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NiCd battery electrodes, C-150

A research program to develop and evaluate electrodes for a nongassing negative limited nickel-cadmium cell is described. The concept of the negative limited cell and its implications on electrode structure are discussed. The key element is the development of a cadmium electrode with high hydrogen overvoltage. For this, Teflon-bonded Cd electrodes and silver-sinter based Gc electrodes were manufactured and in preliminary experiments their physical and electrochemical characteristics were evaluated. Hydrogen evolution on cadmium was found to occur approximately 100 mV more cathodic than on silver. Both electrode structures exhibit a fairly sharp potential rise at the end of the charging cycle and the advent of gas evolution occurs at potentials between -1.2 and -1.3 V versus a Hg/HgO reference electrode. These results are compared with conventional Ni-sinter based Cd electrodes.

Holleck, G.

Recent results from the Viking Labeled Release experiment on Mars

The Labeled Release (LR) life detection experiment seeks detection of heterotrophic metabolism by monitoring radio-active gas evolution following the addition of a radioactive nutrient containing seven C-14 labeled organic substrates to surface material. LR results obtained on Mars prior to conjunction showed rapid evolution of radioactive counts upon addition of the nutrient to a fresh surface sample. The responses at both landing sites were quite similar. The additional results summarized in the present paper provide further information on the gas kinetics following a second injection of nutrient and on the effect of 'cold sterilization' of the Martian surface material. Specifically, it is shown that the production of gas from the LR nutrient is remarkably uniform; after reaction approaches completion, addition of more nutrient results in a net loss of the radioactive gas; the reactant in the Mars soil is completely inhibited by heating the soil to 160 C, and is largely inhibited by heating to 46 C. In contrast, exposure to 18 C for 2 sol (1 sol = 24.6 hr) does not appear to inhibit the reaction.

Levin, G. V.

Simulations of Dynamics and Transport during the September 2002 Antarctic Major Warming

A mechanistic model simulation initialized on 14 September 2002, forced by 100-hPa geopotential heights from Met Office analyses, reproduced the dynamical features of the 2002 Antarctic major warming. The vortex split on approx.25 September; recovery after the warming, westward and equatorward tilting vortices, and strong baroclinic zones in temperature associated with a dipole pattern of upward and downward vertical velocities were all captured in the simulation. Model results and analyses show a pattern of strong upward wave propagation throughout the warming, with zonal wind deceleration throughout the stratosphere at high latitudes before the vortex split, continuing in the middle and upper stratosphere and spreading to lower latitudes after the split. Three-dimensional Eliassen-Palm fluxes show the largest upward and poleward wave propagation in the 0(deg)-90(deg)E sector prior to the vortex split (coincident with the location of strongest cyclogenesis at the model's lower boundary), with an additional region of strong upward propagation developing near 180(deg)-270(deg)E. These characteristics are similar to those of Arctic wave-2 major warmings, except that during this warming, the vortex did not split below approx.600 K. The effects of poleward transport and mixing dominate modeled trace gas evolution through most of the mid- to high-latitude stratosphere, with a core region in the lower-stratospheric vortex where enhanced descent dominates and the vortex remains isolated. Strongly tilted vortices led to low-latitude air overlying vortex air, resulting in highly unusual trace gas profiles. Simulations driven with several meteorological datasets reproduced the major warming, but in others, stronger latitudinal gradients at high latitudes at the model boundary resulted in simulations without a complete vortex split in the midstratosphere. Numerous tests indicate very high sensitivity to the boundary fields, especially the wave-2 amplitude. Major warmings occurred for initial fields with stronger winds and larger vortices, but not smaller vortices, consistent with the initiation of wind-deceleration by upward-propagating waves near the poleward edge of the region where wave 2 can propagate above the jet core. Thus, given the observed 100-hPa boundary forcing, stratospheric preconditioning is not needed to reproduce a major warming similar to that observed. The anomalously strong forcing in the lower stratosphere can be viewed as the primary direct cause of the major warming.

winds

Direct regeneration of degraded LiFePO4 cathodes via a separator-enabled prelithiation strategy

