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At least 757 records · Page 42

Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

The biggest obstacle to the widespread implementation of polymer electrolyte membrane fuel cells (PEMFCs) is their cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited on a rotating disk electrode (RDE) is rarely realized in a membrane electrode assembly (MEA), which is a long-standing challenge for PEMFCs and a cause of low catalyst utilization. To translate the high RDE performance of a catalyst into a MEA, the design of an ideal ionomer/catalyst interface is proposed: a thin, conformal ionomer film covers the maximum surface of a Pt nanoparticle and thus simultaneously maximizes catalyst utilization, (i.e., high mass activity and electrochemically active surface area) and O 2 diffusion rate (i.e., high current density performance) without compromising proton conduction. Building such an interface is a long-standing challenge due to the lack of interaction between the ionomer and catalyst particles, resulting in large ionomer agglomerates and inhomogeneous ionomer coverage over the catalyst nanoparticle, with consequent poor fuel cell performance. In this work, this ionomer/catalyst interface has been engineered, utilizing the electrostatic attraction between positively charged catalyst and negatively charged ionomer particles in a catalyst ink and preserved in a solid catalyst layer. As a result, this interface leads to previously unachieved proton exchange membrane fuel cell performance in terms of both catalyst utilization (75% vs. 45%) and peak/rated power density (i.e., 1.430/0.930 W cm -2 , H 2 /air, cathode Pt loading: 0.1 mgPt cm -2 ) for pure Pt catalysts, even better than those of Pt alloy catalysts. This work demonstrates the formation of an interface in the liquid phase (using ultra-small-angle X-ray scattering in combination with cryo-TEM, isothermal–titration–calorimetry) and the preservation of the interface in the solid catalyst layer (using TEM) and estimates the effective coverage and thickness of the ionomer film (using limiting current density, RDE and fuel cell performance).

