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At least 451 records · Page 25

Tuning the Porous Structure in PMMA-Templated Mesoporous MoO 2 for Pseudocapacitive Li-Ion Electrodes

MoO 2 is an exciting candidate for next-generation energy storage. It can be used for fast-charging applications in nanoscale form, but its kinetic performance is often limited by insulating MoO 3 surface oxide layers. Here, we developed methods to produce polymer-templated porous MoO 2 powders where electrical conductivity was well-maintained throughout the structure, even in the presence of some surface oxidation. Porosity, pore size, and crystallite size were controlled by varying the amount and size of the colloidal templates and through calcination temperature. The electrochemical performance was correlated with nanoscale structure: samples with high porosity, medium pore sizes, and good crystallinity display optimal rate capabilities, with over 100 mAh g −1 delivered in 3 min and 93% capacity retention after 1000 cycles. Kinetic studies were performed on samples with the largest and smallest crystallite sizes to understand the charge storage mechanism. In the sample with the smallest crystallite size, 85% of the total stored charge was capacitive, compared to 60% for the largest crystallite size. Sloping voltage profiles in materials with smaller domain sizes further suggest suppression of intercalation-induced phase transitions. This work thus provides insights into the mechanisms of charge storage in nanoscale MoO 2 and design parameters for the production of fast charging materials.

25 ENERGY STORAGE↗

A Novel Concept for a Deformable Membrane Mirror for Correction of Large Amplitude Aberrations

Very large, light weight mirrors are being developed for applications in space. Due to launch mass and volume restrictions these mirrors will need to be much more flexible than traditional optics. The use of primary mirrors with these characteristics will lead to requirements for adaptive optics capable of correcting wave front errors with large amplitude relatively low spatial frequency aberrations. The use of low modulus membrane mirrors actuated with electrostatic attraction forces is a potential solution for this application. Several different electrostatic membrane mirrors are now available commercially. However, as the dynamic range requirement of the adaptive mirror is increased the separation distance between the membrane and the electrodes must increase to accommodate the required face sheet deformations. The actuation force applied to the mirror decreases inversely proportional to the square of the separation distance; thus for large dynamic ranges the voltage requirement can rapidly increase into the high voltage regime. Experimentation with mirrors operating in the KV range has shown that at the higher voltages a serious problem with electrostatic field cross coupling between actuators can occur. Voltage changes on individual actuators affect the voltage of other actuators making the system very difficult to control. A novel solution has been proposed that combines high voltage electrodes with mechanical actuation to overcome this problem. In this design an array of electrodes are mounted to a backing structure via light weight large dynamic range flextensional actuators. With this design the control input becomes the separation distance between the electrode and the mirror. The voltage on each of the actuators is set to a uniform relatively high voltage, thus the problem of cross talk between actuators is avoided and the favorable distributed load characteristic of electrostatic actuation is retained. Initial testing and modeling of this concept demonstrates that this is an attractive concept for increasing the dynamic range capability of electrostatic deformable mirrors.

Moore, Jim↗

Progress on the Plasmoid Thruster Experiment (PTX)

