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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Achieving Highly Reproducible Results in Graphite-based Li-ion Full Coin Cells

Electrode materials, cathodes or anodes, are mostly evaluated in half coin cells where lithium (Li) metal is used. However, due to the instability nature of Li metal, the cycling performances of the half cells is more likely reflecting Li anode stability instead of the coupled electrodes, questioning the conclusions. Full coin cells utilizing graphite as the anode effectively assesses materials. But the key factors of preparing full coin cells with reproducible performances have rarely been discussed and overlooked leading to many inconsistent results. This work discusses the scientific gap between cell preparation and observed electrochemical performances to unveil the key parameters for achieving consistent and reliable results in full coin cells, critical for effective evaluation of any new materials tested under relevant conditions. The knowledge from this work is broadly applicable in other full cells systems such as Si-based full cells or Na-ion batteries.

Hu, Jiangtao↗
DOE OSTI2025

Ambient Rare Earth Metal Electrodeposition in Nitrogen-Coordinated Silylamide Electrolyte

The transition to a sustainable, low-carbon economy demands energy-efficient and environmentally benign methods for rare earth metal (REM) production. Furthermore, while high-temperature molten salt electrolysis remains energy-intensive, corrosive, and environmentally unfriendly, emerging room-temperature processes based on conventional ionic liquids are also hindered by high viscosity and chemical instability. In this study, a nitrogen-coordinated, water-, oxygen-, and fluorine-free silylamide-based electrolyte is presented as a promising system for room-temperature REM electrodeposition. Derived from commercially available lithium silylamide precursors, the system enables facile synthesis, broad electrochemical stability, and tunable metal–ligand interactions. Electrochemical analysis reveals high voltammetric stripping reversibility, stable cathodic and anodic potentials, and selective neodymium (Nd) deposition at appreciable current densities (>1 mA/cm 2 ), with minimal parasitic reactions. Bulk experiments produced high-purity Nd with reproducible performance across multiple batches. Scaled deposition yielded over 1 g of Nd with near-theoretical mass efficiency (0.40 mg/C) and >90% purity. Using sacrificial dysprosium (Dy) and Nd metal anodes, the system maintained constant Nd loading during extended deposition and enabled cathodic codeposition of stripped anode material, demonstrating the electrolyte’s dual functionality for REM electrorefining. Collectively, this silylamide platform offers a compelling combination of electrochemical robustness, chemical resilience, and process scalability for sustainable ambient REM recovery.

36 - MATERIALS SCIENCE↗
DOE OSTI2024

Acidity-Governed Rules in the Electrochemical Performance of Fluorinated Benzenes for High-Voltage Lithium Metal Batteries

Judicious selection of the optimal fluorobenzene (FB) as a nonsolvating cosolvent for lithium metal batteries (LMBs) is reported. For this work, we found the key correlation between FB structures and cycling stabilities of cells: increased fluorine substitution of FBs results in higher anodic stability but at the expense of reduced reductive stability, and FBs containing three or more fluorine atoms exhibit insufficient anodic stability in the electrolyte system comprised of fluoroethylene carbonate (FEC) and ethyl methyl carbonate (EMC). More importantly, FBs with higher acidity (lower pK a ) due to protons located between two adjacent fluorine atoms tend to be more susceptible to side reactions during cycling. Our results indicate that difluorobenzenes with no “acidic” proton (DFB2 and DFB4) have emerged as the optimal choice with the desired redox stability in high-voltage LMBs. Nuclear magnetic resonance and X-ray photoelectron spectroscopy confirmed these findings, providing guidance for selecting the most suitable FB variants as nonsolvating cosolvents for high-voltage LMBs.

