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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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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Cooling rate and dendrite spacing control in direct metal deposition printed Cu-Fe alloys

Over the last several decades, additive manufacturing (AM) has been primarily used for rapid prototyping or to create novel geometries that would be difficult or impossible to create by normal manufacturing methods. More recently, research has been focused on expanding the list of materials that can be made through additive manufacturing, opening a greater range of material properties for this manufacturing method. Due to the unusual conditions during AM, including the high cooling rates and voxel by voxel method of production, AM parts often have anisotropic material microstructures and properties. In this investigation, the laser power, composition, and nozzle head speed during direct metal deposition of copper-iron alloys was varied to understand how the grain structure within the printed parts could be changed and controlled. The resulting dendrite spacing was measured and compared to calculated cooling rates from Gaussian beams on flat plates under similar material and laser properties, which resulted in a cooling rate to dendrite spacing relationship following an inverse square root, as is found in other dendritic systems [Young and Kerkwood, Metall. Trans. A 6, 197–205 (1975)]. Thus, it is demonstrated that in the Cu-Fe system, dendrite spacing can be controlled through manipulation of printing parameters.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Manipulating the diffusion energy barrier at the lithium metal electrolyte interface for dendrite-free long-life batteries

Abstract Constructing an artificial solid electrolyte interphase (SEI) on lithium metal electrodes is a promising approach to address the rampant growth of dangerous lithium morphologies (dendritic and dead Li 0 ) and low Coulombic efficiency that plague development of lithium metal batteries, but how Li + transport behavior in the SEI is coupled with mechanical properties remains unknown. We demonstrate here a facile and scalable solution-processed approach to form a Li 3 N-rich SEI with a phase-pure crystalline structure that minimizes the diffusion energy barrier of Li + across the SEI. Compared with a polycrystalline Li 3 N SEI obtained from conventional practice, the phase-pure/single crystalline Li 3 N-rich SEI constitutes an interphase of high mechanical strength and low Li + diffusion barrier. We elucidate the correlation among Li + transference number, diffusion behavior, concentration gradient, and the stability of the lithium metal electrode by integrating phase field simulations with experiments. We demonstrate improved reversibility and charge/discharge cycling behaviors for both symmetric cells and full lithium-metal batteries constructed with this Li 3 N-rich SEI. These studies may cast new insight into the design and engineering of an ideal artificial SEI for stable and high-performance lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Stable, high-performance, dendrite-free, seawater-based aqueous batteries

Metal anode instability, including dendrite growth, metal corrosion, and hetero-ions interference, occurring at the electrolyte/electrode interface of aqueous batteries, are among the most critical issues hindering their widespread use in energy storage. Herein, a universal strategy is proposed to overcome the anode instability issues by rationally designing alloyed materials, using Zn-M alloys as model systems (M = Mn and other transition metals). An in-situ optical visualization coupled with finite element analysis is utilized to mimic actual electrochemical environments analogous to the actual aqueous batteries and analyze the complex electrochemical behaviors. The Zn-Mn alloy anodes achieved stability over thousands of cycles even under harsh electrochemical conditions, including testing in seawater-based aqueous electrolytes and using a high current density of 80 mA cm –2 . The proposed design strategy and the in-situ visualization protocol for the observation of dendrite growth set up a new milestone in developing durable electrodes for aqueous batteries and beyond.

25 ENERGY STORAGE↗
DOE OSTI2020

Potassium Metal Batteries: Stable Potassium Metal Anodes with an All-Aluminum Current Collector through Improved Electrolyte Wetting (Adv. Mater. 49/2020)

An explorer is kayaking in uncharted territory, representing the exciting scientific pursuit of emerging metal batteries (MBs). Water is flowing smoothly over the jagged rocks, representing dendrite-free metal anodes as well as enhanced electrolyte wetting, both due to geometrical roughness. The electric eels underneath represent potassium-based energy storage, as they utilize potassium and sodium ions for electricity. In article number 2002908, Pengcheng Liu, David Mitlin, and co-workers present a route via improved electrolyte wetting toward stable potassium metal batteries with an all-aluminum current collector.