A plasmoid, also called a compact toroid, is a compact plasma structure with an integral magnetic field, that may be categorized according to the relative strength of the poloidal and toroidal magnetic field (Bp and Bt, respectively). An object with Bp/Bt much greater than 1 is called a Field Reverse Configuration (FRC); if Bp = Bt, it is called a Spheromak. The plasmoid thruster is a pulsed inductive device which operates by repetitively producing plasmoids that are accelerated and ejected at high velocity. As the process is inductive, this thruster avoids the problem of electrode erosion. Also, the magnetic structure of the plasmoid should suppress thermal and mass losses to the wall, and improve detachment of the plasma exhaust from the thruster. This concept should be capable of producing an Isp of 5,000 seconds and greater, with thrust densities of order 10(exp 5) N/sq m. The plasmoid thruster consists chiefly of a conical theta-pinch coil. Propellant is introduced onto a bias magnetic field, produced by an auxiliary coil, and is then pre-ionized, freezing in the magnetic field. The theta-pinch coil is then energized producing a field aligned anti- parallel to the bias field. The reversed field reconnects with the bias field to form the plasmoid. The magnetic pressure of the reversed field accelerates the plasmoid out of the thruster . A series of experiments have been conducted on the PTX device, which consisted of a single turn conical theta-pinch coil, driven by a 560 nF, 35 kV capacitor bank, which rang at a frequency of 500 kHz, and served all three functions required for formation: pre-ionization, bias field loading, and field reversal. Initial ionization was found to occur in an annular region at the exit plane of the coil, and was found to be reproducible with a variety of gases, including H2, D2, Ar, and an H2/N2 mixture (75% / 25%). A fast gas valve for injecting propellant has been tested, as well as a ringing pre-ionization circuit (operating at 5 Mhz) to better control the plasmoid formation. Velocities as high as 20 km/s have been measured for a plasmoid propagating into a static back-fill of neutral gas. Magnetic field and density measurements indicate that the plasmoid retains its structure well into the down-stream exhaust region, and that it is capable of pushing a dense cloud of neutral gas in front of it. Further experiments will focus on the effects of coil geometry and bias-field strength on the performance of the device. A high-power solid-state switching system is being developed in order to replace the spark-gap switch.

Martin, Adam↗

Rechargeable Manganese Dioxide||Hard Carbon Lithium Batteries in an Ether Electrolyte

Earth-abundant, cost-effective electrode materials are essential for sustainable rechargeable batteries and global decarbonization. Manganese dioxide (MnO 2 ) and hard carbon both exhibit high structural and chemical tunability, making them excellent electrode candidates for batteries. Herein, we elucidate the impact of electrolytes on the cycling performance of commercial electrolytic manganese dioxide in Li chemistry. We leverage synchrotron X-ray analysis to discern the chemical state and local structural characteristics of Mn during cycling, as well as to quantify the Mn deposition on the counter electrode. By using an ether-based electrolyte instead of conventional carbonate electrolytes, we circumvent the formation of a surface Mn(II)-layer and Mn dissolution from Li x MnO 2 . Consequently, we achieved an impressive ~100% capacity retention for MnO 2 after 300 cycles at C/3. To create a lithium metal-lean full cell, we introduce hard carbon as the anode which is compatible with ether-based electrolytes. Commercial hard carbon delivers a specific capacity of ~230 mAh g -1 at 0.1 A g -1 without plateau, indicating a surface-adsorption mechanism. The resulting manganese dioxide||hard carbon full cell exhibits stable cycling and high Coulombic efficiency. Our research provides a promising solution to develop cost-effective, scalable, and safe energy storage solutions using widely available manganese oxide and hard carbon materials.

25 ENERGY STORAGE↗

A high-temperature mixed potential CO gas sensor for in situ combustion control

An in situ, accurate and robust sensor that can sustain a high temperature of above 1000 °C is needed for on-site combustion monitoring because it can give real-time and local data to the control system to adjust the overall combustion efficiency. In this work, we find that nickel oxide (NiO) is a promising sensing material for CO which is a direct indicator of the status of the combustion process of a power plant. Under the conditions of 0.5–3% O 2 and 1000 °C, the fabricated yttrium-stabilized zirconia (YSZ)-based mixed potential sensor using porous NiO demonstrates good sensitivity to CO, showing a signal as high as 36 mV to 1000 ppm CO. The effects of gas transport, structure and geometry of the NiO electrode on the sensing performance are studied. Results show that fast gas transport is much beneficial to improved sensitivity. NiO having a porous structure is much more sensitive to CO than that having a dense structure. But the t90 (time to achieve 90% final signal magnitude) of the former is much longer due to slower gas diffusion inside the pores. It's worth noting that the NiO sensor exhibits a positive relationship with the CO content, opposite to other reported results of mixed potential sensors to detect CO. We find that this might be due to the electrochemical reduction, instead of oxidation of CO during the interaction with NiO at 1000 °C. Selectivity tests on how CO 2 , CH 4 and steam affect CO sensing are also demonstrated. NiO is insensitive to even 10% CO 2 . CH 4 does not shift the average value of the CO sensing response. However, it makes the sensing signal fluctuate more intensively. 2% steam exerts a great influence on NiO sensitivity to CO: it magnifies the sensitivity of the porous NiO electrode to a low CO range of 0–100 ppm, but inhibits its sensitivity to a CO range of 100 ppm to 1000 ppm. Lastly, an 11 day stability test demonstrates the promising stability property of the proposed NiO-based YSZ sensor.

