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At least 523 records · Page 29

Carbon Nanotubes: Applications to Energy Storage Devices

Carbon nanotubes (CNTs) are an extraordinary discovery in the area of science and technology. Engineering them properly holds the promise of opening new avenues for future development of many other materials for diverse applications. Carbon nanotubes have open structure and enriched chirality, which enable improvements the properties and performances of other materials when CNTs are incorporated in them. Energy storage systems have been using carbon nanotubes either as an additive to improve electronic conductivity of cathode materials or as an active anode component depending upon structural and morphological specifications. Furthermore, they have also been used directly as the electrode material in supercapacitors and fuel cells. Therefore, CNTs demand a huge importance due to their underlying properties and prospective applications in the energy storage research fields. There are different kinds of carbon nanotubes which have been successfully used in batteries, supercapacitors, fuel cells and other energy storage systems. This chapter focuses on the role of CNTs in the different energy storage and conversion systems and impact of their structure and morphology on the electrochemical performances and storage mechanisms.

Amin, Ruhul↗

In Situ Foaming of Porous (La 0.6 Sr 0.4 ) 0.98 (Co 0.2 Fe 0.8 ) O 3-δ (LSCF) Cathodes for Solid Oxide Fuel Cell Applications

A binder system containing polyurethane precursors was used to in situ foam (direct foam) a (La{sub 0.6}Sr{sub 0.4}){sub 0.98} (Co{sub 0.2} Fe{sub 0.8}) O{sub 3-{ delta}} (LSCF) composition for solid oxide fuel cell (SOFC) cathode applications. The relation between in situ foaming parameters on the final microstructure and electrochemical properties was characterized by microscopy and electrochemical impedance spectroscopy (EIS), respectively. The optimal porous cathode architecture was formed with a 70 vol% solids loading within a polymer precursor composition with a volume ratio of 8:4:1 (isocyanate: PEG: surfactant) in a terpineol-based ink vehicle. The resultant microstructure displayed a broad pore size distribution with highly elongated pore structure.

30 DIRECT ENERGY CONVERSION↗

Electrochemically Smart Bimetallic Materials Featuring Group 11 Metals: In-situ Conductive Network Generation and Its Impact on Cell Capacity

Our results for this program “Electrochemically smart bimetallic materials featuring Group 11 metals: in-situ conductive matrix generation and its impact on battery capacity, power and reversibility” have been highly successful: 1) we demonstrated material structures which generated in-situ conductive networks through electrochemical activation with increases in conductivity up to 10,000 fold, 2) we pioneered in situ analytical methodology to map the cathodes at several stages of discharge through the use of Energy Dispersive X-ray Diffraction (EDXRD) to elucidate the kinetic dependence of the conductive network formation, and 3) we successfully designed synthetic methodology for direct control of material properties including crystallite size and surface area which showed significant impact on electrochemical behavior.

30 DIRECT ENERGY CONVERSION↗

Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

30 DIRECT ENERGY CONVERSION↗

Solid oxide fuel cell systems with hot zones having improved reactant distribution

A Solid Oxide Fuel Cell (SOFC) system having a hot zone with a center cathode air feed tube for improved reactant distribution, a CPOX reactor attached at the anode feed end of the hot zone with a tail gas combustor at the opposing end for more uniform heat distribution, and a counter-flow heat exchanger for efficient heat retention.

30 DIRECT ENERGY CONVERSION↗

Method of forming catalyst layer by single step infiltration

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

30 DIRECT ENERGY CONVERSION↗

Efficient electrocatalytic conversion of CO 2 to ethanol enabled by imidazolium-functionalized ionomer confined molybdenum phosphide

An effective electrochemical carbon dioxide reduction reaction (eCO 2 RR) requires the discovery of a catalytic system that is highly active and selective for multi-carbon products together with superior CO 2 diffusion at a catalyst layer to minimize the reduction barriers. Here, we found a catalytic system that uses molybdenum phosphide (MoP) nanoparticles covered by imidazolium-functionalized ionomer (Im) that promotes CO 2 diffusion at the catalyst layer toward the catalyst surface, where CO 2 is reduced to ethanol (C 2 H 5 OH). The electrochemical results with the MoP-Im co-catalyst show a C 2 H 5 OH production Faradaic efficiency and a cathodic energy efficiency of 77.4% and 63.3%, respectively, at a potential as low as - 200 mV vs. RHE. The electrochemical experiments along with our physicochemical characterizations indicate that the Im improves CO 2 diffusion and balances water content resulting in a higher CO 2 -to-water ratio at the catalyst layer and fine-tunes the electronic properties of Mo atoms at the MoP surface. Finally, in-situ Raman spectroscopy reveals that a high number of adsorbed *CO intermediates on the surface and a higher binding strength of *CO intermediates on the Mo surface sites in the presence of imidazolium molecules are the main reasons for a superior C-C coupling and thereby the improved C 2 H 5 OH formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a preprototype sabatier CO2 reduction subsystem

