Thomas Weissbach

Selective formation of hydrogen and hydroxyl radicals by electron beam irradiation and their reactivity with perfluorosulfonated acid ionomer.

Selective formation and reactivity of hydrogen (H(•)) and hydroxyl (HO(•)) radicals with perfluorinated sulfonated ionomer membrane, Nafion 211, is described. Selective formation of radicals was achieved by electron beam irradiation of aqueous solutions of H2O2 or H2SO4 to form HO(•) and H(•), respectively, and confirmed by ESR spectroscopy using a spin trap. The structure of Nafion 211 after reaction with H(•) or HO(•) was determined using calibrated (19)F magic angle spinning NMR spectroscopy. Soluble residues of degradation were analyzed by liquid and solid-state NMR. NMR and ATR-FTIR spectroscopy, together with determination of ion exchange capacity, water uptake, proton conductivity, and fluoride ion release, strongly indicate that attack by H(•) occurs at the tertiary carbon C-F bond on both the main and side chain; whereas attack by HO(•) occurs solely on the side chain, specifically, the α-O-C bond.

Hexamethyl-p-terphenyl poly(benzimidazolium): a universal hydroxide-conducting polymer for energy conversion devices

A hydroxide-conducting polymer, HMT-PMBI, which is prepared by methylation of poly[2,2′-(2,2′′,4,4′′,6,6′′-hexamethyl-p-terphenyl-3,3′′-diyl)-5,5′-bibenzimidazole] (HMT-PBI), is utilized as both the polymer electrolyte membrane and ionomer in an alkaline anion-exchange membrane fuel cell and alkaline polymer electrolyzer. A fuel cell operating between 60 and 90 °C and subjected to operational shutdown, restarts, and CO2-containing air demonstrates remarkable in situ stability for >4 days, over which its performance improved. An HMT-PMBI-based fuel cell was operated at current densities >1000 mA cm−2 and power densities of 370 mW cm−2 at 60 °C. When similarly operated in a water electrolyzer with circulating 1 M KOH electrolyte at 60 °C, its performance was unchanged after 8 days of operation. Methodology for up-scaled synthesis of HMT-PMBI is presented, wherein >½ kg is synthesized in six steps with a yield of 42%. Each step is optimized to achieve high batch-to-batch reproducibility. Water uptake, dimensional swelling, and ionic conductivity of HMT-PMBI membranes exchanged with various anions are reported. In the fully-hydrated chloride form, HMT-PMBI membranes are mechanically strong, and possess a tensile strength and Youngs modulus of 33 MPa and 225 MPa, respectively, which are significantly higher than Nafion 212, for example. The hydroxide anion form shows remarkable ex situ chemical and mechanical stability and is seemingly unchanged after a 7 days exposure to 1 M NaOH at 80 °C or 6 M NaOH at 25 °C. Only 6% chemical degradation is observed when exposed to 2 M NaOH at 80 °C for 7 days. The ease of synthesis, synthetic reproducibility, scale-up, and exceptional in situ and ex situ properties of HMT-PMBI renders this a potential benchmark polymer for energy conversion devices requiring an anion-exchange material.

Poly(phenylene) and m-Terphenyl as Powerful Protecting Groups for the Preparation of Stable Organic Hydroxides

Four benzimidazolium hydroxide compounds, in which the C2-position is attached to a phenyl group possessing hydrogen, bromine, methyl groups, or phenyl groups at the ortho positions, are prepared and investigated for stability in a quantitative alkaline stability test. The differences between the stability of the various protecting groups in caustic solutions are rationalized on the basis of their crystal structures and DFT calculations. The highest stability was observed for the m-terphenyl-protected benzimidazolium, showing a half-life in 3 M NaOD/CD3OD/D2O at 80 °C of 3240 h. A high-molecular-weight polymer analogue of this model compound is prepared that exhibits excellent mechanical properties, high ionic conductivity and ion-exchange capacity, as well as remarkable hydroxide stability in alkaline solutions: only 5% degradation after 168 h in 2 M KOH at 80 °C. This is the most stable hydroxide-conducting benzimidazolium polymer to date.

Structural effects on the nano-scale morphology and conductivity of ionomer blends

The role of graft and diblock ionomer architecture on the morphology and properties of ionomer/fluoropolymer blends is examined. The graft copolymer consists of a partially fluorinated backbone of P(VDF-co-CTFE) and partially sulfonated polystyrene (PS) side chains while the diblock copolymer consists of a block of P(VDF-co-HFP) and a partially sulfonated PS block. These ionomers are blended with fluoropolymers possessing a chain length that matches the average sequence length of the fluorous block segment of the ionomer. The results from this study are surprising: graft ionomers are primarily insensitive to blending due to the incorporation of the non-ionic fluorous polymers into the domains of the perfluorinated backbone which does not deleteriously affect the interconnecting proton conducting ionic clusters. In contrast, diblock ionomers are highly sensitive to the addition of fluoropolymers and despite the observation that ionic channels are retained, water sorption is decreased due to the increased volume of the non-ionic domains, which decreases proton mobility and proton conductivity.

Sulfo-phenylated terphenylene copolymer membranes and ionomers.

The copolymerization of a prefunctionalized, tetrasulfonated oligophenylene monomer was investigated. The corresponding physical and electrochemical properties of the polymers were tuned by varying the ratio of hydrophobic to hydrophilic units within the polymers. Membranes prepared from these polymers possessed ion exchange capacities ranging from 1.86 to 3.50 meq g-1 and exhibited proton conductivities of up to 338 mS cm-1 (80 °C, 95 % relative humidity). Small-angle X-ray scattering and small-angle neutron scattering were used to elucidate the effect of the monomer ratios on the polymer morphology. The utility of these materials as low gas crossover, highly conductive membranes was demonstrated in fuel cell devices. Gas crossover currents through the membranes of as low as 4 % (0.16±0.03 mA cm-2 ) for a perfluorosulfonic acid reference membrane were demonstrated. As ionomers in the catalyst layer, the copolymers yielded highly active porous electrodes and overcame kinetic losses typically observed for hydrocarbon-based catalyst layers. Fully hydrocarbon, nonfluorous, solid polymer electrolyte fuel cells are demonstrated with peak power densities of 770 mW cm-2 with oxygen and 456 mW cm-2 with air.