Abstract
We propose a dynamical theory of how the chemical energy stored in a battery generates the electromotive force (emf). In this picture, the battery's half-cell acts as an engine, cyclically extracting work from its underlying chemical disequilibrium. We show that the double layer at the electrode-electrolyte interface can exhibit a rapid self-oscillation that pumps an electric current, thus accounting for the persistent conversion of chemical energy into electrical work equal to the emf times the separated charge. We suggest a connection between this mechanism and the slow self-oscillations observed in various electrochemical cells, including batteries, as well as the enhancement of the current observed when ultrasound is applied to the half-cell. Finally, we propose more direct experimental tests of the predictions of this dynamical theory. This journal is
| Original language | English |
|---|---|
| Pages (from-to) | 9428-9439 |
| Number of pages | 12 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 23 |
| Issue number | 15 |
| Early online date | 23 Mar 2021 |
| DOIs | |
| Publication status | Published - 21 Apr 2021 |
Bibliographical note
Funding Information:We thank Luuk Wagenaar and Lotte Schaap for fruitful discussions and critical questions. AJ also thanks Esteban Avendaño, Diego González, Mavis Montero, and Roberto Urcuyo for educating him on electrochemical double layers. RA was supported by the International Research Agendas Programme (IRAP) of the Foundation for Polish Science (FNP), with structural funds from the European Union (EU). DG-K was supported by the Gordon and Betty Moore Foundation as a Physics of Living Systems Fellow (grant no. GBMF45130). AJ was supported by the Polish National Agency for Academic Exchange (NAWA)’s Ulam Programme (project no. PPN/ULM/2019/1/00284). EvH was supported by the research programme ENW XS (grant no. OCENW.XS.040), financed by the Dutch Research Council (NWO). EvH and RA also gratefully acknowledge the support of the Freiburg Institute of Advanced Study (FRIAS)’s visitors’ program during the first stages of this collaboration.
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