25 ENERGY STORAGE↗
DOE OSTI2021

Dendrite inhibiting electrolytes for metal-based batteries

A metal-based battery includes at least one metal electrode immersed within an electrolyte that includes: (1) an aprotic solvent; (2) a simple halogen containing material; and (3) optionally a metal salt that includes a complex halogen containing anion. The simple halogen containing material may include a metal halide salt that includes a metal cation selected from the group including but not limited to lithium and sodium metal cations. The metal halide salt may also include a halide anion selected from the group consisting of fluoride, chloride, bromide and iodide halide anions. The use of the metal halide salt within the metal-based battery provides enhanced cycling ability within the metal-based battery. Also contemplated are additional simple halogen containing material additives that may enhance cycling performance of a metal-based battery.

Archer, Lynden A.↗
DOE OSTI2023

Precise Tailoring of Lithium-Ion Transport for Ultralong-Cycling Dendrite-Free All-Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries can address crucial challenges regarding insufficient battery cycling life and energy density. The demonstration of long-cycling dendrite-free all-solid-state lithium metal batteries requires precise tailoring of lithium-ion transport of solid-state electrolytes (SSEs). Here, in this work, a proof of concept is reported for precise tailoring of lithium-ion transport of a halide SSE, Li 3 InCl 6 , including intragranular (within grains) but also intergranular (between grains) lithium-ion transport. Lithium-ion migration tailoring mechanism in crystals is developed by unexpected enhanced Li, In, and Cl vacancy populations and lower energy barrier for hopping. The lithium-ion transport tailoring mechanism between the grains is determined by the elimination of voids between grains and the formation of unexpected supersonic conducting grain boundaries, boosting the lithium dendrite suppression ability of SSE. Due to boosted lithium-ion conduction and dendrite-suppression ability, the all-solid-state lithium metal batteries coupled with Ni-rich LiNi 0.83 Co 0.12 Mn 0.05 O 2 cathodes and lithium metal anodes demonstrate breakthroughs in electrochemical performance by achieving extremely long cycling life at a high current density of 0.5 C (2000 cycles, 93.7% capacity retention). This concept of precise tailoring of lithium-ion transport provides a cost, time, and energy efficient solution to conquer the remaining challenges in all-solid-state lithium-metal batteries for fast developing electric vehicle markets.

25 ENERGY STORAGE↗
DOE OSTI2025

Chemo‐Mechanics Interplay Dictates Interface Instability and Asymmetry in Plating and Stripping of Sodium Metal Electrodes

Abstract The development of practical sodium (Na) metal batteries is hindered by key challenges including dendrite growth, dead metal formation, and unstable solid electrolyte interphase (SEI) growth. A fundamental understanding of the chemo‐mechanical interactions at the Na/SEI interface is critical for designing stable Na metal electrodes. In this work, the coupled electrochemical‐mechanical processes governing the morphological evolution and stability of Na metal during plating and stripping are investigated. The heterogeneous nature of transport and morphological interactions at the Na/SEI interface is revealed to result in nonuniform mechanical overpotentials and reaction fronts, eventually leading to Na filaments or pits. The spatio‐temporal evolution of stress heterogeneities during Na plating and stripping is shown to be asymmetric, manifesting in varying morphological nonuniformities and instability modes. The crucial role of external pressure in modulating the electrochemical‐transport interactions, the mechanical response of Na, and the localized reaction currents and stresses at the Na/SEI interface is demonstrated. At different external pressure conditions, the correlation between transport heterogeneities in the SEI and the onset and propagation of interface instability has been delineated. This work highlights the need for synergistic tailoring of external pressure and SEI heterogeneity toward achieving stable electrodeposition and dissolution in Na metal electrodes.

