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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 73 records · Page 4

A pseudo-two-dimensional (P2D) model for FeS 2 conversion cathode batteries

Conversion cathode materials are gaining interest for secondary batteries due to their high theoretical energy and power density. However, practical application as a secondary battery material is currently limited by practical issues such as poor cyclability. To better understand these materials, we have, for this study, developed a pseudo-two-dimensional model for conversion cathodes. We apply this model to FeS 2 – a material that undergoes intercalation followed by conversion during discharge. The model is derived from the half-cell Doyle–Fuller–Newman model with additional loss terms added to reflect the converted shell resistance as the reaction progresses. We also account for polydisperse active material particles by incorporating a variable active surface area and effective particle radius. Using the model, we show that the leading loss mechanisms for FeS 2 are associated with solid-state diffusion and electrical transport limitations through the converted shell material. The polydisperse simulations are also compared to a monodisperse system, and we show that polydispersity has very little effect on the intercalation behavior yet leads to capacity loss during the conversion reaction. Finally, we provide the code as an open-source Python Battery Mathematical Modeling (PyBaMM) model that can be used to identify performance limitations for other conversion cathode materials.

25 ENERGY STORAGE↗

High performance aluminum-air flow batteries through double-face architecture and laser-modified and friction-stir processed 3D anode

Aluminum-air batteries (AAB) are regarded as one of the most promising beyond-lithium high-energy-density storage candidates. Here, this paper introduces a three-dimensional (3D) Al 7075 anode enabled by femtosecond laser and friction-stir process which, along with a special double-face anode architecture provides world-class performance. Electrochemical characterizations prove that the corrosion resistance of the modified 3D Al 7075 FSP anode was enhanced, and electrochemically active surface area (ECSA) was increased compared with that of normal Al 7075 anode. Friction-stir processing reduced the mean grain size from 30 μm to 3 μm. The discharge performance of 3D Al 7075 FSP anode is shown to be quite stable, and the average values of energy density are significantly increased from 2256 mWh g –1 to 2941 mWh g –1 at 100 mA cm –2 . In a double-face flowing Al-air battery system, the 3D Al 7075 FSP anode exhibited significantly better electrocatalytic performance (discharge voltage of 0.76 V at 400 mA cm –2 , and power density of 337.8 mW cm –2 ) than that of a commercial Al 7075 anode.

25 ENERGY STORAGE↗

Multi-phase characterization of pitch-carbon coated nano-silicon anodes for lithium-ion batteries

Silicon (Si) is a leading next-generation Li-ion battery anode candidate that meets rigorous performance demands for portable power including enhanced power and energy density with robust cycling performance. However, a series of complex and interrelated reactions lead to reduced calendar life in Si-containing systems and therefore challenge practical adoption. In the present work, we probe the mechanisms underlying observed performance improvements by adding a pitch-carbon coating onto nano-Si material. We pair solid-phase (X-ray photoemission spectroscopy, Fourier-transform infrared), semi-volatile phase (solid-phase microextraction-gas chromatography-mass spectrometry), and gas-phase (gas chromatography-flame-ionization detector) characterization signals to comprehensively evaluate the impact of pitch-carbon coating on the evolution of the Si solid-electrolyte interphase (SEI) and the associated impacts on electrode/electrolyte reactivity. The pitch-carbon is found to serve as a physicochemical barrier, reducing the electro-active surface area for Si/electrolyte reactivity and preventing Si oxidation. Further, the pitch-carbon coating promotes the evolution of a more-favorable SEI by subsuming substantial functionality typically associated with the fluoroethylene carbonate (FEC) electrolyte additive - such as alkoxide scavenging and suppression of transesterification pathways - and by shifting the competitive electrolyte degradation pathways' favorability. The multi-phase characterization approach enables holistic end-products evaluation from complex (electro)chemical interfacial reactions, which informs a robust interpretation of the carbon coating's role in electrochemical performance improvements. The present mechanistic evaluation aids the rational design for improved nano-Si materials.

