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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 91 records · Page 5

Assessing the coating implications of slurry formulations in NCMA and LFMP blend cathodes for lithium-ion batteries

This paper investigates the implications of slurry formulations and electrode processing on the performance of lithium-ion battery (LIB) cathodes, focusing on Nickel Cobalt Manganese Aluminum (NCMA) and Lithium Ferro Manganese Phosphate (LFMP) blends. Through a comprehensive examination of electrode processing steps, from material selection to coating application, we elucidate the critical role of processing parameters in shaping electrode morphology and electrochemical behavior. Rheological studies reveal the influence of slurry composition on viscosity and flow behavior, highlighting the importance of achieving optimal rheological properties for uniform coating deposition. Electrochemical characterization, including cyclic voltammetry and rate capability tests, unveils the electrochemical behavior of NCMA, LFMP, and their blend, showcasing the synergistic effects of material blending on battery performance. In conclusion, our findings underscore the intricate relationship between slurry formulation, electrode processing, and LIB performance, offering valuable insights for the design and optimization of high-performance electrode materials for next-generation batteries.

25 ENERGY STORAGE↗

High-Energy and High-Power NMP-Free, Designer NMC 811 Cathodes with Ultra-Thick Architectures Processed by Electrophoretic Deposition

This project focused on electrode engineering and reducing the weight of inactive components in the battery cells. Additionally, the project focused on optimizing the ‘electrophoretic deposition’ technique developed by PPG industries for aqueous processing of electrodes. During this project team has screened several binders suitable for electrophoretic deposition of electrodes. Additionally, we developed a nice strategy to deposit a low cost and scalable oxide coating on the surface of cathode materials. ORNL team performed the research under this CRADA at DOE’s Battery Manufacturing Facility (BMF) at ORNL.

99 GENERAL AND MISCELLANEOUS↗

High-Energy and High-Power NMP-Free, Designer NMC 811 Cathodes with Ultra-Thick Architectures Processed by Electrophoretic Deposition

This project focused on electrode engineering and reducing the weight of inactive components in the battery cells. Additionally, the project focused on optimizing the ‘electrophoretic deposition’ technique developed by PPG industries for aqueous processing of electrodes. During this project team has screened several binders suitable for electrophoretic deposition of electrodes. Additionally, we developed a nice strategy to deposit a low cost and scalable oxide coating on the surface of cathode materials. ORNL team performed the research under this CRADA at DOE’s Battery Manufacturing Facility (BMF) at ORNL.

25 ENERGY STORAGE↗

Promoting electrochemical rates by concurrent ionic-electronic conductivity enhancement in high mass loading cathode electrode

Enhancing the fast charging capacity of thick electrodes with high mass loading is imperative in expediting the widespread adoption of electric vehicles. Nonetheless, the insufficient charge transfer kinetics of thick electrodes hinder the movement of effective electrons and ions, hence diminishing capacity at high current rates. In this work, we applied sustainable and biodegradable cellulose nanocrystals (CNCs) as electrode additives. It is the first time to simultaneously improve the electronic conductivity by optimizing the carbon dispersion and establishing electron transfer networks, as well as boosting the ionic conductivity of electrodes by shortening the ion transfer pathway. Specifically, the LiNi 0.6 Mn 0.2 Co 0.2 O 2 electrodes incorporating 1% dual functional CNCs additive exhibit improved effective electrical conductivity from 0.11 to 0.16 S/m and risen effective ionic conductivity from 0.36 to 0.62 S/m, in comparison to counterpart electrodes without CNCs. Therefore, the 1% CNC electrode with a high mass loading of 27.0 mg/cm 2 delivers a discharge capacity of 128 mAh/g at 1 C, which is superior to that of the CNC-free electrodes (95 mAh/g). In short, this study presents a novel environmentally friendly, economically viable, and dual-functional electrode additive that enhances both electronic and ionic conductivities with the aim of facilitating the widespread adoption of fast-charging high mass loading electrodes.