20 FOSSIL-FUELED POWER PLANTS↗

Role of Curvature in Stabilizing Boron-Doped Nanocorrugated Graphene

Boron-doped carbon nanostructures have attracted great interest recently because of their remarkable electrocatalytic performance comparable to or better than that of conventional metal catalysts. In a previous work (Carbon 123, 605 (2017)), we reported that along with significant performance improvement, B doping enhances the oxidation resistance of few-layer graphene (FLG) that provides increased structural stability for intermediate-temperature fuel-cell electrodes. In general, detailed characterization of the atomic and electronic structure transformations that occur in B-doped carbon nanostructures during fuel-cell operation is lacking. In this work, we use aberration-corrected scanning transmission electron microscopy, nanobeam electron diffraction, and electron energy-loss spectroscopy (EELS) to characterize the atomic and electronic structures of B-doped FLG before and after fuel-cell operation. These data point to the nanoscale corrugation of B-doped FLGs as the key factor responsible for increased stability and high corrosion resistance. In conclusion, the similarity of the 1s to π* and σ* transition features in the B K-edge EELS to those in B-doped carbon nanotubes provides an estimate for the curvature of nanocorrugation in B-FLG.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation Shielding System Using a Composite of Carbon Nanotubes Loaded with Electropolymers

Single-wall carbon nanotubes (SWCNTs) coated with a hydrogen-rich, electrically conducting polymer such as polyethylene, receive and dissipate a portion of incoming radiation pulse energy to electrical signals that are transmitted along the CNT axes, and are received at energy-dissipating terminals. In this innovation, an array of highly aligned nanowires is grown using a strong electric field or another suitable orientation procedure. Polyethylene (PE), polymethymlethacrylate (PMMA), or other electrically conducting polymer is spin-coated onto the SWCNTs with an average thickness of a few hundred nanometers to a few tenths of micrometers to form a PE/SWCNT composite. Alternatively, the polymer is spin-coated onto the nanowire array or an anodized alumina membrane (AAM) to form a PE/metal core shell structure, or PE can be electropolymerized using the SWCNTs or the metal nanowires as an electrode to form a PE/SWCNT core shell structure. The core shell structures can be extruded as anisotropic fibers. A monomer can be polymerized in the presence of SWCNTs to form highly cross-linked PE/SWCNT films. Alternatively, Pb colloid solution can be impregnated into a three-dimensional PE/SWCNT nanostructure to form a PW/SWCNT/Pb composite structure. A face-centered cubic (FCC) arrangement provides up to 12 interconnection channels connected to each core, with transverse channel dimensions up to 20 nm, with adequate mechanical compressive strength, and with an associated electrical conductivity of around 3 Seimens/cm for currents ranging from 0.01 to 10 mA. This threedimensional nanostructure is used as a host material to house appropriate radiation shielding material such as hydrogen- rich polymer/CNT structures, metal nanoparticles, and nanowires. Thicknesses of this material required to attenuate 10 percent, 50 percent, and 90 percent of an incident beam (gamma, X-ray, ultraviolet, neutron, proton, and electron) at energies in the range of 0 440 MeV are being determined, for example, by measuring fluence rate reduction. For example, a radiation field arrives first at an exposed surface of the innovation and produces an associated first electric field within the metal-like fingers of the three-dimensional nanostructure. This field is intensified near the exposed tips of the fingers, and this intensified field generates an intensified second electric field near the adjacent exposed tips of the coated CNSs. This generates an associated electrical current in the CNSs, and the associated electropolymer coating. The current is received by the second substrate transport component and is transported to the dissipation mechanism located contiguously to the second substrate.

