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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 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma Sintering

Spark plasma sintering (SPS) has been successfully used to produce all-solid-state lithium-ion batteries (ASSLibs). Both regular and functionally graded electrodes are implemented into novel three-layer and five-layer battery designs together with solid-state composite electrolyte. The electrical capacities and the conductivities of the SPS-processed ASSLibs are evaluated using the galvanostatic charge-discharge test. Experimental results have shown that, compared to the three-layer battery, the five-layer battery is able to improve energy and power densities. Scanning electron microscopy (SEM) is employed to examine the microstructures of the batteries especially at the electrode–electrolyte interfaces. It reveals that the functionally graded structure can eliminate the delamination effect at the electrode–electrolyte interface and, therefore, retains better performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrochemical cleaning: An in-Situ method to reverse chromium poisoning in solid oxide fuel cell cathodes

Chromium poisoning is one of the primary factors that affect solid oxide fuel cell (SOFC) durability. In this study, an electrochemical cleaning method has been employed to reverse the effects of chromium poisoning. Two cells were fabricated and poisoned under identical conditions by operating them at 800°C in the presence of a Cr source. Both poisoned cells exhibited a significant reduction in maximum power density and an increase in polarization resistance. One of the poisoned cells, designated as the baseline cell, was cooled to room temperature after poisoning. Microstructural observation of the baseline cell showed significant contamination of the cathode active layer by chromium oxide and (Cr,Mn) spinel deposits. The other poisoned cell was electrochemically cleaned for two hours under a mild electrolytic condition. As a result of the electrochemical cleaning process, the chromium oxide deposits were substantially removed leading to a significant reduction of Cr concentration in the cathode, especially at the cathode/electrolyte interface. Furthermore, a substantial fraction of the cell performance loss was also reversed. To the best of our knowledge, this is a first demonstration of reversing the effects of chromium poisoning using a rapid in-situ process.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Lithium nitride coatings deposited by magnetron sputtering on sulfide electrolytes for solid-state batteries

Lithium nitrides have been considered as promising candidates for interfacial layers in solid-state lithium batteries (SSBs). Previously reported lithium nitride (Li 3 N) coatings were mostly prepared by the reaction between lithium metal and nitrogen gas, which makes it challenging for their thickness control and integration in SSBs. In this study, we prepare Li 3 N via magnetron sputtering for the first time, and apply the resulting coating directly on sulfide solid-state electrolyte. A much smaller impedance increase associated with improved cycling performance is observed in lithium metal symmetric cell. These results demonstrate the feasibility of depositing Li 3 N via magnetron sputtering and its application in SSBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Lithium‐Containing Hybrid SEI Layer Enabling High Mass Loading and Anode‐Less Sodium Metal Batteries

The continuous rupturing and rebuilding of unstable solid electrolyte interphase (SEI) layer during cycling would block Na + diffusion and induce Na dendrite formation, ultimately limiting the practical application of high-energy-density sodium metal batteries. Herein, a hybrid SEI layer containing Li-species is dexterously constructed on the surface of sodium metal anode. Li-containing inorganic components (Li 3 N, LiF, and Li 2 CO 3 ) are introduced to stabilize the Na/electrolyte interface and enhance the mechanical and diffusion kinetic properties of the SEI layer, which can reduce the side reactions and gas generation, regulate Na + flux during cycling and promote rapid Na + migration for uniform dendrite-free Na deposition. As a result, the constructed Na symmetric cells achieve low overpotential and long cycle life of 5900, 1800, and 500 h at current densities of 3, 10, and 30 mA cm −2 , respectively. Furthermore, the full cells paired with the Na₃V₂(PO₄)₃ cathode demonstrate high specific capacity and excellent cycle stability, even at an ultra-high cathode loading of 39.3 mg cm −2 and a low N/P ratio (negative/positive electrode capacity ratio of 1.21).

