Guinevere A. Giffin

Interplay between Structure and Relaxations in Perfluorosulfonic Acid Proton Conducting Membranes

This study focuses on changes in the structure of ionomer membranes, provided by the 3M Fuel Cells Component Group, as a function of the equivalent weight (EW) and the relationship between the structure and the properties of the membrane. Wide-angle X-ray diffraction results showed evidence of both non-crystalline and crystalline ordered hydrophobic regions in all the EW membranes except the 700 EW membrane. The spectral changes evident in the vibrational spectra of the 3M membranes can be associated with two major phenomena: (1) dissociation of the proton from the sulfonic acid groups even in the presence of small amounts of water; and (2) changes in the conformation or the degree of crystallinity of the poly(tetrafluoroethylene) hydrophobic domains both as a function of EW and membrane water content. All the membranes, regardless of EW, are thermally stable up to 360 °C. The wet membranes have conductivities between 7 and 20 mS/cm at 125 °C. In this condition, the conductivity values follow VTF behavior, which suggests that the proton migration occurs via proton exchange processes between delocalization bodies (DBs) that are facilitated by the dynamics of the host polymer. The conductivity along the interface between the hydrophobic and hydrophilic domains makes a larger contribution in the smaller EW membranes likely due to the existence of a greater number of interfaces in the membrane. The larger crystalline domains present in the higher EW membranes provide percolation pathways for charge migration between DBs, which reduces the probability of charge transfer along the interface. Therefore, at higher EWs although there is charge migration along the interface within the hydrophobic-hydrophilic domains, the exchange of protons between different DBs is likely the rate-limiting step of the overall conduction process.

Ionic liquid-based electrolytes for “beyond lithium” battery technologies

Growing energy demands and the shift to renewable energy sources will result in increased need for efficient energy storage. To anticipate and satisfy these demands, electrochemical energy storage technologies beyond those based on lithium chemistries are being explored. These “beyond lithium” battery technologies, which are based on metals such as sodium, magnesium, aluminum and zinc, have advantages particularly in terms of raw material abundance and cost, but are still in the early stages of research and development as compared to lithium-ion batteries. One of the significant challenges common to all these technologies is the development of safe and reliable electrolytes. Here, an overview of the use of ionic liquids (IL) as electrolytes for “beyond lithium” battery technologies is provided. The current state of IL-based electrolytes is presented for several different battery chemistries. The advantages of ILs and challenges from the perspective of the electrolyte are emphasized. The idea of electrolyte development based on understanding of why they work the way they do is highlighted.

Molecular Relaxations in Magnesium Polymer Electrolytes via GHz Broadband Electrical Spectroscopy

GHz broadband electrical spectroscopy (G-BES) is adopted to investigate the molecular relaxations and interactions occurring within the system in an oxygen- and water-free atmosphere in the 300 kHz-20 GHz and -40 to 250 °C frequency and temperature ranges, respectively. A new electrolyte for magnesium secondary batteries that can transfer magnesium ions efficiently is presented. This electrolyte is based on polyethylene glycol 400 and a polymeric form of δ-MgCl2 . The information obtained by G-BES is crucial for studying the conduction mechanism of these new electrolytes.

Vibrational Spectroscopy of Secondary Amine Salts: 1. Assignment of NH2+ Stretching Frequencies in Crystalline Phases

The NH(2)(+) stretching modes of secondary amine salts have been previously studied, but the band assignments are inconsistent between the various studies. This paper assigns characteristic NH(2)(+) group frequencies between approximately 2500 and 2400 cm(-1). Crystal structures of four diamine salts are reported here. Vibrational frequencies were calculated with the B3LYP hybrid Hartree-Fock/density functional method and the 6-31G(d) split-valence plus polarization basis set, and the results are in agreement with the experimental frequencies. Deuterium dilution experiments result in a group of sharply featured bands between the NH(2)(+) and the ND(2)(+) stretching bands. These bands, located between 2200 and 2100 cm(-1), are attributed to modes that contain contributions from coupled N-H and N-D stretching motions.

Effect of high pressure CO2 on the structure of PMMA: a FT-IR study.

Conformational changes in polymer films exposed to high-pressure CO(2) have been investigated with Fourier transform infrared (FT-IR) spectroscopy. The experimental setup, based on a custom-made stainless steel optical cell with CaF(2) windows, allows measurements in a CO(2) environment for pressures up to 6 MPa, in a temperature range from 293 to 353 K and in the mid-infrared (1000-4000 cm(-1)). Poly(methyl methacrylate) (PMMA), a polymer with a side group (C-type), was studied to monitor the spectral changes as a function of CO(2) pressure and was compared to poly(D,L-lactic-co-glycolic acid) (PLGA), a polymer without a side group (B-type). By monitoring the characteristic carbonyl bands, conformational changes that occur due to molecular interactions between the high-pressure CO(2) and the polymers were explored at a constant pressurization rate (0.02 MPa/min) and temperature. Spectral changes are observed only for PMMA, where the vibrational band at 1680 cm(-1) disappears with increasing pressure. The spectra of PLGA do not show any significant change in the presence of high pressure CO(2) in the investigated range. The behavior of the absorbance peak as a function of pressure and temperature highlights the presence of dynamic cross-links (DCs) between the side groups of PMMA films obtained by solvent casting below the glass transition temperature of the polymer. The spectral features are correlated using a model that accounts for CO(2) diffusion and the relaxation kinetics of the polymer chains in the thin film. The disappearance of the vibrational band attributed to the DCs for PMMA is related to the glass transition temperature, and a retrograde vitrification phenomenon is observed. This approach can be considered a useful alternative to magnetic suspended balance for the study of polymer-gas systems.

