Inorganic Backbone Ionomers: Design and Dielectric Response of Single-ion Conducting Polymers

Open Access
Author:
Bartels, Joshua Michael
Graduate Program:
Materials Science and Engineering
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
September 22, 2015
Committee Members:
  • Ralph H Colby, Dissertation Advisor
  • James Patrick Runt, Committee Chair
  • Michael Anthony Hickner, Committee Member
  • Harry R Allcock, Special Member
Keywords:
  • Ionomers
  • Dielectric Spectroscopy
  • Polysiloxane
  • Polyphosphazene
  • Conducting Polymer
Abstract:
Ion-conducting polymers were studied primarily through the use of dielectric spectroscopy. The conclusions drawn from ion conduction models of the dielectric data are corroborated by additional independent experiments, including x-ray scattering, calorimetry, prism coupling, and DFT calculations. The broad concern of this dissertation is to understand and clarify a path forward in ion conducting polymer research. This is achieved by considering low-Tg ionomers and the advantages imparted by siloxane and phosphazene backbones. The most successful dielectric spectroscopy model for the materials studied is the electrode polarization model (EP), whereas other models, such as the Dyre random barrier model, fail to describe the experimental results. Seven nonionic ether oxygen (EO) containing polymers were studied in order to observe the effect that backbone chemistry has on dipole motion. Conventional carbon-carbon backbone EO-containing polymers show no distinct advantage over similar EO-pendant polysiloxane or polyphosphazene systems. The mobility and effective backbone Tg imparted by the inorganic backbones are comparable. A short EO pendant results in a lower static dielectric constant due to restricted motion of dipoles close to the chain. The flexibility and chemical versatility of inorganic backbone polymers motivates further study of two ionomer systems. A polypohosphazene iodide conducting system was characterized by dielectric spectroscopy and x-ray scattering. Two end “tail” functionalization of the ammonium ion were used, a tail with two EOs and an alkyl tail of six carbons. This functional group plays an important role in ion dynamics and can wrap around the ion and self-solvate when EOs are present. The iodide-ammonium ionomers are observed to have unusually large high-frequency dielectric constants due to atomic polarization of ions. The strength of the atomic polarization scales with ion content. The aggregation state of ions is able to be determined from analysis of the static dielectric constant and show excellent agreement with x-ray scattering and DFT calculations, each ionomer strongly favoring the formation of quadrupoles. Finally a polysiloxane ionomer was considered and was mixed with three anion and/or cation solvating additives, tetraglyme, tetraethylene glycol, and branched poly(ethylenimine). The EP model of the dielectric response gives the conducting ion concentration and the mobility of conducting ions and shows an increase in conducting ion concentration with both anion solvating and cation solvating additives. The static dielectric constant indicates an increased preference for ion pairs when anion receptors are present. Most interestingly, the additive that best decreased the glass transition temperature and increased the static dielectric constant did not result in the best dc conductivity. The best dc conductivity resulted from tetraglyme because it solvated cations without interacting with the polymer. High ion conductivities have not been observed in polymer systems that decouple charge transport from polymer motion, and therefore low Tg ionomers are the natural path forward for commercially viable ionomers. Inorganic backbone polymers impart a low Tg without bringing any strong disadvantage to ionomers. These materials are very important for developing superior ion conductors and should be pursued in future ionomer research.