Diffusion kinetic↗
DOE OSTI2023

Coupling of Adhesion and Anti-Freezing Properties in Hydrogel Electrolytes for Low-Temperature Aqueous-Based Hybrid Capacitors

Solid-state zinc-ion capacitors are emerging as promising candidates for large-scale energy storage owing to improved safety, mechanical and thermal stability and easy-to-direct stacking. Hydrogel electrolytes are appealing solid-state electrolytes because of eco-friendliness, high conductivity and intrinsic flexibility. However, the electrolyte/electrode interfacial contact and anti-freezing properties of current hydrogel electrolytes are still challenging for practical applications of zinc-ion capacitors. Here, we report a class of hydrogel electrolytes that couple high interfacial adhesion and anti-freezing performance. The synergy of tough hydrogel matrix and chemical anchorage enables a well-adhered interface between hydrogel electrolyte and electrode. Meanwhile, the cooperative solvation of ZnCl 2 and LiCl hybrid salts renders the hydrogel electrolyte high ionic conductivity and mechanical elasticity simultaneously at low temperatures. More significantly, the Zn||carbon nanotubes hybrid capacitor based on this hydrogel electrolyte exhibits low-temperature capacitive performance, delivering high-energy density of 39 Wh kg –1 at –60 °C with capacity retention of 98.7% over 10,000 cycles. With the benefits of the well-adhered electrolyte/electrode interface and the anti-freezing hydrogel electrolyte, the Zn/Li hybrid capacitor is able to accommodate dynamic deformations and function well under 1000 tension cycles even at –60 °C. This work provides a powerful strategy for enabling stable operation of low-temperature zinc-ion capacitors.

25 ENERGY STORAGE↗
DOE OSTI2023

Revealing the effect of LiOH on forming a SEI using a Co magnetic “probe”

The solid-electrolyte-interphase (SEI) plays a critical role in lithium-ion batteries (LIBs) because of its important influence on electrochemical performance, such as cycle stability, coulombic efficiency, etc. Although LiOH has been recognized as a key component of the SEI, its influence on the SEI and electrochemical performance has not been well clarified due to the difficulty in precisely controlling the LiOH content and characterize the detailed interface reactions. Here, a gradual change of LiOH content is realized by different reduction schemes among Co(OH) 2 , CoOOH and CoO. With reduced Co nanoparticles as magnetic “probes”, SEI characterization is achieved by operando magnetometry. By combining comprehensive characterization and theoretical calculations, it is verified that LiOH leads to a composition transformation from lithium ethylene di-carbonate (LEDC) to lithium ethylene mono-carbonate (LEMC) in the SEI and ultimately results in capacity decay. This work unfolds the detailed SEI reaction scenario involving LiOH, provides new insights into the influence of SEI composition, and has value for the co-development between the electrode materials and electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2024

Using the Principals of Electrochemistry to Understand and Overcome the Complicated Degradation Mechanisms of Silicon Anodes in Lithium-Ion Batteries [Slides]

Battery technology is the most significant problem facing widespread market adoption of battery electric vehicles (BEVs). The low energy density of state-of-the-art lithium-ion electrode materials leaves BEV owners and prospective buyers with lower ranges than a comparable internal combustion engine (ICE) vehicle, and vulnerable to a nascent fast charging network. Silicon has the potential to increase the anode energy density by nearly ten times compared to the incumbent material (graphite) and make BEVs a more competitive transportation option. However, lithiated silicon is extremely reactive towards components of the electrolyte and forms a heterogeneous, complicated, and dynamic solid at its surface known as the solid electrolyte interphase (SEI). Ideally, the SEI would passivate the silicon surface, but continuous chemical degradation persists even when the battery is not operating. This reactivity reduces silicon anode lifetimes well below the necessary standards for BEVs. The NREL-led Silicon Consortium Project is dedicated to understanding and solving these mechanisms of degradation. Here, I will discuss an electrochemical method that provides deep insights into the silicon interface during battery operation. I will link these observations to fundamental electrochemical principals and how they translate into actionable strategies that extend the lifetime of silicon anodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Conversion Kinetics and Ionic Conductivity in Na-β”-Alumina + YSZ (Naβ”AY) Sodium Solid Electrolyte via Vapor Phase Conversion Process

