Origin of H2 Evolution in LIBs: H2O Reduction vs. Electrolyte Oxidation

Gassing in lithium-ion batteries (LIBs) is a serious challenge, especially at high voltage and elevated temperature. In this study, we use On-line Electrochemical Mass Spectrometry (OEMS) and a two-compartment cell with a newly developed aluminum edge-seal to elucidate the origin of H-2 evolution in LIBs. We demonstrate that the new sealing is entirely impermeable for gaseous and liquid species, thus allowing us to measure the true H-2 evolution from H2O reduction at a graphite electrode, without interference from the lithium counter-electrode. We further report that graphite//NMC full-cells without any diffusion barrier between anode and cathode show enhanced H-2 generation, especially for high charging potentials and at elevated temperature. We propose that the diffusion of protic electrolyte oxidation species (R-H+) from the cathode to the anode and their subsequent reduction is the origin of enhanced H-2 gassing. To prove this hypothesis, methanesulfonic acid is added to the electrolyte as a chemical source of protons. At the negative graphite electrode, all H+ can be quantitatively reduced to H-2. By the use of the electrolyte additives vinylene carbonate (VC) and lithium bis(oxalato) borate (LiBOB), less H-2 evolution is observed, since the reduction of both H2O and R-H+ is hindered by a more effective SEI on graphite. Finally, we demonstrate that the Al-sealed diffusion barrier between anode and cathode can stop the diffusion of oxidation products to the anode and therefore essentially eliminates the generation of H-2 caused by high cathode potentials. (C) The Author(s) 2016. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. All rights reserved.