25 ENERGY STORAGE↗

Depth-Resolved Lithiated Gradients in Pristine and Laser-Ablated Anodes During Fast Charging

Laser ablating 3D electrode microstructures is a technique to improve Li-ion battery fast-charge performance. This technique has been theoretically proposed and electrochemically validated previously in the literature. The fundamental principle underlying laser ablation is that the ablated features reduce Li-ion transport pathways, improving access to the electrode active material near the current collector. This, in turn, promotes more homogeneous electrode utilization. The present study seeks to directly affirm the physics attributed to laser ablation using operando high-speed synchrotron X-ray diffraction. In this study, depth-resolved graphite lithiation gradients are measured operando during high-rate (15 min) charging. The depth-resolved lithiation dynamics of both ablated and non-ablated anodes are compared. The results highlight that the laser-ablated graphite electrode has notably more homogeneous utilization as compared to the non-ablated electrode. Additionally, the ablated electrode has a significant delay in reaching the maximum graphite lithiation at the separator, indicating less propensity for lithium plating. During low rate delithiation/discharge (2 hr), the two cells' lithiation gradients converge. Notably, a calibrated physics-based electrochemical model accurately reflects experimental findings, suggesting the potential to use pseudo-4D models not only to optimize laser ablation parameters in fast-charge capable electrodes but also to guide fast charging protocols that avoid lithium plating.

25 ENERGY STORAGE↗

Advancing the Performance of Lithium-Rich Oxides in Concert with Inherent Complexities: Domain-Selective Substitutions

Historically, modifications to Li- and Mn-rich (LMR) cathodes have been studied in relation to their efficacy in solving challenges such as oxygen loss and voltage fade, which are inherent to the activation process of these electrodes. However, even in the presence of these phenomena, well-optimized LMR cathodes show considerable promise as earth-abundant options, particularly if other barriers to implementation can be overcome or mitigated. As the complex mechanisms of LMR electrodes are known to stem from the local, chemical inhomogeneities that define the nanocomposite domain nature of these oxides, strategies aimed at manipulating the performance of activated electrodes, irrespective of voltage fade, through domain-selective modifications, could prove instructive. In this work, we use a novel synthesis process aimed at influencing the site occupancy of substituted Sn 4+ , as an example 4+ cation, into a Co-free Li 1.13 Mn 0.57(1–x) Sn 0.57x Ni 0.3 O 2 LMR oxide. We show that Sn 4+ can be selectively substituted into Li-rich environments. The consequences are revealed to be both chemical and morphological, and the domain-selective doping strategy provides a knob for directed control of the low state-of-charge impedance behavior. In conclusion, these results reveal new clues and insights with respect to further advancing the practical relevance of LMR cathode particles and electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

An engineered lactate oxidase based electrochemical sensor for continuous detection of biomarker lactic acid in human sweat and serum

Lactate levels in humans reveal intensity and duration of exertion and provide a critical readout for the severity of life-threatening illnesses such as pediatric sepsis. Using the lactate oxidase enzyme (Lox) from Aerococcus viridians, we demonstrated its functionality for lactate electrochemical sensing in physiological fluids in a lab setting. The structure and dynamics of LOx were validated by crystallography, X-ray scattering, and hydroxyl radical protein footprinting. This provided a validated protein template for understanding and designing an enzyme-based electrochemical sensing elements. Using this template, LOx enzyme variants were generated and compared. Comparison of the variants demonstrates that one exhibits effective lactate sensing at significantly reduced operating voltages. Additionally, we demonstrate that the four hexahistidine-tags on each enzyme tetramer are sufficient for immobilization to create a durable, functional sensor, with no need for a covalent attachment, enabling self-immobilization and eliminating the need for additional immobilization steps. The functionality of the LOx enzyme variants was verified at physiological lactate concentrations in both human serum (0–4 mM) and artificial sweat (0–100 mM) using 3-electrode setups for analysis of the three variants in parallel. Accuracy of measurement in both artificial sweat and human serum were high. Employing a microfluidic flow cell, we successfully monitored varying lactate levels in physiological fluids continuously over a 2h period. Overall, this optimized LOx enzyme, which self-immobilizes onto gold sensing electrodes, facilitates efficient and reliable lactate detection and continuous monitoring at reduced operating voltages suitable for further development towards commercial use.

