Revealing the role of phosphoric acid in all-vanadium redox flow batteries with DFT calculations and in situ analysis
Literature Information
Fabio Jonas Oldenburg, Marta Bon, Daniele Perego, Daniela Polino, Teodoro Laino, Lorenz Gubler
The present work suggests the use of a mixed water-based electrolyte containing sulfuric and phosphoric acid for both negative and positive electrolytes of a vanadium redox flow battery. Computational and experimental investigations reveal insights on the possible interactions between the vanadium ions in all oxidation states and sulphate, bisulphate, dihydrogen phosphate ions and phosphoric acid. In situ cycling experiments and ion-specific electrochemical impedance measurements confirmed a significant lowering of the charge-transfer resistance for the reduction of V(III) ions and, consequently, an increase of the voltaic efficiency associated with the negative side of the battery. This increase of performance is attributable to the complexation of this oxidation state by phosphoric acid. So far, mixed acids have mainly been discussed with the focus on V(V) solubility. In this work we rationalize the impact of the mixed acids on the electrochemical efficiency opening new strategies on how to improve the cycling performance with ionic additives.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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