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Artificial nano Si 3 N 4 derived solid electrolyte interphase enables dendrite-free lithium cycling, effectively suppressing dendrite growth and delivering stable, long-term Li metal anode performance.
Parameters are estimated for a hypothetical, well stirred, continuous-feed electrolytic cell that converts 20 percent of a lunar soil feedstock to O2 gas, 26 percent to Fe-Si metal, 13 percent to spinel, and 41 percent to slag. Advantages of a molten Fe-Si cathode for trapping metal on reduction, a relatively conductive steady-state composition in equilibrium with spinel (a proposed container material), and close electrodes (less than 1 cm cathode-anode distance) are discussed. To produce 1 ton of O2, about 6 MHW of energy are required for the electrolysis and IR heating within the melt, and another about 6 MHW may be introduced as waste heat through internal resistance of the electrodes. Thus, to produce 1 ton of O2 per 24 hours, about 0.5 MW of power delivered to the cell would be required.
An important aspect of lunar mining will be the extraction of volatiles, particularly oxygen, from lunar rocks. Thermodynamic data show that oxygen could readily be recovered by fluorination of abundant lunar anorthite, CaAl2Si2O8. Fluorine is the most reactive element, and the only reagent able to extract 100 percent of the oxygen from any mineral, yet it can safely be stored or reacted in nickel or iron containers. The general fluorination reaction, mineral + 2F2 = mixed fluorides = O2, has been used for more than 30 years at a laboratory scale by stable-isotope geochemists. For anorthite, metallic Al and Si may be recovered from the mixed fluorides by Na-reduction, and CaO via exchange with Na2O; the resulting NaF may be recycled into F2 and Na by electrolysis, using lanthanide-doped CaF2 as the inert anode.
In order to test the instruments aboard the Advanced X-ray Astrophysics Facility (AXAF) some modifications will need to be made in the X-ray Calibration Facility at Marshall. Several of these modifications involve the X-ray source and the monitor. The source was redesigned to increase the spectral purity of the beam and decrease its polarization by minimizing the number of bremsstrahlung photons in the beam. This was accomplished by utilizing an annular electron gun which allowed the beam to take off antiparallel to the direction at which electrons are incident on the anode. Two other features of the source are the conical anode which decreases the effective spot size and a rotatable anode and filter wheel which allow the operator to change targets without breaking vacuum. The monitor is an important part of the facility because it is used to determine the X-ray flux at the target. A commercially available solid-state detector, Si(Li), should be used along with appropriate proportional counters for monitoring. This detector will be particularly useful when energy or wavelength dispersive instruments are tested because of its good resolution.
A diamond anvil cell is described which was developed for studying hydrogen and other materials to pressure above 100 PGa, including measurements at low temperature. The benefits of X-ray diffraction using synchrotron radiation and using a fixed anode source are examined as well as the optimization of X-ray diffraction at low temperature. A Ge diode detector was incorporated into apparatus for measuring optical absorption, reflectance, and fluorescence in order to enable luminescence studies and Raman spectra were obtained. Results of experiments on Si, Ge, GaP, InAs, hydrogen, benzene, nitrogen, graphite, and the superconductor CeCu2Si2 are given.
Protonic ceramic electrolysis cells (PCECs) are an attractive green H 2 production technology, given their intermediate-temperature operating range and ability to produce dry H 2 . However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr 0.9 Y 0.1 O 3–δ (BPY) in comparison to the benchmark Ba 1–x Co 0.4 Fe 0.4 Z r0.1 Y 0.1 O 3–δ (BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O 2 during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO x H y . Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.
