Layer-by-layer polypyrrole coated graphite oxide and graphene nanosheets as catalyst support materials for fuel cells

For the production of advanced types of catalyst support materials, the distinguished properties of graphene nanosheets were combined with the structural properties of conducting polypyrrole by the incorporation of graphene nanosheets into a polymer matrix by the proposed simple and low-cost fabrication technique. A precise tuning of electrical conductivity and thermal stability was achieved by controlling the polymer thickness of randomly dispersed graphene nanosheets. Initially, graphene nanosheets were fabricated in large quantities via a mild chemical synthetic route involving graphite oxidation, ultrasonic treatment, and chemical reduction. Then, polypyrrole/graphene nanosheet composites with improved conductivity, thermal stability, and high surface area were synthesized by in situ polymerization with the different pyrrole feed ratios. Although graphite oxide sheets have electrically insulating property, partially oxidized graphite oxide was also utilized as conductive fillers in polymer matrix. However, polypyrrole/graphene nanosheet composites have better electrical conductivity than polypyrrole/graphite oxide composites

Surface modifications of graphene-based polymer nanocomposites by different synthesis techniques

With the appropriate surface treatments, graphene sheets can be separated from graphite material and the layer-to-layer distance can be extended. In the present work, graphene nanosheets (GNS) were separated from graphite by an improved, safer and mild method including the steps of oxidation, thermal expansion, ultrasonic treatment and chemical reduction. For the production of advanced polymer nanocomposites, the distinguished properties of GNS were combined with the structural properties of conducting polypyrrole by the proposed simple and low-cost fabrication technique. The changes in surface morphologies and surface functional groups were estimated by controlling the polymer coating on graphite oxide (GO) sheets, expanded GO and GNS

Layer-by-layer polypyrrole coated graphite oxide and graphene nanosheets as catalyst support materials for fuel cells

For the production of advanced type of catalyst support materials, the distinguished properties of graphene nanosheets were combined with the structural properties of conducting polypyrrole by the incorporation of graphene nanosheets into a polymer matrix by the proposed simple and low-cost fabrication technique. A precise tuning of electrical conductivity and thermal stability was also achieved by controlling the thickness of randomly dispersed graphene nanosheets by a layer-by-layer polymer coating. Initially, graphene nanosheets were fabricated in large quantities via a mild chemical synthetic route involving graphite oxidation, ultrasonic treatment and chemical reduction. Then, polypyrrole/graphene nanosheet composites with improved conductivity, thermal stability and high surface area were synthesized by in situ polymerization with the different pyrrole feed ratios. Although graphite oxide sheets have electrically insulating property, partially oxidized graphite oxide was also utilized as conductive fillers in polymer matrix. However, polypyrrole/graphene nanosheet composites have better electrical conductivity than polypyrrole/graphite oxide composites

Novel graphene-based electrodes for energy storage devices

Graphene sheets have exceptional electrical, mechanical and optical properties. Graphene-based nanocomposites can be utilized as an electrode for the fabrication of energy storage devices for practical applications. Graphene nanosheets were produced by an enhanced technique including graphite oxidation, ultrasonic treatment, expansion, and chemical reduction

Radiation grafted membranes

The development of proton-exchange membranes for fuel cells has generated global interest in order to have a potential source of power for stationary and portable applications. The membrane is the heart of a fuel cell and the performance of a fuel cell depends largely on the physico-chemical nature of the membrane and its stability in the hostile environment of hydrogen and oxygen at elevated temperatures. Efforts are being made to develop membranes that are similar to commercial Nafion membranes in performance and are available at an affordable price. The radiation grafting of styrene and its derivatives onto existing polymer films and subsequent sulfonation of the grafted films has been an attractive route for developing these membranes with requiredchemistry and properties. The process of radiation grafting offers enormous possibilities for design of the polymer architecture by careful variation of the irradiation and the grafting conditions. A wide range of crosslinkers are available, which introduce stability to the membrane during its operation in fuel cells. Crosslinking of the base polymer prior to grafting has also been an attractive means of obtaining membranes with better performance. A systematic presentation is made of the grafting process into different polymers,the physical properties of the resultant membranes, and the fuel cell application of these membranes

Novel ETFE based radiation grafted poly(styrene sulfonic acid-co-methacrylonitrile) proton conducting membranes with increased stability

Styrene radiation grafted ETFE based proton conducting membranes are subject to degradation under fuel cell operating conditions and show a poor stability. Lifetimes exceeding 250 h can only be achieved with crosslinked membranes. In this study, a novel approach based on the increase of the intrinsic oxidative stability of uncrosslinked membranes is reported. Hence, the co-grafting of styrene with methacrylonitrile (MAN), which possesses a protected α-position and strong dipolar pendant nitrile group, onto 25 μm ETFE base film was investigated. Styrene/MAN co-grafted membranes were compared to a styrene based membrane in durability tests in single H2/O2 fuel cells. It is shown that the incorporation of MAN considerably improves the chemical stability, yielding fuel cell lifetimes exceeding 1000 h. The membrane preparation based on the co-grafting of styrene and MAN offers the prospect of tuning the MAN content and introduction of a crosslinker to enhance the oxidative stability of the resulting fuel cell membranes