A preoprototype Sabatier CO2 Reduction Subsystem was successfully designed, fabricated and tested. The lightweight, quick starting reactor utilizes a highly active and physically durable methanation catalyst composed of ruthenium on alumina. The use of this improved catalyst permits a single straight through plug flow design with an average lean component H2/CO2 conversion efficiency of over 99% over a range of H2/CO2 molar ratios of 1.8 to 5 while operating with flows equivalent to a crew size of one person steadystate to 3 persons cyclical (equivalent to 5 persons steady state). The reactor requires no heater operation after start-up even during simulated 55 minute lightside/39 minute darkside orbital operation over the above range of molar ratios and crew loadings. The subsystem's operation and performance is controlled by a microprocessor and displayed on a nineteen inch multi-colored cathode ray tube.

Kleiner, G. N.↗

Development of the NASA/FLAGRO computer program

A preliminary version of a new computer program has been developed for calculating crack propagation in cyclically loaded structures. The new program, titled NASA/FLAGRO, has numerous enhanced features over previous programs used for safe life analysis on space systems. The essential features of the new program consist of modular design, promptive input using a cathode ray tube terminal, improved crack growth rate analytical methods, many new crack case solutions, and incorporation of user-defined files for material properties and fatigue spectrums. Also, five options made available in the program are to compute: (1) safe life of a part with a preexisting crack; (2) critical crack size for a specified stress level; (3) stress-intensity factor numerical values for making comparisons or checks of solutions; (4) least-squares fit of growth rate equations to crack growth rate data; and (5) the conversion of a versus N data to Delta K versus da/dN.

Forman, Royce G.↗

Eliminating the Imbalanced Mobility Bottlenecks via Reshaping Internal Potential Distribution in Organic Photovoltaics

The imbalanced carrier mobility remains a bottleneck for performance breakthrough in even those organic solar cells (OSCs) with recorded power conversion efficiencies (PCEs). Herein, a counter electrode doping strategy is proposed to reshape the internal potential distribution, which targets to extract the low mobility carriers at far end. Device simulations reveal that the key of this strategy is to partially dope the active layer with a certain depth, therefore it strengthens the electric field for low mobility carriers near counter electrode region while avoids zeroing the electric field near collection electrode region. Taking advantage of these, PCE enhancements are obtained from 15.4% to 16.2% and from 16.9% to 18.0%, respectively, via cathode p-doping and anode n-doping. Extending its application from opaque to semitransparent devices, the PCE of dilute cell rises from 10.5% to 12.1%, with a high light utilization efficiency (LUE) of 3.5%. The findings provide practical solutions to the core device physical problem in OSCs.

14 SOLAR ENERGY↗

Bioelectrochemical biorefining for the conversion of hydrogenous matter to hydrogen gas and other useful products

A method for the substantially complete conversion of hydrogenous matter to higher value product, the method comprising: (i) subjecting the hydrogenous matter to a substantially complete deconstruction process in which an aqueous phase containing a multiplicity of deconstructed compounds is produced; and (ii) contacting the aqueous phase with an anode of a microbial electrolysis cell, the anode containing a community of microbes thereon which oxidatively degrade one or more of the oxygenated organic compounds in the aqueous phase to produce protons and free electrons at the anode, wherein the protons and free electrons are transported to the cathode to produce hydrogen gas or a valuable reduced organic compound at the cathode upon application of a suitable cell potential across the anode and cathode. The invention is also directed to an apparatus for practicing the method described above.

