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Using galvanostatic electroforming of Bi1-xSbx nanowires to control composition, crystallinity, and orientation

Journal of Materials Research

Limmer, Steven J.; Medlin, Douglas L.; Siegal, Michael P.; Hekmaty, Michelle A.; Lensch-Falk, Jessica L.; Erickson, Kristopher J.; Pillars, Jamin R.; Yelton, W.G.

Using galvanostatic pulse deposition, we studied the factors influencing the quality of electroformed Bi1-xSbxnanowires with respect to composition, crystallinity, and preferred orientation for high thermoelectric performance. Two nonaqueous baths with different Sb salts were investigated. The Sb salts used played a major role in both crystalline quality and preferred orientations. Nanowire arrays electroformed using an SbI3-based chemistry were polycrystalline with no preferred orientation, whereas arrays electroformed from an SbCl3-based chemistry were strongly crystallographically textured with the desired trigonal orientation for optimal thermoelectric performance. From the SbCl3 bath, the electroformed nanowire arrays were optimized to have nanocompositional uniformity, with a nearly constant composition along the nanowire length. Nanowires harvested from the center of the array had an average composition of Bi0.75Sb0.25. However, the nanowire compositions were slightly enriched in Sb in a small region near the edges of the array, with the composition approaching Bi0.700.30.

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Planarized arrays of aligned, untangled multiwall carbon nanotubes with Ohmic back contacts

Journal of Materials Research

Friedman, Caitlin R.; Limmer, Steven J.; Howell, Stephen W.; Laros, James H.; Siegal, Michael P.

Vertically aligned, untangled planarized arrays of multiwall carbon nanotubes (MWNTs) with Ohmic back contacts were grown in nanopore templates on arbitrary substrates. The templates were prepared by sputter depositing Nd-doped Al films onto W-coated substrates, followed by anodization to form an aluminum oxide nanopore array. The W underlayer helps eliminate the aluminum oxide barrier that typically occurs at the nanopore bottoms by instead forming a thin WO3 layer. The WO3 can be selectively etched to enable electrodeposition of Co catalysts with control over the Co site density. This led to control of the site density of MWNTs grown by thermal chemical vapor deposition, with W also serving as a back electrical contact. Ohmic contact to MWNTs was confirmed, even following ultrasonic cutting of the entire array to a uniform height.

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Role of Cu-Ion doping in Cu-α-MnO2 nanowire electrocatalysts for the oxygen reduction reaction

Journal of Physical Chemistry C

Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; Rodriguez, Marko A.; Brumbach, Michael T.; Coker, Eric N.; Limmer, Steven J.

The role of Cu-ion doping in α-MnO2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Cu-doped α-MnO2 nanowires (Cu-α-MnO2) were prepared with varying amounts (up to ∼3%) of Cu2+ using a hydrothermal method. The electrocatalytic data indicate that Cu-α-MnO2 nanowires have up to 74% higher terminal current densities, 2.5 times enhanced kinetic rate constants, and 66% lower charge transfer resistances that trend with Cu content, exceeding values attained by α-MnO2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn3+ content at the surface of the Cu-α-MnO2 nanowires. The Mn3+/Mn4+ couple is the mediator for the rate-limiting redox-driven O2/OH- exchange. O2 adsorbs via an axial site (the eg orbital on the Mn3+ d4 ion) at the surface or at edge defects of the nanowire, and the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O2 adsorbates and faster rates of reduction. A smaller crystallite size (roughly half) for Cu-α-MnO2 leading to a higher density of (catalytic) edge defect sites was also observed. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline electrolyte and an increase in Mn3+ character at the surface of the oxide. © 2014 American Chemical Society.

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Nanoporous carbon for electrochemical capacitors

Yelton, William G.; Siegal, Michael P.; Bunker, B.C.; Limmer, Steven J.

Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

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Size effects in Ni/Ni(OH)2 nanomaterials for electrochemical capacitors

Limmer, Steven J.; Yelton, William G.; Bunker, B.C.

Electrochemical capacitors based on redox-active metal oxides show great promise for many energy-storage applications. These materials store charge through both electric double-layer charging and faradaic reactions in the oxide. The dimensions of the oxide nanomaterials have a strong influence on the performance of such capacitors. Not just due to surface area effects, which influence the double-layer capacitance, but also through bulk electrical and ionic conductivities. Ni(OH)2 is a prime candidate for such applications, due to low cost and high theoretical capacity. We have examined the relationship between diameter and capacity for Ni/Ni(OH)2 nanorods. Specific capacitances of up to 511 F/g of Ni were recorded in 47 nm diameter Ni(OH)2 nanorods.

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Nanoporous carbon for electrochemical capacitors

Limmer, Steven J.; Yelton, William G.; Siegal, Michael P.; Overmyer, Donald L.; Bunker, B.C.

Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

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32 Results
32 Results