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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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84 records · Page 5

Femtosecond diffraction and dynamic high pressure science

Solid-state material at high pressure is prevalent throughout the Universe, and an understanding of the structure of matter under such extreme conditions, gleaned from x-ray diffraction, has been pursued for the best part of a century. The highest pressures that can be reached to date (2 TPa) in combination with x-ray diffraction diagnosis have been achieved by dynamic compression via laser ablation. The past decade has witnessed remarkable advances in x-ray technologies, with novel x-ray Free-Electron-Lasers (FELs) affording the capacity to produce high quality single-shot diffraction data on timescales below 100 fs. We provide a brief history of the field of dynamic compression, spanning from when the x-ray sources were almost always laser-plasma based, to the current state-of-the art diffraction capabilities provided by FELs. We give an overview of the physics of dynamic compression, diagnostic techniques, and the importance of understanding how the rate of compression influences the final temperatures reached. We provide illustrative examples of experiments performed on FEL facilities that are starting to give insight into how materials deform at ultrahigh strain rates, their phase diagrams, and the types of states that can be reached. We emphasize that there often appear to be differences in the crystalline phases observed between the use of static and dynamic compression techniques. We give our perspective on both the current state of this rapidly evolving field and some glimpses of how we see it developing in the near-to-medium term.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Intralattice-bonded phase-engineered ultrahigh-Ni single-crystalline cathodes suppress strain evolution

Single crystallization remains a debated strategy for advancing Ni-rich cathode materials. While it mitigates particle cracking and improves tap density by eliminating particle boundaries, extended diffusion pathways introduce volumetric and lattice distortions, compromising electrochemical and structural stability. These challenges hinder the commercialization of high-Ni single-crystal cathodes, calling for a reassessment of their viability. Here, in this study, we report a structural design: intralattice-bonded phase single-crystal LiNi 0.92 Co 0.03 Mn 0.05 O 2 (IBP-SC92). This architecture maintains structural integrity while shortening diffusion pathways, resulting in almost zero electrochemical degradation during cycling. The robust structure and fast ion transport mitigate lattice strain, as confirmed by multiscale high-resolution diffraction and imaging techniques, preventing intragranular cracks and irreversible phase transitions. As a result, IBP-SC92 shows outstanding cycling stability, with nearly 100% capacity retention after 100 cycles in half cells and 94.5% retention after 1,000 cycles in full cells. This redefined single-crystal cathode represents a significant step towards the industrial adoption of high-energy-density materials.

36 MATERIALS SCIENCE↗

Mechanical rolling formation of interpenetrated lithium metal/lithium tin alloy foil for ultrahigh-rate battery anode

To achieve good rate capability of lithium metal anodes for high-energy-density batteries, one fundamental challenge is the slow lithium diffusion at the interface. Here we report an interpenetrated, three-dimensional lithium metal/lithium tin alloy nanocomposite foil realized by a simple calendering and folding process of lithium and tin foils, and spontaneous alloying reactions. The strong affinity between the metallic lithium and lithium tin alloy as mixed electronic and ionic conducting networks, and their abundant interfaces enable ultrafast charger diffusion across the entire electrode. Furthermore, we demonstrate that a lithium/lithium tin alloy foil electrode sustains stable lithium stripping/plating under 30 mA cm -2 and 5 mAh cm -2 with a very low overpotential of 20 mV for 200 cycles in a commercial carbonate electrolyte. Cycled under 6 C (6.6 mA cm -2 ), a 1.0 mAh cm -2 LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode maintains a substantial 74% of its capacity by pairing with such anode.

25 ENERGY STORAGE↗

Mechanical and self-healing behavior of low carbon engineered cementitious composites reinforced with PP-fibers

While the ultrahigh tensile ductility and superior durability of Engineered Cementitious Composites (ECC) have been demonstrated, the relatively high energy and carbon intensity, as well as high material cost present potential impediments to broader ECC applications. The objective of this research is to develop a more sustainable and cost-effective ECC. The ordinary Portland cement (OPC) and the commonly used PVA fiber in conventional ECC were replaced by limestone calcined clay cement (LC3) and polypropylene (PP) fiber, respectively. The ECC compressive strength, tensile stress-strain relationship, and microcrack self-healing behavior were studied at three water to binder ratios (0.3, 0.2, 0.16). The novel LC3-PP-ECC showed a tensile strain capacity of greater than 6% and an intrinsically tight crack width below 82 μm when loaded to 1% tensile strain. Further, the LC3-PP-ECC demonstrated efficient recovery of the composite tensile ductility and ultimate tensile strength through self-healing. Compared to typical ECC made with OPC and PVA fiber, the material cost, embodied energy and carbon footprint of LC3-PP-ECC are reduced by 61%, 45%, and 48%, respectively. Here, the superior mechanical properties and durability combined with the low environmental impact and cost for material production promote LC3-PP-ECC as a sustainable material for structural and non-structural applications.