25 ENERGY STORAGE↗
DOE OSTI2024

SEI Formation and Lithium-Ion Electrodeposition Dynamics in Lithium Metal Batteries via First-Principles Kinetic Monte Carlo Modeling

The stabilization and enhanced performance of lithium metal batteries (LMBs) depend on the formation and evolution of the Solid Electrolyte Interphase (SEI) layer as a critical component for regulating the Li metal electrodeposition processes. This study employs a first-principles kinetic Monte Carlo (kMC) model to simulate the SEI formation and Li + electrodeposition processes on a lithium metal anode, integrating both the electrochemical electrolyte reduction reactions and the diffusion events giving place to the SEI aggregation processes during battery charge and discharge processes. The model replicates the competitive interactions between organic and inorganic SEI components, emphasizing the influence of the cycling regime. Results indicate that grain boundaries within the SEI facilitate faster lithium-ion transport compared to crystalline regions, crucial for improving the performance and stability of LMBs. The findings underscore the importance of dynamic SEI modeling for further development of next-generation high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Accommodation of Silicon in an Interconnected Copper Network for Robust Li-Ion Storage

Silicon (Si)-based materials are one of the most promising anodes to be applied in rechargeable lithium ion batteries. However, the active Si/electrolyte interface causes continuous side reactions and poor conductivity, which significantly decreases the cycling stability. Cu is the only metallic current collector that has been known to promote electron conduction and lithium-ion transfer without alloying reaction occurrence. However, to the best current knowledge, scalable interface engineering incorporating Cu has not been reported. In this study, this conductive Cu interface (CCI) is constructed through a self-assembly carbothermic reduction method to achieve efficient protection of Si/electrolyte interfaces while allowing for fast Li + diffusion. The energy barrier of lithium-ion diffusion through Cu is calculated to be 0.1965 eV, which is much lower than that through Au, Fe, and Ni films. Benefiting from the enhanced interfacial protection and kinetics of Si with CCI, a fading rate of only 0.068% is maintained for 1000 cycles and an aerial capacity of 4.78 mAh cm -2 is achieved after 280 cycles, which is comparable to the industry standards required for practical application.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Rejuvenating dead lithium supply in lithium metal anodes by iodine redox

Inactive lithium (more frequently called dead lithium) in the forms of solid-electrolyte interphase and electrically isolated metallic lithium is principally responsible for the performance decay commonly observed in lithium metal batteries. A fundamental solution of recovering dead lithium is urgently needed to stabilize lithium metal batteries. In this paper, we quantify the solid-electrolyte interphase components, and determine their relation with the formation of electrically isolated dead lithium metal. We present a lithium restoration method based on a series of iodine redox reactions mainly involving I 3 - /I - . Using a biochar capsule host for iodine, we show that the I 3 - /I - redox takes place spontaneously, effectively rejuvenating dead lithium to compensate the lithium loss. Through this design, a full-cell using a very limited lithium metal anode exhibits an excellent lifespan of 1,000 cycles with a high Coulombic efficiency of 99.9%. We also demonstrate the design with a commercial cathode in pouch cells. Cycling lithium batteries often results in inactive lithium that no longer participates in redox reactions, leading to performance deterioration. Here the authors use an iodic species to react with inactive lithium, bringing it back to life and thus making batteries last longer.

25 ENERGY STORAGE↗
DOE OSTI2023

Topology-enhanced mechanical stability of swelling nanoporous electrodes

Abstract Materials like silicon and germanium offer a 10-fold improvement in charge capacity over conventional graphite anodes in lithium-ion batteries but experience a roughly threefold volume increase during lithiation, which challenges ensuring battery integrity. Nanoporous silicon, created by liquid-metal-dealloying, is a potentially attractive anode design to mitigate this challenge, exhibiting both higher capacity and extended cycle lifetimes. However, how nanoporous structures accommodate the large volume change is unknown. Here, we address this question by using phase-field modeling to produce nanoporous particles and to investigate their elastoplastic swelling behavior and fracture. Our simulations show that enhanced mechanical stability results from the network topology consisting of ligaments connected by bulbous, sphere-like nodes. The ligaments forcefully resist elongation while the nodes, behaving like isolated spherical particles, experience large stresses driving fracture. However, being smaller compared to a sphere of the same volume as the entire nanoporous particle, the nodes are more protected against fracture.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Rational Design of Weakly‐Solvating Molecules for Salt‐In‐Pre‐Ionic‐Liquid Electrolytes for Li Metal Batteries