25 ENERGY STORAGE↗

Design, Synthesis, and Evaluation of Noble Metal Nanoparticles and In Situ-Decorated Carbon-Supported Nanoparticle Electrocatalysts Using Hypergolic Reactions

Here, we report the first synthesis of metal nanoparticles and supported metal nanoparticles on carbon by using hypergolic reactions. Specifically, we report the synthesis of noble metal nanoparticles (Pt, Ag, and Au) using sodium hydride (NaH) as both an ignition trigger and a reducing agent for the corresponding metal salt precursors. In addition, we report the one-step, in situ synthesis of Pt nanoparticles supported on carbon by adding sucrose as the carbon source. The hypergolically synthesized nanoparticles display elliptical morphology and are more crystalline compared with those conventionally synthesized in solution using sodium borohydride (NaBH 4 ). When tested as electrocatalysts, the hypergolic Pt nanoparticles exhibit more than 2 times higher specific electrochemical active surface area (ECSA) and a higher half-wave potential (E 1/2 ) of 0.94 V vs the reversible hydrogen electrode (RHE) compared to the conventionally synthesized ones. In addition, the electrocatalyst based on the in situ synthesized carbon that was decorated with the Pt nanoparticles synthesized hypergolically outperforms an analogous, state of the art, commercial PtC system. For example, the former shows an attractive E 1/2 (0.94 V) compared with 0.9 V for the commercial PtC. Accelerated durability tests (ADT) in an alkaline environment add another advantage. After 10 000 cycles, the hypergolically synthesized system shows a smaller reduction of E 1/2 and less degradation compared to the commercial PtC (10 mV compared to ∼30 mV). The work described here represents the first reported synthesis using hypergolic reactions of metal nanoparticles as well as supported metal nanoparticles. The properties of the resulting electrocatalysts demonstrate the versatility and promise of the new approach in materials synthesis and open new avenues for further investigation as electrocatalysts.

Chalmpes, Nikolaos↗

Inverse Consequences of the SnO 2 Protection Layers on Pt/C Catalysts in Proton-Exchange Membrane Fuel Cells

Proton-exchange membrane fuel cells (PEMFCs) are promising energy-conversion systems, offering an appealing blend of high energy efficiency and low environmental impact. However, carbon corrosion of PEMFCs is known to significantly degrade their performance, remaining a critical challenge to overcome. In this study, we applied a Nb-doped SnO 2 (Nb-SnO 2 ) nanoparticle coating on Pt/C catalysts as a protective layer, with the Sn/C ratio in the precursors varying from 0.25:1 to 2.0:1. Contradictory behaviors of the coated Pt/C catalysts were observed at different Sn/C ratios. The Sn/C = 1.0 sample exhibited improved electrochemically active surface area retention after 500 cycles of accelerated stress testing (AST) but with more significant polarization and resistance increase observed in the polarization curves. In addition, agglomeration of Nb-SnO 2 particles was observed at a higher Sn/C ratio in the AST of a membrane electrode assembly, with less shrinkage of the total thickness of the Nb-SnO 2 -coated Pt/C electrode. We speculate that formation of Nb-SnO 2 agglomerates occurs once the protective layer is broken down or the unprotected carbon surface is corroded and that these Nb-SnO 2 agglomerates increase the tortuosity of the electron pathways and significantly increase the cell polarization.

30 DIRECT ENERGY CONVERSION↗

Enhanced Catalytic Activity of a Vanadium-Doped Mesoporous Octahedral Molecular Sieve-2 (K-OMS-2) toward Hydrogen Evolution Reaction

Hydrogen evolution reaction (HER) is the cathodic reaction in electrochemical water splitting that produces H 2 in a renewable pathway, primarily to be used in fuel cells. K-OMS-2, a manganese octahedral molecular sieve, has the potential to replace Pt as a catalyst for HER due to its redox and electrochemical properties, which can be further improved by doping metal cations into the K-OMS-2 framework. In this work, we synthesized 1, 5, and 10% vanadium- (V) doped mesoporous K-OMS-2 under mild acidic reaction conditions. Here, the mesoporous nature of the samples was confirmed by BET analysis. X-ray photoelectron spectroscopy confirmed that Mn has 2+, 3 +, and 4+ oxidation states, and V is present as V 4+ in V-K-OMS-2 samples. HER performance of 1% V-K-OMS-2 in an acidic medium shows the best activity with -0.32 V overpotential. The overpotential was lowered by 0.56 V upon doping 1% V into the K-OMS-2 framework. The 1% V-K-OMS-2 material has a Tafel slope of 129 mV/decay and an electrochemically active surface area (ECSA) of 127.5 cm 2 ECSA .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyvinyl Alcohol Anion Exchange Resin Composite Membrane with Co@Cu Core–Shell Particles for Direct Borohydride Fuel Cell Applications