Sodium ion batteries have been receiving increasing attention and may see potential revival in the near future, particularly in large-scale grid energy storage coupling with wind and solar power generation, due to the abundant sodium resources, low cost, and sufficiently high energy density. Among the known sodium ion conductors, the Na-β”-alumina electrolyte remains highly attractive because of its high ionic conductivity. This study focuses on the vapor phase synthesis of a Na-β”-Alumina + YSZ (Naβ”AY) composite sodium electrolyte, which has higher mechanical strength and stability than conventional single phase β”-Alumina. The objectives are the measurement of conversion kinetics through a newly developed weight-gain based model and the determination of sodium ionic conductivity in the composite electrolyte. Starting samples contained ~70 vol% α-Alumina and ~30 vol% YSZ (3 mol% Y 2 O 3 stabilized Zirconia) with and without a thin alumina surface layer made by sintering in air at 1600 °C. The sintered samples were placed in a powder of Na-β”-alumina and heat-treated at 1250 °C for various periods. Sample dimensions and weight were measured as a function of heat treatment time. The conversion of α-Alumina in the α-Alumina + YSZ composite into Naβ”AY occurred by coupled diffusion of sodium ions through Na-β”-alumina and of oxygen ions through YSZ, effectively diffusing Na2O. From the analysis of the time dependence of sample mass and dimensions, the effective diffusion coefficient of Na 2 O through the sample, D eff , was estimated to be 1.74 x 10 -7 cm2 s -1 , and the effective interface transfer parameter, k eff , was estimated as 2.33 x 10 -6 cm s -1 . By depositing a thin alumina coating layer on top of the bulk composite, the chemical diffusion coefficient of oxygen through single phase Na-β”-alumina was estimated as 4.35 x 10 -10 cm 2 s -1 . An AC impedance measurement was performed on a fully converted Naβ”AY composite, and the conductivity of the composite electrolyte was 1.3 x 10 -1 S cm -1 at 300 °C and 1.6 x 10 -3 S cm -1 at 25 °C, indicating promising applications in solid state or molten salt batteries at low to intermediate temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Voltage-Dependent First-Principles Barriers to Li Transport within Li-Ion Battery Solid Electrolyte Interphases

Charging a Li-ion battery requires Li-ion transport between the cathode and the anode. This Li-ion transport is dependent on (among other factors) the electrostatic environment that the ion encounters within the solid electrolyte interphase (SEI), which separates the anode from the surrounding electrolyte. A previous first-principles work has illuminated the reaction barriers through likely atomistic SEI environments but has had difficulty accurately reflecting the larger electrostatic potential landscape that an ion encounters moving through the SEI. In this work, we apply the recently developed quantum continuum approximation (QCA) technique to provide an equilibrium electronic potentiostat for first-principles interface calculations. Using QCA, we calculate the potential barrier for Li-ion transport through LiF, Li 2 O, and Li 2 CO 3 SEIs along with LiF–LiF and LiF–Li 2 O grain boundaries, all paired with Li metal anodes. Here, we demonstrate that the SEI potential barrier is dependent on the electrochemical potentials of the anode in each system. Finally, we use these techniques to estimate the change in the diffusion barrier for a Li ion moving in a LiF SEI as a function of the anode potential. We find that properly accounting for interface and electronic voltage effects significantly lowers reaction barriers compared with previous literature results.

25 ENERGY STORAGE↗
DOE OSTI2026

Unveiling the mechanism of lithium-mediated nitrogen reduction via operando X-ray scattering in a flow cell with hydrogen oxidation

