Effect of pristine graphene incorporation on charge storage mechanism of three-dimensional graphene oxide: superior energy and power density retention

In the race of gaining higher energy density, carbon's capacity to retain power density is generally lost due to defect incorporation and resistance increment in carbon electrode. Herein, a relationship between charge carrier density/charge movement and supercapacitance performance is established. For this purpose we have incorporated the most defect-free pristine graphene into defective/sacrificial graphene oxide. A unique co-solvent-based technique is applied to get a homogeneous suspension of single to bi-layer graphene and graphene oxide. This suspension is then transformed into a 3D composite structure of pristine graphene sheets (GSs) and defective N-doped reduced graphene oxide (N-RGO), which is the first stable and homogenous 3D composite between GS and RGO to the best of our knowledge. It is found that incorporation of pristine graphene can drastically decrease defect density and thus decrease relaxation time due to improved associations between electrons in GS and ions in electrolyte. Furthermore, N doping is implemented selectively only on RGO and such doping is shown to improve the charge carrier density of the composite, which eventually improves the energy density. After all, the novel 3D composite structure of N-RGO and GS greatly improves energy and power density even at high current density (20 A/g). © The Author(s) 2016.1

Palladium Membrane with High Density of Large-Angle Grain Boundaries to Promote Hydrogen Diffusivity

A higher density of large-angle grain boundaries in palladium membranes promotes hydrogen diffusion whereas small-angle grain boundaries suppress it. In this paper, the microstructure formation in 10 µm thick palladium membranes is tuned to achieve a submicronic grain size above 100 nm with a high density of large-angle grain boundaries. Moreover, changes in the grain boundaries’ structure is investigated after exposure to hydrogen at 300 and 500 °C. To attain large-angle grain boundaries in Pd, the coating was performed on yttria-stabilized zirconia/porous Crofer 22 APU substrates (intended for use later in an ultracompact membrane reactor). Two techniques of plasma sprayings were used: suspension plasma spraying using liquid nano-sized powder suspension and vacuum plasma spraying using microsized powder as feedstock. By controlling the process parameters in these two techniques, membranes with a comparable density of large-angle grain boundaries could be developed despite the differences in the fabrication methods and feedstocks. Analyses showed that a randomly oriented submicronic structure could be attained with a very similar grain sizes between 100 and 500 nm which could enhance hydrogen permeation. Exposure to hydrogen for 72 h at high temperatures revealed that the samples maintained their large-angle grain boundaries despite the increase in average grain size to around 536 and 720 nm for vacuum plasma spraying and suspension plasma spraying, respectively

Elucidating the performance limitations of alkaline electrolyte membrane electrolysis : dominance of anion concentration in membrane electrode assembly

Anion exchange membrane water electrolyzers (AEMWEs) offer a cost‐effective technology for producing green hydrogen. Here, an AEMWE with atmospheric plasma spray non‐precious metal electrodes was tested in 0.1 to 1.0 M KOH solution, correlating performance with KOH concentration systematically. The highest cell performance was achieved at 1.0 M KOH (ca. 0.4 A cm-2 at 1.80 V), which was close to a traditional alkaline electrolysis cell with ≈6.0 M KOH. The cell exhibited 0.13 V improvement in the performance in 0.30 M KOH compared with 0.10 M KOH at 0.5 A cm−2. However, this improvement becomes more limited when further increasing the KOH concentration. Electrochemical impedance and numerical simulation results show that the ohmic resistance from the membrane was the most notable limiting factor to operate in low KOH concentration and the most sensitive to the changes in KOH concentration at 0.5 A cm-2. It is suggested that the effect of activation loss is more dominant at lower current densities; however, the ohmic loss is the most limiting factor at higher current densities, which is a current range of interest for industrial applications.Projekt DEA

One step electrochemical fabrication of high performance Ni@Fe-doped Ni(oxy)hydroxide anode for practical alkaline water electrolysis

