Development and application of a 3-electrode setup for the operando detection of side reactions in Li-Ion batteries

Join us to learn about the development and application of a 3-Electrode setup for the operando detection of side reactions in Li-Ion batteries.

Detecting parasitic side reactions originating both from the cathode active materials (CAMs) and the electrolyte is paramount for developing more stable cell chemistries for Li-ion batteries. This talk will present a method for the qualitative analysis of oxidative electrolyte oxidation, as well as the quantification of released lattice oxygen and transition metal ions (TM ions) from the CAM. It is based on a 3-electrode cell design employing a Vulcan carbon-based sense electrode (SE) that is held at a controlled voltage against a partially delithiated lithium iron phosphate (LFP) counter electrode (CE). At this SE, reductive currents can be measured while polarizing a CAM or carbon working electrode (WE) against the same LFP CE. In voltametric scans, we show how the SE potential can be selected to specifically detect a given side reaction during CAM charge/discharge, allowing, e.g., to discriminate between lattice oxygen, protons, and dissolved TMs. Furthermore, it is shown via On-line Electrochemical Mass Spectrometry (OEMS) that O2 reduction in the here-used LP47 electrolyte consumes ~2.3 electrons/O2. Using this value, the lattice oxygen release deduced from the 3-electrode setup upon charging of the NCA WE is in good agreement with OEMS measurements up to NCA potentials >4.65 VLi. At higher potentials, the contributions from the reduction of TM ions can be quantified by comparing the integrated SE current with the O2 evolution from OEMS

Lennart Reuter is a PhD student in the group of Prof Hubert A Gasteiger at the Chair of Technical Electrochemistry at TUM. His research focused on the interfacial processes in lithium-ion batteries that govern calendar life, cycle stability, and rate capability. He advanced the on-line electrochemical mass spectrometry (OEMS) technique to investigate gas evolution mechanisms from interfacial side reactions at the cathode and anode. His work also explored how SEI formation and graphite structural changes affect Li⁺ transport, using impedance spectroscopy and complementary analysis techniques.

Leonhard J Reinschluessel is currently a PhD candidate at at the Chair of Technical Electrochemistry in the Gasteiger research group at the Technical University of Munich (TUM). His current work encompasses an in-depth understanding of the complex interplay of cathode- and electrolyte degradation mechanisms in lithium-ion batteries using operando lab-based and synchrotron techniques. He received his MSc in chemistry from TUM, where he investigated the mitigation of aging of FeNC-based cathode catalyst layers in PEMFCs in his thesis at the Gasteiger group Electrochemistry at TUM. His research focused on the interfacial processes in lithium-ion batteries that govern calendar life, cycle stability, and rate capability. He advanced the on-line electrochemical mass spectrometry (OEMS) technique to investigate gas evolution mechanisms from interfacial side reactions at the cathode and anode. His work also explored how SEI formation and graphite structural changes affect Li⁺ transport, using impedance spectroscopy and complementary analysis techniques.