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At least 163 records · Page 9

High tensile alloy of copper to mitigate current collector deformation in silicon electrodes for lithium-ion batteries

The volumetric changes of silicon electrodes, along with the strong adhesive properties of certain binders, can lead to plastic deformation of the current collector and create damage in the electrode coating. Here, in this study, we report a detailed study of silicon coatings on a high-tensile alloy (HTA) foil of copper with strength over twice that of conventional copper foils. The HTA current collectors with high mechanical strength can mitigate plastic deformation upon continuous cycling. At moderate areal capacities (2.5–3 mAh cm −2 ), conventional copper foils show significant wrinkling after only a few electrochemical cycles, whereas the HTA foils remain intact. We demonstrate viability of the HTA foils in large format xx6395 pouch cells, in which the HTA current collectors remain intact even at an areal capacity of 4.5 mAh cm −2 ; in contrast, wrinkles form in conventional copper current collectors increasing the likelihood of lithium plating. Computational studies show that stresses generated during cycling of silicon electrodes are very high in the current collector and at the current collector-coating interface, explaining the wrinkling of conventional Cu foils. Our studies highlight importance of current collector to solve the electrochemical and chemo-mechanical performance challenges associated with high-loading silicon electrodes.

Chemo-mechanical degradation↗

A Holistic Stabilization of the Anode in Lithium‐Sulfur Batteries Through a Ternary Alloy Fusion

The anode in lithium–sulfur batteries (LSBs) is plagued by not only inhomogeneous lithium (Li) deposition, but also by parasitic side-reactions. Often, a thick anode (∼400 µm) is used to compensate for these drawbacks, lowering gravimetric and volumetric energy densities. In this work, we demonstrate a ternary alloy anode fabricated via scalable thermal fusion of Li with aluminum (Al) and tellurium (Te) to cohesively address these issues. The Al–Li skeleton serves to homogenize Li deposition as well as reinforce the anode, allowing it to be rolled down to low thicknesses. Te incorporation suppresses the reaction of Li with polysulfides (Li 2 Sn) to form lithium sulfide (Li 2 S) and electrolyte degradation. It can also facilitate the formation of polytellurosulfides (Li 2 Te x Sy), which are far more conducive to Li + -ion diffusion. Even under a lean electrolyte/sulfur (E/S) ratio of 8 µL mg −1 and a low negative/positive (N/P) ratio of 3, capacities over 900 mA h g −1 at a C/5 rate are obtained in cells with Li–Te–Al anodes with a capacity retention of 80% after 70 cycles. In comparison, the baseline lithium-metal anode retains only 35% after 50 cycles. Furthermore, the Li–Te–Al anodes confer a 24% boost to gravimetric energy density at the pouch cell level.

25 ENERGY STORAGE↗

Effects of Thermal Exposure on Properties of Al-Li Alloys

Aluminum-Lithium (Al-Li) alloys offer significant performance benefits for aerospace structural applications due to their higher specific properties compared with conventional Al alloys. For example, the application of Al-Li alloy 2195 to the space shuffle external cryogenic fuel tank resulted in weight savings of over 7,000 lb, enabling successful deployment of International Space Station components. The composition and heat treatment of 2195 were optimized specifically for strength-toughness considerations for an expendable cryogenic tank. Time-dependent properties related to reliability, such as thermal stability, fatigue, and corrosion, will be of significant interest when materials are evaluated for a reusable cryotank structure. Literature surveys have indicated that there is limited thermal exposure data on Al-Li alloys. The effort reported here was designed to establish the effects of thermal exposure on the mechanical properties and microstructure of Al-Li alloys C458, L277, and 2195 in plate gages. Tensile, fracture toughness, and corrosion resistance were evaluated for both parent metal and friction stir welds (FSW) after exposure to temperatures as high as 300 F for up to 1000 hrs. Microstructural changes were evaluated with thermal exposure in order to correlate with the observed data trends. The ambient temperature parent metal data showed an increase in strength and reduction in elongation after exposure at lower temperatures. Strength reached a peak with intermediate temperature exposure followed by a decrease at highest exposure temperature. Friction stir welds of all alloys showed a drop in elongation with increased length of exposure. Understanding the effect of thermal exposure on the properties and microstructure of Al-Li alloys must be considered in defining service limiting temperatures and exposure times for a reusable cryotank structure.