A persistent challenge in lithium-ion batteries is the loss of active lithium due to the solid electrolyte interphase (SEI) formation and associated side reactions. While prelithiation employing lithium replenishment separator (LRS) has been proven effective in compensating for lithium loss, previous studies have largely been accompanied by gas evolution or solid residue formation during the prelithiation process. To surmount this challenge, we present a LRS based on 4-fluoro-1,2-dihydroxybenzene lithium salt (LiDF), capable of mitigating lithium loss while producing decomposition products that integrate directly into the electrolyte as functional additives which can assist with the stability of the SEI, free from gas or solid formation, thus establishing a sustainable and environmentally benign strategy for lithium compensation. Incorporation of the LRS enables the pristine LiFePO4||graphite (Gr) full cell to achieve 10.8% higher capacity than the cell with a polypropylene separator (PPS) after 200 cycles at 0.5C. Remarkably, the degraded LiFePO4 (D-LFP)||Gr full cell with the LRS exhibits a 135.8% capacity improvement over the PPS-based cell after 500 cycles. These findings establish the LRS as a powerful approach for both boosting high-performance lithium-ion batteries and recovering the capacity of degraded batteries.

Tao, Fujun

A literature review and inventory of the effects of environment on the fatigue behavior of metals

The current state of knowledge of the effects of gas environments (at atmospheric pressure and below) on the fatigue behavior of metals is reviewed. Among the topics considered are the mechanisms proposed to explain the differences observed in the fatigue behavior of vacuum- and air-tested specimens, the effects of environment on the surface topography of fatigue cycled specimens, the effect of environment on the various phases of the fatigue phenomenon, the effect of prolonged exposure to vacuum on fatigue life, the variation of fatigue life with decreasing gas pressure, and gas evolution during fatigue cycling. Analysis of the findings of this review indicates that hydrogen embrittlement is primarily responsible for decreased fatigue resistance in humid environments, and that dislocations move more easily during tests in vacuum than during test in air. It was found that fatigue cracks generally initiated and propagated more rapidly in air than in vacuum. Prolonged exposure to vacuum does not adversely affect fatigue resistance. The variation of fatigue life with decreasing gas pressure is sometimes stepped and sometimes continuous.

Hudson, C. M.

Research on rechargeable oxygen electrodes.

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Giner, J.

Characterizing Hazardous Gases from NMC811 Materials and Coin Cells with TGA and Tube-Furnace FTIR-MS Evolved-Gas-Analysis

Abuse testing is useful for informing the risks of different battery chemistries but has been limited to larger formats. This paper conducted thermal abuse tests at the smaller coin cell level to determine its relevance in specifying vent gas flammability and toxicity. A nitrogen purge carried the evolved gases into a parallel Fourier-transform infrared spectrometer (FTIR) and a mass spectrometer (MS) downstream of the tube furnace. The experimental system was validated by comparing evolved gas data for single components between the tube furnace system and a thermogravimetric analysis (TGA) instrument. Multiple samples were tested during validation, including CaCO3, electrolyte, delithiated NMC 811 cathode, and lithiated graphite anode. Temperature-resolved gas evolution of HF, CO2, CO, H2, and hydrocarbons from isolated components helped to characterize the emission sources. A previously unreported H2 generation mechanism was found. It was shown that the reduced NMC cathode acts as a catalyst to crack polypropylene-decomposed hydrocarbons into H2 at around 450 degrees C. It was also shown, while studying LiPF6 thermal decomposition, that using the tube furnace with a coin cell casing as the sample holder has some advantages for evolved-gas analysis of environmentally sensitive samples relative to testing in TGA instruments. After validation with single components, a fully charged NMC 811 coin cell was failed in the tube furnace. The measured evolved gases were found to be a combination of the species measured from the single component tests. H2 formation related to the reduced cathode was found to have greater abundance than H2 formed from the anode. Hydrogen fluoride emission factors and diethyl carbonate conversion emission factors assist in understanding the gaseous hazards for larger format cells.

