Ordering and stability in conducting polypyrrole

X-ray diffraction (XRD) was employed to characterize electrochemically synthesized polypyrrole (PPy) films with 1,5-naphthalene disulfonate (1,5-NDS) counterions treated with simple acid and base. Results show that the as-synthesized film is amorphous with short-range ordering in the polymer backbone. This ordering is soon lost after thermal ageing at 150°C for 60 days and there is evidence of counterion degradation. Base treatment of the PPy/1,5-NDS films has similar effects leading to a complete loss of ordering in the polymer backbone and dedoping of the polymer. Acid treatment at high temperatures increases the ordering of the polymer backbone and results in the development of a secondary interdopant peak confirming that ion exchange has occurred. Conductivity of the PPy was also increased substantially. The enhanced ordering was maintained even after thermal ageing. Room-temperature acid treatment also results in improved ordering of the polymer as well as the counterion but the increase in conductivity is only marginal and most of the ordering is soon lost after thermal ageing. Increase in ordering of the polymer structure seems to lead to better conductivity, although not necessarily improved thermal stability.

An XRD/XPS approach to structural change in conducting PPy

Electrochemically synthesised polypyrrole (PPy) with 1,5 naphthalene disulfonate (1,5-NDS) counterions treated with simple acid and base was characterised using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The as synthesised film was found to be amorphous with short-range ordering in the polymer backbone. Ordering was lost after thermal ageing with evidence of counterion degradation. Base treatment lead to loss of ordering as well as dedoping of the polymer whereas acid treatment at high temperature increases short range ordering. Conductivity was also increased dramatically with evidence of ion exchange. Ordering induced by the treatment was maintained even after thermal ageing.

Direct measurement of surface forces due to charging of solids immersed in a nonpolar liquid

Direct measurements of a long-range force between charged solid surfaces in a nonpolar liquid are presented for the first time. Measurements were made between mica surfaces in solutions of the anionic surfactant sodium di-2-ethylhexylsulfosuccinate (AOT) at millimolar concentrations in n-decane using a surface force apparatus which has been modified to improve its sensitivity for detecting a weak and long-range force. Modifications include a magnetic drive system, the use of a weak cantilever spring with the apparatus mounted in a vertical configuration, and a detailed consideration of the interference optics to allow accurate measurements of surface separations up to several micrometers. The results show a repulsion that is well fitted by theoretical curves based on a model in which only counterions enter the calculation, in other words, in the absence of a reservoir of ions in the solvent. Fitting the theory to the data allows an estimate of the mica surface charge density of ∼1 mC/m². A mechanism for surface charging of mica in this solution is proposed, which includes a role for trace amounts of water that are inevitably present and adsorbed surface aggregates of AOT. The relevance of the results to previously observed charge stabilization of colloids in nonaqueous solvents is discussed.

Decoupled ion conduction in poly(2-acrylamido-2-methyl-1-propane-sulfonic acid) homopolymers

As the focus on developing new polymer electrolytes continues to intensify in the area of alternative energy conversion and storage devices, the rational design of polyelectrolytes with high single ion transport rates has emerged as a primary strategy for enhancing device performance. Previously, we reported a series of sulfonate based copolymer ionomers based on using mixed bulky quaternary ammonium cations and sodium cations as the ionomer counterions. This led to improvements in the ionic conductivity and an apparent decoupling from the Tg of the ionomer. In this article, we have prepared a new series of ionomers based on the homopolymer of poly(2-acrylamido-2-methyl-1-propane-sulfonic acid) using differing sizes of the ammonium counter-cations. We observe a decreasing Tg with increasing the bulkiness of the quaternary ammonium cation, and an increasing degree of decoupling from Tg within these systems. Somewhat surprisingly, phase separation is observed in this homopolymer system, as evidenced from multiple impedance arcs, Raman mapping and SEM. The thermal properties, morphology and the effect of plasticizer on the transport properties in these ionomers are also presented. The addition of 10 wt% plasticizer increased the ionic conductivity between two and three orders of magnitudes leading to materials that may have applications in sodium based devices. This journal is

Increased ion conduction in dual cation [sodium][tetraalkylammonium] poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide-co-ethylacrylate] ionomers

© The Royal Society of Chemistry. Solid-state polymer electrolytes, as an alternative to traditional liquid electrolytes, have been intensively investigated for energy conversion and storage devices. The transport rate of single ions is the key to their high performance. For application in emerging sodium batteries, we have developed three dual-cation polymeric ionomers, which contain bulky tetraalkylammonium ions in addition to the sodium ion. The sizes and relative contents of the ammonium ions vary relative to the sodium ion contents. Comparative studies of ion dynamics, thermal properties, phase behaviours and ionic conductivities were carried out, taking advantage of various spectroscopic and thermal chemistry methods. The ion conductivities of the ionomers are greatly enhanced by the introduction of bulky counterions, as a result of the additional free volume and decreased sodium ion association. Raman spectroscopy and thermal analysis as well as the solid-state nuclear magnetic resonance studies are used to probe the conductivity behaviour.