Lithium metal batteries (LMBs) promise step‐changes in energy densities but suffer from poor cycle life due to unstable electrolyte‐lithium interfaces. Conventional carbonate electrolytes exhibit excessive lithium‐ion solvation and low oxidative stability, leading to rapid capacity loss. Herein, we report a rationally designed weakly‐solvating cyclic sulfonamide, 1‐trifluoromethanesulfonyl)amide pyrrolidine (TFMSPyr), which integrates an electron‐withdrawing trifluoromethanesulfonyl functional group at pyrrolidinic‐N. TFMSPyr acts as a pre‐ionic‐liquid solvent that forms intrinsically localized, anion‐dominated solvation, coupling molecular architecture, solvation topology, and transport dynamics. As a result, LiFSI based salt‐in‐pre‐ionic‐liquid (SIPIL) electrolytes exhibit high lithium‐ion transference number, oxidative stability > 5 V versus Li/Li + and anion‐derived solid electrolyte interphases (SEI). Li||Cu cells with SIPIL deliver a first cycle Coulombic efficiency (CE) of ≈ 99% with average CE of 99.2% for 100 cycles, and lithium half‐cells with lithium iron phosphate (LFP) cathode exhibit 82% capacity retention after 400 cycles with CE of 99.98%. In anode‐free full cells, 95% of initial capacity is retained after 63 cycles with an average CE of 99.5%. These results demonstrate that molecular engineering of solvents offers a powerful pathway to stabilize lithium metal interfaces and enable practical Anodeless LMBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Molecular Layer Deposition of Crosslinked Polymeric Lithicone for Superior Lithium Metal Anodes

In this work, we for the first time developed a novel lithium-containing crosslinked polymeric material, a lithicone that enables excellent protection effects over lithium (Li) metal anodes. This new lithicone was synthesized via an accurately controllable molecular layer deposition (MLD) process, in which lithium tert -butoxide (LTB) and glycerol (GL) were used as precursors. The resultant LiGL lithicone was analyzed using a suite of characterizations. Furthermore, we found that the LiGL thichicone could serve as an exceptional polymeric protection film over Li metal anodes. Our experimental data revealed that the Li electrodes coated by this LiGL lithicone can achieve a superior cycling stability, accounting for an extremely long cyclability of >13,600 Li-stripping/plating cycles and having no failures so far in Li/Li symmetric cells at a current density of 5 mA/cm 2 and an areal capacity of 1 mAh/cm 2 . We found that, with a sufficient protection by this LiGL coating, Li electrodes could realize long-term stable cyclability with little formation of Li dendrites and solid electrolyte interphase. This novel LiGL represents a facile and effective solution to the existing issues of Li anodes and potentially paves a technically feasible route for lithium metal batteries.

Meng, Xiangbo↗
DOE OSTI2025

Interlayer Design for Halide Electrolytes in All‐Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state lithium‐metal batteries (ASSLMBs) are promising for transportation electrification due to their superior safety and high energy density. Lithium halide electrolytes provide excellent processing flexibility, high ionic conductivity, and anodic stability (>4.1 V), making them highly compatible with high‐voltage cathodes, surpassing sulfide electrolytes (<2.1 V). Nevertheless, halide electrolytes suffer from low cathodic stability and form an electronically conductive interphase with lithium, resulting in a critical current density (CCD) of nearly zero. Herein, Li 3 YbCl 6 electrolytes are synthesized that are kinetically stable with lithium by forming an electronic insulating solid electrolyte interphase. Guided by critical overpotential criteria, a PI 3 interlayer is designed that transforms into Li 6 PI 3 upon contact with lithium, substantially reducing the interfacial resistance of Li 3 YbCl 6 against lithium to 34 Ω and achieving a high critical overpotential of 114 mV. By substituting Yb with Lu, Li 3 LuCl 6 electrolytes with Li 6 PI 3 interlayers reach a CCD of 1.0 mA cm −2 at a capacity of 1.0 mAh cm −2 , comparable to sulfide electrolytes but with higher oxidation stability. Additionally, Li 6 PI 3 enables stable cycling of Li//Li cells with Li 3 LuCl 6 electrolytes at 0.5 mA cm −2 for 400 cycles and maintains 86.5% capacity in Li//LiCoO 2 cells after 220 cycles at 30 °C, paving the way for high‐performance ASSLMBs.

