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58 records · Page 4

Structural and chemical evolutions of a magnesium vanadium oxide cathode under electrochemical cycling in magnesium batteries

The design of cathode materials that remain chemically and structurally stable during repetitive ion insertion and extraction poses a significant challenge in developing multivalent batteries. The cycling stability of traditional metal oxide-based cathode is challenged by sluggish diffusion of multivalent cations and parasitic reactivity at interfacial regimes, including the cathode electrolyte interphase layer (CEI). Understanding the reactions at the cathode-electrolyte interface, particularly those induced by non-stoichiometric surface layers, is a crucial design parameter for both cathode materials and electrolytes. Here, in this study, we employed multimodal analysis, including in situ and ex situ X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) to examine the surface reactions and subsequent structural and chemical evolutions of the CEI on high voltage magnesium vanadium oxide (MgV 2 O 4 ) spinel cathode during the Mg 2+ insertion/extraction processes. The results revealed that the presence of non-stoichiometric surface layers in the magnesium vanadium oxide cathode drive the decomposition of bis(trifluoromethanesulfonyl)imide (TFSI - ) anion, leading to the formation of the CEI layer. The CEI layer could inhibit the Mg 2+ ion transfer processes. Accompanying this reactivity-driven degradation, the magnesium vanadium oxide cathode undergoes pulverization, forming clusters of nanosized particles. This process likely improves cycling ability by creating new intercalation sites and shortening the diffusion pathway for the Mg 2+ cations. This study demonstrates that controlling surface stoichiometry and engineering morphological properties are critical design parameters for high performance cathodes for multivalent batteries.

25 ENERGY STORAGE↗

Step Bunching: Influence of Impurities and Solution Flow

Step bunching results in striations even at relatively early stages of its development and in inclusions of mother liquor at the later stages. Therefore, eliminating step bunching is crucial for high crystal perfection. At least 5 major effects causing and influencing step bunching are known: (1) Basic morphological instability of stepped interfaces. It is caused by concentration gradient in the solution normal to the face and by the redistribution of solute tangentially to the interface which redistribution enhances occasional perturbations in step density due to various types of noise; (2) Aggravation of the above basic instability by solution flowing tangentially to the face in the same directions as the steps or stabilization of equidistant step train if these flows are antiparallel; (3) Enhanced bunching at supersaturation where step velocity v increases with relative supersaturation s much faster than linear. This v(s) dependence is believed to be associated with impurities. The impurities of which adsorption time is comparable with the time needed to deposit one lattice layer may also be responsible for bunching; (4) Very intensive solution flow stabilizes growing interface even at parallel solution and step flows; (5) Macrosteps were observed to nucleate at crystal corners and edges. Numerical simulation, assuming step-step interactions via surface diffusion also show that step bunching may be induced by random step nucleation at the facet edge and by discontinuity in the step density (a ridge) somewhere in the middle of a face. The corresponding bunching patterns produce the ones observed in experiment. The nature of step bunching generated at the corners and edges and by dislocation step sources, as well as the also relative importance and interrelations between mechanisms 1-5 is not clear, both from experimental and theoretical standpoints. Furthermore, several laws controlling the evolution of existing step bunches have been suggested, though unambiguous conclusions are still missing. Addressing these issues is the major goal of the present project. The theory addressing the above problem, experimental methods, several figures which include: (1) the spatial wave numbers at which the system is neutrally stable as a function of growth velocity for linear kinetics and supersaturation for nonlinear kinetics; (2) a schematic of the experiment of lysozyme crystal growing under conditions of natural convection; (3) fluctuations in time, t, of the normal growth rate, R(t), vicinal slope, p(t) and Fourier Spectra of R(t), discussions and conclusions are presented.

Chernov, A. A.↗

Exposure of Highly Reflective Far-Ultraviolet Coatings to LEO Environment for TRL Advancement for the Habitable Worlds Observatory

