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Whereas the major potential of the development of lithium-based cells is commonly attributed to the use of solid polymer electrolytes (SPE) to replace liquid ones, the possibilities of the improvement of the applicability of the fuel cell is often attributed to the novel electrolytic materials belonging to various structural families. In both cases, the transport properties of the electrolytes significantly affect the operational parameters of the galvanic and fuel cells incorporating them. Amongst them, the transference number (TN) of the electrochemically active species (usually cations) is, on the one hand, one of the most significant descriptors of the resulting cell operational efficiency while on the other, despite many years of investigation, it remains the worst definable and determinable material parameter. The paper delivers not only an extensive review of the development of the TN determination methodology but as well tries to show the physicochemical nature of the discrepancies observed between the values determined using various approaches for the same systems of interest. The provided critical review is supported by some original experimental data gathered for composite polymeric systems incorporating both inorganic and organic dispersed phases. It as well explains the physical sense of the negative transference number values resulting from some more elaborated approaches for highly associated systems.

Transference Number Determination in Poor-Dissociated Low Dielectric Constant Lithium and Protonic Electrolytes