Influence of complexing agents and solvents

In the example above, a short-chain poly(ethylene glycol) was added to a rigid polyelectrolyte to plasticise the material and thereby increase polymer-solvent motion in the vicinity of mobile ions. This strategy has been widely explored as a means of improving ion transport in electrolytes. 

The addition of a cryptand to some polyelectrolytes leads to significant increases in conductivity and in some cases IR and Raman spectroscopy demonstrate that the cryptand breaks up the ion-ion interactions (Chen, Doan, Ganapathiappan, Ratner and Shriver, 1991 Doan, Ratner and Shriver, 1991). Apparently the reduction of ion association more than offsets the reduction in mobility of the cation-crypt complex, which has a larger effective radius than the simple cation. It is also possible that the cryptand-ion complex is rendered more mobile by the reduction of polymer-cation complex formation, but this point has not been investigated in any detail. 

Since the chelating ligand forms a strong complex with cations it is conceivable that this complex formation would lead to slow transfer of the ion into a cathode material  

This issue has been investigated using amalgam cathodes, and the indications are that the cryptand has negligible influence on the rate of incorporation of a sodium ion into the amalgam (Chen et ai, 1991 Doan et al, 1991). One of the most interesting applications of the cryptands is that they increase the mobility of dipositive ions in polymer electrolytes (Chen and Shriver, 1991). 

Mg has been studied in a polyelectrolyte system where the counterion is a phosphazene-bound sulphonate group. In this case the finite but low conductivity is due to Mg migration. A large increase in conductivity is noted when a bicyclic ligand, crypt [2.1.1.], is introduced (Hancock and Martell, 1988). Apparently, the cation-anion and cation-polymer interactions are reduced by complex formation, resulting in a more mobile cation, despite its larger effective radius. 

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