Over the past several years, our team at the NASA Goddard Space Flight Center (GSFC), in collaboration with the Jet Propulsion Laboratory (JPL) and the Naval Research Laboratory (NRL), have developed several new protected Al coating technologies with improved Far-Ultraviolet (FUV) reflectance performance and more robust environmental stability. These include Al protected with lithium-based fluoride (LiF) coatings such as hot deposited LiF (eLiF), XeF 2 -passivated LiF coatings (XeLiF), Li 3 AlF 6 overcoats, AlF 3 (plasma passivated), and XeF 2 passivated MgF 2 coatings (XeMgF 2 ). However, despite these developments, relatively little experimental information exists regarding the long-term stability of these coatings after simultaneous exposure to the Low Earth Orbit (LEO) environment. To evaluate their environmental durability and advance their Technology Readiness Level (TRL), representative samples of these coating technologies, Al+XeLiF, Al+eLiF, Al+Li 3 AlF 6 , Al+AlF 3 , Al+XeMgF 2 , and bare Al as reference samples, were flown onboard the International Space Station (ISS) as part of the Materials International Space Station Experiment 20 (MISSE-20). The MISSE platform is operated by Aegis Aerospace for relatively long-duration (e.g. 6 months) external exposure experiments in a space environment. The coatings were deposited on ULE and Zerodur substrates, and witness samples deposited on the same coatings runs, but on glass slides were left on Earth as control. A subset of the flight samples were fitted with MgF 2 windows to reduce direct exposure to atomic oxygen (AO) and charged particles, and still let through UV and other types of radiation on these samples. After approximately 6 months of exposure in the forward-facing (RAM) direction, the samples were returned to Earth and characterized by performing FUV/NUV/VIS/NIR reflectance measurements to quantify degradation, spectroscopic ellipsometry to evaluate coating thickness and optical constants, atomic force microscopy (AFM) to quantify surface roughness evolution during the flight in the ISS. The MgF 2 protective windows were also analyzed through FUV transmission measurements. Comparison with the witness samples left on the ground and with the flown bare Al samples (with just the naturally occurring Al 2 O 3 layer) provided a quantitative assessment of coating thickness variations, optical performance degradation, and morphological changes induced by prolonged exposure to the LEO environment.

Far Ultraviolet (FUV)↗

Micrometer to Atomic Scale Characterisation of Primitive Astromaterials Using A Novel Method, Metis-Fa: A Coordinated Atom Probe Tomography, Transmission Electron Microscopy and NanoSIMS Approach