25 ENERGY STORAGE↗

Dynamic, Adaptive, Systems and Materials: Complex, Simple and Emergent Behaviors

This program has been funded by DoE/BES for twenty years. It has moved into and out of various subjects as it has developed, but it has retained its focus on complexity and complex systems. The project has evolved in the following way: Self-Assembly and Biomimetic Self-Assembly: All self-assembling systems depend upon a minimum of two types of interaction: a repulsion and an attraction. For the familiar molecular systems, attractive interactions are typically hydrogen bonds and electrostatic interactions. Repulsive interactions include steric effects, hydrophobic effects (in biological systems), and charge-charge repulsion. We have expanded this repertoire to include surface interactions, magnetic interactions, and others. I list these systems in the order in which we have explored them: i) A key emphasis in current work is in understanding how the movement of ions in a magnetic field (the Lorentz effect) interacts with catalytic systems. We have demonstrated that an acceleration in rate of reduction of CO 2 to CO can be accomplished by applying an external magnetic field. This acceleration is largely due to the application of the Lorentz effect on mass transport at the catalyst’s surface. ii) We have also extensively explored the influence of electrostatics, as exhibited in self-assembling systems, by tribocharging. iii) Another key system involves surface tension effects; examples include interactions between heavy particles floating at a liquid-air interface, and interacting by changes in surface area; interactions of bubbles and bubble rafts, behaviors of bubble trains in microfluidic networks, and behaviors of microorganisms in constraining environments. iv) This work has intentionally de-emphasized biological systems; but it does include some work on protein-ligand interactions and interactions among microorganisms. v) We have also explored applications of some of these effects, these explorations include bubble rafts as diffraction gratings, exploration of the structures that can be obtained by tribocharging and uses of these structures in exploring nucleation and melting of crystals. vi) Although not a major focus of this work, several other topics have emerged and offer opportunities for future work. These include the behavior of bubble trains and bubble rafts in microfluidic systems. A particularly interesting example is the formation of bubble trains that repeat in the alteration of large and small bubbles according to rules we do not presently understand, but are uniquely large-period oscillating systems. These systems offer a new route into understanding the instabilities of the type represented by oscillations. vii) We have also begun exploratory projects on magnetic levitation (especially to determine molecular density), and information storage (in molecules). Magnetic Levitation: Self-assembling and biomimetic systems require both attraction and repulsion. We have used electrostatics (tribocharging), interfacial free-energies (surface tension and related forces) and others. Potential uses include reconfigurable diffraction gratings and liquid lenses; exploration of mechanisms in tribocharging; tunneling in EGaIn junctions; and bubble trains (especially in micro-fluidic systems). Examples of systems representing these topics is included in the following papers: Complexity: Disks rotating at a water-air interface; Benard-Marangoni effects; Vortex-Crystals from spinning magnetic disks (Marangoni effects); EGaIn Electrode to study quantum tunneling; Self-Assembly of electrostatically-charged metallic spheres (electrets); Dynamically reconfigurable lens; Using computational designs of ligands for enzymes; Electrostatic self-assembly by tribocharging; Monodisperse bubble trains in microchannel systems; Inverted dripping faucet; Flames; Printing of micro-organisms to regenerate the “ink” of printing device; Using micro-organisms to move loads (“microoxen”); Motion of bacterial swarms near surfaces; Making monodisperse particles in microfluidic systems; Coding/decoding of information stored in droplet trains in microfluidic networks; Magnetic levitation; and Information storage. i) Tribocharging. The change in focus of this work on electrets from the fundamentals of charging to applications of these materials in studying self-assembly using electrostatic interactions. ii) Bubbles in Microchannels. The realization that systems of bubbles in microchannels represented a major opportunity to study complexity in a very tractable system, and the development of a semi-quantitative theory of this subject. iii) Flames. The growth of “flames” remains an exploratory subject for the research, although their currently relatively little active work involving it ongoing. iv) Systems with Microorganisms. The removal of work in biological systems from this project. Based on work supported in this program, we now have a significant project on the development of microfluidic tools for studying C. elegans (a nematode), but this work was not appropriate for a program focused on complexity, and we developed separate support for it. (It is, however, an example of successful seeding of a new area by BES.) The work on electrets has gone through a period in which a part of the program was the subject of a MURI; the focus of this work was to develop materials that did not charge electrostatically on friction or contact. The MURI is now over, and the work on dynamic self-assembly (supported by BES) is the major focus. “Flames” has also enjoyed synergistic support, in terms of a project supported by DARPA on flame suppression (in the absence of extinguishing agents, using acoustic and electrostatic interactions). This work was helpful in understanding some of the basics of flames, but is entirely distinct from the BES focus in complexity. A growing interest is in the Lorentz effect. The Lorentz effect is the force exerted on charged particles (electrons, ions, charged molecules) when they move through a perpendicular magnetic field. The Lorentz effect is almost ubiquitous in modern technology: examples of applications include electric motors, dynamos, cathode ray tubes, many batteries, and most systems that control electrical currents with magnetic forces. We have begun to explore the Lorentz effect in electrochemical systems and heterogeneous catalytic systems involving charged organic species and inorganic ions. This work is still at an early stage, but initial studies that Lorentz effects can be large when ions move through magnetic fields, or magnetic fields move in the presence of ions.

36 MATERIALS SCIENCE↗

Kinetics and transport at AMTEC electrodes. II - Temperature dependence of the interfacial impedance of Na(g)/porous Mo/Na-Beta-double prime alumina

The exchange current, transfer coefficient, mass-transport parameters, and electrode capacitance at the Na(g)/porous Mo/Na-Beta-double prime alumina solid electrolyte (BASE) phase boundary have been evaluated from 740 to 1220 K. The transfer coefficient exhibits a value close to 0.5 and the exchange current is dominated by collision frequency, with no significant activation energy. Since the porous Mp-electrode adopts a fairly regular microstructure on the BASE surface, the magnitude of the exchange current of mature electrodes directly depends on the actual contact zone of the porous metal film with the BASE ceramic, and decreases slightly as grain growth occurs. The exchange currents and the mass-transport parameters derived for very porous, thin Mo electrodes indicate that the charge-transfer reaction occurs at a small fraction of the interface. High-frequency limiting capacitance and resistance values due to the interface show potential dependence and a value on the order of 1 F/sq m and 0.1-1.0 Ohm-sq cm.

