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Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

Developing active and durable air electrodes for efficient oxygen reactions is challenging for protonic ceramic cells (PCCs), especially at temperatures below 550°C. Here, in this study, we report a rationally designed conformal coating with a high-entropy PrNi 0.2 Mn 0.2 Co 0.2 Fe 0.2 Cu 0.2 O 3−δ (PNMCFC) perovskite structure on the surface of a state-of-the-art PrBaCo 2 O 5+δ (PBC) air electrode. The formed hybrid air electrode (PNMCFC-PBC) shows faster surface oxygen kinetics and a more stable phase structure in high-humidity air than the bare PBC electrode. Further density functional theory calculations suggest that the conformal coating mitigates Ba segregation at the interface and improves oxygen-related reactions, enhancing overall stability and electrocatalytic performance. The cells with the developed hybrid electrodes show encouraging electrochemical performance at 550°C: a polarization resistance of 0.72 Ω cm 2 , a peak power density of 1.30 W cm −2 , an electrolysis current density of −1.36 A cm −2 at 1.3 V, and reasonable operating stabilities (∼200 h at 550°C).

30 DIRECT ENERGY CONVERSION↗

Perspectives and progress on wurtzite ferroelectrics: Synthesis, characterization, theory, and device applications

Wurtzite ferroelectrics are an emerging material class that expands the functionality and application space of wide bandgap semiconductors. Promising physical properties of binary wurtzite semiconductors include a large, reorientable spontaneous polarization, direct band gaps that span from the infrared to ultraviolet, large thermal conductivities and acoustic wave velocities, high mobility electron and hole channels, and low optical losses. The ability to reverse the polarization in ternary wurtzite semiconductors at room temperature enables memory and analog type functionality and quasi-phase matching in optical devices and boosts the ecosystem of wurtzite semiconductors, provided the appropriate combination of properties can be achieved for any given application. In this article, advances in the design, synthesis, and characterization of wurtzite ferroelectric materials and devices are discussed. Highlights include: the direct and quantitative observation of polarization reversal of ~135 μC/cm 2 charge in Al 1-x B x N via electron microscopy, Al 1-x B x N ferroelectric domain patterns poled down to 400 nm in width via scanning probe microscopy, and full polarization retention after over 1000 h of 200 °C baking and a 2× enhancement relative to ZnO in the nonlinear optical response of Zn 1-x Mg x O. In conclusion, the main tradeoffs, challenges, and opportunities in thin film deposition, heterostructure design and characterization, and device fabrication are overviewed.

30 DIRECT ENERGY CONVERSION↗

Opportunities and challenges in process modeling and simulation of electrochemical systems

Electrochemical technologies have garnered intense interest in both academic research and industrial applications due to their potential to increase energy efficiency and reduce carbon footprint. However, electrochemical process fundamentals have been absent from the chemical process simulators available to millions of chemical engineers worldwide. To expedite process research and development of electrochemical technologies in the chemical industry, it is imperative that essential electrochemical process fundamentals be incorporated into process simulators to support modeling and simulation of electrochemical processes. Here, this study examines three process fundamentals key to the research and development of electrochemical processes: electrochemical reaction kinetics, electrolyte thermodynamics, and heat and mass transfer. It further illustrates application of these process fundamentals with a case study modeling an electrochemical process for the conversion of acrylonitrile to adiponitrile. The modeling example highlights the roles of applied voltage on reaction rates, and electron flow rates on the performance of electrochemical processes. It suggests that the applied voltage and electron flow rates are two unique concepts that should be included in simulators for electrochemical processes.

09 BIOMASS FUELS↗

Improving protonic ceramic electrochemical cell performance via a dual-phase reaction-sintered bilayer electrolyte