60 APPLIED LIFE SCIENCES↗

High‐Loading Lithium‐Sulfur Batteries with Solvent‐Free Dry‐Electrode Processing

Abstract Lithium‐sulfur (Li‐S) batteries, with their high energy density, nontoxicity, and the natural abundance of sulfur, hold immense potential as the next‐generation energy storage technology. To maximize the actual energy density of the Li‐S batteries for practical applications, it is crucial to escalate the areal capacity of the sulfur cathode by fabricating an electrode with high sulfur loading. Herein, ultra‐high sulfur loading (up to 12 mg cm −2 ) cathodes are fabricated through an industrially viable and sustainable solvent‐free dry‐processing method that utilizes a polytetrafluoroethylene binder fibrillation. Due to its low porosity cathode architecture formed by the binder fibrillation process, the dry‐processed electrodes exhibit a relatively lower initial capacity compared to the slurry‐processed electrode. However, its mechanical stability is well maintained throughout the cycling without the formation of electrode cracking, demonstrating significantly superior cycling stability. Additionally, through the optimization of the dry‐processing, a single‐layer pouch cell with a loading of 9 mg cm −2 and a novel multi‐layer pouch cell that uses an aluminum mesh as its current collector with a total loading of 14 mg cm −2 are introduced. To address the reduced initial capacity of dry‐processed electrodes, strategies such as incorporating electrocatalysts or employing prelithiated active materials are suggested.

Chemistry↗

Stress evolution and creep deformation in solid-oxide electrolysis cell systems – Dynamic modeling and multi-objective optimization to maximize stack life and efficiency

Here, this study develops a thermal stress model of solid-oxide electrolysis cells (SOECs) including a model for creep strain and failure probability that is integrated with a dynamic plant-wide model of a hydrogen production process. Uncertainties in key material properties of the cell are quantified to assess their impact on stress profile variability. The oxygen electrode is found to have about 10 times higher failure probability compared to the fuel electrode. The study shows that if the stack operation is not optimized, cycling operation would lead to stress build-up eventually leading to catastrophic failure. A dynamic optimization problem is set up for obtaining the optimal operational profile considering a variable hydrogen production rate. Due to the tradeoff between the efficiency and stress build-up, the dynamic optimization problem is multi-objective. It is observed that the optimizer can considerably reduce the stress build-up (i.e., can increase the stack life) albeit at the cost of a lower efficiency thus exhibiting strong tradeoffs between capital and operating costs. For example, if the stack would be replaced in 0.5 yr, specific energy requirement would be 48.5 kWh/kg H 2 while for a stack replacement time of about 6 yr, the specific energy requirement rises by about 4.2 %.

SOEC↗

Performance Prediction of High‐Entropy Perovskites La 0.8 Sr 0.2 Mn x Co y Fe z O 3 with Automated High‐Throughput Characterization of Combinatorial Libraries and Machine Learning

Perovskite oxides form a large family of materials with applications across various fields, owing to their structural and chemical flexibility. Efficient exploration of this extensive compositional space is now achievable through automated high-throughput experimentation combined with machine learning. In this study, we investigate the composition–structure–performance relationships of high-entropy La 0.8 Sr 0.2 Mn x Co y Fe z O 3±𝞭 perovskite oxides (0 < x, y, z <1; x+y+z≈1) for application as oxygen electrodes in Solid Oxide Cells. Following the deposition of a continuous compositional map using thin-film combinatorial pulsed laser deposition, compositional, structural, and performance properties are characterized using six different techniques with mapping capabilities. Random forests effectively model electrochemical performance, consistently identifying Fe-rich oxides as optimal compounds with the lowest area-specific resistance values for oxygen electrodes at 700 °C. Additionally, the models identify a statistical correlation between oxygen sublattice distortion—derived from spectral analysis of Raman-active modes—and enhanced performance.

high entropy oxides↗

Dual-function lignin monomers enable high-performance graphene electrodes via interface confinement and proton transfer enhancement