Williams, R. M.↗

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Hooker, M. W.↗

The Effect of Artificial SEIs on Lithium Metal Anode Morphology and Conductivity

Lithium metal has often been termed the “holy grail” of battery technology, due to its high capacity (2,061 mAh/cm3) and low electrochemical potential (-3.04 V vs. SHE). However, lithium’s beneficially low potential also causes it to be highly reactive in the presence of organic solvents, making it difficult to harness the high energy capabilities for rechargeable batteries. Common failure of lithium metal batteries occurs by rapid dendrite growth leading to a hazardous short-circuit. Various methods have been brought forth to better understand the fundamental mechanisms of lithium metal batteries, as well as modifications made to better stabilize lithium metal. A common route of modification is done through interface engineering, with attempts to artificially provide a stable, homogeneous solid-electrolyte interface (SEI). The stability of the SEI has direct effects on the heterogeneity of the electrode surface, which initiates a waterfall effect of for progressive reactions such as dendrite growth, dead lithium accumulation, and electrolyte consumption. This work aims to produce a mixed LiI-LiF artificial SEI to improve ionic conductivity while retaining a high elastic modulus.

25 ENERGY STORAGE↗

Multiscale Electrochemomechanics Interaction and Degradation Analytics of Sn Electrodes for Sodium-Ion Batteries

Sodium-ion batteries have emerged as a strong contender among the beyond lithium-ion chemistries due to elemental abundance and the low cost of sodium. Tin (Sn) is a promising alloying electrode with high capacity, redox reversibility, and earth abundance. Tin electrodes, however, undergo a series of intermediate reactions exhibiting multiple voltage plateaus upon sodiation/desodiation. Phase transformations related to incomplete sodiation in tin during cycling, in the presence of a frail solid electrolyte interphase layer, can quickly weaken the structural stability. The structural dynamics and reactivity of the electrode/electrolyte interface, being further dependent on the size and morphology of the active material particle in the presence of different electrolytes, dictate the electrode degradation and survivability during cycling. Here, we paint a comprehensive picture of the underpinnings of the electrochemical and mechanics coupling and electrode/electrolyte interfacial interactions in alloying Sn electrodes. We elicit the fundamental role of electrode/electrolyte complexations in the Sn electrode structure-property-performance relationship based on multimodal analytics, including electrochemical, microscopy, and tomography analyses.

25 ENERGY STORAGE↗

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗

Exploring chemical speciation at electrified interfaces using detailed continuum models

We present a local free-energy functional-based generic continuum model for material interfaces with a specific emphasis on electrified solid/liquid interfaces. The model enables a description of multicomponent phases at interfaces and includes the effects of specific non-electrostatic interactions (specific adsorption), ion size disparity, and the explicit presence of neutral species. In addition to the optimization of electrostatic, non-electrostatic, and steric forces, the model can be easily modified to explore the effects of other channels for equilibration, including local chemical transformations driven by equilibrium constants and electrochemical reactions driven by the electrode potential. In this way, we show that, upon accounting for these effects, local speciation in the vicinity of the interface can be drastically different from what is expected from restricted models and minor species (from the bulk perspective) may become dominant due to the effects of local pH. We evaluate the ionic contribution to the surface tension at the interface and show how this could impact the structure of air/liquid interfaces. On the same footing, an attempt to describe electrochemical metal dissolution is made. The model allows estimates of the mutual population of newly produced ions depending on their charge and size and could be useful for interpretation of electrochemical and spectroscopic measurements if the dissolution involves different metal ions (species). With these advances, the proposed model may be used as an ingredient within a hybrid ab initio-continuum methodology to model biased interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bonds over Electrons: Proton Coupled Electron Transfer at Solid–Solution Interfaces

This Perspective argues that most redox reactions of materials at an interface with a protic solution involve net proton-coupled electron transfer (PCET) (or other cation-coupled ET). This view contrasts with the traditional electron-transferfocused view of redox reactions at semiconductors, but redox processes at metal surfaces are often described as PCET. Taking a thermodynamic perspective, transfer of an electron is typically accompanied by a stoichiometric proton, much as the chemistry of lithium-ion batteries involves coupled transfers of e – and Li + . The PCET viewpoint implicates the surface–H bond dissociation free energy (BDFE) as the preeminent energetic parameter and its conceptual equivalents, the electrochemical ne – /nH + potential versus the reversible hydrogen electrode (RHE) and the free energy of hydrogenation, ΔG° H . These parameters capture the thermochemistry of PCET at interfaces better than electronic parameters such as Fermi energies, electron chemical potentials, flatband potentials, or band-edge energies. A unified picture of PCET at metal and semiconductor surfaces is presented. Exceptions, limitations, implications, and future directions motivated by this approach are described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bio-inspired interfaces for easy-to-recycle lithium-ion batteries