Protonic ceramic electrochemical cells (PCCs) are promising energy conversion devices, but their fabrication remains challenging. In particular, the typical electrolytes for PCCs such as BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3−δ (7111) and BaCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3−δ (4411) suffer from intrinsic barium evaporation issues during high-temperature sintering. This tendency towards barium loss, combined with their highly refractory nature, leads to a tradeoff between sinterability and chemical stability. To address this tradeoff, we propose a bilayer electrolyte combining layers of 4411 and 7111 materials that is designed to enhance sinterability and conductivity through dual-phase reactive sintering. Our findings demonstrate that the bilayer structure exhibits shrinkage behavior closely matched to that of the fuel electrode substrate, with a higher shrinkage compared to a single-layer 4411 electrolyte. Utilizing this bilayer electrolyte structure, our PCCs achieve a peak power density of 637 mW∙cm −2 in fuel-cell mode and a current density of 1060 mA∙cm −2 at 1.3 V in electrolysis mode at 600 °C. Our PCCs demonstrate high Faradaic efficiency of 83% at 1.3 V and 500 °C. Hybrid distribution of relaxation times (DRT) polarization mapping further reveals that the bilayer structure reduces Ohmic and polarization resistance in both fuel-cell and electrolysis modes.

ceramic processing↗

Enhancing Direct Electrochemical CO 2 Electrolysis by Introducing A-Site Deficiency for the Dual-Phase Pr(Ca)Fe(Ni)O 3-δ Cathode

High-temperature CO 2 electrolysis via solid oxide electrolysis cells (CO 2 –SOECs) has drawn special attention due to the high energy convention efficiency, fast electrode kinetics, and great potential in carbon cycling. However, the development of cathode materials with high catalytic activity and chemical stability for pure CO 2 electrolysis is still a great challenge. In this work, A-site cation deficient dual-phase material, namely (Pr 0.4 Ca 0.6 ) x Fe 0.8 Ni 0.2 O 3-δ (PCFN, x = 1, 0.95, and 0.9), has been designed as the fuel electrode for a pure CO 2 –SOEC, which presents superior electrochemical performance. Among all these compositions, (Pr 0.4 Ca 0.6 ) 0.95 Fe 0.8 Ni 0.2 O 3-δ (PCFN95) exhibited the lowest polarization resistance of 0.458 Ω cm 2 at open-circuit voltage and 800 °C. The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm -2 at 1.5 V and 800 °C, which is 76% higher than that of single cells with stoichiometric Pr 0.4 Ca 0.6 Fe 0.8 Ni 0.2 O 3-δ (PCFN100) cathode. The effects of A-site deficiency on materials' phase structure and physicochemical properties are also systematically investigated. Such an enhancement in electrochemical performance is attributed to the promotion of effective CO 2 adsorption, as well as the improved electrode kinetics resulting from the A-site deficiency.

30 DIRECT ENERGY CONVERSION↗

Towards a Deeper Fundamental Understanding of (Al,Sc)N Ferroelectric Nitrides

Density functional theory (DFT) calculations, within the virtual crystal alloy approximation, are performed, along with the development of a Landau-type model employing a symmetry-allowed analytical expression of the internal energy and having parameters determined from first principles, to investigate properties and energetics of Al1-xScxN ferroelectric nitrides in their hexagonal forms. These DFT computations and this model predict the existence of two different types of minima, namely, the fourfold-coordinated wurtzite (WZ) polar structure and a five-fold coordinated paraelectric hexagonal phase (denoted as H5), for any Sc composition up to 40%. The H5 minimum progressively becomes the lowest-energy state within hexagonal symmetry as the Sc concentration increases from 0 to 0.4. Furthermore, the model points to several key findings. Examples include the crucial role of the coupling between polarization and strains to create the WZ minimum, in addition to polar and elastic energies, and that the origin of the H5 state overcoming the WZ phase as the global minimum within hexagonal symmetry when increasing the Sc composition mostly lies in the compositional dependency of only two parameters-one linked to the polarization and another one being purely elastic in nature. Other examples are that forcing Al1-xScxN systems to have no or a weak change in lattice parameters when heating them allows us to reproduce their finite-temperature polar properties well and that a value of the axial ratio close to that of the ideal WZ structure implies a large polarization at low temperatures but not necessarily at high temperatures because of the ordered-disordered character of the temperature-induced formation of the WZ state. Such findings should allow for a better fundamental understanding of (Al,Sc)N ferroelectric nitrides, which may be used to design efficient devices having, e.g., low operating voltages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical cleaning: An in-Situ method to reverse chromium poisoning in solid oxide fuel cell cathodes