Graphene oxide (GO)-based energy storage faces dual bottlenecks: unsustainable reduction methods and sluggish proton transfer kinetics. Here, we introduce a groundbreaking green strategy using lignin-derived vanillyl alcohol (VA) as a dual-function monomer to simultaneously address these challenges. By thermally annealing GO/VA films at mild temperatures (<100 °C), VA triggers an interface-confined reduction of GO while self-polymerizing into redox-active oligomers (P-VA) that intercalate between graphene layers. This dual role-reducing agent and proton highway enables a 3D conductive network with minimized graphene restacking, abundant redox sites, and rapid H + transport pathways. Density Functional Theory (DFT) reveals how P-VA optimizes proton dynamics, while the resulting rGO-P-VA4-T90 electrode achieves a record volumetric capacitance of 311.1F/cm 3 (777.8F/cm 2 ) and retains 87.8 % capacity after 10,000 cycles. Flexible solid-state supercapacitors deliver 94.2 μWh/cm 2 energy density at 63.8 μW/cm 2 , rivaling state-of-the-art devices. Furthermore, this work redefines sustainable graphene engineering, merging biomass valorization with high-performance energy storage in a scalable, eco-friendly paradigm.

Graphene oxide reduction↗

Shape Matters: Understanding the Effect of Electrode Geometry on Cell Resistance and Chemo-Mechanical Stress

Rechargeable batteries that incorporate shaped three-dimensional electrodes have been shown to have increased power and energy densities when compared to a conventional geometry, i.e. a planar cathode and anode that sandwich an electrolyte. Electrodes can be shaped to enable a higher active material loading, while keeping ion transport distances small. However, the relationship between electrical and mechanical performance of shaped electrodes remains poorly understood. Many electrode designs have been explored, where the electrodes are individually shaped or intertwined, and advances in manufacturing and shape/topology optimization have made such designs a reality. Here, we explore sinusoidal half cells and interdigitated full cells. First, we use a simple electrostatics model to understand the cell resistance as a function of shape. Here we focus on low-temperature conditions, where the electrolyte conductivity decreases relative to that of the electrode; here, LiPF 6 EC:DMC electrolyte and MnO 2 electrode are considered. Next, we use a chemo-mechanics model to examine the stress that arises due to intercalation-driven volume expansion. We show that shaped electrodes provide a significant reduction in resistance in low-temperature conditions, however, they exhibit unfavorable stress concentrations. Overall, we find that the fully interdigitated electrodes may provide the best balance with respect to this resistance-stress trade-off.

25 ENERGY STORAGE↗

Phase segregation of a composite air electrode unlocks the high performance of reversible protonic ceramic electrochemical cells

One breakthrough in developing highly efficient air electrodes for reversible protonic ceramic electrochemical cells (R-PCECs) is optimizing the sluggish oxygen reduction and water oxidation reactions. Here, we present a novel composite material with a nominal formula of high-entropy Ce 0.2 Ba 0.2 Sr 0.2 La 0.2 Ca 0.2 CoO 3–δ (CBSLCC) that spontaneously self-assembles to three-phase electrocatalysts composed of deficient Ce 0.2–y Ba 0.2 Sr 0.2–x La 0.2–x Ca 0.2 CoO 3–δ (CD-CBSLCC), CeO 2 , and La 0.5 Sr 0.5 CoO 3–δ (LSC). Mechanistic studies corroborate that oxygen reduction may occur on entire air electrode surfaces, followed by water formation preferentially at or near CD-CBSLCC. The CeO 2 phase could provide or consume protons to facilitate the oxygen evolution/reduction kinetics in R-PCECs. The developed electrodes demonstrate a record-high electrochemical performance in dual modes of fuel cells and electrolysis cells, delivering a peak power density of 1.66 W cm –2 at 600 °C and a current density of –1.76 A cm –2 at 1.3 V and 600 °C. Finally, excellent operational stabilities of the fuel cell (200 h at 600 °C), electrolysis cell (200 h at 600 °C), and reversible cycling (548 h at 550 °C) provide a promising and reliable step towards realizing the commercialization of R-PCECs.