09 BIOMASS FUELS↗

Fuel Cell Membrane Electrode Assemblies with Ultra-Low Pt Nanofiber Electrodes (Final Report)

H 2 /air fuel cell membrane-electrode-assemblies (MEAs) were fabricated with electrospun particle/polymer nanofiber mat cathodes (0.1 mg Pt /cm 2 or 0.2 mg Pt /cm 2 Pt/C, PtCo/C or PtNi/C) and anodes (0.1 mg/cm 2 Pt/C), where the binder was a mixture of acid-form perfluorosulfonic acid ionomer (e.g., Nafion™) and poly(acrylic acid) (PAA) carrier polymer or sodium-form PFSA with a carrier polymer of either PAA or polyethylene oxide (PEO). For the latter two cases, the water-soluble carrier was removed from the fibers after electrospinning. MEAs with Pt/C anode/cathode catalyst loadings of 0.1 mg Pt /cm2 each, an 1100 EW PFSA binder (Nafion™ dispersion), and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions, e.g., a maximum power density of 919 mW/cm 2 at 100% RH and 832 mW/cm 2 at 40% RH for a test at 80 °C and 200 kPa abs . The high power at low RH was attributed to nm-size pores within the fibers that trap water via capillary condensation thus maintaining a high proton conductivity of the PFSA binder in the cathode and especially the anode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder. At the same time, micro-porosity between fibers in the cathode allows for fast removal of electrogenerated water, thus minimizing cathode flooding. Nanofiber MEAs with Pt alloy catalyst cathodes also performed well, where a fibrous PtCo/C catalyst cathode at a loading of 0.1 mg/cm 2 produced 20% more power than a conventional powder cathode MEA, e.g., a maximum power density of 1,045 mW/cm 2 vs. 869 mW/cm 2 at 80 °C, 100% RH, and 200 kPa abs , and a PtNi/C fiber cathode MEAs prepared with Na+-form Nafion + PEO generated a maximum power of 820 mW/cm 2 at 40% RH. Fiber electrode MEAs with a neat Nafion binder (prepared from Na+-form Nafion + PEO or PAA) where the cathode Pt loading was ~0.1 mg/cm 2 exhibited a 25% loss in maximum power at 30,000 metal dissolution cycles, as compared to a 12% loss when the cathode binder was H+-form Nafion + PAA. The performance of a fiber mat electrode MEA with Pt/C catalyst (0.2 mg/cm 2 cathode loading and 0.1 mg/cm 2 anode loading) was excellent. At 80 oC and 200 kPa abs , the maximum power density was 1104 mW/cm 2 . The maximum power was independent of feed gas humidity for 40 < RH < 100%. The power loss after a metal dissolution AST (30,000 voltage cycles) was only 13%.

08 HYDROGEN↗

Operating Stresses and Their Effects on Degradation of LSM-Based SOFC Cathodes

The performance of solid oxides fuel cells (SOFCs) with four different Mn excess of lanthanum strontium manganite (LSM) -based cathodes were examined under different temperatures (1,000 °C, 900 °C), current densities (0, 380, and 760 mA cm -2 ), and cathode atmospheres (p O 2 )=0.1,0.15,0.21) for durations ranging from 58 to 1,008 h. Each yttria-stabilized zirconia (YSZ) electrolyte-supported “button” cell had a porous Ni/YSZ composite anode and a porous LSM/YSZ composite cathode. The cells’ output voltage versus time were recorded and electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) measurements were performed every 24 hours. The total area specific resistance (ASR) was calculated from these measurements. The values of ASR from both EIS and LSV were comparable between each other but lower than that from durability test. Distribution of relaxation times (DRT) analysis was performed to investigate the electrochemical processes and their corresponding relaxation frequencies as well as their attributions to the total ASR. The series resistance and parallel resistance that obtained from the equivalent circuit fit of the Nyquist plot were higher at low temperature and low p O 2 regardless of LSM compositions. The area of the peaks derived from DRT analysis increased with time during individual tests. The microstructures of the tested cells were examined using scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM/EDS). Manganese oxide particles were observed near the cathode-electrolyte interface after prolonged (1,008 h) testing in air of a cell with LSM of 11% manganese excess, and after a short test (58 h) under low oxygen (p O 2 = 0.10) in a cell with LSM of 5% manganese excess. However, the role of MnOx in cell degradation is still unknown.