Chromium poisoning is one of the primary factors that affect solid oxide fuel cell (SOFC) durability. In this study, an electrochemical cleaning method has been employed to reverse the effects of chromium poisoning. Two cells were fabricated and poisoned under identical conditions by operating them at 800°C in the presence of a Cr source. Both poisoned cells exhibited a significant reduction in maximum power density and an increase in polarization resistance. One of the poisoned cells, designated as the baseline cell, was cooled to room temperature after poisoning. Microstructural observation of the baseline cell showed significant contamination of the cathode active layer by chromium oxide and (Cr,Mn) spinel deposits. The other poisoned cell was electrochemically cleaned for two hours under a mild electrolytic condition. As a result of the electrochemical cleaning process, the chromium oxide deposits were substantially removed leading to a significant reduction of Cr concentration in the cathode, especially at the cathode/electrolyte interface. Furthermore, a substantial fraction of the cell performance loss was also reversed. To the best of our knowledge, this is a first demonstration of reversing the effects of chromium poisoning using a rapid in-situ process.

30 DIRECT ENERGY CONVERSION↗

X-Ray Emission from the Millisecond Pulsar J1012+5307

The recently discovered 5.3 ms pulsar J1012+5307 at a distance of 520 pc is in an area of the sky which is particularly deficient in absorbing gas. The column density along the line of sight is less than 7.5 x 10(exp 19)/sq cm, which facilitates soft X-ray observations. Halpern reported a possible ROSAT PSPC detection of the pulsar in a serendipitous, off-axis observation. We have now confirmed the X-ray emission of PSR J1012+5307 in a 23 ksec observation with the ROSAT HRI. A point source is detected within 3 sec. of the radio position. Its count rate of 1.6 +/- 0.3 x 10(exp -3)/s corresponds to an unabsorbed 0.1 - 2.4 keV flux of 6.4 x 10(exp -14) ergs/sq cm s, similar to that reported previously. This counts-to-flux conversion is valid for N(sub H) = 5 x 10(exp 19)/sq cm, and either a power-law spectrum of photon index 2.5 or a blackbody of kT = 0.1 keV. The implied X-ray luminosity of 2.0 x 10(exp 30) ergs/ s is 5 x 10(exp -4) of the pulsar's spin-down power E, and similar to that of the nearest millisecond pulsar J0437-4715, which is nearly a twin of J1012+5307 in P and E. We subjected the 37 photons (and 13 background counts) within the source region to a pulsar search, but no evidence for pulsation was found. The pulsar apparently emits over a large fraction of its rotation cycle, and the absence of sharp modulation can be taken as evidence for surface thermal emission, as favored for PSR J0437-4715, rather than magnetospheric X-ray emission which is apparent in the sharp pulses of the much more energetic millisecond pulsar B1821-24. A further test of of the interpretation will be made with a longer ROSAT observation, which will increase the number of photons collected by a factor of 5, and permit a more sensitive examination of the light curve for modulation due to emission from heated polar caps. If found, such modulation will be further evidence that surface reheating by the impact of particles accelerated along open field lines operates in these approx. 10(exp 9) yr old pulsars.

Halpern, Jules P.↗

Search for Pulsations from a Nearby Millisecond Pulsar and Wasilewski 49: Mirror for a Hidden Seyfert 1 Nucleus