The lithium-mediated nitrogen reduction reaction (Li-NRR) is currently the most promising strategy for electrochemical ammonia synthesis. In this study, we present an operando grazing incidence wide angle X-ray scattering (GI WAXS) investigation using an improved electrochemical flow cell that enables hydrogen oxidation at the anode and thereby eliminates the need of a sacrificial proton donor. The improved cell design also increases nitrogen availability and mass transport, achieving ammonia faradaic efficiencies (FEs) up to 36%. This setup allows direct analysis of reaction intermediates and the solid electrolyte interphase (SEI) using state-of-the-art diglyme-based electrolytes. We identify lithium amide (LiNH2) as the only stable, crystalline intermediate, providing direct insight into the Li-NRR mechanism. Notably, in diglyme-based electrolytes, the SEI composition differs significantly from that in tetrahydrofuran-based systems, with reduced LiF content and the formation of previously unreported crystalline diglyme–lithium salt complexes. These species likely influence ammonia selectivity and long-term stability. Our findings highlight how the electrolyte composition and cell architecture govern Li-NRR selectivity and efficiency, offering a foundation for the rational design of next-generation SEI layers and solid electrolytes to enable scalable electrochemical ammonia synthesis.

Deissler, Niklas H. [Technical Univ. of Denmark, L↗
DOE OSTI2024

Unraveling Morphology and Chemistry Dynamics in Fluoroethylene Carbonate Generated Silicon Anode Solid Electrolyte Interphase Across Delithiated and Lithiated States: Relative Cycling Stability Enabled by an Elastomeric Polymer Matrix

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ∼350% volume expansion. Understanding the SEI dynamic morphology and chemistry evolution from delithiated to lithiated states is thereby paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the dynamics of the FEC-SEI may provide hints toward engineering the Si interface. Herein, complementary ATR-FTIR, AFM, tip IR, and XPS probing reveal the presence of an elastomeric polycarbonate-like matrix in the FEC-generated SEI which is absent from the FEC-free SEI. Adding FEC to the baseline 1 M LiPF 6 in EC:EMC (1:1) electrolyte promotes formation of a thinner and more conformal SEI, and subdues morphology and chemistry changes between consecutive half-cycles. From AFM, morphological stabilization of the FEC-SEI occurs earlier. Furthermore, conventional SEI biproducts such as Li 2 CO 3 and LiEDC appear in reduced quantities in the FEC-SEI implying a reduced quantity of Li-consuming species. The thin polymeric FEC-SEI enables deeper (de)lithiation of silicon. In conclusion, the enhanced mechanical compliance, chemical invariance, and reduced Li inventory consumption of the FEC-SEI are logically the key features underlying the Si cycling enhancement by FEC.

25 ENERGY STORAGE↗
DOE OSTI2024

Binary Cation Matrix Electrolyte and Its Effect on Solid Electrolyte Interphase Suppression and Evolution of Si Anode

An unstable solid electrolyte interphase (SEI) has been recognized as one of the biggest challenges to commercializing silicon (Si) anodes for high-energy-density batteries. This work thoroughly investigates a binary cation matrix of Mg 2+ +Li + electrolyte and its role in SEI development, suppression, and evolution of a Si anode. Findings demonstrate that introducing Mg ions dramatically reduces the SEI growth before lithiation occurs, primarily due to the suppression of solvent reduction, particularly ethylene carbonate (EC) reduction. The Mg 2+ alters the Li + cation solvation environment as EC preferably participates in the oxophyllic Mg 2+ solvation sheath, thereby altering the solvent reduction process, resulting in a distinct SEI formation mechanism. The initial SEI formation before lithiation is reduced by 70% in the electrolyte with the presence of Mg 2+ cations. While the SEI continues to develop in the postlithiation, the inclusion of Mg ions results in an approximately 80% reduction in the postlithiation SEI growth. Continuous electrochemical cycling reveals that Mg 2+ plays a crucial role in stabilizing the deep-lithiated Si phases, which effectively mitigates side reactions, resulting in controlled SEI growth and stable interphase while eliminating complex Li x Si y formation. Mg ions promote the development of a notably more rigid and homogeneous SEI, characterized by a reduced dissipation (ΔD) in the Mg 2+ +Li + ion matrix compared to the solely Li + system. In conclusion, this report reveals how the Mg 2+ +Li + ion matrix affects the SEI evolution, viscoelastic properties, and electrochemical behavior at the Si interface in real time, laying the groundwork for devising strategies to enhance the performance and longevity of Si-based next-generation battery systems.