Singla, Aditya [School of Mechanical Engineering P↗
DOE OSTI2020

Stabilizing Dendritic Electrodeposition by Limiting Spatial Dimensions in Nanostructured Electrolytes.

The tendency of metals to form uncontrolled dendritic morphologies during electrodeposition hinders the development of safe and reliable metal batteries. Multiphase nanostructured electrolytes can suppress dendritic growth if the mechanical modulus of the electrolyte is high relative to that of the metal or if the conducting channels are confined to nanoscale dimensions. Direct visualization and analysis of electrodeposition within polymeric nanostructures elucidates the structure-property relationships and mechanisms underlying the suppression of dendrite growth. Here, we fabricate precisely structured multiphase films composed of nanochannels of a polymeric electrolyte in a background of nonconductive polymer on top of coplanar electrodes. The devices enable imaging and analysis of electrodeposition behavior as a function of channel width by scanning electron microscopy. We find that electrodeposition is confined to individual conductive channels and that radial propagation of the dendritic morphology is suppressed in channels for which the width is smaller than the characteristic dendritic nucleation size.

Sharon, Daniel↗
DOE OSTI2023

Long‐Life Lithium‐Metal Batteries with an Ultra‐High‐Nickel Cathode and Electrolytes with Bi‐Anion Activity

Abstract Anion chemistry in electrolytes can greatly dictate the nature and quality of passivation layers on both cathode and anode surfaces. This will be more significant when it comes to highly reactive Li‐metal anode and aggressive high‐nickel cathodes. Herein, a competitive bi‐anion activity is found in electrolytes with the co‐existence of two anions, which leads to a controlled Li‐salt decomposition kinetics and entirely favorable interphasial chemistry on both Li‐metal anode and ultrahigh‐nickel cathode. The proposed bi‐anion localized high‐concentration electrolytes are demonstrated to exhibit superior electrochemical compatibility toward Li metal and long‐term cycling stabilities under both 4.4 and 4.6 V in Li‐metal batteries with ultrahigh‐nickel cathode. This study sheds fresh light on dendrite‐free Li‐metal anodes and provides guidance to achieve high‐energy‐density batteries.

Chemistry↗
DOE OSTI2022

Stable Anode–Free All–Solid–State Lithium Battery through Tuned Metal Wetting on the Copper Current Collector

A stable anode-free all-solid-state battery (AF-ASSB) with sulfide-based solid-electrolyte (SE) (argyrodite Li 6 PS 5 Cl) is achieved by tuning wetting of lithium metal on “empty” copper current-collector. Lithiophilic 1 µm Li 2 Te is synthesized by exposing the collector to tellurium vapor, followed by in situ Li activation during the first charge. The Li 2 Te significantly reduces the electrodeposition/electrodissolution overpotentials and improves Coulombic efficiency (CE). During continuous electrodeposition experiments using half-cells (1 mA cm –2 ), the accumulated thickness of electrodeposited Li on Li 2 Te–Cu is more than 70 µm, which is the thickness of the Li foil counter-electrode. Full AF-ASSB with NMC811 cathode delivers an initial CE of 83% at 0.2C, with a cycling CE above 99%. Additionally, cryogenic focused ion beam (Cryo-FIB) sectioning demonstrates uniform electrodeposited metal microstructure, with no signs of voids or dendrites at the collector-SE interface. Electrodissolution is uniform and complete, with Li 2 Te remaining structurally stable and adherent. By contrast, an unmodified Cu current-collector promotes inhomogeneous Li electrodeposition/electrodissolution, electrochemically inactive “dead metal,” dendrites that extend into SE, and thick non-uniform solid electrolyte interphase (SEI) interspersed with pores. Density functional theory (DFT) and mesoscale calculations provide complementary insight regarding nucleation-growth behavior. Unlike conventional liquid-electrolyte metal batteries, the role of current collector/support lithiophilicity has not been explored for emerging AF-ASSBs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Sodium–Antimony–Telluride Intermetallic Allows Sodium-Metal Cycling at 100% Depth of Discharge and as an Anode-Free Metal Battery