Five studies are reported in this final report. The recently discovered 5.3 ms pulsar J1012+5307 at a distance of 520 pc is in an area of the sky which is particularly deficient in absorbing gas. The column density along the line of sight is less than 7.5 x 10(exp 19) CM(exp -2) which facilitates soft X-ray observations. Halpern reported a possible ROSAT Position Sensitive Proportional Counter (PSPC) detection of the pulsar in a serendipitous, off-axis observation. We have now confirmed the X-ray emission of PSR J1012+,5307 in a 23 ksec observation with the ROSAT High Resolution Imager (HRI). A point source is detected within 3" of the radio position. Its count rate of 1.6 +/- 0.3 x 10(exp -3) s(exp -1) corresponds to an unabsorbed 0. 1-2.4 keV flux of 6.4 x 10(exp -14) ergs cm(exp -2) s(exp -1), similar to that reported previously. This counts-to-flux conversion is valid for N(sub H) = 5 x 10(exp 19) cm(exp -2), and either a power-law spectrum of photon index 2.5 or a blackbody of kT = 0.1 keV. The implied X-ray luminosity of 2.0 x 10(exp 30) ergs s(exp -1) is 5 X 10(exp -4) of the pulsar's spin-down power dot-E, and similar to that of the nearest millisecond pulsar J0437-4715, which is nearly a twin of J1012+5307 in P dot-E. We subjected the 37 photons (and 13 background counts) within the source region to a pulsar search, but no evidence for pulsation was found. The pulsar apparently emits over a large fraction of its rotation cycle, and the absence of sharp modulation can be taken as evidence for surface thermal emission, as is favored for PSR J0437-4715, rather than magnetospheric X-ray emission which is apparent in the sharp pulses of the much more energetic millisecond pulsar B1821-24. A further test of this interpretation will be made with a longer ROSAT observation, which will increase the number of photons collected by a factor of 5, and permit a more sensitive examination of the light curve for modulation due to emission from heated polar caps. If found, such modulation will be further evidence that surface reheating by the impact of particles accelerated along open fiel;d lines operates in these approximately 10(exp -9) year old pulsars. In a second study, a new AM Her star serendipitously in a 25 day observation was detected with the EUVE satellite. A coherent period of 85.82 min is present in the EUVE Deep Survey imager light curve of this source. A spectroscopic optical identification is made with a 19th magnitude blue star that has H and He emission lines, and broad cyclotron humps typical of a magnetic cataclysmic variable. A lower limit to the polar magnetic field of 50 MG is estimated from the spacing of the cyclotron harmonics. EUVE J0425.6-5714 is also detected in archival ROSAT HRI observations spanning two months, and its stable and highly structured light curve permits us to fit a coherent ephemeris linking the ROSAT and EUVE data over a 1.3 yr gap. The derived period is 85.82107 +/- 0.00020 min, and the ephemeris should be accurate to 0.1 cycles until the year 2005. A narrow but partial X-ray eclipse suggests that this object belongs to the group of AM Her stars whose viewing geometry is such that the accretion stream periodically occults the soft X-ray emitting accretion spot on the surface of the white dwarf. A non-detection of hard X-rays from ASCA observations that are contemporaneous with the ROSAT HRI shows that the soft X-rays must dominate by at least an order of magnitude, which is consistent with a known trend among AM Her stars with large magnetic field. This object should not be confused with the Seyfert galaxy IH 0419-577 (= LB 1727), another X-ray/EUV source which lies only 3'95 away, and was the principal target of these monitoring observations. In a third report; the identity of the persistent high-energy (> 100 MeV) gamma-ray sources in the Galaxy, still largely a mystery is investigated. The second installment of the EGRET (2EG) lists a total of 128 sources, of which 51 are likely or possibly identified with AGNs, five with rotation-powered pulsars, and one is the LMC. There are 71 unidentified sources, of which 33, or almost half, lie in the narrow band of absolute value of b < 10 degrees along the Galactic plane. This excess of low-latitude sources must, therefore, constitute a Galactic population that is either similar to the already identified gamma-ray pulsars, or an entirely new class of gamma-ray emitters associated with the disk population. We are continuing our program, begun in A06, that is aimed at intermediate-latitude sources, arguing that X-ray detection of them is the most plausible method of identifying the Galactic population. The sources at high latitude must statistically be mostly AGNS, and are more straightforwardly identified through radio and optical means. For the fourth report, identification of the EGRET Source the identity of the persistent, high-energy gamma-ray sources in the Galactic plane is a mystery. The most likely scenario is a population of middle-aged pulsars, many of which could be radio quiet like Geminga. We have an ongoing program of ROSAT, VLA, and optical observations of selected EGRET error circles at intermediate Galactic latitude. For one of these fields, at (l, b) = (106 degrees, +3), our complete census of X-ray and radio sources, reveals a remarkable association between a radio shell with unique properties, and a complete census of X-ray and radio sources reveals a remarkable association between a radio shell with unique properties, and a compact X-ray source. Further observations are needed to determine whether or not this source has a hard X-ray spectrum like that of other gamma ray pulsars and, ideally, to find its pulsations. A fifth report reviews, Wasilewski 49, an interacting pair of Seyfert galaxies at z = 0.063, one of which contains a hidden Seyfert I nucleus as evidenced by broad wings on its Balmer lines.

