Abstract
Molecular and ionic assemblies at electrode/liquid electrolyte interfaces, i.e., the electric double layer (EDL), define battery performance by directing the formation of stable interphases. An unstable interphase can hamper metal-cation diffusion, lead to continuous electrolyte consumption, and also promote non-uniform electrochemical processes like dendrite formation. The co-selection of electrolyte chemistry and initial cycling conditions together are generally considered for the design of desirable interphases. At the same time, the dielectric nature of the electrode material is largely ignored, notwithstanding the high unreliability of the assumption that the nature of the EDL and the mechanism of the interphase formation at metallic and semiconductive electrodes are identical. Here we show that the dielectric nature of the charged electrode greatly affects the interfacial metal-anion-solvent composition; therefore, different interphase chemistry will be formed, suggesting different initial cycling conditions need to be established on a case-by-case basis to form the desired interphase. This phenomenon correlates with the metal ion solvation chemistry and the adsorption of species at the electrified electrode due to the competition of van der Waals and coulombic interactions.
Original language | English |
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Pages (from-to) | 3919-3931 |
Number of pages | 13 |
Journal | Energy and Environmental Science |
Volume | 16 |
Issue number | 9 |
DOIs | |
State | Published - Jul 19 2023 |
Externally published | Yes |
Funding
D. A. R., F. C., M. F., and P. C. H. acknowledge the Australian Research Council (ARC) for funding via the Australian Centre for Electromaterials Science, grant CE140100012. M. F., F. C. and P. C. H. acknowledge ARC grant DP210101172. ANS acknowledges ARC funding through the Future Fellowship (FT200100317). The simulation work was undertaken with the assistance of resources provided at the NCI National Facility systems at the Australian National University through the National Computational Merit Allocation Scheme supported by the Australian Government. The authors gratefully acknowledge CIC energiGUNE for providing the NaFePO4 cathode material. D. A. R., F. C., M. F., and P. C. H. acknowledge the Australian Research Council (ARC) for funding via the Australian Centre for Electromaterials Science, grant CE140100012. M. F., F. C. and P. C. H. acknowledge ARC grant DP210101172. ANS acknowledges ARC funding through the Future Fellowship (FT200100317). The simulation work was undertaken with the assistance of resources provided at the NCI National Facility systems at the Australian National University through the National Computational Merit Allocation Scheme supported by the Australian Government. The authors gratefully acknowledge CIC energiGUNE for providing the NaFePO cathode material. 4