Simon D. Poynton

Anion-exchange membranes for alkaline polymer electrolyte fuel cells: comparison of pendent benzyltrimethylammonium- and benzylmethylimidazolium-head-groups

Radiation-grafted alkaline anion-exchange membranes (AAEM) containing pendent groups with either benzyltrimethylammonium (BTM) or benzylmethylimidazolium (BMI) functionality were successfully synthesised from the same base membrane and with identical ion-exchange capacities. The conductivity of the new BMI-AAEM is comparable to the BTM-benchmark AAEM. The fuel cell performance obtained with the BMI-AAEM was, however, significantly poorer due to in situ AAEM degradation. FT-Raman spectroscopic studies on the stability of the two head-groups at 60 °C in aqueous potassium hydroxide (1 mol dm−3) indicates that the BMI-group is intrinsically less chemically stable in strongly alkaline conditions compared to the BTM-benchmark head-group. However, the stabilities of both head-groups are improved when treated at 60 °C in lower pH aqueous carbonate and bicarbonate solutions (1 mol dm−3). Contrary to a portion of the prior literature, there appears to be no real advantage in using anion-exchange polymer electrolytes containing pendent imidazolium groups in highly alkaline systems.

A Carbon Dioxide Tolerant Aqueous‐Electrolyte‐Free Anion‐Exchange Membrane Alkaline Fuel Cell

Despite over a century of study and decades of intensive research, few fuel cell products have appeared on the market. The major inhibitor to mass commercialisation is cost. H2/air alkaline fuel cells (AFCs) containing KOH(aq) electrolyte promise the lowest cost devices, with the ability to use non-Pt catalysts. The fundamental problem with AFCs is that the KOH(aq) electrolyte reacts with CO2 (cathode air supply) to form carbonate species, which lowers cell performance and lifetime (formation of carbonate precipitates in electrodes and reduction of OH concentration in electrolyte). However, the carbonate content of a aqueous-electrolyte-free (metal-cation-free) alkaline anion-exchange membrane (AAEM), that was pre-exchanged to the CO3 form, decreased when operated in H2/air and methanol/air fuel cells. This remarkable result is contrary to prior wisdom; AAEMs inherently prevent carbonate performance losses when incorporated into AFCs. This experiment was made possible only by the recent breakthrough development of an alkaline interface ionomer, which allows fabrication of membrane electrode assemblies that do not require incorporation of metal hydroxides species to perform well.

Alkaline polymer electrolytes containing pendant dimethylimidazolium groups for alkaline membrane fuel cells

Novel anion exchange membranes (AEMs), based on poly(phenylene oxide) (PPO) chains linked to pendant 1,2-dimethylimidazolium (DIm) functional groups, have been prepared for evaluation in alkaline polymer electrolyte membrane fuel cells (APEFCs). Successful functionalisation of the PPO chains was confirmed using 1H-NMR and FT-IR spectroscopies. The ionic conductivities of the resulting DIm–PPO AEMs at 30 °C are in the ranges of 10–40 mS cm−1 and 18–75 mS cm−1 at 60 °C. The high ionic conductivities are attributed to the highly developed microstructures of the membranes, which feature well-defined and interconnected ionic channels (confirmed by atomic force microscopy, AFM, measurements). Promisingly, the ion-exchange capacities (IECs) of the DIm–PPO AEM are maintained after immersion in an aqueous KOH solution (2 mol dm−3) for 219 h at 25 °C; a previously developed monomethyl imidazolium PPO analogue AEM (Im–PPO) showed a significant decline in IEC on similar treatment. This reduction in undesirable attack by the OH− conducting anions is ascribed to an increase in steric interference and removal of the acidic C2 proton [in the monomethyl Im-groups] by the methyl group in the DIm cationic ring. Moreover, the maximum power densities produced in simple beginning-of-life single cell H2/O2 fuel cell tests increased from 30 mW cm−2 to 56 mW cm−2 when switching from the Im–PPO AEM (fuel cell temperature = 50 °C) to the DIm–PPO-0.54 AEM (fuel cell temperature = 35 °C) respectively (even with the use of lower temperatures).