Halpern, Jules P.↗

Non-volatile magnon transport in a single domain multiferroic

Antiferromagnets have attracted significant attention in the field of magnonics, as promising candidates for ultralow-energy carriers for information transfer for future computing. The role of crystalline orientation distribution on magnon transport has received very little attention. In multiferroics such as BiFeO 3 the coupling between antiferromagnetic and polar order imposes yet another boundary condition on spin transport. Thus, understanding the fundamentals of spin transport in such systems requires a single domain, a single crystal. We show that through Lanthanum (La) substitution, a single ferroelectric domain can be engineered with a stable, single-variant spin cycloid, controllable by an electric field. The spin transport in such a single domain displays a strong anisotropy, arising from the underlying spin cycloid lattice. Our work shows a pathway to understanding the fundamental origins of magnon transport in such a single domain multiferroic.

30 DIRECT ENERGY CONVERSION↗

Performance Losses and Current-Driven Recovery from Cation Contaminants in PEM Water Electrolysis

Water contaminants are a common cause of failure for polymer electrolyte membrane (PEM) electrolyzers in the field as well as a confounding factor in research on cell performance and durability. In this study, we investigated the performance impacts of feed water containing representative tap water cations at concentrations ranging from 0.5–500 μ M, with conductivities spanning from ASTM Type II to tap-water levels. We present multiple diagnostic signatures to help identify the presence of contaminants in PEM electrolysis cells. Through analysis of polarization curves and impedance spectroscopy to understand the origins of performance losses, we found that a switch from the acidic to alkaline hydrogen evolution mechanism is a key factor in contaminated cell behavior. Finally, we demonstrated that this mechanism switching can be harnessed to remove cation contaminants and recover cell performance without the use of an acid wash. We demonstrated near-complete recovery of cells contaminated with sodium and calcium, and partial recovery of a cell contaminated with iron, which was further investigated by post-mortem microscopy. The improved understanding of contaminant impacts from this work can inform development of strategies to mitigate or recover performance losses as well as improve the consistency and rigor of electrolysis research.

30 DIRECT ENERGY CONVERSION↗

Raman-shifting an ArF excimer laser to generate new lines for obtaining optical diagnostic based information in flow fields

The application of tunable excimer lasers in combustion and flow diagnostics is almost routine nowadays. The properties of this laser system that enable density and temperature measurements in supersonic and hypersonic flow fields to be conducted are its high power, high repetition rate, and high spectral brightness. The limitation imposed by this system on these measurements is the paucity of lines in the wavelength region, the vacuum-ultraviolet, where species of interest, such as OH, N2, O2, H2, H2O, CO, NO, etc., are susceptible to electronic excitation to high-lying states. To circumvent this problem one normally resorts to nonlinear optical techniques such as frequency conversion via stimulated Raman scattering (SRS), more commonly known as Raman shifting or Raman mixing, to extend these nonintrusive and nonperturbing techniques to the shorter wavelengths in the VUV region and, for that matter, to longer wavelengths in the infrared region, if the need arises. The theoretical basis of SRS and its application are well documented in the literature. In essence, the Raman shift is a consequence of the inelastic scattering of the incident radiation by the sample. Most of the scattered radiation from the molecules of the sample is unchanged in frequency. However, a small fraction of the incident radiation is changed in frequency. This shift is a result of the fact that some of the incident photons on colliding with the molecules of the sample give up some of their energy and emerge with a lower energy resulting in the lower-frequency Stokes radiation. Other incident photons may increase their energy by colliding with the vibrationally excited molecules of the medium and emerge as higher-frequency antistokes radiation. The generation of the latter is the main objective of this project. The process, however, depends on several factors, including the beam quality of the pump laser, the cross-section of the gaseous medium, the gas pressure, and the ambient temperature of the gas near the focal region. Furthermore, since the Raman shifting process is polarization sensitive, it is necessary to have all of the laser energy in a single polarization. These factors were taken into consideration in the execution of the project. The implementation of the Raman shift was accomplished by focusing the 193 nm output of an ArF excimer laser (Lamda-Physik LPX 150) into a 1-meter long high pressure recirculating Raman cell filled with H2 gas. The laser system was modified in order to improve the mode quality of the pump beam to enhance the Raman shifting. To accomplish this feat, a prism beam expander and grating on the oscillator discharge provided wavelength tuning over the excimer gain profile. Furthermore, a triple-pass configuration, as opposed to unstable resonator optics, was employed in the operation of the amplifier cavity so that when the oscillator output radiation, focused by a 51-cm focal length fused silica lens through a 50 micron pinhole (serving as a spatial filter) and recollimated with a 25-cm focal length lens, was fed into the amplifier, it was injection locked, thereby providing tunable radiation with relatively low divergence. The forward scattered radiation emanating from the impingement of the modified pump beam on the Raman cell was detected using an energy meter after the latter had been separated from it using a dispersing prism.

