Highly conductive polymer electrolyte amorphous

High conductivity but a complete lack of dimensional stability is not a recipe for success. The viscosity of some completely amorphous, high conductivity polymer electrolyte materials including MEEP and certain early, over-plasticized PEO-based systems, is too low for the electrolyte to remain in position. 

HIGH CONDUCTIVITY IN AN AMORPHOUS CROSSLINKED SILOXANE POLYMER ELECTROLYTE... 

Solvent-free polymer-electrolyte-based batteries are still developmental products. A great deal has been learned about the mechanisms of ion conductivity in polymers since the discovery of the phenomenon by Feuillade et al. in 1973 [41], and numerous books have been written on the subject. In most cases, mobility of the polymer backbone is required to facilitate cation transport. The polymer, acting as the solvent, is locally free to undergo thermal vibrational and translational motion. Associated cations are dependent on these backbone fluctuations to permit their diffusion down concentration and electrochemical gradients. The necessity of polymer backbone mobility implies that noncrystalline, i.e., amorphous, polymers will afford the most highly conductive media. Crystalline polymers studied to date cannot support ion fluxes adequate for commercial applications. Unfortunately, even the fluxes sustainable by amorphous polymers discovered to date are of marginal value at room temperature. Neat polymer electrolytes, such as those based on poly(ethyleneoxide) (PEO), are only capable of providing viable current densities at elevated temperatures, e.g., >60°C. 

Because the conductivity of polymer electrolytes is generally low, thin batteries are assembled (50-200 pm) with electrolyte thickness ranging from 20 to 50 pm. Conventional polymer electrolytes based on PEO and lithium salts, owing to their high crystallinity, reach useful conductivity values only at temperatures above 60 °C, i.e., above the melting temperature of the crystalline phase. If the low conductivity at room temperature prevents their application for consumer electronics, this does not represent an obstacle for electric vehicles, for which an operating temperature higher than that of the transition in the amorphous phase is expected. 

In conclusion the introduction of metal oxide into the polymer matrix has significantly improved the amorphicity, mechanical, thermal and ionic conductivity of polymer electrolytes. Novel analytical devices based on nanostructured metal oxides and CPs are cost-effective, highly sensitive due to the large surface-to-volume ratio of the nanostructure, and additionally show excellent selectivity when coupled to bio-recognition molecules with simple design [99-102]. 

Atomic force microscopy (AFM) and electrochemical atomic force microscopy (ECAFM) have proven usefiil for the study of nucleation and growth of electrodeposited CP films on A1 alloy [59]. AFM was used to study adhesion between polypyrrole and mild steel [60], whereas electric force microscopy (EFM) has been used to study local variations in the surface potential (work function) of CP films [61]. AFM with a conductive tip permits a nanoscale AC impedance measurement of polymer and electrolyte interfaces, permitting differentiation between highly conductive amorphous regions and less-conductive crystalline regions of the CP film [62]. 

In terms of crystalline structure, this means that a channel of sufficient size must link the accessible sites in order that ion diffiision is not hindered if channels are too large with respect to the ion radius, ions can be trapped. In polymers, the region of high conductivity is found in the homogeneous, elastomeric amorphous phase and the presence of partial crystallinity inhibits conduction. The motion of mobile ions is strongly linked to that of polymer segments and ionic conductivity drops to extremely low values below 7 where the chain segment motions are frozen. Both anions and cations are mobile in many polymer/salt electrolytes. 

To achieve high conductance, both reasonable conductivity and mechanical stability in a thin film form are required. Semi-crystalline polymers have superior mechanical characteristics but vastly inferior conductivity properties to those which are fully amorphous (and well above their Tg), since ionic motion does not occur in the crystalline regions. The design of an optimized electrolyte for battery use is in fact more strongly dictated by morphological considerations (which are affected by the choice of dissolved salt) than by the selection of a system containing a solute with a high cationic transference number. 

Itaconates of structure II in which n = 1-5 are amorphous polymers. Their Li salt complexes, however, retain the amorphous morphology only when n 2. Even the amorphous electrolytes show low conductivity apparently because of large increases in the Tg upon complexation with Li salts. It is apparent that the amorphous morphology of a polymer electrolyte should be complemented by high polymer fluidity in order to have good conductivity at ambient temperatures. 

Indeed, one matter of concern in the development of new polymer ionic membranes lies in the fact that their high conductivity is often associated with amorphous, low-viscosity phases. Therefore, in their conductive form, these membranes behave like soft solids with poor mechanical stability their direct use in LPBs may give rise to those problems commonly met in conventional liquid electrolyte systems, such as leakage, loss of interfacial contacts and short circuits. Under these circumstances, one of the most useful feature of LPBs, namely the solid-state configuration, would then be lost. Consequently, it is of key importance to assure that the polymer electrolyte membrane maintains good mechanical properties even in its conductive state. 

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