Structural electroneutrality in Onsager–Stefan–Maxwell transport with charged species
نویسندگان
چکیده
We present a method to embed local electroneutrality within Onsager–Stefan–Maxwell electrolytic-transport models, circumventing their formulation as differential systems with an algebraic constraint. Flux-explicit transport laws are developed for general multicomponent electrolytes, in which the ionic conductivity, component diffusivities, and transference numbers relate Stefan–Maxwell coefficients through invertible matrix calculations. A construction we call ‘salt–charge basis’ implements Guggenheim’s transformation of species electrochemical potentials into combinations describing minimal set neutral components, leaving unique combination associated electricity. Defining conjugate concentrations fluxes that preserve structures Gibbs function energy dissipation retains symmetric Onsager reciprocal relations. The framework reproduces Newman’s constitutive binary electrolytes Pollard–Newman molten salts; also propose salt solutions two-solvent blends, such lithium-ion-battery electrolytes. Finally, simulate potentiostatic Hull cell containing non-ideal electrolyte concentration-dependent properties.
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ژورنال
عنوان ژورنال: Electrochimica Acta
سال: 2023
ISSN: ['1873-3859', '0013-4686']
DOI: https://doi.org/10.1016/j.electacta.2022.141769