Charge/discharge processes of organic radical batteries based on the radical polymer's redox reaction are largely influenced by carbon fibers consisting in the composite electrodes to help electron transfer. To find the optimal structure of the composite electrodes, the dominant electron transfer processes were determined by ac impedance measurement of the composite electrodes. A strong correlation between the overall electron transfer resistance of the composite electrodes and the materials of the current collector suggests that the electric conduction to the current collector through the contact resistance should be crucial. It was also confirmed that the charge/discharge performance of the composite electrode was related to the overall electron transfer resistance of the composite electrode. These results indicated that the charge/discharge performance of the radical battery was dominated by the interfacial electron transfer processes at the current collector/carbon fiber interface and that the rate performance would be much improved by suitably designing the interfacial structure.
The formation constants, KML+, for 1:1 complexes of 15-crown-5 (15C5), 18-crown-6 (18C6), and dibenzo-24-crown-8 (DB24G8) with alkali metal ions and the limiting ionic molar conductivities, λ°, of the complexed cations in propylene carbonate have been determined at 25 °C conductometrically. The KML+ value series about the same alkali metal ion among the crown ethers are given in the order 18C6>>DB24C8>15C5. The KML+ sequences of the alkali metal ions with 15C5, 18C6, and DB24C8 are Li+>Na+>K+>Rb+>Cs+, K+>Na+>Rb+>>Cs+, and Na+>K+>Rb+≥Cs+, respectively. The indication is that the ability of the alkali metal ions to form complexes with the three crown ethers is not always affected primarily by the relative sizes of the alkali metal ions and the crown ether cavity. In each case of 18C6 and DB24C8 the λ° values of the alkali metal ions are nearly equal, while in the case of 15C5 there are considerably differences, suggesting that in the former case the charge of the alkali metal ion trapped in the crown ether cavity is effectively shielded. This is not true in the latter case.
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