08 HYDROGEN↗

On the origin of permanent performance loss of anion exchange membrane fuel cells: Electrochemical oxidation of phenyl group

The durability of alkaline anion exchange membrane fuel cells (AEMFCs) is a critical requirement for implementing this technology in cost-effective energy conversion. However, the lifetime of current AEMFCs is short, ca. < 1,000 h and the cause of the performance loss over time is poorly understood. Here, we investigate the origin of AEMFC unrecoverable performance loss. We diagnosed the recoverable performance loss induced by carbonation and anode flooding during an extended-term test with transient operating conditions. Multiple extended-term tests under current densities and the electrochemical and analytical analyses suggest that the most prominent permanent performance loss of AEMFCs occurs by phenol formation as a result of electrochemical phenyl oxidation of cathode ionomeric binder. The produced phenol is acidic and neutralizes the quaternary ammonium group to lower the local pH. Finally, the impact of this degradation pathway is discussed to explain the reported lifetime performance of current AEMFCs.

08 HYDROGEN↗

An In 0.42 Ga 0.58 N tunnel junction nanowire photocathode monolithically integrated on a nonplanar Si wafer

Group III-nitride semiconductors exhibit many ideal characteristics for solar water splitting, including a tunable energy bandgap across nearly the entire solar spectrum and suitable band edge positions for water oxidation and proton reduction under visible and near-infrared light irradiation. To date, however, the best reported energy conversion efficiency for III-nitride semiconductor photocathodes is still below 1%. Here we report on the demonstration of a relatively efficient p-type In 0.42 Ga 0.58 N photocathode, which is monolithically integrated on an n-type nonplanar Si wafer through a GaN nanowire tunnel junction. The open pillar design, together with the nonplanar Si wafer can significantly maximize light trapping, whereas the tunnel junction reduces the interfacial resistance and enhances the extraction of photo-generated electrons. In addition, photodeposited Pt nanoparticles on InGaN nanowire surfaces significantly improve the cathodic performance. The nanowire photocathode exhibits a photocurrent density of 12.3 mA cm -2 at 0 V vs. RHE and an onset potential of 0.79 V vs. RHE under AM 1.5G one-sun illumination. Here, the maximum applied bias photon-to-current efficiency reaches 4% at ~0.52 V vs. RHE, which is one order of magnitude higher than the previously reported values for III-nitride photocathodes. Significantly, no performance degradation was measured for over 30 hours solar water splitting with a steady photocurrent density ~12 mA cm -2 without using any extra surface protection, which is attributed to the spontaneous formation of N-terminated surfaces of InGaN nanowires to protect against photocorrosion.

42 ENGINEERING↗

Direct observation of bi-alkali antimonide photocathodes growth via in operando x-ray diffraction studies

Alkali antimonides have a long history as visible-light-sensitive photocathodes. This work focuses on the process of fabrication of the bi-alkali photocathodes, K{sub 2}CsSb. In-situ synchrotron x-ray diffraction and photoresponse measurements were used to monitor phase evolution during sequential photocathode growth mode on Si(100) substrates. The amorphous-to-crystalline transition for the initial antimony layer was observed at a film thickness of 40 Å . The antimony crystalline structure dissolved upon potassium deposition, eventually recrystallizing upon further deposition into K-Sb crystalline modifications. This transition, as well as the conversion of potassium antimonide to K{sub 2}CsSb upon cesium deposition, is correlated with changes in the quantum efficiency.

36 MATERIALS SCIENCE↗

A scalable, biopolymer-based microenvironment for electrochemical CO 2 conversion to multicarbon products with current densities over 2 A cm −2

The electrochemical CO 2 reduction reaction (CO 2 RR) relies heavily on the surrounding microenvironment to promote formation of desirable multicarbon (C 2+ ) products. However, microenvironment control to achieve high C 2+ yields at industrially relevant current densities remains a crucial challenge. We report that chitosan, cellulose and chitin biopolymer coatings on CO 2 RR electrocatalysts enhance the microenvironment by increasing local CO 2 /CO concentration, reducing local water activity and providing suitable ion conductivity and local pH. This facile approach achieves C 2+ Faradaic efficiencies of 90 ± 1.7% at 1.6 A cm −2 and C 2+ Faradaic efficiency = 83 ± 3.2% at 2.2 A cm −2 with a formation rate of 5,926 μmol h −1 cm −2 . Importantly, within the cathode, these ion-conductive hydrophilic biopolymers can fully substitute traditional hydrophobic ionomers/binders, such as Nafion, challenging previous assumptions about the non-viability of hydrophilic materials for selective CO 2 RR due to excess interfacial H 2 O. These findings unveil key insights into microenvironment design to enhance C–C coupling through a simple method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