Chemistry↗
DOE OSTI2023

Phase engineering of layered anode materials during ion-intercalation in Van der Waal heterostructures

Transition metal dichalcogenides (TMDs) are a class of 2D materials demonstrating promising properties, such as high capacities and cycling stabilities, making them strong candidates to replace graphitic anodes in lithium-ion batteries. However, certain TMDs, for instance, MoS 2 , undergo a phase transformation from 2H to 1T during intercalation that can affect the mobility of the intercalating ions, the anode voltage, and the reversible capacity. In contrast, select TMDs, for instance, NbS 2 and VS 2 , resist this type of phase transformation during Li-ion intercalation. This manuscript uses density functional theory simulations to investigate the phase transformation of TMD heterostructures during Li-, Na-, and K-ion intercalation. The simulations suggest that while stacking MoS 2 layers with NbS 2 layers is unable to limit this 2H → 1T transformation in MoS 2 during Li-ion intercalation, the interfaces effectively stabilize the 2H phase of MoS 2 during Na- and K-ion intercalation. However, stacking MoS 2 layers with VS 2 is able to suppress the 2H → 1T transformation of MoS 2 during the intercalation of Li, Na, and K-ions. The creation of TMD heterostructures by stacking MoS 2 with layers of non-transforming TMDs also renders theoretical capacities and electrical conductivities that are higher than that of bulk MoS 2 .

25 ENERGY STORAGE↗
DOE OSTI2025

Fine‐Tuning Li‐Ion Solvation Structure by Enhanced Solvent‐Diluent Interactions for Long‐Cycling Lithium Metal Batteries

Achieving durable lithium (Li) metal anodes in liquid electrolytes remains challenging, primarily due to the instability of the formed solid-electrolyte interphases (SEIs). Modulating the Li-ion solvation structures is pivotal in forming a stable SEI for stabilizing Li metal anodes. Here a strategy is developed to fine-tune the Li-ion solvation structures through enhanced dipole–dipole interactions between the Li-ion-coordinated solvent and the non-Li-ion-coordinating diluent, for creating a stable SEI in the developed binary salt electrolyte. The enhanced dipole–dipole interactions weaken the coordination between Li-ions and the solvents while strengthening the interaction between Li-ions and dual anions, thereby facilitating the Li-ion transport and a robust anion-derived SEI with a distinct bilayer structure. Consequently, the developed electrolyte exhibited exceptional electrochemical performance in high energy-density Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cells, with long calendar life, stable cyclability at 1 C, and reliable operation between 25 and −20 °C, and it also demonstrat remarkable cycling stability for a Li||NMC811 pouch cell with projected energy density of 402 Wh kg −1 , maintaining 80% capacity retention over 606 cycles under practical conditions.

25 ENERGY STORAGE↗
DOE OSTI2020

A High-Rate Aqueous Proton Battery Delivering Power Below -78 °C via an Unfrozen Phosphoric Acid

Lithium-sulfur batteries are attractive for automobile and grid applications due to their high theoretical energy density and the abundance of sulfur. Despite the significant progress in cathode development, lithium metal degradation and the polysulfide shuttle remain two critical challenges in the practical application of Li-S batteries. Development of advanced electrolytes has become a promising strategy to simultaneously suppress lithium dendrite formation and prevent polysulfide dissolution. Here, a new class of concentrated siloxane-based electrolytes, demonstrating significantly improved performance over the widely investigated ether-based electrolytes are reported in terms of stabilizing the sulfur cathode and Li metal anode as well as minimizing flammability. Through a combination of experimental and computational investigation, it is found that siloxane solvents can effectively regulate a hidden solvation-ion-exchange process in the concentrated electrolytes that results from the interactions between cations/anions and solvents. As a result, it could invoke a quasi-solid-solid lithiation and enable reversible Li plating/stripping and robust solid-electrolyte interphase chemistries. The solvation-ion-exchange process in the concentrated electrolytes is a key factor in understanding and designing electrolytes for other high-energy lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Highly Conductive Polyoxanorbornene‐Based Polymer Electrolyte for Lithium‐Metal Batteries