In this work, repeated cold rolling and folding is employed to fabricate a metallurgical composite of sodium–antimony–telluride Na 2 (Sb 2/6 Te 3/6 Vac 1/6 ) dispersed in electrochemically active sodium metal, termed “NST-Na.” This new intermetallic has a vacancy-rich thermodynamically stable face-centered-cubic structure and enables state-of-the-art electrochemical performance in widely employed carbonate and ether electrolytes. NST-Na achieves 100% depth-of-discharge (DOD) in 1 m NaPF 6 in G2, with 15 mAh cm –2 at 1 mA cm –2 and Coulombic efficiency (CE) of 99.4%, for 1000 h of plating/stripping. Sodium-metal batteries (SMBs) with NST-Na and Na 3 V 2 (PO 4 ) 3 (NVP) or sulfur cathodes give significantly improved energy, cycling, and CE (>99%). An anode-free battery with NST collector and NVP obtains 0.23% capacity decay per cycle. Imaging and tomography using conventional and cryogenic microscopy (Cryo-EM) indicate that the sodium metal fills the open space inside the self-supporting sodiophilic NST skeleton, resulting in dense (pore-free and solid electrolyte interphase (SEI)-free) metal deposits with flat surfaces. The baseline Na deposit consists of filament-like dendrites and “dead metal”, intermixed with pores and SEI. Density functional theory calculations show that the uniqueness of NST lies in the thermodynamic stability of the Na atoms (rather than clusters) on its surface that leads to planar wetting, and in its own stability that prevents decomposition during cycling.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Surface diffusion manifestation in electrodeposition of metal anodes

Metal anode-based battery systems have been deemed indispensable towards energy storage renaissance engendering extensive research into strategies countering dendritic growth of metal electrodeposition. Fundamentally, the morphological evolution of a material is uniquely characterized by the heights of its self-diffusion barrier across multiple pathways. Herein, based on a coarse-grained kinetic Monte Carlo method, we derive insights into the nucleation and growth of metallic electrodeposits in liquid electrolytes, governed by surface self-diffusion characteristics cognizant of the diverse diffusion routes including terrace, away from step and interlayer pathways. We deconvolve the roles played by each of these surface diffusion mechanisms in conjunction with the electrochemical reaction rate on the deposition morphology regime (film vs. mossy vs. fractal). We identify interlayer diffusion as the predominant morphology-determining mechanism; dendrite-free deposition even at moderate current rates constrains this diffusion barrier to an upper limit. Additionally, we highlight subtle features amidst the realm of the morphological growth assortment that connect to the cell's electrochemical performance. Finally, we delineate morphological features of Li, Na, Mg and Al based on their respective surface diffusion barriers and applied overpotentials, and provide a baseline for the interpretation of experimental observations. This fundamental study sheds light on the mesoscale underpinnings of morphological variances in mono-valent and multi-valent metal electrodeposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

An Organic Carboxylate Host for Stable Sodium Metal Batteries

Sodium metal batteries (SMBs) hold great promise for the development of high-energy, sustainable energy storage solutions, but their practical deployment is hampered by unstable solid electrolyte interphases, uncontrollable sodium dendrite growth, and low Coulombic efficiency (CE) during repeated Na plating/stripping cycles. To address these challenges, we introduce an organic interlayer, containing perylenetetracarboxylic dianhydride sodium salt (Na4PT), on the surface of Cu current collector. This interlayer forms a sodiophilic organic interphase that lowers the nucleation barriers for sodium deposition and guides the formation of the interphase through polar carbonyl/carboxylate sites and a π-conjugated organic framework. A dendrite-free sodium metal anode is achieved using Na4PT coated Cu current collector. Under capacity-limited Na plating/stripping, Na||Na4PT@Cu half-cells deliver reversible capacities of 500 and 1,000 mAh g−1 at 0.1 and 1 A g−1 for 500 cycles with average CE above 99%. Post-cycling scanning electron microscopy and X-ray photoelectron spectroscopy measurements confirm that Na4PT@Cu promotes compact and uniform Na deposits and supports the formation of a stable interphase with reduced parasitic decomposition, directly correlating interfacial chemistry/morphology with high plating/stripping reversibility. These results highlight organic carboxylate coating as a practical interface engineering strategy for dendrite-free SMBs.