25 ENERGY STORAGE

Frost-weathering on Mars - Experimental evidence for peroxide formation

The weathering of silicates by frost is investigated in relation to the formation of surface peroxides to which Viking biology experiment results have been attributed. Samples of the minerals olivine and pyroxene were exposed to water vapor at -11 to -22 C and resultant gas evolution and pH were monitored. Experiments reveal the formation of an acidic oxidant upon interaction of the mineral and H2O frost at subfreezing temperatures, which chemical indicators have suggested to be chemisorbed hydrogen peroxide. A model for the formation of chemisorbed peroxide based on the chemical reduction of the mineral by surface frost is proposed, and it is predicted that the perioxide would decay at high temperatures to H2O and adsorbed O, consistent with the long-term storage and sterilization behavior of the soil oxidants observed in the Viking Gas Exchange and Labeled Release experiments.

Huguenin, R. L.

The Effect of Surface Induced Flows on Bubble and Particle Aggregation

Almost 20 years have elapsed since a phenomenon called "radial specific coalescence" was identified. During studies of electrolytic oxygen evolution from the back side of a vertically oriented, transparent tin oxide electrode in alkaline electrolyte, one of the authors (Sides) observed that large "collector" bubbles appeared to attract smaller bubbles. The bubbles moved parallel to the surface of the electrode, while the electric field was normal to the electrode surface. The phenomenon was reported but not explained. More recently self ordering of latex particles was observed during electrophoretic deposition at low DC voltages likewise on a transparent tin oxide electrode. As in the bubble work, the field was normal to the electrode while the particles moved parallel to it. Fluid convection caused by surface induced flows (SIF) can explain these two apparently different experimental observations: the aggregation of particles on an electrode during electrophoretic deposition, and a radial bubble coalescence pattern on an electrode during electrolytic gas evolution. An externally imposed driving force (the gradient of electrical potential or temperature), interacting with the surface of particles or bubbles very near a planar conducting surface, drives the convection of fluid that causes particles and bubbles to approach each other on the electrode.

Guelcher, Scott A.

Elucidating Gas Reduction Effects of Organosilicon Additives in Lithium-Ion Batteries

Lithium-ion batteries (LIBs) with nonaqueous liquid electrolytes are prone to gas generation at elevated voltages and temperatures, degrading battery performance and posing serious safety risks. Organosilicon (OS) additives are an emerging candidate solution for gassing problems in LIBs, but a detailed understanding of their functional mechanisms remains elusive. In this work, we present a combined computational and experimental study to elucidate the gasreducing effects of OS additives. Cell volume measurements and gas chromatography–mass spectrometry reveal that OS additives can substantially reduce gas evolution in LIBs, particularly CO 2 regardless of source. Through density functional theory calculations, we identify multiple plausible pathways for CO 2 evolution, including (1) nucleophile-induced ring-opening of ethylene carbonate (EC) and the subsequent electro-oxidation and (2) direct electro-oxidation of lithium carbonate (Li 2 CO 3 ). Correspondingly, we find that OS additives function via two primary mechanisms: (1) scavenging of nucleophiles such as superoxide (O 2 •– ), peroxide (O 2 2– ), and carbonate ion (CO 3 2– ); (2) oligomerization with ethylene carbonate oxide ion and ethylene dicarbonate ion. Moreover, we discover that OS additives possess strong lithium coordination affinity, which helps further reduce the nucleophilic reaction energies and hence increases their nucleophile-scavenging efficiency. Finally, we provide a mechanistic interpretation for the enhanced gasreduction effects observed with fluorinated OS compounds, corroborated by surface analysis results from X-ray photoelectron spectroscopy. Our study offers the first molecular-level insights into how OS additives contribute to reduced gas formation in LIBs, paving the way for improved safety and performance of LIBs.