Koker, Edmond B.↗

Soot and Sulfuric Acid from Aircraft: Is There Enough to Cause Detrimental Environmental E-kCTSs?

Aerosol from aircraft can affect the environment in three ways: First, soot aerosol has been implicated to cause Icing-tern ozone depletion at mid-latitudes in the lower stratosphere at a rate of approx. 5% per decade. This effect is in addition and unrelated to the polar ozone holes which are strongly influenced by heterogeneous chemistry on polar stratospheric clouds. Second, the most obvious effect of jet aircraft is the formation of visible contrails in the upper troposphere. The Salt Lake City region experienced an 8% increase in cirrus cloud cover over a 15-year period which covariates with an increase in regional commercial air traffic. If soot particles act as freezing nuclei to cause contrail formation heterogeneously, they would be linked to a secondary effect to cloud modification that very likely is climatologically important. Third, a buildup of soot aerosol could reduce the single scatter albedo of stratospheric aerosol from 0.993+0.004 to 0.98, a critical value that has been postulated to separate stratospheric cooling from warming. Thus arises an important question: Do aircraft emit sufficient amounts of soot to have detrimental effects and warrant emission controls? During the 1996 SUCCESS field campaign, we sampled aerosols in the exhaust wake of a Boeing 757 aircraft and determined emission indices for sulfuric acid (EI(sub H2SO4) = 9.0E-2 and 5.0E-1 g/kg (sub FUEL) for 75 and 675 ppm fuel-sulfur, respectively) and soot aerosol (2.2E-3 less than EI(sub SOOT) = l.lE-2 g/kg (sub FUEL)). The soot particle analysis accounted for their fractal nature, determined electron-microscopically, which enhanced the surface area by a factor of 26 and the volume 11-fold over equivalent-volume spheres. The corresponding fuel-sulfur to H2SO4 conversion efficiency was 10% (for 675 ppmm fuel-S) and 37% (for 75 ppmm fuel-S). Applying the H2SO4 emission index to the 1990 fuel use by the worlds commercial fleets of 1.3E11 kg, a conversion efficiency of 30% of 500 ppmm fuel-S would have led to an annual contribution to the atmospheric sulfur budget by aircraft of 2.E7 kg H2SO4. This is about one part in 1.E4 of anthropogenic sulfate from other sources. The soot emission index given above yielded a 1990 injection of soot aerosol by aircraft of 1.E6 kg. Thus, soot amounts to only five percent of the aerosol generated by aircraft. Its reactivity with ozone would have to be 20 times that of sulfuric acid particles to make it chemically significant. Nevertheless, the findings, of stratospheric soot loadings commensurate with aircraft fuel consumption, based on the emission index given above and the assumption of stratospheric residence times of the order of one year implicate aircraft as stratospheric polluters. A trend similar to soot of H2SO4 aerosol loading could not be deciphered, neither from in situ measurements nor SAGE II satellite extinction, against the "noise" due to volcanic eruptions. Observation of soot particles at 20 km altitude which, if emitted by aircraft were generated at 10-12 km altitude, suggests a displacement of those particles against gravity. Because eddy mixing is virtually absent in the lower stratosphere and isentropic mixing explains lofting to only about 15 km, radiometric forces acting on morphologically and chemically asymmetric soot particles must be considered a possibility. The consequence could be an extended residence time of soot against that of sulfuric acid aerosol that would lower the single scatter albedo with time.

