Composite Manganese Oxide Percolating Networks as a Suspension Electrode for an Asymmetric Flow Capacitor
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Gold and glassy carbon working electrode materials are compared as suitable substrates for the hydrogen oxidation reaction with Ni(PCy2Nt-Bu2)2(BF4)2 used as a catalyst. Voltammetric responses showing electrocatalytic hydrogen oxidation mediated by the homogeneous electrocatalyst Ni(PCy2Nt-Bu2)2(BF4)2 are identical at glassy carbon and gold electrodes, which shows that gold electrode can be used for hydrogen oxidation reaction. This work is supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under FWP 56073.
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Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5
The complex coupling of atomic, chemical, and electronic transformations across multiple length scales underlies the performance of electrochemical energy storage devices. Here, the coupling of chemistry with atomic- and nanoscale structure in iron conversion electrodes is resolved by combining pair distribution function (PDF) and small-angle X-ray scattering (SAXS) analysis for a series of Fe fluorides, oxyfluorides, and oxides. The data show that the anion chemistry of the initial electrode influences the abundance of atomic defects in the Fe atomic lattice. This, in turn, is linked to different atom mobilities and propensity for particle growth. Competitive nanoparticle growth in mixed anion systems contributes to a distinct nanostructure, without the interconnected metallic nanoparticles formed for single anion systems.
Metal nanowire (MNW) transparent electrodes have been widely developed for their promising sheet resistance (Rs)–transmittance (T) performance, excellent mechanical flexibility, and facile synthesis. How to lower the junction resistance without compromising optical transmittance has become the key issue in enhancing their performance. Here we combine electrospinning and electroless deposition to synthesize interconnected, ultralong MNW networks. For both silver and copper nanowire networks, the Rs and T values reach around 10 Ω/sq and 90%, respectively. This process is scalable and takes place at ambient temperature and pressure, which opens new opportunities for flexible electronics and roll-to-roll large-scale manufacturing.
Here, we report the first direct measurement of the chemistry and extent of reactivity between a lithium ion battery electrode surface (Si) and a liquid electrolyte (1.2M LiPF6-3:7 wt% ethylene carbonate:dimethyl carbonate). We estimate that this layer is 3.6 nm thick and partially originates from the consumption of the silicon surface.
Preparing electrodes made of metals like stainless steel, for use inside DC high voltage electron guns, is a labor-intensive and time-consuming process. In this paper, the authors report the exceptional high voltage performance of aluminum electrodes coated with hard titanium nitride (TiN). The aluminum electrodes were comparatively easy to manufacture and required only hours of mechanical polishing using silicon carbide paper, prior to coating with TiN by a commercial vendor. The high voltage performance of three TiN-coated aluminum electrodes, before and after gas conditioning with helium, was compared to that of bare aluminum electrodes, and electrodes manufactured from titanium alloy (Ti-6Al-4V). Following gas conditioning, each TiN-coated aluminum electrode reached −225 kV bias voltage while generating less than 100 pA of field emission (<10 pA) using a 40 mm cathode/anode gap, corresponding to field strength of 13.7 MV/m. Smaller gaps were studied to evaluate electrode performance at higher field strength with the best performing TiN-coated aluminum electrode reaching ∼22.5 MV/m with field emission less than 100 pA. These results were comparable to those obtained from our best-performing electrodes manufactured from stainless steel, titanium alloy and niobium, as reported in references cited below. The TiN coating provided a very smooth surface and with mechanical properties of the coating (hardness and modulus) superior to those of stainless steel, titanium-alloy, and niobium electrodes. These features likely contributed to the improved high voltage performance of the TiN-coated aluminum electrodes.
With lower site density and turnover frequency, platinum group metal (PGM)-free catalysts based electrodes are often greater than 50 mu m thick in order to increase performance across the fuel cell operating range. Consequently, PGM-free electrodes have an additional bulk electrode transport resistance beyond the local or aggregate level transport in thin platinum-based electrodes. In parallel to the development of more active and durable PGM-free catalysts, advancements in understanding the interplay between PGM-free electrode fabrication, bulk-electrode transport, proton conductivity and performance are needed. Here, the relationship between ionic and gas phase transport through the electrode thickness is modified by adjusting electrocatalyst and ionomer flocculation/interaction at the ink level. The influence of the ink composition (water/n-propanol content) is examined via various in-situ electrochemical and ex-situ characterization techniques and the resulting electrode structure/performance relationship contrasted with electrode performance robustness across a range of relative humidity (RH). For the electrocatalyst examined here, a water-rich (82 wt% H2O) ink formulation was favorable for operation at high RH due to improved molecular diffusion through larger electrode pores. In contrast, the improved interactions between ionomer and electrocatalyst enabled a more robust electrode and higher performance during low RH operation for the 50 wt% H2O content ink.