McKay, Chris↗

Chemical preintercalation of magnesium ions into ⍺-MoO 3 structure for improved electrochemical stability in Li-ion cells

Chemical preintercalation of layered materials, used as electrodes in intercalation-based energy storage devices, represents a promising strategy to enhance electrochemical stability and extend cycle life. However, standardized synthesis approaches for the chemical preintercalation of diverse ions into various layered materials are lacking, necessitating the development of specific synthesis routes for each ion and layered phase combination. In this study, we present the first successful demonstration of Mg 2+ ion chemical preintercalation into the interlayer region of α-MoO 3 , revealing its stabilizing effect during cycling in non-aqueous Li-ion cells. Using ethanol during hydrothermal treatment facilitated molybdenum reduction, which was critical for Mg 2+ ion preintercalation. Interestingly, we found that Mg preintercalation was accompanied by the incorporation of water. Mg-preintercalated α-MoO 3 exhibited enhanced charge storage capacity, electrochemical stability, and power capability compared to pristine α-MoO 3 electrodes. This improved performance is attributed to the structural stabilization provided by Mg 2+ pillars, which prevent undesirable phase transformations during repeated Li intercalation/deintercalation, and increased Li + ion diffusion due to the shielding of electrostatic interactions between electrochemically cycled ions and the α-MoO 3 lattice, enabled by structural water. In conclusion, our study offers new insights into developing chemical preintercalation synthesis approaches that can be broadly applied to a wide range of pillaring ions and layered material hosts.

25 ENERGY STORAGE↗

Multifunctional nanopore electrode array method for characterizing and manipulating single entities in attoliter-volume enclosures

Structurally regular nanopore arrays fabricated to contain independently controllable annular electrodes represent a new kind of architecture capable of electrochemically addressing small collections of matter—down to the single entity (molecule, particle, and biological cell) level. Furthermore, these nanopore electrode arrays (NEAs) can also be interrogated optically to achieve single entity spectroelectrochemistry. Larger entities such as nanoparticles and single bacterial cells are investigated by dark-field scattering and potential-controlled single-cell luminescence experiments, respectively, while NEA-confined molecules are probed by single molecule luminescence. By carrying out these experiments in arrays of identically constructed nanopores, massively parallel collections of single entities can be investigated simultaneously. The multilayer metal–insulator design of the NEAs enables highly efficient redox cycling experiments with large increases in analytical sensitivity for chemical sensing applications. NEAs may also be augmented with an additional orthogonally designed nanopore layer, such as a structured block copolymer, to achieve hierarchically organized multilayer structures with multiple stimulus-responsive transport control mechanisms. Finally, NEAs constructed with a transparent bottom layer permit optical access to the interior of the nanopore, which can result in the cutoff of far-field mode propagation, effectively trapping radiation in an ultrasmall volume inside the nanopore. Furthermore, the bottom metal layer may be used as both a working electrode and an optical cladding layer, thus, producing bifunctional electrochemical zero-mode waveguide architectures capable of carrying out spectroelectrochemical investigations down to the single molecule level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Research on the noise produced by large scale structure in supersonic jets

Using a dual electrode glow discharge excitation device, a method of mode selection into either the n = 0 or n = + or - 1 azimuthal modes was developed and tested by Fourier analyzing experimental azimuthal phase and amplitude data. On a M = 2.1 moderate Reynolds number (Re = 68,000) jet with a laminar boundary layer, under n = 0 or n = +1 excitation, coherent axial wave evolution, mean flow, and sound pressure level directivity measurements were performed. The boundary layer of this same jet was excited usng a grit coating on the nozzle wall, and bandpassed axial wave evolution data obtained and compared to the masurements made by previous workers on a conventional high Reynolds number jet (Re = 5,000,000) using a hot-film type probe.

