The relation between the nanoscale morphology and associated device properties in conjugated polymer/fullerene bulk‐heterojunction “plastic solar cells” is investigated. We perform complementary measurements on solid‐state blends of poly[2‐methoxy‐5‐(3,7‐dimethyloctyloxy)]‐1,4‐phenylenevinylene (MDMO‐PPV) and the soluble fullerene C60 derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl [6,6]C61 (PCBM), spin‐cast from either toluene or chlorobenzene solutions. The characterization of the nanomorphology is carried out via scanning electron microscopy (SEM) and atomic force microscopy (AFM), while solar‐cell devices were characterized by means of current–voltage (I–V) and spectral photocurrent measurements. In addition, the morphology is manipulated via annealing, to increase the extent of phase separation in the thin‐film blends and to identify the distribution of materials. Photoluminescence measurements confirm the demixing of the materials under thermal treatment. Furthermore the photoluminescence of PCBM clusters with sizes of up to a few hundred nanometers indicates a photocurrent loss in films of the coarser phase‐separated blends cast from toluene. For toluene‐cast films the scale of phase separation depends strongly on the ratio of MDMO‐PPV to PCBM, as well as on the total concentration of the casting solution. Finally we observe small beads of 20–30 nm diameter, attributed to MDMO‐PPV, in blend films cast from both toluene and chlorobenzene.
Anion exchange membrane fuel cells (AEMFCs) have attracted extensive attention in the recent years, primarily due to the distinct advantage potentials they have over the mainstream proton exchange membrane fuel cells. The anion exchange membrane (AEM) is the key component of AEMFC systems. Due to the unique characteristics of water management in AEMFCs, understanding the water mobility through AEMs is key for this technology, as it significantly affects (and limits) overall cell performances. This work presents a study of the equilibrium state and kinetics of water uptake (WU) for AEMs exposed to vapor source H2O. We investigate different AEMs that exhibit diverse water uptake behaviors. AEMs containing different backbones (fluorinated and hydrocarbon-based backbones) and different functional groups (various cations as part of the backbone or as pendant groups) were studied. Equilibrium WU isotherms are measured and fitted by the Park model. The influence of relative humidity and temperature is also studied for both equilibrium and dynamic WU. A characteristic time constant is used to describe WU kinetics during the H2O sorption process. To the best of our knowledge, this is the first time that WU kinetics has been thoroughly investigated on AEMs containing different backbones and cationic functional groups. The method and analysis described in this work provides critical insights to assist with the design of the next generation anion conducting polymer electrolytes and membranes for use in advanced, high-performance AEMFCs.
Abstract:We have developed ah ighly active nanostructured iridium catalyst for anodes of proton exchange membrane (PEM) electrolysis.C lusters of nanosized crystallites are obtained by reducing surfactant-stabilized IrCl 3 in water-free conditions.T he catalyst shows af ive-fold higher activity towards oxygen evolution reaction (OER) than commercial Ir-black. The improved kinetics of the catalyst are reflected in the high performance of the PEM electrolyzer (1 mg Ir cm À2 ), showing an unparalleled low overpotential and negligible degradation. Our results demonstrate that this enhancement cannot be only attributed to increased surface area, but rather to the ligand effect and low coordinate sites resulting in ahigh turnover frequency (TOF). The catalyst developed herein sets ab enchmark and as trategy for the development of ultra-low loading catalyst layers for PEM electrolysis.
A quantitative in situ investigation of the structure of the catalytic layer of polymer electrolyte membrane fuel cells using material-sensitive and conductive atomic force microscopy is reported. The distribution and size of the ionomer phase at the surface of the catalytic layer is retrieved from adhesion force mappings, measured at high humidity and up to 75 °C. The average ionomer layer thickness varies between 7 and 13 nm for three differently prepared samples, as concluded from the histograms. Evidence of a lamellar structure of the thinner ionomer layers is presented. A significant thinning of the ionomer layers after long-term fuel cell operation is observed.
High membrane conductivity is one of the key parameters in polymer electrolyte fuel cell applications. We introduce an electrochemical atomic force microscopy method that provides simultaneously the surface topography of a Nafion 112 membrane and the conductivity of ion channels with an unprecedented resolution of ca. 10 nm. For given conditions, a large fraction of the channel ports is found to conduct exactly the same number of protons per unit time. This is taken as evidence for an optimum pore size and structure for proton conduction, or alternatively, for an efficient connectivity of the ion channel network, so that the same conductivity is measured at all exit pores. The time response following a potential step and the influence of the relative humidity on the transport properties is investigated. The method will be of relevance for tailoring the production technology to yield an optimised micromorphology, and it permits detailed tests of membrane models and provides data for theoretical modelling of proton conductivity.
High efficiencies, wide operation range and rapid response time have motivated the recent interest in proton exchange membrane (PEM) electrolysis for hydrogen generation with surplus electricity. However, degradation at high current densities and the associated mechanism has not been thoroughly explored so far. In this work, membrane electrode assemblies (MEA) from different suppliers are aged in a commercial PEM electrolyzer (2.5 N m 3 H 2 h -1 ), operating up to 4 A cm -2 for more than 750 h. In all cases, the cell voltage (E cell ) decreases during the testing period. Interestingly, the cells with Ir-black anodes exhibit the highest performance with the lowest precious metal loading (1 mg cm -2 ). Electrochemical impedance spectroscopy (EIS) shows a progressive decrease in the specific exchange current, while the ohmic resistance decreases when doubling the nominal current density. This effect translates into an enhancement of cell efficiency at high current densities. However, Ir concurrently leaches out and diffuses into the membrane. No decrease in membrane thickness is observed at the end of the tests. High current densities do not lead to lowering the performance of the PEM electrolyzer over time, although MEA components degrade, in particular the anode.
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