Shah, Sandeep↗

The Origin of Improved Performance in Boron‐Alloyed Silicon Nanoparticle‐Based Anodes for Lithium‐Ion Batteries

Stabilizing the solid electrolyte interphase (SEI) remains a key challenge for silicon‐based lithium‐ion battery anodes. Alloying silicon with secondary elements like boron has emerged as a promising strategy to improve the cycle life of silicon anodes, yet the underlying mechanism remains unclear. To address this knowledge gap, how boron concentration influences battery performance is systematically investigated. These results show a near‐monotonic increase in cycle lifetime with higher boron content, with boron‐rich electrodes significantly outperforming pure silicon. Additionally, silicon‐boron alloy anodes exhibit nearly three times longer calendar life than pure silicon. Through detailed mechanistic analysis, alternative contributing factors are systematically ruled out, and it is proposed that improved passivation arises from a strong permanent dipole at the nanoparticle surface. This dipole, formed by undercoordinated and highly Lewis acidic boron, creates a static, ion‐dense layer that stabilizes the electrochemical interface, reducing parasitic electrolyte decomposition and enhancing long‐term stability. These findings suggest that, within the SEI framework, the electric double layer is an important consideration in surface passivation. This insight provides an underexplored parameter space for optimizing silicon anodes in next‐generation lithium‐ion batteries.

25 ENERGY STORAGE↗

Aluminum 2195 T8 Gore Development for Space Launch System Core and Upper Stage

Gores are pie-shaped panels that are welded together to form the dome ends of rocket fuel tanks as shown in figure 1. Replacing aluminum alloy 2219 with aluminum (Al)-lithium (Li) alloy 2195 as the Space Launch System (SLS) cryogenic tank material would save enormous amounts of weight. In fact, it has been calculated that simply replacing Al 2219 gores with Al 2195 gores on the SLS core stage domes could save approximately 3,800 pound-mass. This is because the Al-Li 2195 alloy exhibits both higher mechanical properties and lower density than the SLS baseline Al 2219 alloy. Indeed, the known advantages of Al 2195 led to its use as a replacement for Al 2219 in the shuttle external tank program. The required thicknesses of Al 2195 gores for either SLS core stage tanks or upper stage tanks will depend on the specific design configurations. The required thicknesses or widths may exceed the current experience base in the manufacture of such gores by the stretch-forming process. Accordingly, the primary objective of this project was to enhance the formability of Al 2195 by optimizing the heat treatment and stretch-forming process for gore thicknesses up to 0.75 inches, which envelop the maximum expected gore thicknesses for SLS tank configurations.

Volz, Martin↗

Alloying Interlayers for Anode‐Less Lithium‐Metal Polymer Batteries

Anode‐less lithium‐metal batteries potentially offer further increased energy densities. However, the Coulombic efficiency (CE) of lithium plating and stripping, as a classical measure of Li inventory reversibility, is commonly still insufficient for achieving long‐lasting rechargeable batteries. Herein, the potential benefits of employing thin (20 nm) metal interlayers of Ag, Pt, and Au on Cu to alloy with Li in Cu||Li half‐cells and induce homogeneous Li plating with poly(ethylene oxide)‐based electrolytes are investigated. Interestingly, not all alloying interlayers enable a higher CE compared to neat Cu foil with 84%—specifically Ag@Cu with only 81%, while the best performing one, Au@Cu, provides a substantially increased CE of 91%. While generally the formation of “dead lithium” is found to be the major source of CE, this appears to be less pronounced in the case of Au@Cu, indeed. Further improvement can be achieved by carefully adjusting the cell voltage to a region in which the continuous de‐/alloying is suppressed, yielding a further enhanced CE of 94%, thus highlighting the need for a comprehensive approach to design suitable electrode chemistries and designs beyond a “simple” material improvement.

anode-less battery↗

Transmission electron microscopy characterization of microstructural features of Al-Li-Cu alloys

A transmission electron microscopy (TEM) examination of aluminum-lithium-copper alloys was conducted. The principal purpose is to characterize the nature, size, and distribution of stringer particles which result from the powder metallurgy (P/M) processing of these alloys. Microstructural features associated with the stringer particles are reported that help explain the stress corrosion susceptibility of the powder metallurgy-processed Al-Li-Cu alloys. In addition, matrix precipitation events are documented for a variety of heat treatments and process variations. Hot rolling is observed to significant alter the nature of matrix precipitation, and the observations are correlated with concomitant mechanical property variations.