Pueschel, R. F.↗

Anode Upcycling via Tailored Solvent Treatment

To achieve a truly closed-loop direct recycling process for lithium-ion batteries, all component materials must be recovered. To date, direct recycling method development has primarily focused on the high-value transition-metal cathode materials, while the inherently lower-value graphite has been challenging to recover in a cost-effective manner. However, end-of-life graphite contains a unique engineered value due to the presence of the solid electrolyte interphase (SEI). Growth of the SEI during the cell's active lifetime stabilizes the electronically reactive graphite surface through an irreversible consumption of Li, and thus necessitates both excess lithiation of the cathode and a costly and time-intensive formation procedure during manufacturing. An optimized pre-formed SEI that capitalizes on existing SEI components from end-of-life batteries has the potential to significantly reduce cathode lithiation requirements and eliminate the critical bottleneck of formation cycling during cell remanufacturing. Further, retaining Li at the anode obviates the need for a separate Li leaching and recovery step, improving the overall efficiency of the direct recycling line. In this work, we present a novel approach to "upcycling" spent graphite through use of tailored chemical treatment to remove adverse (i.e., highly resistive and/or poorly passivating) SEI species while retaining beneficially passivating components. We have explored a rational set of solvents spanning a range of polarity, proticity, and molecular size to evaluate structure-property-performance relationships between applied solvent(s), removed and remaining SEI species, and electrochemical response of the resulting graphite product. Further, we have developed and optimized a robust and holistic analysis procedure that couples symmetric-cell electrochemical testing, multi-modal materials characterization, and advanced electrochemical modeling. These analysis results inform a set of correlative metrics for graphite performance relative to both solvent properties and upcycled SEI composition. We demonstrate effective tunability in the residual SEI composition by varying solvent identity and concentration, and report on several promising solvent systems that achieve comparable or performance to pristine graphite.

anode recycling↗

Fission Surface Power Technology Development Testing at NASA's Early Flight Fission Test Facility

Fission surface power (FSP) systems could be used to provide power anytime, anywhere on the surface of the Moon or Mars. FSP systems could be used at polar locations, at locations away from the poles, or in permanently shaded regions, with excellent performance at all sites. A potential reference 40 kWe option has been devised that is cost-competitive with alternatives while providing more power for less mass anywhere on the lunar surface. The reference FSP system (FSPS) is also readily extensible for use on Mars. At Mars the system would be capable of operating through global dust storms and providing year-round power at any Martian latitude. Under the NASA Exploration Technology Development Program (ETDP), NASA and the Department of Energy (DOE) have begun technology development on Fission Surface Power (FSP). The primary customer for this technology is the NASA Constellation Program which is responsible for the development of surface systems to support human exploration on the moon and Mars. The objectives of the FSP technology project are: 1) Develop FSP concepts that meet expected surface power requirements at reasonable cost with added benefits over other options. 2) Establish a hardware-based technical foundation for FSP design concepts and reduce overall development risk. 3) Reduce the cost uncertainties for FSP and establish greater credibility for flight system cost estimates. 4) Generate the key products to allow Agency decision-makers to consider FSP as a viable option for flight development. To be mass efficient, FSP systems must operate at higher coolant temperatures and use different types of power conversion than typical terrestrial systems. The primary reason is the difficulty in rejecting excess heat to space. Although many options exist, NASA s current reference FSP system uses a fast spectrum, pumped-NaK cooled reactor coupled to a Stirling power conversion subsystem. The reference system uses technology with significant terrestrial heritage while still providing excellent performance on the surface of the moon or Mars. Recent testing at NASA s Early Flight Fission Test Facility (EFF-TF) has helped assess the viability of the reference FSP system, and has helped evaluate methods for system integration. In June, 2009, a representative pumped NaK loop (provided by Marshall Space Flight Center) was coupled to a Stirling power converter (provided by Glenn Research Center) and tested at various conditions representative of those that would be seen during actual FSP system operation. In all areas, performance of the integrated system exceeded project goals. High-temperature NaK pump testing has also been performed at the EFF-TF, as has testing of methods for providing long-duration NaK purity.