PdNi hollow nanoparticles for improved electrocatalytic oxygen reduction in alkaline environments

Palladium-nickel (PdNi) hollow nanoparticles were synthesized via a modified galvanic replacement method using Ni nanoparticles as sacrificial templates in an aqueous medium. X-ray diffraction and transmission electron microscopy show that the as-synthesized nanoparticles are alloyed nanostructures and have hollow interiors with an average particle size of 30 nm and shell thickness of 5 nm. Compared with the commercially available Pt/C or Pd/C catalysts, the synthesized PdNi/C has superior electrocatalytic performance towards the oxygen reduction reaction, which makes it a promising electrocatalyst for alkaline anion exchange membrane fuel cells and alkali-based air-batteries. The electrocatalyst is finally examined in a H2/O2 alkaline anion exchange membrane fuel cell; the results show that such electrocatalysts could work in a real fuel cell application as a more efficient catalyst than state-of-the-art commercially available Pt/C.

The alkali stability of radiation-grafted anion-exchange membranes containing pendent 1-benzyl-2,3-dimethylimidazolium head-groups

Radiation-grafted anion-exchange membranes (AEM) containing pendent benzyltrimethylammonium, 1-benzyl-3-methylimidazolium and 1-benzyl-2,3-dimethylimidazolium functional head-groups were synthesised with ion-exchange capacities in the range 1.7–1.9 meq g−1. The ionic conductivities of the AEMs were also comparable (24.5 ± 1.8 mS cm−1 at 50 °C). The alkali stability (in aqueous potassium hydroxide (1 mol dm−3) at 60 °C) of the 1-benzyl-2,3-dimethylimidazolium head-groups was superior to the 1-benzyl-3-methylimidazolium but inferior to the benzyltrimethylammonium benchmark head-groups. Radiation-grafted AEMs containing pendent 1-benzyl-2,3-dimethylimidazolium head-groups are not suitable for application in electrochemical devices containing highly alkaline environments.

Aromatic polyelectrolytes via polyacylation of pre-quaternized monomers for alkaline fuel cells

To overcome alkali-resistant and synthetic hurdles to alkaline anion-exchange membranes (AAEMs) for alkaline fuel cells, the polyacylation of pre-quaternized monomers as a straightforward and versatile approach has been proposed for the first time. Via this approach, novel aromatic anion-exchange polyelectrolytes featuring a long pendent spacer (i.e., –O–(CH2)4–) instead of a conventional benzyl-type spacer (i.e., –CH2–) are successfully synthesized, and exhibit not only high OH− and CO32− conductivity (91 mS cm−1 and 51 mS cm−1 at 60 °C, respectively) but also outstanding alkaline stability (e.g., no degradation of ammonium groups after aging in 6 mol dm−3 NaOH at 60 °C for 40 days). Using this kind of AAEM, a promising peak power density of 120 mW cm−2 is obtained on a preliminary H2/O2 single cell at 50 °C. This powerful synthetic approach together with exceptional membrane properties should pave the way to the practical application of this kind of AAEMs in alkaline fuel cells.

An optimised synthesis of high performance radiation-grafted anion-exchange membranes