Sunlight-powered artificial leaves for the production of formate from CO 2 are an attractive route to solar fuels, yet existing solar formate devices remain low in performance, and their architecture and material choices are underexplored. Herein, we report the fabrication of two distinct fully integrated, self-standing solar formate device architectures and elucidate the underlying design principles and material selection strategies. The first architecture integrates a Si photocathode with a BiVO 4 photoanode and utilizes a highly active Pd catalyst for CO 2 reduction. It represents the first artificial leaf device comprising two photoelectrodes (excluding photovoltaic [PV]-biased electrodes) for effective formate production under single-beam illumination. The second architecture employs a dark cathode and a dark anode driven by a 4-junction perovskite solar cell and uses a highly stable Bi catalyst for CO 2 reduction. This device delivers a record-high formate production rate of 174 µmol h −1 with a remarkable solar-to-formate energy efficiency of 2% among all artificial leaf devices reported to date. Finally, these results demonstrate the feasibility and outline the design principles of both PV-free and PV-assisted device architectures in solar fuel production.
This effort aimed to explore the use of refractory alloys as long-lifetime electrode materials for use in a molten regolith electrolysis (MRE) reactor, a technology that can produce oxygen (O2) from regolith. To find a material capable of withstanding the high temperatures and corrosive nature of molten regolith, first-principles thermodynamic calculations were performed on platinum group metals in the presence of iron (Fe) and silicon (Si) to determine favorable compositions for resisting unwanted secondary phases that could form on the surface of the material. As a result of these first-principles calculations, the kinetic properties of elements such as aluminum (Al), Fe, and Si can be more easily derived, which would provide insight into the longevity of such a material when used in an MRE reactor. The effort funded by this CIF project mapped the entire phase diagram of platinum group metals, which is beneficial not only to MRE where high temperatures and molten material are present, but also aerospace applications like turbine materials, terrestrial metal processing techniques, and energy storage applications. This project narrowed a broad spectrum of refractory metals down to a small list of alloys that would be able to survive not only the high temperatures of an MRE reactor, but also the thermodynamic forces that would cause inferior alloys to form secondary phases, which would ultimately consume the electrodes of the reactor. This research needs to be followed up with experimental demonstrations of these alloys in an MRE environment.
The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.
Room temperature measurements of the turn-off time (t(sub q)) are reported for several packaged, npnp developmental power thyristors based on 4H-type SiC and rated 400 V, 2 A. Turn-off is effected by a 50 V pulse of applied reverse voltage, from a state of a steady 1 A forward current. Plots of t(sub q) against the ramp rate (dV(sub AK)/dt) of reapplied forward voltage are presented for preset values of limiting anode-to-cathode voltage (V(sub AK,max)). The lowest t(sub q) measured was about 180 ns. A rapid rise of these t(sub q) curves was observed for values of V(sub AK,max) that are only about a fifth of the rated voltage, whereas comparative t(sub q) plots for a commercial, fast turn-off, Si-based thyristor at a proportionately reduced V(sub AK,max) showed no such behavior. Hence these SiC thyristors may have problems arising from material defects or surface passivation. The influence the R-C-D gate bypass circuit that was used is briefly discussed.
Electrolytic extraction of O2 from molten lunar soil is conceptually simple and thus a candidate process for producing O2 on the Moon. Possible container and electrode materials are being tested for durability in corrosive high-temperature silicate melts and looking for complications that might increase energy requirements. Gaseous oxygen is being produced by electrolysis of 1-2 gram quantities of silicate melts in spinel (MgAl2O4) crucibles; in these melts, spinel is a stable phase. The concentration of FeO was kept low because FeO decrease O2 production efficiency. Platinum electrodes were placed about 0.5 cm apart in the melt. The spinel crucible was still intact after 40 minutes of electrolysis, when the experiment was halted for examination. The Pt anode was also intact; its Pt was maintained in a dynamci state in which the anode was continuously oxidized but quickly reduced again by the silicate melt, inhibiting migration of Pt away from the anode. In melts with low concentrations of Al2O3 + SiO2 (2 wt percent), the energy of resistance heating was only approximately equal to 10 to 20 percent of the theoretical amount required to produce O2. In melts substantially more concentrated in Al2O3 + SiO2, higher melt viscosity resulted in frothing that, in the worst case, caused high enough melt resistivities to raise the energy requirements to nearly 10 times theoretical. Both Fe and Si are produced at the cathode; in iron-rich melts, a- and c-iron and molten ferrosilicon were observed. Production was also observed at the cathode of a previously unrecognized gas; which is not yet identified. The solubility of metallic species was measured in silicate melts. They are too low to reduce significantly the efficiency of O2 production.
