Impedance spectroscopy studies of poly (methyl methacrylate)-lithium salts polymer electrolyte systems

In the present work, five systems of samples have been prepared by the solution casting technique. These are the plasticized poly(methyl methacrylate) (PMMA-EC) system, the LiCF3SO3 salted-poly(methyl methacrylate) (PMMA-LiCF3SO3) system, the LiBF4 salted-poly(methyl methacrylate) (PMMA-LiBF4) System, the LiCF3SO3 salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF3SO3) system, and the LiBF4 salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]LiBF4) system. The conductivities of the films from each system are characterized by impedance spectroscopy. The room temperature conductivity in the pure PMMA sample and (PMMA-EC system is 8.57x 10(-13) and 2.71 x 10(-11) S cm respectively. The room conductivity for the highest conducting sample in the (PNINIA-LiCF3SO3), (PMMA-LiBF4), ([PMMA-EC]-LiCF(3)SO3 and ([PMMA-EC]LiBF4) systems is 3.97 x 10(-6), 3.66 x 10(-7), 3.40 x 10(-5), and 4.07 x 10(-7) S cm(-1), respectively. The increase in conductivity is due to the increase in number of mobile ions, and decrease in conductivity is attributed to ion association. The increase and decrease in the number of ions can be implied from the dielectric constant, epsilon(r)-frequency plots. The conductivity-temperature studies are carried out in the temperature range between 303 and 373 K. The results show that the conductivity is increased when the temperature is increased and obeys Arrhenius rule. The plots of loss tangent against temperature at a fixed frequency have showed a peak at 333 K for the ([PMMA-EC]-LiBF4) system and a peak at 363 K for the ([PMM-EC]-LiCF3SO3) system. This peak could be attributed to P-relaxation, as the measurements were not carried out up to glass transition temperature, Tg. It may be inferred that the plasticizer EC has dissociated more LiCF3SO3 than LiBF4 and shifted the loss tangent peak to a higher temperature

Enhancement of anhydrous proton transport by supramolecular nanochannels in comb polymers

Transporting protons is essential in several biological processes as well as in renewable energy devices, such as fuel cells. Although biological systems exhibit precise supramolecular organization of chemical functionalities on the nanoscale to effect highly efficient proton conduction, to achieve similar organization in artificial systems remains a daunting challenge. Here, we are concerned with transporting protons on a micron scale under anhydrous conditions, that is proton transfer unassisted by any solvent, especially water. We report that proton-conducting systems derived from facially amphiphilic polymers that exhibit organized supramolecular assemblies show a dramatic enhancement in anhydrous conductivity relative to analogous materials that lack the capacity for self-organization. We describe the design, synthesis and characterization of these macromolecules, and suggest that nanoscale organization of proton-conducting functionalities is a key consideration in obtaining efficient anhydrous proton transport