High performance benzyltrimethylammonium-type alkaline anion-exchange membranes (AEM), for application in electrochemical devices such as anion-exchange membrane fuel cells (AEMFC), were prepared by the radiation grafting (RG) of vinylbenzyl chloride (VBC) onto 25 μm thick poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by amination with trimethylamine. Reductions in the electron-beam absorbed dose and amount of expensive, potentially hazardous VBC were achieved by using water as a diluent (reduced to 30–40 kGy absorbed dose and 5 vol% VBC) instead of the prior state-of-the-art method that used organic propan-2-ol diluent (required 70 kGy dose and 20 vol% VBC monomer). Furthermore, the water from the aqueous grafting mixture was easily separated from the residual monomer (after cooling) and was reused for a further grafting reaction: the resulting AEM exhibited an ion-exchange capacity of 2.1 mmol g−1 (cf. 2.1 mmol g−1 for the AEM made using a fresh grafting mixture). The lower irradiation doses resulted in mechanically stronger RG-AEMs compared to the reference RG-AEM synthesised using the prior state-of-the-art method. A further positive off-shoot of the optimisation process was the discovery that using water as a diluent resulted in an enhanced (i.e. more uniform) distribution of VBC grafts as proven by Raman microscopy and corroborated using EDX analysis: this led to enhancement in the Cl− anion-conductivities (up to 68 mS cm−1 at 80 °C for the optimised fully hydrated RG-AEMs vs. 48 mS cm−1 for the prior state-of-the-art RG-AEM reference). A down-selected RG-AEM with an ion-exchange capacity = 2.0 mmol g−1, that was synthesised using the new greener protocol with a 30 kGy electron-beam absorbed dose, led to an exceptional beginning-of-life H2/O2 AEMFC peak power density of 1.16 W cm−2 at 60 °C in a benchmark test using industrial standard Pt-based electrocatalysts and unpressurised gas supplies: this was higher than the 0.91 W cm−1 obtained with the reference RG-AEM (IEC = 1.8 mmol g−1) synthesised using the prior state-of-the-art protocol.

Preparation of radiation-grafted powders for use as anion exchange ionomers in alkaline polymer electrolyte fuel cells

A novel alkaline exchange ionomer (AEI) was prepared from the radiation-grafting of vinylbenzyl chloride (VBC) onto poly(ethylene-co-tetrafluoroethylene) [ETFE] powders with powder particle sizes of less than 100 μm diameter. Quaternisation of the VBC grafted ETFE powders with trimethylamine resulted in AEIs that were chemically the same as the ETFE-based radiation-grafted alkaline anion exchange membranes (AAEM) that had been previously developed for use in low temperature alkaline polymer electrolyte fuel cells (APEFC). The integration of the AEI powders into the catalyst layers (CL) of both electrodes resulted in a H2/O2 fuel cell peak power density of 240 mW cm−2 at 50 °C (compared to 180 mW cm−2 with a benchmark membrane electrode assembly containing identical components apart from the use of a previous generation AEI). This result is promising considering the wholly un-optimised nature of the AEI inclusion into the catalyst layers.

N-doped crumpled graphene derived from vapor phase deposition of PPy on graphene aerogel as an efficient oxygen reduction reaction electrocatalyst.

Nitrogen-doped crumpled graphene (NCG) is successfully synthesized via vapor phase deposition of polypyrrole onto graphene aerogel followed by thermal treatment. The NCG was explored as an electrocatalyst for the oxygen reduction reaction, showing comparable electrocatalytic performance with the commercial Pt/C in alkaline membrane exchange fuel cells because of the well-regulated nitrogen doping and the robust micro-3D crumpled porous nanostructure.

Membrane and Electrode Materials for Alkaline Membrane Fuel Cells

This paper and the associated presentation will describe the latest developments regarding alkaline anion exchange membrane (AAEM) fuel cells at Surrey. The program of work conducted has been targeted at the materials development of both membranes and electrodes containing alkaline ionomers and as such has focused on H-2/O-2 fuel cell testing. Radiation-grafted AAEMs can be made with fully hydrated thicknesses between 18 - 80 mu m with conductivities in water of up to 0.06 S cm(-2) at 60 degrees C. A peak power density of 230 mW cm(geo)(-2) and a maximum current density at full discharge of 1.3 A cm(geo)(-2) have been obtained in a H-2/O-2 fuel cell at 50 degrees C with a 18 mu m AAEM and Toray carbon paper based electrodes (Pt/C(20%mass), 0.5 mg(pt) cm(geo)(-2) loading) that were treated with Surreys first generation alkaline ionomer. A future priority is the development of the next generation alkaline ionomer.