25 ENERGY STORAGE

Evolution of Hot Gas in Elliptical Galaxies

This theory grant was awarded to study the curious nature, origin and evolution of hot gas in elliptical galaxies and their surrounding groups. Understanding the properties of this X-ray emitting gas has profound implications over the broad landscape of modern astrophysics: cosmology, galaxy formation, star formation, cosmic metal enrichment, galactic structure and dynamics, and the physics of hot gases containing dust and magnetic fields. One of our principal specific objectives was to interpret the marvelous new observations from the XMM and Chandru satellite X-ray telescopes.

Mathews, William G.

Hybrid Doping Strategy with High‐Entropy Cu/Fe Surface Modification and Zr Bulk Incorporation for Ni‐Rich Cathodes

A hybrid doping strategy combining Zr 4+ bulk doping with high-entropy Cu 2+ /Fe 3+ surface doping is developed to enhance the structural and interfacial stability of Ni-rich layered oxide cathodes. Cu and Fe are selectively introduced at the particle surface via a surface-selective ion-exchange process, forming a ≈15 nm Fe-rich layer while preserving the layered framework. Compared to the pristine cathode, the hybrid sample exhibits significantly improved electrochemical performance in both half-cell and full-cell configurations. In half-cells, the hybrid retains 88.5% and 90.2% after 100 cycles at 1C under 4.6 and 4.5 V, respectively. During high-voltage full-cell cycling, the hybrid cathode maintains over 80% capacity retention, whereas the pristine counterpart retains less than 10% under identical conditions over the same cycling period. XPS, EELS, and DEMS analyses confirm improved oxygen retention, suppressed gas evolution, and stable surface chemistry, while DFT calculations indicate enhanced Me–O bonding in the selected Fe 0.75 Cu 0.25 (Mn 1/16 Co 2/16 Ni 13/16 )O 2 surface composition, which is identified through DFT-calculated mixing energy reaching a minimum at this ratio, indicating the most thermodynamically favorable configuration. In conclusion, these results demonstrate the effectiveness of this hybrid doping strategy in mitigating coupled degradation pathways in Ni-rich cathodes.

15 GEOTHERMAL ENERGY

Chemical factors controlling the behaviour of oxide cathodes in batteries

Oxide cathodes enable high-energy lithium-ion and sodium-ion batteries, with their performances fundamentally governed by three interrelated chemical factors: electronic configuration, chemical bonding, and chemical reactivity. Here, we illustrate how these factors dictate the redox energy, structural stability, ionic and electronic transport, and interfacial behavior in both layered oxide and polyanion oxide cathodes. We discuss how crystal-field effects and octahedral-site stabilization energies influence cation migration, and how inductive effects tune bond covalency and operating voltages. We also explain how chemical bonding governs thermal stability, gas evolution, and first-cycle capacity loss, and how alignment of transition-metal redox band with the oxygen 2p band determines electrolyte reactivity. Comparison between lithium and sodium layered oxides further reveals how differences in Li-O and Na-O bond ionicity affect chemical reactivity. Finally, we outline strategies including compositional tuning, surface doping, and electrolyte optimization, and emphasize how high-throughput, data-driven approaches in guiding the design of next-generation oxide cathodes.

25 ENERGY STORAGE

Unraveling interphase-driven failure pathways in LiMn0.6Fe0.4PO4/graphite pouch cells

LiMnxFe1−xPO4 (LMFP) is a promising high-voltage, thermally stable, and earth-abundant cathode material, yet its practical application is limited by interphase instability and Mn dissolution. In this work, we systematically evaluate LiMn0.6Fe0.4PO4/graphite pouch cells using three electrolyte formulations including control carbonate electrolyte, control + 2 wt% vinylene carbonate (VC), and control + 2 wt% VC + 1 wt% 1,3,2-dioxathiolane 2,2-dioxide (DTD), to establish how electrolyte composition governs interphase chemistry and long-term degradation. Electrochemical testing shows that both additives are preferentially reduced prior to ethylene carbonate (EC) during cell formation, generating robust cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) layers that suppress gas evolution and raise the first-cycle coulombic efficiency to 89.3%. Additionally, the dual-additive electrolyte delivers the most stable performance, retaining over 85% capacity after 600 cycles while minimizing impedance growth under long-term cycling at C/3 and 40 °C. Soft X-ray absorption spectroscopy confirms that VC + DTD effectively suppresses electrolyte oxidation at the cathode surface, and micro-X-ray fluorescence shows substantially reduced Mn dissolution and deposition on the graphite anode. Density functional theory simulations further provided insights into the structural and energetic influences of alkoxide species on the cathode surface, proposing a Mn2+ extraction mechanism. The combined experimental and computational findings establish a mechanistic link between electrolyte composition and interphase evolution, highlighting the effectiveness of electrolyte engineering for extending the operational lifetime of LMFP-based lithium-ion batteries.

