Effect of morphology of nanoscale hydrated channels on proton conductivity in block copolymer electrolyte membranes.

Hydrated membranes with cocontinuous hydrophilic and hydrophobic phases are needed to transport protons in hydrogen fuel cells. Herein we study the water uptake and proton conductivity of a model fuel cell membrane comprising a triblock copolymer, polystyrenesulfonate-block-polyethylene-block-polystyrenesulfonate (S-SES), as a function of water activity in both humid air and liquid water. We demonstrate that the water uptake and proton conductivity of S-SES membranes equilibrated in liquid water are fundamentally different from values obtained when they were equilibrated in humid air. The morphological underpinnings of our observations were determined by synchrotron small-angle X-ray scattering and cryogenic scanning transmission electron microscopy. A discontinuous increase in conductivity when nearly saturated humid air is replaced with liquid water coincides with the emergence of heterogeneity in the hydrated channels: a water-rich layer is sandwiched between two polymer-rich brushes. While the possibility of obtaining heterogeneous hydrated channels in polymer electrolyte membranes has been discussed extensively, to our knowledge, this is the first time that direct evidence for the formation of water-rich subdomains is presented.

Morphology and thermodynamic properties of a copolymer with an electronically conducting block: poly(3-ethylhexylthiophene)-block-poly(ethylene oxide).

We report on the synthesis and morphology of a block copolymer, poly(3-(2'-ethylhexyl)thiophene)-b-poly(ethylene oxide) (P3EHT-b-PEO), that conducts both electrons and ions. We show that in the melt state the P3EHT-b-PEO chains self-assemble to produce traditional nanoscale morphologies such as lamellae and gyroid. This is in contrast to a majority of previous studies on copolymers with electronically conducting blocks wherein a nanofibrillar morphology is obtained. Our approach enables estimation of the Flory-Huggins interaction parameter, χ. The segregation strength between the two blocks is controlled through the addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). For the salt-free sample, the gyroid morphology, obtained in the melt state, is transformed into lamellae below the melting temperature of the P3EHT block. This is due to the "breaking out" of the crystalline phase. For the salt-containing sample, P3EHT-b-PEO has a lamellar morphology in both melt and crystalline states (confined crystallization).

Absence of Schroeder's paradox in a nanostructured block copolymer electrolyte membrane.

This is a study of morphology, water uptake, and proton conductivity of a sulfonated polystyrene-block-polyethylene (PSS-PE) copolymer equilibrated in humid air with controlled relative humidity (RH), and in liquid water. Extrapolation of the domain size, water uptake, and conductivity obtained in humid air to RH = 100% allowed for an accurate comparison between the properties of PSS-PE hydrated in saturated vapor and in liquid water. We demonstrate that extrapolations of domain size and water uptake on samples equilibrated in humid air are consistent with measurements on samples equilibrated in liquid water. Small (5%) differences in proton conductivity were found in samples equilibrated in humid air and liquid water. We argue that differences in transport coefficients in disordered heterogeneous systems, particularly small differences, present no paradox whatsoever. Schroeder's Paradox, wherein properties of polymers measured in saturated water vapor are different from those obtained in liquid water, is thus not observed in the PSS-PE sample.

Design of a humidity controlled sample stage for simultaneous conductivity and synchrotron X-ray scattering measurements.

We report on the design and operation of a novel sample stage, used to simultaneously measure X-ray scattering profiles and conductivity of a polymer electrolyte membrane (PEM) surrounded by humid air as a function of temperature and relative humidity. We present data obtained at the Advanced Light Source and Stanford Synchrotron Radiation Laboratory. We demonstrate precise humidity control and accurate determination of morphology and conductivity over a wide range of temperatures. The sample stage is used to study structure-property relationships of a semi-crystalline block copolymer PEM, sulfonated polystyrene-block-polyethylene.

Design of Cluster-free Polymer Electrolyte Membranes and Implications on Proton Conductivity.

Nanoscale ionic aggregates are ubiquitous in copolymers containing charged and uncharged monomers. In most cases, these clusters persist when these polymers are hydrated and ion-conducting channels percolate through the sample. We argue that these clusters impede ion motion due to (1) the requirement that ions must hop across ion-free regions in the channels as they are transported from one cluster to the next, and (2) increased counterion condensation due to proximity of fixed acid groups in the clusters. Block copolymers wherein the size of the ion-containing microphase is 6 nm or less provides one approach for eliminating the clusters.