25 ENERGY STORAGE↗
DOE OSTI2026

Pressure Heterogeneity and Material Utilization in Thin-Film Solid-State Cathodes

Intimate interfacial contact between the solid electrolyte and the cathode active material is critical for maximizing cathode utilization in solid-state batteries. However, volume changes during electrochemical cycling induce internal stresses that drive interfacial degradation, particularly under nonuniform stack pressure. In this study, we employ in situ energy-dispersive X-ray diffraction tomography to visualize and quantify reaction heterogeneities across a 3 mm-diameter solid-state cathode with a well-defined interface. Our results reveal that regions under a lower stack pressure exhibit reduced material utilization and reversibility, which negatively affect the high-pressure regions. Interfacial degradation further impedes lithium-ion transport and amplifies microscale reaction heterogeneity. These findings highlight the critical role of stack pressure distribution in governing interfacial stability and electrochemical performance, offering important design insights into practical solid-state battery systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electrolyte-Assisted Hydrogen Cycling in Lithium and Sodium Alanates at Low Pressures and Temperatures

An investigation of electrolyte-assisted hydrogen storage reactions in complex aluminum hydrides (LiAlH4 and NaAlH4) reveals significantly reduced reaction times for hydrogen desorption and uptake in the presence of an electrolyte. LiAlH4 evolves ~7.8 wt% H2 over ~3 h in the presence of a Li-KBH4 eutectic at 130 °C compared to ~25 h for the same material without the electrolyte. Similarly, NaAlH4 exhibits 4.8 wt% H2 evolution over ~4 h in the presence of a diglyme electrolyte at 150 °C compared to 4.4 wt% in ~15 h for the same material without the electrolyte. These reduced reaction times are composed of two effects, an increase in reaction rates and a change in the reaction kinetics. While typical solid state dehydrogenation reactions exhibit kinetics with rates that continuously decrease with the extent of reaction, we find that the addition of an electrolyte results in rates that are relatively constant over the full desorption window. Fitting the kinetics to an Avrami-Erofe’ev model supports these observations. The desorption rate coefficients increase in the presence of an electrolyte, suggesting an increase in the velocities of the reactant-product interfaces. In addition, including an electrolyte increases the growth parameters, primarily for the second desorption steps, resulting in the observed relatively constant reaction rates. Similar effects occur upon hydrogen uptake in NaH/Al where the presence of an electrolyte enables hydrogenation under more practical low temperature (75 °C) and pressure (50 bar H2) conditions.

25 ENERGY STORAGE↗
NASA NTRS1989

Thin metal electrode for AMTEC

An electrode having higher power output is formed of a thin, porous film (less than 1 micrometer) applied to a beta-alumina solid electrolyte (BASE). The electrode includes an open grid, current collector such as a series of thin, parallel, grid lines applied to the thin film and a plurality of cross-members such as loop of metal wire surrounding the BASE tube. The loops are electrically connected by a bus wire. The overall impedance of the electrode considering both the contributions from the bulk BASE and the porous electrode BASE interface is low, about 0.5 OHM/cm.sup.2 and power densities of over 0.3 watt/cm.sup.2 for extended periods.

