Liquid polymer electrolytes
This thesis is concerned with ion-ion and ion-polymer interactions over a wide concentration range in polymer electrolytes with a view to shedding new light on the mechanism of ion migration. Additionally, the electrochemical stability window of these electrolytes on platinum and vitreous carbon electrodes has been thoroughly investigated. The final part of this thesis is concerned with determining the feasibility of polymer electrolytes as electrolytes in a new type of energy storage device, a double layer capacitor which incorporates activated carbon cloth electrodes. Conductivities and viscosities of solutions of Li, Na and K thiocyanates in low-molecular-weight, non-crystallizable liquid copolymers of ethylene oxide (EO) and propylene oxide (PO) have been measured. The curves of molar conductance versus sqrt c show well-defined maxima and minima. The conductivity is independent of copolymer molecular-weight but is enhanced by raising the EO content of the copolymer. The results are interpreted in terms of a model for ion migration in which ion association and redissociation effects play an important role. It is proposed that the characteristic properties of liquid polymer electrolytes can only be satisfactorily explained if the current is largely anionic. The electrochemical stability window of these electrolytes on platinum is dominated by the presence of a water reduction peak starting at approximately -1.0V which limits the overall stability to approximately 2V. The onset of water reduction is displaced to more negative potentials (-3.0V), thus increasing the stability window, on vitreous carbon electrodes. The value of the double layer capacitance on vitreous carbon electrodes (15-30muF cm-2) agrees well with published data. The double layer capacitance of activated carbon cloth electrodes is lower than anticipated. The importance of faradaic charging and discharging currents to the successful operation of double layer capacitors is indicated but no problems relating to the specific use of polymer electrolytes in such devices were found.