Multiple computational and experimental techniques are used to understand the nanoscale morphology and water/proton transport properties in a series of sulfonated Diels–Alder poly(phenylene) (SDAPP) membranes over a wide range of temperature, hydration, and sulfonation conditions. New synthetic methods allow us to sulfonate the SDAPP membranes to much higher ion exchange capacity levels than has been previously possible. Nanoscale phase separation between the hydrophobic polymer backbone and the hydrophilic water/sulfonic acid groups was observed for all membranes studied. We find good agreement between structure factors calculated from atomistic molecular dynamics (MD) simulations and those measured by X-ray scattering. With increasing hydration, the scattering ionomer peak in SDAPP is found to decrease in intensity. This intensity decrease is shown to be due to a reduction of scattering contrast between the water and polymer and is not indicative of any loss of nanoscale phase separation. Both MD simulations and density functional theory (DFT) calculations show that as hydration levels are increased, the nanostructure morphology in SDAPP evolves from isolated ionic domains to fully percolated water networks containing progressively weaker hydrogen bond strengths. The conductivity of the membranes is measured by electrical impedance spectroscopy and the equivalent proton conductivity calculated from pulsed-field-gradient (PFG) NMR diffusometry measurements of the hydration waters. Comparison of the measured and calculated conductivity reveals that in SDAPP the proton conduction mechanism evolves from being dominated by vehicular transport at low hydration and sulfonation levels to including a significant contribution from the Grötthuss mechanism (also known as structural diffusion) at higher hydration and sulfonation levels. The observed increase in conductivity reflects the impact that changing hydration and sulfonation have on the morphology and hydrogen bond network and ultimately on the membrane performance.
We describe a set of precise single-ion conducting polymers that form self-assembled percolated ionic aggregates in glassy polymer matrices and have decoupled transport of metal cations. These precise single-ion conductors (SICs), synthesized by a scalable ring-opening metathesis polymerization, consist of a polyethylene backbone with a sulfonated phenyl group pendant on every fifth carbon and are fully neutralized by a counterion X+ (Li+, Na+, or Cs+). Experimental X-ray scattering measurements and fully atomistic molecular dynamics (MD) simulations are in good agreement. The MD simulations show that the ionic groups nanophase separate from the polymer backbone to form percolating ionic aggregates. Using graph theory, we find that within the Li+- and Na+-neutralized polymers the percolated aggregates exhibit planar and ribbon-like configurations at intermediate length scales, while the percolated aggregates within the Cs+-neutralized polymers are more isotropic. Electrical impedance spectroscopy measurements show that the ionic conductivities exhibit Arrhenius behavior, with conductivities of 10–7 to 10–6 S/cm at 180 °C. In the MD simulations, the cations move between sulfonate groups in the percolated aggregates, larger ions travel further, and overall cations travel further than the polymer backbones, indicating a decoupled ion-transport mechanism. Thus, the percolated ionic aggregates in these polymers can serve as pathways to facilitate decoupled ion motion through a glassy polymer matrix.
We analyze the dynamics from microsecond-long, atomistic molecular dynamics (MD) simulations of a series of precise poly(ethylene-co-acrylic acid) ionomers neutralized with lithium, with three different spacer lengths between acid groups on the ionomers and at two temperatures. At short times, the intermediate structure factor calculated from the MD simulations is in reasonable agreement with quasi-elastic neutron scattering data for partially neutralized ionomers. For ionomers that are 100% neutralized with lithium, the simulations reveal three dynamic processes in the chain dynamics. The fast process corresponds to hydration librations, the medium-time process corresponds to local conformational motions of the portions of the chains between ionic aggregates, and the long-time process corresponds to relaxation of the ionic aggregates. At 600 K, the dynamics are sufficiently fast to observe the early stages of lithium-ion motion and ionic aggregate rearrangements. In the partially neutralized ionomers with isolated ionic aggregates, the Li-ion-containing aggregates rearrange by a process of merging and breaking up, similar to what has been observed in coarse-grained (CG) simulations. In the 100% neutralized ionomers that contain percolated ionic aggregates, the chains remain pinned by the percolated aggregate at long times, but the lithium ions are able to move along the percolated aggregate. Here, the ion dynamics are also qualitatively similar to those seen in previous CG simulations.
Designing polymers with controlled nanoscale morphologies and scalable synthesis is of great interest in the development of fluorine-free materials for proton exchange membranes in fuel cells. This study focuses on a precision polyethylene with phenylsulfonic acid branches at every 5 th carbon, p5PhSA, with a high ion-exchange capacity (4.2 mmol/g). The polymers selfassemble into hydrophilic and hydrophobic co-continuous nanoscale domains. In the hydrated state, the hydrophilic domain, comprised of the polar sulfonic acid moieties and water, serves as a pathway for efficient mesoscopic proton conductivity. The morphology and proton transport of p5PhSA are evaluated under hydrated conditions using in situ X-ray scattering and electrochemical impedance spectroscopy techniques. At 40 °C and 95% relative humidity, the proton conductivity of p5PhSA is 0.28 S/cm, which is four times greater than Nafion™ 117 under the same conditions. Atomistic molecular dynamics (MD) simulations are also used to elucidate the interplay between the structure and the water dynamics. The MD simulations show strong nanophase separation between the percolated hydrophilic and hydrophobic domains over a wide range of water contents. The percolated hydrophilic nanoscale domain facilitates the rapid proton transport in p5PhSA and demonstrates the potential of precise hydrocarbon-based polymers as processible and effective proton exchange membranes.
Single-ion conducting polymers (SICs) are promising candidates for the next generation of safer polymer electrolytes due to their stability and high transference number. However, the conductivity in SICs is often limited by the mobility of the polymer backbone as the ion mobility is coupled to segmental relaxations. We present polymer blend electrolytes, consisting of a precise s i n g l e L i -i o n c o n d u c t i n g p o l y m e r w i t h a (trifluoromethanesulfonyl)imide anion pendant group and a low molar mass poly(ethylene oxide) (PEO). Dielectric relaxation spectroscopy is used to probe both the ion transport properties and segmental dynamics of these blends, and X-ray scattering is used to evaluate their morphology. PEO associates with the ionic groups of the SIC, forming a miscible blend with pathways that promote ion transport. At a high PEO content (an ethylene oxide to Li + ratio of 10), ionic conductivities greater than 10 −5 and 10 −4 S cm −1 are achieved at 90 and 130 °C, respectively. A comparison of conductivities and polymer relaxation times shows that the high PEO content blends exhibit superionic transport, in which there is some decoupling of the Li-ion motion from the backbone mobility. This superionic transport is uncommon in single Li-ion conductors above the glass transition temperature, thus this work presents a critical step toward establishing design rules for superionic transport in SICs.
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