We report a polyvinyl alcohol anion exchange resin composite membrane, functionalized with Co and Cu ions, is reported for use in direct borohydride fuel cells (DBFCs). The CoCu-functionalized membrane has a 30.5% lower fuel permeability than that of a blank membrane. Meanwhile, the cell performance of the DBFC can also be improved by employing the CoCu-functionalized membrane, reaching a maximum power density of 304 mW·cm –2 at 60 °C. High-resolution fluorescence images directly demonstrate the formation of Cu/Co core–shell structure microparticles in the CoCu membrane, which not only reduces the Co content but also increases the active surface area of Co species in CoCu-functionalized membranes, resulting in the improvement of cell performance.

36 MATERIALS SCIENCE↗

Heuristics for Molten-Salt Synthesis of Single-Crystalline Ultrahigh-Nickel Layered Oxide Cathodes

In pursuit of Li-ion batteries with higher energy density, ultrahigh-nickel layered oxides are a leading candidate for next-generation cathode materials. Single-crystalline morphology offers a neat solution to the poor stability of ultrahigh-Ni cathodes; a lower active surface area mitigates electrolyte decomposition at high voltages, and the elimination of grain boundaries improves mechanical resilience and increases volumetric energy density. However, single-crystal cathodes possess their own challenges, several of which originate from synthesis at elevated temperatures meant to induce grain growth. Molten-salt synthesis is an alternative method for obtaining single crystals, accelerating grain growth through the presence of a molten flux without the need for increased temperature. Herein, we offer heuristic guidelines for molten-salt synthesis, discussing key factors for designing reaction mixtures and the necessary exploratory research for novel molten salt/cathode systems. Here, the influence of different salts and synthesis conditions on the morphology and properties of single-crystal LiNiO 2 is presented. It is found that oxidative salts, such as Li 2 O 2 and LiNO 3 , are crucial to supplementing dissolution of gaseous oxygen into the molten phase. Through these discussions, this work aims to provide a set of overarching principles for obtaining higher-quality single-crystal layered oxide cathodes and engender more rigorous and impactful investigation into their fundamental nature and applications.

25 ENERGY STORAGE↗

One-Step Synthesis and Operando Electrochemical Impedance Spectroscopic Characterization of Heterostructured MoP–Mo 2 N Electrocatalysts for Stable Hydrogen Evolution Reaction

Here this study presents a novel synthesis of self-standing MoP and Mo 2 N heterostructured electrocatalysts with enhanced stability and catalytic performance. Facilitated by the controlled phase and interfacial microstructure, the seamless structures of these catalysts minimize internal resistivity and prevent local corrosion, contributing to increased stability. The chemical synthesis proceeds with etching step to activate the surface, followed by phosphor-nitriding in a chemical vapor deposition chamber to produce MoP-Mo 2 N@Mo heterostructured electrocatalysts. X-ray diffraction analyses confirm the presence of MoP, Mo 2 N, and Mo phases in the electrocatalyst. Morphology studies using scanning electron microscopy characterizes the hierarchical growth of structures, indicating successful formation of the heterostructure. X-ray photoelectron spectroscopy (XPS) analyses of the as-synthesized and post-catalytic activity samples reveal the chemical shift in terms of binding energy (BE) of Mo 3d XPS peak, especially after catalytic activity. The XPS BE shifts attributed to changes in oxidation state, electron transfer, and surface reconstruction during catalysis. Electrochemical evaluation of the catalysts demonstrates the superior performance of the MoP-Mo 2 N@Mo heterostructured catalyst in hydrogen evolution reactions (HER), with lower overpotentials and enhanced Tafel slopes. Stability tests reveal changes in double layer capacitance over time, suggesting surface reconstruction and increased active surface area during catalysis. Operando electrochemical impedance spectroscopy (EIS) further elucidates the dynamic changes in resistance and charge transfer during HER. Overall, comprehensive understanding of the synthesis, characterization, and electrochemical behavior of the developed MoP-Mo 2 N@Mo heterostructured electrocatalyst as presented in this paper highlights their potential utilization in sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Studying the Durability of Molybdenum Carbide Aerogel as an Electrocatalyst Support for Proton Exchange Membrane Fuel Cells