42 ENGINEERING↗

Local Chemical Clustering Enabled Ultrahigh Capacitive Energy Storage in Pb-Free Relaxors

Designing Pb-free relaxors with both a high capacitive energy density (W rec ) and high storage efficiency (η) remains a remarkable challenge for cutting-edge pulsed power technologies. Local compositional heterogeneity is crucial for achieving complex polar structure in solid solution relaxors, but its role in optimizing energy storage properties is often overlooked. Here, in this paper, we report that an exceptionally high W rec of 15.2 J cm –3 along with an ultrahigh η of 91% can be achieved through designing local chemical clustering in Bi 0.5 Na 0.5 TiO 3 –BaTiO 3 -based relaxors. A three-dimensional atomistic model derived from neutron/X-ray total scattering combined with reverse Monte Carlo method reveals the presence of subnanometer scale clustering of Bi, Na, and Ba, which host differentiated polar displacements, and confirming the prediction by density functional theory calculations. This leads to a polar state with small polar clusters and strong length and direction fluctuations in unit-cell polar vectors, thus manifesting improved high-field polarizability, steadily reduced hysteresis, and high breakdown strength macroscopically. The favorable polar structure features also result in a unique field-increased η, excellent stability, and superior discharge capacity. Our work demonstrates that the hidden local chemical order exerts a significant impact on the polarization characteristic of relaxors, and can be exploited for accessing superior energy storage performance.

25 ENERGY STORAGE↗

Ferrielectricity in the Archetypal Antiferroelectric, PbZrO 3

Antiferroelectric materials, where the transition between antipolar and polar phase is controlled by external electric fields, offer exceptional energy storage capacity with high efficiencies, giant electrocaloric effect, and superb electromechanical response. PbZrO 3 is the first discovered and the archetypal antiferroelectric material. Nonetheless, substantial challenges in processing phase pure PbZrO 3 have limited studies of the undoped composition, hindering understanding of the phase transitions in this material or unraveling the controversial origins of a low-field ferroelectric phase observed in lead zirconate thin films. Here, leveraging highly oriented PbZrO 3 thin films, a room-temperature ferrielectric phase is observed in the absence of external electric fields, with modulations of amplitude and direction of the spontaneous polarization and large anisotropy for critical electric fields required for phase transition. The ferrielectric state observations are qualitatively consistent with theoretical predictions, and correlate with very high dielectric tunability, and ultrahigh strains (up to 1.1%). This work suggests a need for re-evaluation of the fundamental science of antiferroelectricity in this archetypal material.

36 MATERIALS SCIENCE↗

Modeling assisted synthesis of Zr-doped Li 3-x In 1-x Zr x Cl 6 with ultrahigh ionic conductivity for lithium-ion batteries

All-solid-state lithium-ion batteries (ASSLBs) are an important milestone for the future of energy storage because of their capability of impressive energy density and outstanding safety. However, oxide and sulfide solid-state electrolytes (SSEs) suffer from either low ionic conductivity or poor chemical stability. In contrast, halide-based SSEs, are promising as candidate materials owing to high conductivity, good stability, and broad cathode compatibility. Though element doping of the SSEs is an effective and common approach to further improve their electrochemical properties, dopant exploration and optimization through solely experimental trials are both costly and time-consuming. For this aspect, computational simulations for dopant element and concentration screening are adopted in this research and zirconium is selected as a suitable dopant for Li 3 InCl 6 . Further, the synthesized Li 2.75 In 0.75 Zr 0.25 Cl 6 exhibited Li ionic conductivity of 5.82 x 10 -3 Scm -1 at room temperature, which is the highest among reported halide SSEs. The ASSLB formed with Li 2 CoO 2 -Li 2.75 In 0.75 Zr 0.25 Cl 6 -Li/In delivers a high initial capacity of 129.3 mAh∙g -1 . Conclusively, this work provides an effective approach which combines computational modeling and experimental verification for the development of halide SSEs with improved stability and conductivity. The successful design approach and compelling results provide further possibilities and capabilities in future SSE research.