Introduction: Presolar grains preserve isotopic, chemical and microstructural records of physical and chemical processing, and formation mechanisms within a vast range of evolved stellar systems, the interstellar medium, solar nebula and their parent bodies. These evolutionary records are preserved at the micrometric to atomic scale, requiring coordinated studies to expand our understanding of evolutionary processes occurringthroughout ours and external stellar systems [1]. NanoSIMS enabled rapid in situ identification and isotopic characterisation of presolar grains and their stellar origins using 17O/16O and 18O/16O, and 13C/12C isotopic ratios [1]. Coordination with transmission electron microscopy (TEM) revealed crystallographic and localised contextual relationships and quantitively constrained their major and minor compositions [1]. However, trace elements cannot be quantified, the most sensitive geochemical tracers of environmental conditions, essential to unravelling the chemical record of their evolutionary pathway and parent stellar systems [2-3] . Furthermore, owing to the combination of technical limitations (only 5 – 7 isotopes can be measured per NanoSIMS run) and their small grain sizes of 100 nm < 3 μm (with rare exceptions in nanodiamonds (2 nm ≤) and SiC (< 40 μm)), the number of measurable isotopes per grain volume is limited [1,3] . Through more comprehensive isotopic studies of presolar grains, NanoSIMS studies have shown the importance of the latter, identifying Fe and Mg as important indicators of nuclear synthetic processing and their stellar origins, respectively [4- 5]. Coordination of NanoSIMS and Atom Probe Tomography (APT) revealed morphological signatures, and isotopic and chemical signatures at major to trace levels without requirements for preselection of elements [6]. However, crystallographic signatures in localized contextual relationships cannot be measured. Consequently, coordination of NanoSIMS, TEM and APT is essential to gain access to almost all contextual, structural and geochemical signatures within each presolar grain.Transmission electron microscopy requires a 100 nm thin lamella which is unstable in APT and would not produce any viable data. Atom probe tomography requires a needle-shaped specimen which when measured in TEM removes the local context, impacts the quality of the TEM diffraction images due to the shank angle of the needle, and can alter the chemistry of beam sensitive materials from the higher degree of surface exposure at the tip. To address these issues, we developed METIS-Fa (Multi-technical measurements of Electron Transparent materials using an Indium Sandwich - a FIB approach). A novel method which enables coordination of NanoSIMS, TEM and APT for generalized and targeted studies of individual grains, including beam sensitive materials, without compromising sample preparation requirements for TEM and APT. This method requires only indium and a Focus Ion Beam (FIB), minimizing the movement of fragile materials while still enabling preparation of TEM lamella into APT needles. Samples: Initial experimental development and testing of the method occurred at Astromaterials Research and Exploration Science (ARES), Johnson Space Centre (JSC), NASA and APT measurements and needle preparation occurred at JdLC, Curtin University. Synthetic silicate samples were used as analogs for presolar silicates when performing a trial run of the method. Samples were extracted from a polished thin section created at JSC, NASA, comprised of 38 wt.% Si, 17 wt.% FeO, 13 wt.% MgO, 12 wt.% Al, 11 wt.% Ca based on electron microprobe analysis (EMPA) [8] . Experimental details, pressure and temperature conditions were presented in [8] and references therein. Testing of the capability to target individual grains in mineral matrices using this method for acquisition in APT, measured matrix regions in meteoritic thin sections of primitive meteorites. These meteorites and their identified presolar grains for future targeted studies are detailed in [9]. Techniques: The TEM-FIB lamella were prepared using a FIB. An e-beam assisted pt deposition was used as a protective coating for the synthetic and meteoritic samples. When targeting individual grains, a secondary e-beam assisted pt deposition button is placed over the desired grain before the protective coating to denote its location. A JEOL 2500SE field-emission TEM was used for high-resolution imaging, energy-dispersive X-ray (EDX) and electron diffraction data.TheMETIS-Fa method was experimentally designed, tested and executed using a FIB at ARES, JSCNASA. Needles for APT were prepared using the Tescan Lyra3 GM Dual Beam Focus Ion Beam (FIB) Field Emission SEM (FE-SEM) at the JdLC, Curtin University. Atom probe tomography measurements were conducted using a CAMECA Local Electrode Atom Probe, LEAP 4000X HR. Two pure indium needles were analyzed initially to constraining acquisition parameters and stability under the beam. Manual acquisition was required to maintain evaporation of specimen’s at the apex and monitor interactions with measurement parameters. Experimental Design: Indium foil is pressed onto an Al stub with a pneumatic press and mounted into the FIB adjacent to the TEM-FIB lamella of interest. Using a FIB, two indium slices (5 μm x ~300 nm x 3 μm) are extracted from indium foil and aligned with the TEM-FIB lamella before touching the TEM-FIB lamella. Each slice is then attached through cold welding to the FIB-TEM lamella. This approach eliminates the need for chemical treatments and proved effective for aligning the Indium within the region of interest for APT, holding it in place for up to 4 days during testing.Once both indium slices are attached within their pre-determined region per grain targeting requirements, they are gradually melted onto the FIB-TEM lamella.When targeting a specific grain, measurements should be taken of the pt button and its distance from edge to edge of the lamella before and after sandwiching. A secondary button should be placed over the same region after the Indium slices have been attached to improve precision when preparing APT needles. Results: Figure 1 shows two indium slices melted onto a FIB-TEM lamella, adding additional bulk for preparation into APT needles as shown in Figure 2 [7] . The latter was essential so samples could be measured in TEM and APT without compromising sample preparation requirements and consequently data quality and acquisition stability. METIS-Fa proved effective forimproving geometry. Figure 3 shows a successful APTrun of the synthetic silicate. EMPA, TEM and APTshowed no chemical alterations. During targetingtesting, a solar silicate grain was successfully identifiedand measured in TEM, and prepared into an APTneedle. However, the indium was melted too long during sample preparation, causing expansion andformation of internal porosity leading to sample loss.Conclusion: METIS-Fa greatly expands the number of isotopic and chemical signatures measured per grain volume, and enables measurements of contextual, structural, crystallographic, isotopic and geochemical signatures within individual grains. Gaining access to such a vast range of evolutionary signatures required for expanding our understanding of external stellar and planetary systems and the evolution of our solar system. This method was designed for application to a vast range of phases including being sensitive materials and thus provides a way for coordination of NanoSIMS, TEM and APT not just for the study of presolar grains and by extension primitive astromaterials, but studies in a vast range of other fields including the geosciences and material sciences.Acknowledgments: Thankyou to ARES, JSC, NASA; JdLC Curtin University and Space Science Technology Centre for the use of laboratory facilities and funding [confirm].

Nicole D Nevill↗