Abstract This present study illustrates the synthesis and preparation of polyoxanorbornene‐based bottlebrush polymers with poly(ethylene oxide) (PEO) side chains by ring‐opening metathesis polymerization for solid polymer electrolytes (SPE). In addition to the conductive PEO side chains, the polyoxanorbornene backbones may act as another ion conductor to further promote Li‐ion movement within the SPE matrix. These results suggest that these bottlebrush polymer electrolytes provide impressively high ionic conductivity of 7.12 × 10 −4 S cm −1 at room temperature and excellent electrochemical performance, including high‐rate capabilities and cycling stability when paired with a Li metal anode and a LiFePO 4 cathode. The new design paradigm, which has dual ionic conductive pathways, provides an unexplored avenue for inventing new SPEs and emphasizes the importance of molecular engineering to develop highly stable and conductive polymer electrolytes for lithium‐metal batteries (LMB).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tailoring Interfaces in Solid-State Batteries Using Interfacial Thermochemistry and Band Alignment

Solid-state lithium ion batteries have enhanced thermal stability compared to batteries using liquid electrolytes. Although their practical implementation is limited by undesired side reactions between the electrode and electrolyte, different modification strategies have been proposed to stabilize these reactive interfaces. These approaches have been primarily based upon bulk materials properties, however, which may not necessarily be representative of the chemistry at the solid/solid interface. In this work, first principles calculations and X-ray scattering experiments are used to elucidate molecular-level reactivity and develop design principles for tailored interfaces based on surface and interfacial properties. Because of its well-known instability, the interface between the Li metal anode and the lithium lanthanum titanate (LLTO) solid electrolyte is applied as a model system. Density functional theory calculations are used to describe bulk, surface, and interfacial thermochemistry of the Li/LLTO system, and interfacial reconstruction is probed using ab initio molecular dynamics. These simulations of the Li/LLTO interface demonstrate facile decomposition concomitant with reduction of Ti 4+ ions. Based on further insights from computational analysis of the surface band edge positions, La 2 O 3 is proposed as an interlayer coating and is shown to provide an energetic barrier for interfacial charge transfer and decomposition reactions from X-ray reflectivity measurements and theoretical calculations. The findings in this work suggest that design strategies based on surface and interfacial properties can be used to kinetically stabilize electrode/electrolyte interfaces in solid-state batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Abstract Spinel‐type LiNi 0.5 Mn 1.5 O 4 (LNMO) is one of the most promising 5 V‐class cathode materials for Li‐ion batteries that can achieve high energy density and low production costs. However, in liquid electrolyte cells, the high voltage causes continuous cell degradation through the oxidative decomposition of carbonate‐based liquid electrolytes. In contrast, some solid‐state electrolytes have a wide electrochemical stability range and can withstand the required oxidative potential. In this work, a thin‐film battery consisting of an LNMO cathode with a solid lithium phosphorus oxynitride (LiPON) electrolyte is tested and their interface before and after cycling is characterized. With Li metal as the anode, this system can deliver stable performance for 600 cycles with an average Coulombic efficiency >99%. Neutron depth profiling indicates a slight overlithiated layer at the interface prior to cycling, a result that is consistent with the excess charge capacity measured during the first cycle. Cryogenic electron microscopy further reveals intimate contact between LNMO and LiPON without noticeable structure and chemical composition evolution after extended cycling, demonstrating the superior stability of LiPON against a high voltage cathode. Consequently, design guidelines are proposed for interface engineering that can accelerate the commercialization of a high voltage cell with solid or liquid electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2026

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↗
DOE OSTI2020

A polymeric composite protective layer for stable Li metal anodes

Lithium (Li) metal is a promising anode for high-performance secondary lithium batteries with high energy density due to its highest theoretical specific capacity and lowest electrochemical potential among anode materials. However, the dendritic growth and detrimental reactions with electrolyte during Li plating raise safety concerns and lead to premature failure. Herein, we report that a homogeneous nanocomposite protective layer, prepared by uniformly dispersing AlPO 4 nanoparticles into the vinylidene fluoride-co-hexafluoropropylene matrix, can effectively prevent dendrite growth and lead to superior cycling performance due to synergistic influence of homogeneous Li plating and electronic insulation of polymeric layer. The results reveal that the protected Li anode is able to sustain repeated Li plating/stripping for >750 cycles under a high current density of 3 mA cm -2 and under a practical specific capacity of 2 mAh cm -2 . Moreover, full-cell Li-ion battery is constructed by using LiFePO 4 and protected Li as a cathode and anode, respectively, rendering a stable capacity after 400 charge/discharge cycles. The current work presents a promising approach to stabilize Li metal anodes for next-generation Li secondary batteries.

25 ENERGY STORAGE↗