Mclaughlin, D. K.↗

An advanced low-cost cathode composed of graphene-coated Na 2.4 Fe 1.8 (SO 4 ) 3 nanograins in a 3D graphene network for ultra-stable sodium storage

Iron-based electrodes have attracted great attention for sodium storage because of the distinct cost effectiveness. However, exploring suitable iron-based electrodes with high power density and long duration remains a big challenge. Herein, a spray-drying strategy is adopted to construct graphene-coated Na 2.4 Fe 1.8 (SO 4 ) 3 nanograins in a 3D graphene microsphere network. The unique structural and compositional advantages endow these electrodes to exhibit outstanding electrochemical properties with remarkable rate performance and long cycle life. Additionally, mechanism analyses further explain the outstanding electrochemical properties from the structural aspect.

25 ENERGY STORAGE↗

Epitaxial Ferroelectric Hf 0.5 Zr 0.5 O 2 with Metallic Pyrochlore Oxide Electrodes

The synthesis of fully epitaxial ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) thin films through the use of a conducting pyrochlore oxide electrode that acts as a structural and chemical template is reported. Such pyrochlores, exemplified by Pb 2 Ir 2 O 7 (PIO) and Bi 2 Ru 2 O 7 (BRO), exhibit metallic conductivity with room-temperature resistivity of <1 mΩ cm and are closely lattice matched to yttria-stabilized zirconia substrates as well as the HZO layers grown on top of them. Evidence for epitaxy and domain formation is established with X-ray diffraction and scanning transmission electron microscopy, which show that the c-axis of the HZO film is normal to the substrate surface. The emergence of the non-polar-monoclinic phase from the polar-orthorhombic phase is observed when the HZO film thickness is ≥≈30 nm. Furthermore, thermodynamic analyses reveal the role of epitaxial strain and surface energy in stabilizing the polar phase as well as its coexistence with the non-polar-monoclinic phase as a function of film thickness.

36 MATERIALS SCIENCE↗

The Linkage Between Electro-Chemical Mechanical Instabilities in Battery Materials

Battery chemistry must be diversified to achieve a sustainable energy landscape by effectively utilizing renewable energy sources. Alkali metal-ion, all-solid-state, metal–air batteries, and multivalent batteries offer unique cost, safety, raw material abundance, energy, and power density solutions. However, realizing these “beyond Li-ion batteries” must uncover their working principles and performance & property relationships. In this aspect, mitigating chemo-mechanical instabilities in the structure and surface of the electrodes plays a crucial role in their performance. Unfortunately, the coupling between electrochemical and mechanical interactions is often poorly understood due to a lack of operando characterization. Here, this review article explains the working principles of curvature measurement and digital image correlation for measuring stress and strain generations in battery materials. We provided specific examples of how these operando mechanical measurements shed light on instabilities in alkali metal ion electrodes, solid electrolytes, Li-O 2 batteries, and aqueous Zn-ion batteries. Operando mechanical measurements offer an effective way to map changes in the physical fingerprint of the battery materials, therefore providing crucial information to elucidate instabilities in battery materials.

25 ENERGY STORAGE↗

Impact of Cation Insertion on Semiconducting Polymer Thin Films toward Electrochemical Energy Conversion