25 ENERGY STORAGE↗

A dynamically bare metal interface enables reversible magnesium electrodeposition at 50 mAh cm −2

Understanding and facilitating pure magnesium nucleation/growth electrodeposition behavior with ultrahigh Coulombic efficiency is complicated by the phenomenon of solid electrolyte interphase (SEI) formation in state-of-the-art, halogen-free magnesium electrolytes. Defining the electrolyte properties necessary to achieve ideal electrodeposition/stripping (E/S) thus remains elusive. Here, in this work, we reveal for the first time, rapid magnesium electrodeposition behavior that forms densely aligned, micron-sized thin platelets by establishing a dynamic bare magnesium/electrolyte interface during high-rate net plating. This effectively “SEI-free” interface allows facile magnesium diffusion and migration in stripping with near-unity E/S efficiency under demanding conditions over long-term cycling. The intrinsic electrolyte stability of the salt/solvent at the molecular level is the key to forming such an interface. The efficacy of the dynamic bare interface and an electrodeposited, free-standing magnesium anode is demonstrated in a high-areal-capacity full cell. These findings provide new design principles and fundamental understanding of interfacial chemistry in multivalent metal batteries.

Mg full cell↗

Li 3– x Zr x (Ho/Lu) 1– x Cl 6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

We report two new families of lithium metal chloride solid electrolytes Li 3–x Zr x (M) 1–x Cl 6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm –1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li 3 HoCl 6 , orthorhombic-I Li 3 LuCl 6 , and orthorhombic-II Li 2.4 Zr 0.6 (Ho/Lu) 0.4 Cl 6 . The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li 2.6 Zr 0.4 (Ho/Lu) 0.6 Cl 6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li + /Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li 0.7 Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3 mAh·cm –2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Balancing volumetric and gravimetric uptake in highly porous materials for clean energy

A huge challenge facing scientists is the development of adsorbent materials that exhibit ultrahigh porosity but maintain balance between gravimetric and volumetric surface areas for the onboard storage of hydrogen and methane gas—alternatives to conventional fossil fuels. Here we report the simulation-motivated synthesis of ultraporous metal–organic frameworks (MOFs) based on metal trinuclear clusters, namely, NU-1501-M (M = Al or Fe). Relative to other ultraporous MOFs, NU-1501-Al exhibits concurrently a high gravimetric Brunauer–Emmett–Teller (BET) area of 7310 m 2 g -1 and a volumetric BET area of 2060 m 2 cm -3 while satisfying the four BET consistency criteria. The high porosity and surface area of this MOF yielded impressive gravimetric and volumetric storage performances for hydrogen and methane: NU-1501-Al surpasses the gravimetric methane storage U.S. Department of Energy target (0.5 g g -1 ) with an uptake of 0.66 g g -1 [262 cm 3 (standard temperature and pressure, STP) cm -3 ] at 100 bar/270 K and a 5- to 100-bar working capacity of 0.60 g g -1 [238 cm 3 (STP) cm -3 ] at 270 K; it also shows one of the best deliverable hydrogen capacities (14.0 weight %, 46.2 g liter -1 ) under a combined temperature and pressure swing (77 K/100 bar → 160 K/5 bar).

Science & Technology - Other Topics↗

Mechanically Robust Bismuth-Embedded Carbon Microspheres for Ultrafast Charging and Ultrastable Sodium-Ion Batteries

Advancements in the development of fast-charging and long-lasting microstructured alloying anodes with high volumetric capacities are essential for enhancing the operational efficiency of sodium-ion batteries (SIBs). These anodes, however, face challenges such as declined cyclability and rate capability, primarily due to mechanical degradation reduced by significant volumetric changes (over 252%) and slow kinetics of sodium-ion storage. Herein, we introduce a novel anode design featuring densely packed bismuth (Bi) embedded within highly conductive carbon microspheres to overcome the aforementioned challenges. Remarkably, the high loading Bi anode within carbon microspheres with a high tap density of 2.59 g cm -3 possesses significant mechanical strength exceeding 590 MPa and limits volume swelling of only 10.9% post-sodiation. This anode demonstrates a high volumetric capacity (908.3 mAh cm -3 ), ultrafast chargeability (200 A g -1 , full charge/discharge in just 5.5 s), and outstanding cyclability over 12,000 cycles and maintains exceptional cycling stability even at -30 °C. The full cell paired with a Na 3 V 2 (PO 4 ) 3 cathode retains over 80% capacity after 600 cycles at 36 C, demonstrating a remarkable rate capability of 126 C (full charge/discharge in 28.6 s). Our comprehensive experimental evaluations and chemo-mechanical simulations shed light on the mechanisms underpinning the anode's superior performance. In conclusion, this development marks a significant advancement in the design of durable and fast-charging anodes for high-performance SIBs.

25 ENERGY STORAGE↗