Avalos-Borja, M.↗

Carbon Materials Embedded with Metal Nanoparticles as Anode in Lithium-Ion Batteries

Carbon materials containing metal nanoparticles that can form an alloy with lithium were tested for their capacity and cycle life to store and release lithium electrochemically. Metal nanoparticles may provide the additional lithium storage capacity as well as additional channels to conduct lithium in carbon. The cycle life of this carbon-metal composite can be long because the solid-electrolyte interface (SEI) on the carbon surface may protect both lithium and the metal particles in the carbon interior. In addition, the voids in the carbon interior may accommodate the nanoparticle's volume change, and such volume change may not cause much internal stress due to small sizes of the nanoparticles. This concept of improving carbon's performance to store and release lithium was demonstrated using experimental cells of C(Pd)/0.5M Lil-50/50 (vol.%) EC and DMC/Li, where C(Pd) was graphitized carbon fibers containing palladium nanoparticles, EC was ethylene carbonate, and DMC was dimethyl carbonate. However, such improvement was not observed if the Pd nanoparticles are replaced by aluminum, possibly because the aluminum nanoparticles were oxidized in air during storage, resulting in an inert oxide of aluminum. Further studies are needed to use this concept for practical applications.

Hung, Ching-cheh↗

Exploration of Sn 70 Li 30 alloy as possible material for flowing liquid metal plasma facing components

As an advanced alternative to solid materials, Liquid Metals (LM) may offer more resilient and feasible Plasma Facing Components (PFCs). Particularly, regarding the unavoidable material erosion/degradation produced by particle/heat fluxes in future fusion devices where much longer duty cycles are expected. Furthermore, configurations that propose a flowing LM surface can add the advantage of a continuously fresh and clean layer facing the plasma. Although lithium is the most widely tested option, tin-lithium (SnLi) alloys have been proposed to attempt to combine the positive characteristics of both pure elements and ameliorate the specific issues of lithium. In this work, the potential use of Sn70Li30 alloy in such flowing concepts has been explored by addressing several preliminary and mandatory aspects for its utilization. Key issues such as wettability and compatibility of the alloy with relevant substrates have been studied in a multidisciplinary approach. The data obtained from deposited liquid tin-lithium droplets indicates approximate wetting temperatures of 360 °C, 390 °C and 405 °C for the fresh alloy on 316 stainless steel, molybdenum, and tungsten, respectively. However, the alloy contamination appeared to strongly affect the wetting characteristics of materials, increasing their wetting temperature by ~130 °C in the worst observed cases. Interestingly, in some instances, the instability of the liquid alloy surface was observed in the form of sudden gaseous ejection. The deposited droplets were posteriorly characterized in terms of absolute composition and depth profile by Inductively Coupled PlasmaOptical Emission Spectroscopy (ICP-OES) and Secondary Ion Mass Spectrometry (SIMS-ToF). Additionally, the nature and composition of the boundaries between the substrates and alloy microparticles was investigated by Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), and 3D Laser microscopy. The overall results of this post-mortem characterization revealed that first signs of corrosion induced by both alloy elements (lithium-chromium association and iron-tin intermetallic mixing) were present on 316 stainless steel after short exposures (≤3 h) at temperatures lower than 550 °C. Conversely, molybdenum and tungsten showed good compatibility with the alloy in equivalent conditions. The global implications of these results are finally addressed, focusing on the future perspectives and the more viable scenarios for the eventual utilization of these alloys in flowing liquid metal configurations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

