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More, K. L.

Publications and source records attributed to More, K. L..

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2 -Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s ) due to higher initial Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology

25 ENERGY STORAGE↗

Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg 0.2 MnO 2 ·0.5H 2 O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity of 158 mA h g -1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g -1 ). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g -1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na + ion intercalation.

25 ENERGY STORAGE↗

Catalyst-layer ionomer imaging of fuel cells

Investigation of membrane/electrode assembly (MEA) microstructure has become an essential step to optimize the MEA components and manufacturing processes or to study the MEA degradation. For these investigations, transmission electron microscopy (TEM) is a tool of choice as it provides direct imaging of the different components. TEM is then widely used for analyzing the catalyst nanoparticles and their carbon support. However, the ionomer inside the electrode is more difficult to be imaged. The difficulties come from the fact that the ionomer forms an ultrathin layer surrounding the carbon particles and in addition, these two components, having similar density, present no difference in contrast. In this paper, we show how the recent progresses in TEM techniques as spherical aberration (Cs) corrected HRTEM, electron tomography and X-EDS elemental mapping provide new possibilities for imaging this ionomer network and consequently to study its degradation.

30 DIRECT ENERGY CONVERSION↗

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi 3 polyhedra, transforms in solution by interior erosion into Pt 3 Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi 3 polyhedra are maintained in the final Pt 3 Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt 3 Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

36 MATERIALS SCIENCE↗

Oxide growth stress measurements and relaxation mechanisms for alumina scales grown on FeCrAlY: Oxide growth stress measurements and relaxation mechanisms

Early-stage tensile stress evolution in α-Al 2 O 3 scales during oxidation of FeCrAlY at 1000, 1050, 1100, and 1200 °C was monitored in situ by use of synchrotron radiation. Tensile stress development as a function of oxidation temperature indicated a dynamic interplay between stress generation and relaxation. An analysis of the time dependence of the data indicated that the observed relaxation of the initial tensile stress in the oxide scales at 1100 and 1200°C is dominated by creep in the α-Al 2 O 3 . A thin layer of a (Fe,Cr,Al) oxide was observed at the oxide-gas interface, consistent with a mechanism whereby the conversion of (Fe,Cr,Al) 2 O 3 to α-Al 2 O 3 produces an initial tensile stress in the alumina scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