The NASA Manned Space Program uses an electrocardiograph (ECG) system to monitor astronauts during extravehicular activity (EVA). This ECG system, called the Operational Bioinstrumentation System (OBS), was developed during the Apollo era. Throughout the Shuttle program these electrodes experienced failures during several EVAs performed from the Space Shuttle and International Space Station (ISS) airlocks. An attempt during Shuttle Flight STS-109 to replace the old electrodes with new commercial off-the-shelf (COTS) disposable electrodes proved unsuccessful. One assumption for failure of the STS-109 COTS electrodes was the expansion of trapped gases under the foam electrode pad, causing the electrode to be displaced from the skin. Given that our current electrodes provide insufficient reliability, a number of COTS ECG electrodes were tested at the NASA Altitude Manned Chamber Test Facility. Methods: OBS disposable electrodes were tested on human test subjects in an altitude chamber simulating an Extravehicular Mobility Unit (EMU) operating pressure of 4.3 psia with the following goals: (1) to confirm the root cause of the flight certified, disposable electrode failure during flight STS-109. (2) to identify an adequate COTS replacement electrode and determine if further modifications to the electrodes are required. (3) to evaluate the adhesion of each disposable electrode without preparation of the skin with isopropyl alcohol. Results: There were several electrodes that failed the pressure testing at 4.3psia, including the electrodes used during flight STS-109. Two electrodes functioned well throughout all testing and were selected for further testing in an EMU at altitude. A vent hole placed in all electrodes was also tested as a possible solution to prevent gas expansion from causing electrode failures. Conclusions: Two failure modes were identified: (1) foam-based porous electrodes entrapped air bubbles under the pad (2) poor adhesion caused some electrodes to fail
As the size of a positively biased electrode increases, the nature of the interface formed between the electrode and the host plasma undergoes a transition from an electron-rich structure (electron sheath) to an intermediate structure containing both ion and electron rich regions (double layer) and ultimately forms an electron-depleted structure (ion sheath). In this study, measurements are performed to further test how the size of an electron-collecting electrode impacts the plasma discharge the electrode is immersed in. This is accomplished using a segmented disk electrode in which individual segments are individually biased to change the effective surface area of the anode. Measurements of bulk plasma parameters such as the collected current density, plasma potential, electron density, electron temperature and optical emission are made as both the size and the bias placed on the electrode are varied. Abrupt transitions in the plasma parameters resulting from changing the electrode surface area are identified in both argon and helium discharges and are compared to the interface transitions predicted by global current balance [S. D. Baalrud, N. Hershkowitz, and B. Longmier, Phys. Plasmas 14, 042109 (2007)]. While the size-dependent transitions in argon agree, the size-dependent transitions observed in helium systematically occur at lower electrode sizes than those nominally derived from prediction. The discrepancy in helium is anticipated to be caused by the finite size of the interface that increases the effective area offered to the plasma for electron loss to the electrode.
Sr(Ti 0.3 Fe 0.7 )O 3–δ (STF) and the associated exsolution electrodes Sr 0.95 (Ti 0.3 Fe 0.63 Ru 0.07 )O 3–δ (STFR), or Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3–δ (STFN) are alternatives to Ni-based cermet fuel electrodes for solid oxide electrochemical cells (SOCs). They can provide improved tolerance to redox cycling and fuel impurities, and may allow direct operation with hydrocarbon fuels. However, such perovskite-oxide-based electrodes present processing challenges for co-sintering with thin electrolytes to make fuel electrode supported SOCs. Thus, they have been mostly limited to electrolyte-supported SOCs. Here, we report the first example of the application of perovskite oxide fuel electrodes in novel oxygen electrode supported SOCs (OESCs) with thin YSZ electrolytes, and demonstrate their excellent performance. The OESCs have La 0.8 Sr 0.2 MnO 3–δ –Zr 0.92 Y 0.16 O 2–δ (LSM–YSZ) oxygen electrode-supports that are enhanced via infiltration of SrTi 0.3 Fe 0.6 Co 0.1 O 3–δ , while the fuel electrodes are either Ni-YSZ, STF, STFN, or STFR. Fuel cell power density as high as 1.12 W cm –2 is obtained at 0.7 V and 800 °C in humidified hydrogen and air with the STFR electrode, 60% higher than the same cell made with a Ni-YSZ electrode. Electrolysis current density as high as –1.72 A cm –2 is obtained at 1.3 V and 800 °C in 50% H 2 O to 50% H 2 mode; the STFR cell yields a value 72% higher than the same cell made with a Ni-YSZ electrode, and competitive with the widely used conventional Ni-YSZ-supported cells. The high performance is due in part to the low resistance of the thin YSZ electrolyte, and also to the low fuel electrode polarization resistance, which decreases with fuel electrode in the order: Ni-YSZ > STF > STFN > STFR. The high performance of the latter two electrodes is due to exsolution of catalytic metal nanoparticles; the results are discussed in terms of the microstructure and properties of each electrode material, and surface oxygen exchange resistance values are obtained over a range of conditions for STF, STFN, and STFN. Furthermore, the STF fuel electrodes also provide good stability during redox cycling.
DC high voltage photoelectron guns are used to produce polarized electron beams for accelerator-based nuclear and high-energy physics research. Low-level field emission (∼nA) from the cathode electrode degrades the vacuum within the photogun and reduces the photoelectron yield of the delicate GaAs-based photocathode used to produce the electron beams. High-level field emission (>μA) can cause significant damage the photogun. To minimize field emission, stainless steel electrodes are typically diamond-paste polished, a labor-intensive process often yielding field emission performance with a high degree of variability, sample to sample. As an alternative approach and as comparative study, the performance of electrodes electropolished by conventional commercially available methods is presented. Our observations indicate the electropolished electrodes exhibited less field emission upon the initial application of high voltage, but showed less improvement with gas conditioning compared to the diamond-paste polished electrodes. In contrast, the diamond-paste polished electrodes responded favorably to gas conditioning, and ultimately reached higher voltages and field strengths without field emission, compared to electrodes that were only electropolished. The best performing electrode was one that was both diamond-paste polished and electropolished, reaching a field strength of 18.7 MV/m while generating less than 100 pA of field emission. The authors speculate that the combined processes were the most effective at reducing both large and small scale topography. However, surface science evaluation indicates topography cannot be the only relevant parameter when it comes to predicting field emission performance.