Houts. Michael G.↗

Additive Manufacturing Case Study

Geothermal technologies include an extremely wide range of products required for well construction, completion, production, intervention and surface energy conversion activities. Many of these products are geometrically complex, require multi-step and highly specialized fabrication processes, and are expensive due to the low production numbers typically associated with the geothermal market. These challenges along with the high temperature demands of the geothermal environment have also hindered the adoption of many tools routinely used in the oil & gas industry.Recent advancements in Additive Manufacturing (AM) materials of construction, build volumes and part quality have transitioned the technology from primarily cosmetic prototyping applications to the point where AM can be used to make production parts, even for the most demanding applications. These improved AM capabilities along with the inherent ability of AM to produce complex parts and, in some cases, geometries that cannot be manufactured using conventional casting, machining and joining fabrication approaches motivate an exploration of its potential to positively impact geothermal well construction and operations technologies.Sandia National Labs collaborated with Oak Ridge National Laboratory on a case study examining additive manufacturing opportunities for Geothermal applications. The study focused on designing components with improved performance characteristics that cannot be fabricated conventionally. A rotor for a downhole motor was chosen based on the potential for improving its rotational dynamics. Topology optimization was used as a design method to reduce the rotational inertia of the part while preserving sufficient rotational stiffness to transmit the torque required for the drilling application. The optimization resulted in a nearly 50% reduction in polar moment of inertia while maintaining other desired performance characteristics. The design developed using the topology optimization approach was fabricated using additive manufacturing and cannot be fabricated conventionally. This paper will discuss the design approach, performance improvements and manufacturing methods used to produce the part.

Polsky, Yarom↗

Exploring the Impacts of Conditioning on Proton Exchange Membrane Electrolyzers by In Situ Visualization and Electrochemistry Characterization

For a proton exchange membrane electrolyzer cell (PEMEC), conditioning is an essential process to enhance its performance, reproducibility, and economic efficiency. To get more insights into conditioning, a PEMEC with Ir-coated gas diffusion electrode (IrGDE) was investigated by electrochemistry and in situ visualization characterization techniques. The changes of polarization curves, electrochemical impedance spectra (EIS), and bubble dynamics before and after conditioning are analyzed. The polarization curves show that the cell efficiency increased by 9.15% at 0.4 A/cm 2 , and the EIS and Tafel slope results indicate that both the ohmic and activation overpotential losses decrease after conditioning. The visualization of bubble formation unveils that the number of bubble sites increased greatly from 14 to 29 per pore after conditioning, at the same voltage of 1.6 V. Under the same current density of 0.2 A/cm 2 ; the average bubble detachment size decreased obviously from 35 to 25 µm. Furthermore, the electrochemistry and visualization characterization results jointly unveiled the increase of reaction sites and the surface oxidation on the IrGDE during conditioning, which provides more insights into the conditioning and benefits for the future GDE design and optimization.

08 HYDROGEN↗

Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces

Stress tests are developed for proton exchange membrane electrolyzers that utilize low catalyst loading, elevated potential, and frequent cycling with square- and triangle-waves to accelerate anode catalyst layer degradation during intermittent operation. Kinetics drive performance losses (ohmic/transport secondary) and are accompanied by decreasing exchange current density, decreasing cyclic voltammetric capacitance, and increasing polarization resistance. Decreased kinetics are likely due to a combination of iridium (Ir) migration into electrochemically inaccessible locations in the anode or membrane, Ir particle growth (supported by X-ray scattering), changes in the extent of the Ir oxidation state (supported by X-ray absorption spectroscopy), and anode catalyst layer reordering. Decreasing catalyst/transport layer contact and catalyst/membrane interfacial tearing may add contact resistances and account for increasing ohmic losses. Performance losses for low and moderate catalyst loading, as well as from accelerated and model wind/solar cycling protocols, were likewise dominated by kinetics but vary in severity. Additionally, accelerated cycling (1 cycle per minute) appears to reasonably accelerate relevant loss mechanisms and can be used to project electrolyzer lifetime from anode deterioration. Ongoing accelerated stress test development and studies into performance loss mechanisms will continue to be critical as electrolysis shifts to intermittent power and low-cost applications.

30 DIRECT ENERGY CONVERSION↗