Chen, Chengxiang [University of Miami]↗
DOE OSTI2021

Understanding the Selective Deposition of Li Metal on Nonuniform Electrode Surfaces Using Atomic Force Microscopy

The use of lithium metal in secondary batteries has been impeded by its tendency to form dendrites: branching conductive structures of metal that can lead to capacity loss and, ultimately, internal shorts in the battery. Patterned electrodes, in addition to artificially increasing the current density of cells by increasing the surface area available for reaction, also generate a nonuniform electric field in the vicinity of the electrode surface. This nonuniform electric field, though rapidly screened by the electrolyte, can promote inhomogeneous deposition and Solid Electrolyte Interphase formation. As the consequence of these effects is not theoretically apparent since Solid Electrolyte Interphase volume and conductivity changes can, in principle, offset variations in local current density, we have performed experiments to examine the deposition of Li on nonuniform electrode surfaces using Atomic Force Microscopy. In this work, we measure the local variations in topography, SEI thickness, and composition, and discuss their implications for the formation of dendrites in Li metal.

25 ENERGY STORAGE↗
DOE OSTI2026

Self-Healing Lithium Dendrites through Spontaneous Passivating Layer Formation for Stable Solid-State Lithium–Metal Batteries

All-solid-state lithium–metal batteries have attracted significant attention, owing to their high energy density and superior safety. However, lithium–metal penetration through the solid electrolyte, leading to short-circuiting, remains a critical failure mode that demands comprehensive mitigation strategies. Most existing strategies are effective only prior to the initiation of lithium-dendrite formation and fail once dendrites begin to propagate through the electrolyte. In this study, we propose a self-healing mechanism in which the penetrated lithium reacts with a self-healing agent to form a passivating layer along the particle boundaries. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated into a Li 6 PS 5 Cl solid electrolyte as the self-healing agent to suppress lithium-dendrite propagation even after dendrite formation initiated under high current densities. The self-healing induced by LiTFSI was verified through comprehensive experimental analyses and was further demonstrated in a full-cell configuration. Moreover, LiTFSI incorporation plays an important role in increasing the critical current density by reducing the overall electronic conductivity of the solid electrolyte and facilitating the formation of a robust LiF-containing solid-electrolyte interphase.

25 ENERGY STORAGE↗
DOE OSTI2025

Understanding rate-dependent textured growth in zinc electrodeposition via high-throughput in situ x-ray diffraction

Zn-ion batteries with aqueous electrolytes are promising for large-scale energy storage as they are low-cost, environment-friendly and safe. The commercialization of Zn-ion batteries is hindered by several challenges such as the formation of detrimental Zn dendrites. High current density is previously thought to stimulate the dendritic growth of metals such as Li in electrodeposition. However, our study finds that for metallic Zn negative electrode in Zn-ion batteries, high-current deposition results in a dense and flat Zn layer with a (002) texture, which extends the cycling life. Low-current deposition, on the other hand, leads to a porous and dendritic morphology and a short cycling life. Using a synchrotron-based high-throughput in situ X-ray diffraction method we recently developed, Zn deposition under different conditions is systematically investigated, and a texture formation mechanism is proposed. Based on these findings, we suggest guidelines for designing cycling protocols that enable long-lasting Zn-ion batteries.

36 MATERIALS SCIENCE↗