The recycling of spent lithium-ion batteries has significant potential to benefit our society economically and environmentally as well as preserving raw materials. Although diverse process chains have been applied or under development to recycle batteries, a common, critical issue for battery recycling is the separation of the metallic current collector from the composite film of the electrode. In this study, inspired by the amazing controllable attachment and detachment ability of geckos’ foot-hairs, microscale near-surface architecture is designed on the interface between the current collector and the composite film in lithium-ion batteries, so that it displays controllable and directional adhesion, i.e., enhanced adhesion can be obtained during its lifetime to cope with the substantial volume changes of the composite film upon intercalation and deintercalation, whereas during recycling, the composite layer of the electrode can be easily peeled off from the current collector in a certain direction. We report this study is the first application of structural adhesives for the development of easy-to-recycle lithium-ion batteries. This technology can also be extended to other electronic products to avoid an ever-growing volume of electronic waste. The fundamental understanding on the interfacial adhesion and delamination mechanisms provides a scientific footing for the realization of next-generation easy-to-recycle electronics.

25 ENERGY STORAGE↗

Effect of Electro-Sprayed Porous Electrodes on the Performance and Stability of Water Electrolysis

The efficiency of proton exchange membrane water electrolysis (PEMWE) is a critical issue in realizing the production of green hydrogen. Here, the coexistence of three phases in the catalyst layer of PEMWE causes the mass transport limitation at the interfaces between them. In particular, the vigorous production of gaseous hydrogen and oxygen derived from liquid water is generated in the form of bubbles that seriously deactivate the membrane-electrode assembly (MEA). In this study, we investigated the effect of porous structure in the electrode on the efficiency of hydrogen production at high current density, which is highly related to the mass transport limitation. A widely used commercial catalyst (IrO 2 ) were directly coated on the membrane by the electro-spray method. The porous electrodes on the membrane were formed by the charged catalyst particles that repulsed each other due to the electrostatic forces of the particles. Our membrane electrode assembly (MEA) exhibited outstanding electrolysis performances such as 5.3 A cm -2 and 3.2 A cm -2 at 2.0 V and 1.8 V, respectively, which are the highest values compared with the results published in the current studies. In addition to the porosity, it was confirmed that optimum binder contents positively affect the hydrophobicity and contact resistance of MEA. Through a simple porosity-controlled technique, the performance of PEMWE, in which three phases coexist, can be improved by more than 60 %. Accordingly, we expect that our systematic study on the role of porosity in the electrodes opens a new era to efficiently produce green hydrogen.

catalysts↗

Lithiation of multilayer Ni/NiO electrodes: criticality of nickel layer thicknesses on conversion reaction kinetics

X-ray reflectivity and transmission electron microscopy (TEM) were used to characterize the morphological changes in thin film electrodes with alternating Ni and NiO layers during lithiation as a function of the Ni buffer layer thickness. Complete lithiation of the active NiO layers occurs only when the thickness of the Ni/NiO bilayers are less than 75 Å – a threshold value that is determined by the sum of the Ni quantity in the Ni/NiO bilayer of the multilayer stack. Thicker Ni/NiO bilayers present a kinetic barrier for lithium ion diffusion inside the stack resulting in partial lithiation of the multilayer electrodes in which only the top NiO layer lithiates. Lithiation of NiO layers in a multilayer stack also leads to an interface-specific reaction that is observed to increase the thicknesses of adjacent Ni layers by 3–4 Å and is associated with the formation of a low-density Li 2 O layer, corresponding to an interfacially-driven phase separation of the NiO. Rate dependent cyclic voltammetry studies reveal a linear relation between the peak current and scan rate suggesting that the lithiation kinetics are controlled by charge transfer resistance at the liquid–solid interface.

25 ENERGY STORAGE↗

Extending the Service Life of High–Ni Layered Oxides by Tuning the Electrode–Electrolyte Interphase