30 DIRECT ENERGY CONVERSION↗

Electrochemical Reactions Under Reverse Bias Create Additional Mobile Ions That Enable Hole Tunneling in Metal Halide Perovskite Diodes

Gradual reverse-bias breakdown in metal-halide perovskite diodes and solar cells is thought to originate from hole tunneling through steep bands in an ionic depletion region near the electron-transport layer after positively charged iodine vacancies accumulate near the hole-transport layer (HTL). However, typical reported mobile-ion concentrations near 1 x 10^17 cm-3 are too small to quantitatively explain significant tunneling-current densities and (Zener) breakdown observed near -5 V. Here, we show that inferred mobile-ion concentrations increase by more than 100x, to over 1 x 10^18cm-3 , within just 3 min of reverse bias at -6.0 V in p-i-n perovskite diodes. We attribute this increase to iodide oxidation and coupled iodine vacancy creation that must be balanced by reduction reactions near the HTL. Sub-optimal HTL coverage leads to direct contact between the transparent conducting electrode and perovskite, facilitates reduction events, enables the creation of even larger inferred mobile-ion concentrations (~1 x 10^19cm-3 ), and leads to faster degradation under reverse bias. This explains previous work that showed increased breakdown voltages and improved reverse-bias stability by implementing thick, uniform HTLs.

14 SOLAR ENERGY↗

Design of the EIC hadron storage ring stripline injection kicker with a novel impedance tuning capability

The Electron-Ion Collider (EIC), to be built at Brookhaven National Laboratory, will be a high luminosity (~10 34 cm –2 s –1 ) nuclear science facility. To facilitate EIC experiments, the existing yellow ring of the Relativistic Heavy Ion Collider (RHIC) will be reconfigured to serve as the Hadron Storage Ring (HSR). Designing a stripline injection kicker for the HSR beams, with high magnetic rigidity (~ 82 Tm), poses some technical challenges due to the required large pulsed voltage with long flattop duration, very fast rise time, expected shorter bunch spacing, and potential heating due to higher peak current. In addition, minimizing impedance mismatch in the transition region between the feedthrough and the stripline electrode is challenging. This paper focuses on the mechanical design and optimization of the HSR injection kicker, highlighting a novel impedance tuning capability achieved through an innovative kicker aperture adjustment mechanism. We comprehensively cover the design, including impedance optimization (both beam coupling and characteristic), beam-induced heating, and thermal analysis, and investigation of the maximum electric field due to high voltage signal excitation to ensure safe and reliable operation.

43 PARTICLE ACCELERATORS↗

High-Efficiency Solar-To-Fuel Photoelectrochemistry in Disordered Photonic Glass Electrodes (Final Technical Report)

This project investigated how photonic glass (PG) photoelectrodes—disordered arrangements of dielectric scatterers—can serve as scalable, tunable platforms for light trapping in photoelectrochemical (PEC) solar-to-fuel systems. By leveraging disorder-driven optical phenomena such as multiple scattering resonances and light localization, PG structures offer an alternative to conventional photonic crystals and inverse opals that require high structural precision. The scientific goals were to twofold: (1) develop approaches to predictive models for high performance PG electrodes based on light absorption simulations, and (2) fabricate, characterize, and optimize PG-based photoelectrodes for solar-to-hydrogen and solar-to-fuel photoelectrochemical applications. To overcome the complexity of ensemble optical simulations for disordered materials, the researchers developed a machine-learning-accelerated emulation of all configurations in the design space. With this approach, PG photoelectrodes based on a TiO2 semiconductor were designed to enhance PEC currents of up to one hundred times higher than the equivalent ultra-thin film photoanodes and several times higher than the equivalent photonic crystal. The research also explored integrated systems for electrochemical hydrogen production based on replacing water oxidation with the specific glycerol oxidation electrocatalysis. Overall, the project outlined an approach to a simple-to-fabricate photoelectrode system to drive photoelectrochemical reactions relevant to solar photochemical energy conversion.

14 SOLAR ENERGY↗

Advanced PEM Electrolyzer Membrane for Hydrogen Crossover Mitigation

An unintended reaction in the electrochemical conversion of water to hydrogen in proton exchange membrane (PEM) electrolyzers is the crossover of hydrogen from the anode to the oxygen-containing cathode through the membrane, creating hydrogen losses and safety concerns. Efforts to date have focused on embedding platinum catalysts in perfluorosulfonic (PFSA) membranes to convert H 2 to protons. The objective of this project is to design and develop hydrocarbon (HC) proton exchange membranes (PEMs) that can help overcome the risk of high H 2 crossover in current PEM electrolyzer (ELX) stacks by designing and optimizing the gas recombination catalyst (GRC) within the membrane and membrane electrode assembly (MEA) structure.

08 HYDROGEN↗