Chak, Chanmonirath Michael

A comparison of ceramic and carbon-based reductants for vitrification of low-activity waste

Sucrose is the current baseline additive at the Hanford Waste Treatment and Immobilization Plant in Washington, USA to control foaming during waste feed to glass transitions and the redox state of the glass melt. Alternative reductants are being investigated to alleviate strain on effluent treatment from toxic acetonitrile production from incomplete combustion of sucrose. This study evaluates ceramic additive options including B4C, B6Si, SiC and VB2 in simulated low-activity waste feed, as well as coke dust, probing the feed volume expansion during melting as well as the gas evolution. All alternative reductant options examined significantly reduced acetonitrile production, however there was variability in their effectiveness as foam-reducing agents. VB2 and coke at the appropriate ratios were similarly effective as sucrose in controlling both foam volume and glass redox state, but with considerably less acetonitrile production. B4C, B6Si and SiC showed more promising foam control and very little acetonitrile production, however all of the final glasses were over reduced, i.e., Fe2+/FeT = 0.5. These alternative reductant studies provide operational flexibility to the operation of the vitrification plant, as well as options for alternative raw materials in industrial glass melting.

Rigby, Jessica C. (ORCID:0000000235719977)

Multiscale Cryo Electron Microscopy Reveals Interfacial Degradation and Stabilization in Battery Electrodes

Electrochemical interfaces are dynamic systems, evolving based on their local environment and reactant surface structures. The electrode-electrolyte interface in Li-ion batteries can be protective, limiting parasitic reactions with the electrolyte to passivate the surface [1]. Additionally, this interphase has an impact on the Li-ion transport through that layer based on its composition, bonding environment, and thickness. These parameters are challenging to collect and may vary depending on the electrode surface site investigated relative to its spatial position in a coin cell. This study will detail a multiscale cryogenic electron microscopy approach where millimeter-scale cross-sections through the coin cell batteries were made using a cryogenic stage within a fs-laser plasma focused ion beam (laser PFIB) with complementary energy dispersive X-ray spectroscopy able to detect variations in the composition at electrode interfaces [2]. Microscale cross-sectioning and lamella sample preparation of battery electrodes was conducted at the Center for Integrated Nanotechnologies using a Ga-ion focused ion beam (FIB) with air-free and cryo-transfer [3], followed by nanoscale mapping of composition and bonding within the CEI through cryo-scanning transmission electron microscopy (cryo-STEM) electron energy loss spectroscopy [4]. This multiscale approach enabled identification of millimeter-scale features of a battery stack with visualization of degradation in electrodes such as cracks in cathode particles, gas evolution, and SEI evolution; microscale interfacial characteristics, such as heterogeneity in the SEI or barrier layer and identification of electrolyte networks to the electrode surfaces; and nanoscale measurement of the CEI thickness, mapping of transition metal bonding within the cathode particles to identify loss of active materials, and identification of beneficial electrolyte additives incorporated into the CEI structure. This multiscale approach allows for a statistical understanding of the primary mechanisms and parasitic degradation pathways that impact performance by limiting the ion transport pathways within Li+ batteries.

36 MATERIALS SCIENCE

Plated nickel wire mesh makes superior catalyst bed

Porous nickel mesh screen catalyst bed produces gas evolution in hydrogen peroxide thrust chambers used for attitude control of space vehicles. The nickel wire mesh disks in the catalyst bed are plated in rugose form with a silver-gold coating.

Sill, M.