As a high-energy-density cathode for Li-ion batteries, high-Ni layered oxides, especially with ultrahigh Ni-content, suffer from short lifespans, due in part to their unstable electrode–electrolyte interphase (EEI). Herein, the cycle life of LiNi 0.94 Co 0.06 O 2 is greatly extended by manipulating the EEI with a lithium bis(oxalate) (LiBOB) additive even when operated at a moderately high voltage (4.4 V vs Li/Li + ). Impressively, the capacity retention can be increased from 61 to 80% after 500 cycles in a full cell paired with a graphite anode. Additionally, the presence of LiBOB enables a robust boron- and oxygen-enriched EEI that effectively inhibits continual electrolyte decomposition and offers a stable cathode surface. Moreover, the layered architecture of the cathode–electrolyte interphase (CEI) and the anode–electrolyte interphase (AEI) at the nanometer scale is revealed by time-of-flight secondary ion mass spectrometry. It is demonstrated that the cathode surface chemistry can significantly influence the AEI both chemically and physically, and AEI is modified from a thick “three-layer” to a thin “two-layer” architecture by tuning the cathode surface chemistry with LiBOB. Finally, this work presents a correlation between the EEI characteristics and battery performance and highlights the significance of manipulating surface chemistry in developing stable high-energy-density Li-ion batteries.

25 ENERGY STORAGE↗

Degradation of solid oxide electrolysis cells: Phenomena, mechanisms, and emerging mitigation strategies—A review

Solid oxide electrolysis cell (SOEC) is a promising electrochemical device with high efficiency for energy storage and conversion. However, the degradation of SOEC is a significant barrier to commercial viability. In this review article, the typical degradation phenomena of SOEC are summarized, with great attention into the anodes/oxygen electrodes, including the commonly used and newly developed anode materials. Meanwhile, mechanistic investigations on the electrode/electrolyte interfaces are provided to unveil how the intrinsic factor, oxygen partial pressure , and the electrochemical operation conditions, affect the interfacial stability of SOEC. At last, this paper also presents some emerging mitigation strategies to circumvent long-term degradation, which include novel infiltration method, development of new anode materials and engineering of the microstructure.

36 MATERIALS SCIENCE↗

Heterostructured Au–Ir Catalysts for Enhanced Oxygen Evolution Reaction

Electrochemical water splitting operated under acidic conditions provides a clean approach to generate hydrogen fuels. Currently, the sluggish kinetics of oxygen evolution reaction (OER) at the anode is a bottleneck limiting the acidic water splitting. Here, we report that the OER activity of Ir, one of the most commonly used OER catalysts, can be boosted by forming phase boundaries with Au. Mixed Au and Ir catalysts were synthesized on carbon paper electrodes, which underwent structural evolution under the OER environment to form an Au-Ir interface-rich structure. Compared with Ir catalyst, which requires an overpotential of ~393 mV to achieve a current density of 10 mA/cm 2 in 0.1 M HClO 4 electrolyte, the evolved Au-Ir catalyst shows a lower overpotential at ~351 mV. X-ray photoelectronic spectrum (XPS) study, in conjunction with electrochemical analysis on the surface-site-normalized activity, reveals that the improved OER performance is due to the presence of Au/Ir interfaces in the catalysts. In addition to Ir, the strategy of accelerating OER via Au/Ir interfaces has been further applied to IrCo, IrNi, and IrCu alloy catalysts. Here, with the broad applicability of the strategy demonstrated, this study opens a new route to design OER catalysts for efficient acidic water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial engineering for high performance carbon-based perovskite solar cells

Perovskite solar cells fabricated with carbon-based counter electrodes demonstrate decreased cost, enhanced simplicity and speed of production, and increased stability compared to those produced with standard metallic electrodes. This significant improvement of device stability, cost reduction, and production scalability indicates a promising direction for commercial development and availability of perovskite solar technology. The main limitation of carbon-based perovskite devices is the flawed contact between the carbon electrode and perovskite film which decreases device quality and performance, thereby necessitating treatment of the carbon/perovskite interface. This review provides an overview of the current state of carbon-based perovskite devices, discusses progress in carbon/perovskite interface modification methods, and suggests future directions for the research of carbon electrode/perovskite film interface manipulation.

14 SOLAR ENERGY↗

ASTROS - High-performance CCD tracker for spacecraft

The architecture, capabilities, and testing of the Advanced Star and Target Reference Optical Sensor (ASTROS) I and II are described. The ASTROS I tracker is to be utilized for a UV telescope experiment on a Shuttle flight and is capable of measuring pointing errors of 1.5 microrad, and the ASTROS II tracker is being developed for the Mariner Mark II spacecraft to perform tracking, guiding, and optical navigation functions. The requirements for the two trackers are compared. Consideration is given to star and target tracking, optical navigation, and mass and power constraints. The compositions of the trackers, in particular the sensor, electrode drives, amplifiers and signal clamp, video signal processor, control and timing generator, memories, microprocessor, and interface, are examined.

Dennison, E. W.↗