The Promise of Alloy Anodes for Solid-State Batteries

Solid-state batteries are anext-generation technology that could featureimproved safety and energy density, but reliably integrating high-capacity electrode materials to enable high energy while retaining stablelong-termcycling remains a challenge. Anode materials that alloy with lithium, such as silicon, tin, and aluminum,offer high capacity that canyield high-energy battery cells. The use of alloy anodes in solid-state batteries potentially offers major mechanistic benefits compared to other anode contendersand battery systems, such as lithium metal in solid-state architectures or alloys in liquid-electrolyte batteries. This perspective discusseskey advantagesof alloy anode materials for solid-state batteries, including the avoidance of the short circuiting observed with lithium metal and the chemo-mechanical stabilization of the solid-electrolyte interphase (SEI). We further discuss open research questions and challenges in engineering alloy-anode-based solid-state batteries, with the goal of advancing our understanding and control of alloy anode materialswithin solid-state architectures toward commercial application.

John A Lewis↗

Lessons Learned—Lithium Silicide Hydration Fire

Alkali metals, such as lithium, sodium, potassium, etc., are highly reactive elements. While researchers generally handle these metals with caution, less caution is taken when these elements have been “reacted”. In this work, a recent incident is examined in which a pair of researchers ignited a lithium silicide alloy sample that was assumed to be fully hydrated to lithium hydroxide and, thereby, no longer water-reactive. However, variations in the original chemical composition of the lithium compounds examined resulted in select mixtures failing to hydrate and react completely to lithium hydroxide in the time frame allowed. This gave rise to residual unreacted, water-sensitive lithium silicide which resulted in a violent exothermic reaction with water and autoignition of the produced hydrogen gas. This Article describes this incident and improvements that can be implemented to prevent similar incidents from occurring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Entrained Surface Oxides in RS-PM Aluminum Alloys on Resultant Structures and Properties

The RS-PM aluminum alloys which show less than anticipated toughness properties were studied. After eliminating negative variables such as sodium and potassium in lithium containing alloys, hydrogen in all Al alloys, and trapped impurities from the atomization processing the data pointed to fine oxides, as the primary cause of poor toughness properties. The oxide content of aluminum powders increases with: decreasing powder size, deviations from spherical powder shapes, exposure to moist atmospheres either during atomization or in subsequent powder handling, and alloy compositions which contain significant amounts of lithium, magnesium, cerium, and other reactive elements.

Grant, N. J.↗

Mitigating Interfacial Mismatch between Lithium Metal and Garnet-Type Solid Electrolyte by Depositing Metal Nitride Lithiophilic Interlayer

Solid-state lithium batteries are generally considered as the next-generation battery technology that benefits from inherent nonflammable solid electrolytes and safe harnessing of high-capacity lithium metal. Among various solid-electrolyte candidates, cubic garnet-type Li 7 La 3 Zr 2 O 12 ceramics hold superiority due to their high ionic conductivity (10 –3 to 10 –4 S cm -1 ) and good chemical stability against lithium metal. However, practical deployment of solid-state batteries based on such garnet-type materials has been constrained by poor interfacing between lithium and garnet that displays high impedance and uneven current distribution. Herein, we propose a facile and effective strategy to significantly reduce this interfacial mismatch by modifying the surface of such garnet-type solid electrolyte with a thin layer of silicon nitride (Si 3 N 4 ). This interfacial layer ensures an intimate contact with lithium due to its lithiophilic nature and formation of an intermediate lithium–metal alloy. The interfacial resistance experiences an exponential drop from 1197 to 84.5 Ω cm 2 . Lithium symmetrical cells with Si 3 N 4 -modified garnet exhibited low overpotential and long-term stable plating/stripping cycles at room temperature compared to bare garnet. Furthermore, a hybrid solid-state battery with Si 3 N 4 -modified garnet sandwiched between lithium metal anode and LiFePO 4 cathode was demonstrated to operate with high cycling efficiency, excellent rate capability, and good electrochemical stability. This work represents a significant advancement toward use of garnet solid electrolytes in lithium metal batteries for the next-generation energy storage devices.