New Nanocomposite Hybrid Inorganic–Organic Proton‐Conducting Membranes Based on Functionalized Silica and PTFE

Two types of new nanocomposite proton-exchange membranes, consisting of functionalized and pristine nanoparticles of silica and silicone rubber (SR) embedded in a polytetrafluoroethylene (PTFE) matrix, were prepared. The membrane precursor was obtained from a mechanical rolling process, and the SiO₂ nanoparticles were functionalized by soaking the membranes in a solution of 2-(4-chlorosulfonylphenyl)ethyl trichlorosilane (CSPhEtCS). The membranes exhibit a highly compact morphology and a lack of fibrous PTFE. At 125 °C, the membrane containing the functionalized nanoparticles has an elastic modulus (2.2 MPa) that is higher than that of pristine Nafion (1.28 MPa) and a conductivity of 3.6×10⁻³  S cm⁻¹ despite a low proton-exchange capacity (0.11 meq g⁻¹). The good thermal and mechanical stability and conductivity at T>100 °C make these membranes a promising low-cost material for application in proton-exchange membrane fuel cells operating at temperatures higher than 100 °C.

Broadband electric spectroscopy at high CO2 pressure: dipole moment of CO2 and relaxation phenomena of the CO2-poly(vinyl chloride) system.

Broadband electric spectroscopy (BES) is a technique that shows promise in studying the interactions of dense or supercritical gases with polymers, particularly with respect to chain mobility. Polymers that are treated with dense gases show a reduction in the viscosity, glass transition, and melting temperature. A high pressure cell for BES has been constructed that can be used from ambient temperature and pressure to 353 K and 15 MPa and over a frequency range from 20 Hz to 1 MHz. In the past, the dielectric constant of CO(2) was determined by measurements at only one or two frequency values. New instrumentation and technology allow this experiment to be expanded to cover a wider frequency range. BES measurements of CO(2) do not show any relaxation peaks in the permittivity from 20 Hz to 1 MHz and 1 to 6 MPa. By these measurements, the CO(2) dielectric constant was evaluated between 0.1 and 6 MPa. Cell testing with poly(vinyl chloride) (PVC) at 323 K and CO(2) pressures from 0.1 to 13 MPa indicate an increase in the chain segmental motion at high pressures resulting from a reduction in the glass transition temperature of the PVC-CO(2) system due to plasticization by CO(2).

New nanocomposite proton conducting membranes based on a core–shell nanofiller for low relative humidity fuel cells

New hybrid inorganic–organic proton conducting membranes containing a ZrTa nanofiller dispersed in a Nafion® matrix are described. The ZrTa nanofiller exhibits a “core–shell” morphology, where the harder ZrO2 forms the “core”, which is covered by a “shell” of the softer Ta2O5. The hybrid membranes are thermally stable up to 170 °C. Interactions between the polymer matrix and the nanofiller increase the thermal stability of both the –SO3H groups and the fluorocarbon polymer backbone. In comparison with Nafion, the hybrid membranes have a lower water uptake (W.U.) that depends on the concentration of nanofiller. The residual water, which is approximately 4 wt%, is likely located at the Nafion–nanofiller interface. Infrared results indicate that the nanofiller does not neutralize all of the R–SO3H groups in the hybrid membrane and the small amount of residual water in the material does not cause the dissociation of the R–SO3H protons. Fuel cell tests show that the maximum power density yielded by the membrane electrode assembly (MEA) containing the hybrid membrane is better than that of the MEA containing Nafion, particularly at low values of relative humidity. The hybrid membranes require much less water to conduct protons effectively and are more efficient at retaining water than Nafion at low water activities.

Quaternary Polymer Electrolytes Containing an Ionic Liquid and a Ceramic Filler

In this work, the individual and combined effects of an ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ceramic filler silicon dioxide on the thermal and electrochemical properties of poly(ethylene oxide) electrolytes have been investigated. The electrolyte containing both components has the lowest glass transition (-60 °C) and melting temperatures (27 °C), the highest conductivity at any investigated temperature, and the highest limiting current density (at 40 °C). This solid polymer electrolyte also exhibits the best long-term cycling performance in Li/LiFePO4 cells.

Macromol. Rapid Commun. 14/2016

Back Cover: Quaternary polymer electrolytes, containing PEO, LiTFSI, ionic liquid and ceramic filler, show higher limiting current density, conductivity and improved cycling performance in lithium metal/solid polymer electrolyte/LiFePO4 cells with respect to ternary electrolytes with either ionic liquid or ceramic filler. Further details can be found in the article by V. Sharova, G.-T. Kim, G. A. Giffin, A. Lex-Balducci,* and S. Passerini* on page 1188.