Thin GaAs epi-layers with good crystallographic quality were grown using a (100) Si-substrate on which a thin Ge epi-interlayer was grown by CVD from germane. Both antireflection-coated metal oxide semiconductor (AMOS) and n(+)/p homojunction structures were studied. The AMOS cells were fabricated on undoped-GaAs epi-layers deposited on bulk poly-Ge substrates using organo-metallic CVD film-growth, with the best achieved AM1 conversion efficiency being 9.1%. Both p-type and n(+)-type GaAs growth were optimized using 50 ppm dimethyl zinc and 1% hydrogen sulfide, respectively. A direct GaAs deposition method in fabricating ultra-thin top layer, epitaxial n(+)/p shallow homojunction solar cells on (100) GaAs substrates (without anodic thinning) was developed to produce large area (1 sq/cm) cells, with 19.4% AM1 conversion efficiency achieved. Additionally, an AM1 conversion efficiency of 18.4% (17.5% with 5% grid coverage) was achieved for a single crystal GaAs n(+)/p cell grown by OM-CVD on a Ge wafer.
Silicon based composites have become increasingly popular as potential anodes for lithium-ion batteries due to their large storage capacity and potential ability to generate batteries with energy densities greater than 350 Wh kg −1 . These anodes often see reduced initial columbic efficiency (ICE) due to disruptive volume expansionup to 300% and continuous solid electrolyte interphase (SEI) layer formation. Prelithiation, where an excess reservoir of Li is added to the electrode to compensate for irreversible SEI formation losses during their sample preparation, has proven to solve the issue of immediate capacity loss. Thermal evaporation is a prelithiation technique with limited studies on its effectiveness. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to highlight the benefits of prelithiation via thermal evaporation. ToF-SIMS provides chemical mapping and spatial information in 2D and 3D visualizing the deposition of lithium, identifying Li x Si y alloy and Li x Si y O z silicate formation, and the distribution of lithium passivation into the electrodes. Passivation under different atmospheric conditions, such as inert Argon (Ar) and Ar/ carbon dioxide (CO 2 ), highlights the impact of the environment on the passivation effectiveness and formation of Li x Si y alloy and Li x Si y O z silicate. The ToF-SIMS molecular imaging and depth profiling results indicate that prelithiation via thermal evaporation effectively distributes lithium throughout the depth profile thickness of several hundred nanometers. It induces a greater degree of Li x Si y O z silicate formation over Li x Si y alloy. Our ToF-SIMS characterization results show the effectiveness of thermal evaporation in producing a more stable electrode and an electrode with an effective lithium reserve that can preserve its capacity.
The global shift toward net-zero emissions necessitates resource recovery from wet waste. In this study, we demonstrate the first feasibility of combining pilot-scale microbial electrolytic cells (MECs) with hydrothermal liquefaction (HTL) for simultaneous post-hydrothermal liquefaction wastewater (PHW) treatment and efficient hydrogen (H₂) production to meet biocrude upgrading requirements. Long-term single reactor operation revealed that fixed anode potential enabled rapid startup, and low catholyte pH and high salinity were effective in suppression of cathodic methanogenesis and acetogenesis – resulting in high current density of 16.6 A m –2 and 9.3 A m –2 when feeding synthetic wastewater and PHW respectively. Additionally, the anode biofilm exhibited spatial variations in response to local environmental conditions. In conclusion, onsite parallel or serial operations of multiple MECs showed good performance using actual PHW with a record-high H 2 production rate of 0.5 L L R day –1 for MEC over 10 liters scale, and the optimal chemical oxygen demand (COD)-to-H 2 yield reached 0.127 kg-H 2 per kg-COD, supporting a self-sufficient, closed-loop upgrade to jet fuel.