Semiconducting polymers are being explored for electrochemical and photoelectrochemical energy transformation and storage applications. For these applications, it is critical to understand how ion insertion from the electrolyte into polymer electrodes modulates the polymer electronic structure and electron doping levels. Here, this study explores electrochemical cation insertion in the n-type conjugated redox polymer P90, composed of alternating naphthalene diimide (NDI) acceptor and bithiophene (T2) donor units, where the NDI units are functionalized with heptaethylene glycol (HEG, 90%) and 2-octyl dodecyl (OD, 10%) side chains. By combining in situ techniques (UV-vis absorption and Raman spectroscopies with electrochemistry), structural analysis using ex situ grazing-incidence wide-angle X-ray scattering (GIWAXS), and density functional theory (DFT) calculations, we reveal that dications enable negative polaron and bipolaron formation in the P90 at less reducing potentials while supporting more bipolaron formation than the monocations; moreover, larger dications with smaller hydrated radii increase the maximum P90 electron doping level. We also determine that the monocations lead to more thermodynamically stabilized polarons compared with the dications. These findings highlight the critical role of cation identity in tuning electrochemical charging, charge stabilization, and electronic structure of n-type conjugated redox polymers, providing guidance on the rational design of polymer-based (photo)electrochemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic configurations, from the extremes of classical molecular dynamics of a complete interface with point-charge atoms to correlated electronic structure methods of a single electrode configuration with no dynamics or electrolyte. Here, we review the spectrum of simulation techniques suitable for electrochemistry, focusing on the key approximations and accuracy considerations for each technique. Additionally, we discuss promising approaches, such as enhanced sampling techniques for atomic configurations and computationally efficient beyond density functional theory (DFT) electronic methods, that will push electrochemical simulations beyond the present frontier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Recoverable vs Unrecoverable Voltage Losses and Long-Term Degradation Mechanisms in Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) have recently shown excellent progress in terms of their performance – e.g., achievable power and current density. However, very few AEMFCs have been demonstrated with the ability to operate for a long duration (>1000 h). In addition, it is unknown whether performance losses observed during operation are reversible, irreversible, or a combination of the two. In this study, a high-performance AEMFC operated continuously at 600 mA/cm 2 for 3600 h (150 days) at 80 °C with H 2 /O 2 reacting gases was demonstrated. Throughout testing, the electrochemical properties of the AEMFC were probed to provide information about performance degradation pathways and their degree of reversibility. It was found that a portion of the performance loss that occurs during AEMFC operation was due to suboptimal reaction conditions and can be recovered. At the end of the experiment, the cell was disassembled, and its structure and composition were evaluated at the nanoscale by aberration-corrected scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. The structure and composition of the electrode were compared to cells at the beginning of their operational life. It was found that the primary mechanism for long-term AEMFC performance loss was catalyst agglomeration. During the operational time, there was no evidence of significant polymer degradation, likely due to the high hydration state of the cell. By documenting the long-term changes in high-performing AEMFCs, this work provides important information for the systematic design of cell components and demonstrates the importance of controlling cell operation, which can aid in the commercialization and widespread deployment of low-cost, long-life AEMFCs.

30 DIRECT ENERGY CONVERSION↗

Electrocatalytic Reductive Amination of Aldehydes and Ketones with Aqueous Nitrite

The electrocatalytic utilization of oxidized nitrogen waste for C–N coupling chemistry is an exciting research area with great potential to be adopted as a sustainable method for generation of organonitrogen molecules. The most widely used C–N coupling reaction is reductive amination. In this work, we develop an alternative electrochemical reductive amination reaction that can proceed in neutral aqueous electrolyte with nitrite as the nitrogenous reactant and via an oxime intermediate. We develop a selection criterion for nitrite reduction electrocatalysts suited for oxime electrosynthesis and, in doing so, find Pd to be a highly efficient catalyst for this reaction, reaching an oxime Faradaic efficiency of 82% at −0.21 V vs the reversible hydrogen electrode. The aliphatic or aromatic structure of the carbonyl reactant impacts the efficacy of the catalyst, with aromatic substrates leading to suppressed oxime formation and detrimental reduction of the carbonyl to the alcohol. We developed a Pb/PbO electrocatalyst that selectively performs oxime reduction in the neutral aqueous electrolyte. With acetone as a model substrate, we demonstrate an efficient one-pot, two-step electrochemical reaction for the conversion of acetone to isopropyl amine with 85% yield and 50% global Faradaic efficiency.

catalysts↗