Oxygen evolution reaction (OER) is a rate-determining process in alkaline water electrolysis (AWE). Herein, we report a novel one-step oxidation-electrodeposition (OSOE) approach to generate core@shell nanoarrays-based AWE electrode with outstanding OER performances: an overpotential of 245 mV at 10 mA cm−2 (Tafel slope: 37 mV dec−1), and excellent stability under huge current densities. Moreover, the alkaline (AEL) cell equipped with NM-OSOE-23 anode recorded significant performance improvement of 200 mV lower voltage (2 A cm−1) compared with a similar cell used bare Ni mesh as an anode, which was contributed by notable enhancements of interface contact, anodic charge transfer, and mass transfer. These promising results are attributed to the constructed specific core@shell Ni@Fe-doped Ni(oxy)hydroxide nanoarray architecture on commercial nickel mesh. This study demonstrates this first reported OSOE can be commercialized to make highly efficient anodes enabling next-generation AWE

Palladium Membrane with High Density of Large-Angle Grain Boundaries to Promote Hydrogen Diffusivity

A higher density of large-angle grain boundaries in palladium membranes promotes hydrogen diffusion whereas small-angle grain boundaries suppress it. In this paper, the microstructure formation in 10 µm thick palladium membranes is tuned to achieve a submicronic grain size above 100 nm with a high density of large-angle grain boundaries. Moreover, changes in the grain boundaries’ structure is investigated after exposure to hydrogen at 300 and 500 °C. To attain large-angle grain boundaries in Pd, the coating was performed on yttria-stabilized zirconia/porous Crofer 22 APU substrates (intended for use later in an ultracompact membrane reactor). Two techniques of plasma sprayings were used: suspension plasma spraying using liquid nano-sized powder suspension and vacuum plasma spraying using microsized powder as feedstock. By controlling the process parameters in these two techniques, membranes with a comparable density of large-angle grain boundaries could be developed despite the differences in the fabrication methods and feedstocks. Analyses showed that a randomly oriented submicronic structure could be attained with a very similar grain sizes between 100 and 500 nm which could enhance hydrogen permeation. Exposure to hydrogen for 72 h at high temperatures revealed that the samples maintained their large-angle grain boundaries despite the increase in average grain size to around 536 and 720 nm for vacuum plasma spraying and suspension plasma spraying, respectively

전기화학적 산소 반응을 위한 비귀금속 전이금속과 이종원소를 포함한 새로운 탄소 촉매들의 합성, 특성 분석 및 촉매 활성 평가

prohibitionDoctordCollectio

Superior pore network retention of carbon derived from naturally dried ginkgo leaves and its enhanced oxygen reduction performance

Obtaining a highly porous carbon has always been considered as an essential issue in many electrochemical applications. Ginkgo leaves have not only unique shape and color, but also interesting chemical and medical properties, which have inspired us to investigate them. In present approach, the naturally dried yellow ginkgo leaves, collected in autumn season, are directly used to prepare the porous carbon with simple two-step template-free procedure of pyrolysis at different temperatures followed by acid treatment for removal of inherent mineral salts. Interestingly, it is found that inherent salts present in the resulting carbon backbone can play as porogen to create high amount of pores in the carbon framework when the salts are removed by acid treatment. Effect of alternations in ginkgo leaves structure during the climate change, from spring to autumn, on ORR activity is examined for the first time on the carbons obtained by carbonizing different color, greenish and yellowish, ginkgo leaves at 1000 °C. Yellow leaves can maintain their original tissue structure during the gradual drying in cold weather of late fall, which results in formation of more stable structure, leading to development of much more pores and larger surface area in the resulting carbon. The unforeseen results exhibit surprisingly higher ORR activity for carbon catalyst obtained from yellow leaves (LY-1000) compared with one prepared from green leaves collected in summer, (LG-1000). Higher surface area of LY-1000 is found to be the most important key factor for its enhanced ORR activity. Furthermore, electrocatalytic property of the carbon greatly depends on the carbonization temperature, which is a crucial factor to make a balance between electrical conductivity, heteroatom doping and surface area. As the temperature increases, the heteroatom doping decreases, which is not favorable for ORR, but at the same time, the conductivity and surface area increase, which is beneficial for ORR, indicating intriguing trade-off between them as a function of temperature, which needs to be optimized for best ORR performance. Moreover, present work enables a large-scale production of efficient heteroatom-doped porous carbon from ginkgo leaf waste without using any activation and templating agents. © 2015 Elsevier B.V. All rights reserved.