Here, this study investigates lithium plating texture in anode-free solid-state batteries using synchrotron-based X-ray diffraction. Conventional methods are limited by lithium’s low electron density and softness, which hinders direct interrogation in anode-free solid-state batteries. Results reveal that lithium plating texture is influenced by temperature and current density. Under mild conditions, lithium exhibited a ⟨110⟩ fiber texture. However, higher current densities and elevated temperatures led to a more randomized orientation, suggesting a dependence on plating conditions. The results highlight how the operating and processing conditions for lithium metal can influence the texture of lithium metal and reversible operation.
A development effort underway at the time of reporting the information for this article is devoted to increasing the sensitivity of microchannel plates (MCPs) as detectors of photons and ions by coating the MCPs with nitrides of elements in period III of the periodic table. Conventional MCPs are relatively insensitive to slowly moving, large-mass ions for example, ions of biomolecules under analysis in mass spectrometers. The idea underlying this development is to coat an MCP to reduce its work function (decrease its electron affinity) in order to increase both (1) the emission of electrons in response to impingement of low-energy, large-mass ions and (2) the multiplying effect of secondary electron emission. Of particular interest as coating materials having appropriately low or even negative electron affinities are gallium nitride, aluminum nitride, and ternary alloys of general composition Al(x)Ga(1-x)N (where 0<x<1). These materials exhibit attractively high degrees of chemical, mechanical, and thermal stability plus acceptably high resistance to sputtering. The electron-excitation cross sections of these materials are expected to exceed those of several other materials (including diamond) that are, variously, in use or under development for the same purpose. Moreover, by doping these materials with silicon, one can render them partly electrically conductive, thereby suppressing the undesired accumulation of electric charge that could otherwise occur during bombardment by ions. For experiments, thin films of AlN and GaN both undoped and doped with Si were deposited on commercial MCPs by radio-frequency molecular-beam epitaxy (also known as plasma-assisted molecular-beam epitaxy) at temperatures <200 C. This deposition technique is particularly suitable because (1) MCPs cannot withstand the higher deposition-substrate temperatures used to decompose constituent compounds in some other deposition techniques and (2) in this technique, the constituent Al, Ga, and N are supplied in elemental form, so that there is no need for thermal decomposition at the substrate surface. The nitride films thus formed were, variously, amorphous or polycrystalline. The nitride films were coated with surface layers of gold <100 thick. The MCPs were tested in a standard configuration in which the output stage of a first MCP was coupled to the input stage of a second MCP. Each pair of MCPs was mounted in a standard holder that included front and back contact rings and an anode for collecting the output electrons of the second MCP. The MCP pairs were biased at potentials between 1.7 and 1.9 kV, and count rates measured after preamplification and discrimination. To enable a direct comparison, in one pair, the second MCP was uncoated while the first MCP was coated over half its surface. The coated and uncoated sides of the half-coated MCP were exposed to fluxes of argon ions at kinetic energies of 1.0 and 0.5 keV. At 1.0 keV, the count rate for the coated side was about 2.3 times greater than that for the uncoated side; at 0.5 keV, the count rate for the coated side was about 1.8 times greater than that for the uncoated side.
The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .
High entropy spinel oxides (HEOs), as a new type of anode material with at least five transition metal elements and high theoretical specific capacity, have enormous promise in sodium ion batteries (SIBs). However, the influence of different transition metal elements on the structure and electrochemical performances of HEOs is not clear. Here, in this study, the addition of Mn to HEO can increase the surface oxygen vacancy (O v ) concentration, shorten the band gap, and enhance the electrochemical performance of (FeNiCuCrMn) 3 O 4 @rGO. XPS results show (FeNiCuCrMn)3O4@rGO has the highest surface O v concentration. Ab initio calculations demonstrate that the indirect band gap of (FeNiCuCrMn)3O4@rGO is 0.068 eV. In situ X-ray diffraction and synchrotron X-ray absorption spectroscopy reveal that (FeNiCuCrMn) 3 O 4 @rGO exhibits a zero-strain characteristic with an inconsequential unit cell volume change of 0.2 %. Specifically, (FeNiCuCrMn) 3 O 4 @rGO as anode materials for SIBs show good cyclic stability (with a capacity retention of 84 % at 500 mA g −1 after 3000 cycles). Overall, this work provides a new direction for optimizing transition metal elements in HEOs.