battery diagnostics
  • electrochemistry
  • gold
  • lithium-ion batteries
  • pouch cells
  • reference electrodes
  • thermodynamics
  • titanium oxide


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