25 ENERGY STORAGE↗

Effects of low-pressure air on oxygen contamination and lithium corrosion of a tantalum alloy, T-111, at 980 and 1260 C

The effects were studied of low-pressure air on contamination and corrosion in the tantalum alloy T-111/lithium system at 980 and 1260 C. Capsules of T-111 containing lithium were exposed to six vacuum levels between 1 x 10 to the 8th power and 0.0003 torr by controlled air leakage into a vacuum system. Capsules exposed at 980 C and 0.0002 torr failed from intragranular oxidation. The remainder of the capsules completed the 96-hour tests. The depth of oxygen contamination was greater at 980 C than at 1260 C. Tests made at 0.0001 and 0.00001 torr levels caused large increases in the oxygen content of the T-111. Tests at 0.000001 torr or less produced no significant contamination. No lithium corrosion of the T-111 was observed under any of the conditions.

Gahn, R. F.↗

The effect of fabrication on corrosion in aluminum 2195: Environmental and microstructural considerations

Aluminum alloys containing lithium are particularly attractive to the aerospace structural designer. Lithium's density is only 0.53 g/cc, thus an addition of one weight percent lithium not only increases yield strength, but decreases the density by almost three percent while increasing the modulus by over six percent. The fact that lithium improves these physical properties simultaneously has led to intense study and development of the alloy system. Heretofore, problems in large scale alloy production have retarded commercial development. During the last fifteen years, advances in production technology have rekindled interest in Al-Li alloys, and aluminum suppliers have developed many candidate aerospace materials. However, if these alloys are to be employed successfully, a more complete understanding of their nonequilibrium metallurgy is required. Peel and Starke have each pointed out that an understanding of the weldability of these alloys is a critical step in their implementation. This study addresses the critical lack of information on the environmental compatibility of welded Al 2195 components. Corrosion data for these systems is incomplete, particularly for welded materials exposed to sea water or sea water condensate.

Walsh, Daniel W.↗

Investigation of Methods for Selectively Reinforcing Aluminum and Aluminum-Lithium Materials

Several studies have indicated that selective reinforcement offers the potential to significantly improve the performance of metallic structures for aerospace applications. Applying high-strength, high-stiffness fibers to the high-stress regions of aluminum-based structures can increase the structural load-carrying capability and inhibit fatigue crack initiation and growth. This paper discusses an investigation into potential methods for applying reinforcing fibers onto the surface of aluminum and aluminum-lithium plate. Commercially-available alumina-fiber reinforced aluminum alloy tapes were used as the reinforcing material. Vacuum hot pressing was used to bond the reinforcing tape to aluminum alloy 2219 and aluminum-lithium alloy 2195 base plates. Static and cyclic three-point bend testing and metallurgical analysis were used to evaluate the enhancement of mechanical performance and the integrity of the bond between the tape and the base plate. The tests demonstrated an increase in specific bending stiffness. In addition, no issues with debonding of the reinforcing tape from the base plate during bend testing were observed. The increase in specific stiffness indicates that selectively-reinforced structures could be designed with the same performance capabilities as a conventional unreinforced structure but with lower mass.

Bird, R. Keith↗

Lithium Nucleation of Anode-Free Solid-State Batteries with a Dry Compressible Interlayer

Anode-free lithium batteries offer promising advantages, including increased energy density and the ability to address common mechanistic failures within the cell, thus increasing safety. One way that can make this possible is to control lithium nucleation. This could be achieved by reducing the overpotential required and implanting lithophilic nucleation sites in an anodic interlayer to aid in lithium ion transport and plating. The concept has been utilized in solid-state battery systems where electrolytes are solids with further improved safety and structural longevity. In this presentation, we discuss the use of a silver-holey graphene-based anodic interlayer that can be fabricated via direct dry compression without the use of solvent or binder. The addition of silver to the holey graphene matrix creates a route to lithium plating via a lower-energy intermediate. This idea is supported by the presence of a lithium-silver alloy that forms during the activation step. It is understood that the embedded silver acts as a nucleation site for lithium ions, thereby assisting in even plating. This control, combined with the added cushion of the holey graphene itself, can help reduce dendrite formation, ultimately increasing the safety and lifetime of the solid-state batteries.

Solid state batteries↗