Cross-linker effect in ETFE-based radiation-grafted proton-conducting membranes II. Extended fuel cell operation and degradation analysis

In this study the effect of crosslinker (divinylbenzene (DVB)) content on the chemical stability of poly(ethylene-alt-tetrafluoroethylene) (ETFE) based membranes using an H2O2 solution was carried out. Furthermore, the first long term-testing of single H2/O2 cell over 2180h of an MEA assembled using an optimized ETFE-based membrane prepared by radiation-induced grafting of styrene / DVB and subsequent sulfonation with a graft level of 25 % was carried out. The in situ MEA properties were characterized over the testing period using auxiliary current-pulse resistance, electrochemical impedance spectroscopy, polarization and H2 permeation. It is shown that the crosslinking dramatically improves the ex situ chemical stability, while no significant trend with the crosslinker content was observed. The performance of the tested MEA exhibits a decay rate of 13 μV.h-1 in voltage over the testing time at 500 mA.cm-2 at 80°C, while the hydrogen permeation shows a steady increase over time. This indicates clearly that to some extent changes in the membrane morphology occur over the operating time. The local post mortem analysis of the tested membrane reveals that high degradation was observed in areas adjacent to the O2 inlet and in other areas nearb

Fuel-cell performance of multiply-crosslinked polymer electrolyte membranes prepared by two-step radiation technique

A multiply-crosslinked polymer electrolyte membrane was prepared by the radiation-induced co-grafting of styrene and a bis(vinyl phenyl)ethane (BVPE) crosslinker into a radiation-crosslinked polytetrafluoroethylene (cPTFE) film. We then investigated its H2/O2 fuel-cell performance at 60 and 80ºC in terms of the effect of radiation and chemical crosslinking. At 60ºC, all the membranes initially exhibited similar performance, but only the cPTFE-based membranes were durable at 80ºC, indicating the necessity of radiation crosslinking in the PTFE main chains. Importantly, cell performance of the multiply-crosslinked membrane was found high enough to reach that of a Nafion112 membrane. This is probably because the BVPE crosslinks in the graft component improved the membrane-electrode interface in addition to membrane durability. After severe OCV hold tests at 80 and 95ºC, the performance deteriorated, while no significant change was observed in ohmic resistivity. Accordingly, our membranes seemed so chemically stable that an influence on overall performance loss could be negligible

Graphene manufacture and utilization

An improved, safer and mild method was proposed for the exfoliation of graphene like sheets from graphite to be used in fuel cells. The major aim in the proposed method is to reduce the number of layers in the graphite material and to produce large quantities of graphene bundles to be used as catalyst support in polymer electrolyte membrane fuel cells. Graphite oxide was prepared using potassium dichromate/sulfuric acid as oxidant and acetic anhydride as intercalating agent. The oxidation process seemed to create expanded and leafy structures of graphite oxide layers. Heat treatment of samples led to the thermal decomposition of acetic anhydride into carbondioxide and water vapor which further swelled the layered graphitic structure. Sonication of graphite oxide samples created more separated structures. Morphology of the sonicated graphite oxide samples exhibited expanded the layer structures and formed some tullelike translucent and crumpled graphite oxide sheets. The mild procedure applied was capable of reducing the average number of graphene sheets from 86 in the raw graphite to nine in graphene-based nanosheets. Raman spectroscopy analysis showed the significant reduction in size of the in-plane sp2 domains of graphene nanosheets obtained after the reduction of graphite oxide

Design and modeling of high temperature water free proton exchange membranes in DEA PEMFC operations

Polymer electrolyte membrane fuel cell (PEMFC) is a greatalternative in transportation however there are still some issues onthe application of PEMFC, such as complexity in balance-of-plantdesign and cost of the system. Dead ended anode (sealed offanode) design might be a solution to reduce the complexity ofPEMFC. DEA operation eliminates the expensive hardware, suchas mass flow controllers, hydrogen recovery system andhumidifiers of PEMFC system. Moreover, the DEA operation ofNafion® is experiencing the disadvantages of low operationtemperature (40-80 °C) as the corrosion of the expensiveelectrodes by accumulated water. Beyond it is low operationtemperatures; Nafion® is also expensive and increases the cost ofthe PEMFC. Hence, in this study, the water free, high temperatureand cost competitive radiation induced grafted membranes weresynthesized and tested in both flow through anode (FTA) and deadended anode (DEA) operation in PEMFC