Williams, Roger M.↗
DOE OSTI2023

Interface Design for High‐Performance All‐Solid‐State Lithium Batteries

All‐solid‐state batteries suffer from high interface resistance and lithium dendrite growth leading to low Li plating/stripping Coulombic efficiency (CE) of <90% and low critical current density at high capacity. Here, in this work, both challenges are simultaneously addressed and the Li plating/stripping CE is significantly increased to 99.6% at 0.2 mA cm −2 /0.2 mAh cm −2 , and critical current density (CCD) of > 3.0 mA cm −2 /3.0 mAh cm −2 by inserting a mixed ionic‐electronic conductive (MIEC) and lithiophobic LiF‐C‐Li 3 N‐Bi nanocomposite interlayer between Li 6 PS 5 Cl electrolyte and Li anode. The highly lithiophobic LiF‐C‐Li 3 N‐Bi interlayer with high ionic conductivity (10 −5 S cm −1 ) and low electronic conductivity (3.4×10 −7 S cm −1 ) enables Li to plate on the current collector (CC) surface rather than on Li 6 PS 5 Cl surface avoiding Li 6 PS 5 Cl electrolyte reduction. During initial Li plating on CC, Li penetrates into porous LiF‐C‐Li 3 N‐Bi interlayer and lithiates Bi nanoparticles into Li 3 Bi. The lithiophilic Li 3 Bi and Li 3 N nanoparticles in LiF‐C‐Li 3 N‐Li 3 Bi sub‐interlayer will move to CC along with plated Li, forming LiF‐C/Li 3 N‐Li 3 Bi lithiophobic/lithiophilic sublayer during the following Li stripping. This interlayer enables Co 0.1 Fe 0.9 S 2 /Li 6 PS 5 Cl/Li cell with an areal capacity of 1.4 mAh cm −2 to achieve a cycle life of >850 cycles at 150 mA g −1 . The lithiophobic/lithiophilic interlayer enables solid‐state metal batteries to simultaneously achieve high energy and long cycle life.

25 ENERGY STORAGE↗
DOE OSTI2020

Intrinsic chemical reactivity of solid-electrolyte interphase components in silicon–lithium alloy anode batteries probed by FTIR spectroscopy

Herein we report the solid reaction products from the chemical reaction of aprotic battery electrolyte and three purported components of the Si-based anode SEI : SiO 2 nanoparticles (NPs), lithium silicate (Li x SiO y ) powders, and Si NPs. We use FTIR and classical molecular dynamics/density functional perturbation theory to assess the solid products remaining with these model materials after exposure to electrolyte. The absence of electrochemical bias provides a view of the chemical speciation resulting from early-stage chemical reactivity during battery assembly as well as under open circuit storage conditions. We believe these species represent the initial stages of SEI growth and predict they likely drive subsequent chemical and electrochemical reactions by controlling molecular interactons at the Si active material interface. We find that nominally equivalent materials react differently even before any electrochemistry is performed (e.g., acidic SiO 2 dissolves whereas alkaline SiO 2 is relatively robust), and derive new understanding of the chemical species that could and could not form stable SEI components in Si-based anodes. These results can be used to inform how to passivate Si anode surfaces and potentially generate an artificially engineered SEI that would be stable and enable next-generation battery anodes.

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

Operating Stresses and Their Effects on Degradation of LSM-Based SOFC Cathodes

The performance of solid oxides fuel cells (SOFCs) with four different Mn excess of lanthanum strontium manganite (LSM) -based cathodes were examined under different temperatures (1,000 °C, 900 °C), current densities (0, 380, and 760 mA cm -2 ), and cathode atmospheres (p O 2 )=0.1,0.15,0.21) for durations ranging from 58 to 1,008 h. Each yttria-stabilized zirconia (YSZ) electrolyte-supported “button” cell had a porous Ni/YSZ composite anode and a porous LSM/YSZ composite cathode. The cells’ output voltage versus time were recorded and electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) measurements were performed every 24 hours. The total area specific resistance (ASR) was calculated from these measurements. The values of ASR from both EIS and LSV were comparable between each other but lower than that from durability test. Distribution of relaxation times (DRT) analysis was performed to investigate the electrochemical processes and their corresponding relaxation frequencies as well as their attributions to the total ASR. The series resistance and parallel resistance that obtained from the equivalent circuit fit of the Nyquist plot were higher at low temperature and low p O 2 regardless of LSM compositions. The area of the peaks derived from DRT analysis increased with time during individual tests. The microstructures of the tested cells were examined using scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM/EDS). Manganese oxide particles were observed near the cathode-electrolyte interface after prolonged (1,008 h) testing in air of a cell with LSM of 11% manganese excess, and after a short test (58 h) under low oxygen (p O 2 = 0.10) in a cell with LSM of 5% manganese excess. However, the role of MnOx in cell degradation is still unknown.

08 HYDROGEN↗