Carbon-supported platinum nanoparticles (Pt/C) are currently the state-of-the-art catalyst in proton exchange membrane fuel cells (PEMFCs). Unfortunately, the carbon support lacks the ability to stabilize the metal catalyst, as platinum tends to dissolve and agglomerate, significantly compromising the durability. Herein, we synthesized a ceramic material, molybdenum carbide aerogel (MCAG), and utilized it as a Pt support for PEMFCs, as an alternative for conventional carbon supports. N 2 adsorption and XRD analysis showed that the MCAG possesses a combination of high porosity and a well-defined ceramic crystalline structure. The Pt/MCAG system was studied for its electrocatalytic activity toward ORR in a half-cell and demonstrated satisfactory reaction kinetics and electrochemical active surface area, comparable to the commercial Pt/C. For durability examination, an accelerated stress test (AST) in a single cell was conducted with the Pt/MCAG catalyst at the cathode, following the U.S. DOE electrocatalyst AST protocol. Intermediate polarization curves and cyclic voltammograms were recorded over the course of the AST to monitor the aging process. The results indicated that the MCAG support exhibited superior durability in long-term fuel cell operation compared to a carbon support. The Pt/MCAG system demonstrated stable behavior during the progressive stages of the AST, retaining more than 50% of its initial performance by the end of the test, whereas carbon-supported Pt preserved only 30%.

25 ENERGY STORAGE↗

X-ray Micro-Computed Tomography for Structural Analysis of All-Solid-State Battery at Pouch Cell Level

Characterizing the microstructure of all-solid-state batteries (ASSBs) during fabrication and operation is vital for their advancement, particularly as scaling to pouch cell levels introduces challenges in probing large-scale microstructural evolution. This work highlights the potential of synchrotron X-ray micro-computed tomography (sXCT) as a nondestructive, rapid (<30 min), and high-resolution technique for visualizing and quantifying key microstructural features, including overhang, porosity, contact loss, active surface area, and tortuosity, in all-solid-state pouch cells. The large field of view (up to millimeters) of sXCT enables detailed analysis at an industry-relevant scale, bridging the gap between laboratory research and commercial applications. Furthermore, integrating realistic sXCT-derived 3D models into multiphysics simulations could provide insights into chemo-mechanical degradation, particularly at the edges of the pouch cells, offering a pathway for designing robust, high-performance ASSBs. This perspective establishes sXCT as an indispensable tool for advancing both the understanding and the engineering of next-generation energy storage systems.

25 ENERGY STORAGE↗

Metal Foam Morphology Affects the Run to Run Reproducibility of OER Using Nickel Catalysts

Nickel (Ni) foam-based electrodes are excellent catalysts for the oxygen evolution reaction; however, we found that the random pore-size distribution of Ni foams contributes to a significant variability in electrochemically active surface area, compromising experimental reproducibility. We provide insights into quantifying this critical material property, verified by four electrochemical laboratories.

25 ENERGY STORAGE↗

Two-Dimensional Tantalum Carbo-Selenide for Hydrogen Evolution

Herein, we report the synthesis of two-dimensional Ta 2 Se 2 C (2D-Ta 2 Se 2 C) nanosheets using electrochemical lithiation in multilayer Ta 2 Se 2 C followed by sonication in deionized water. Multilayer Ta 2 Se 2 C was obtained via solid-state synthesis of Fe x Ta 2 Se 2 C followed by chemical etching of Fe. 2D-Ta 2 Se 2 C exhibited promising electrocatalytic activity for the hydrogen evolution reaction from water compared to multilayer Ta 2 Se 2 C and 2D-TaSe 2 . 2D-Ta 2 Se 2 C showed an overpotential at 10 mA·cm -2 (η 10 ) of 264 mV, a Tafel slope of 91 mV·dec -1 , and an electrochemically active surface area of 17.61 m ECSA 2 ·g catalyst -1 . The high performance could be attributed to the large surface area of single sheets which hence maximizes the number of exposed catalytic sites and increased density of vacancies, observed with transmission electron microscopy, during synthesis and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thickness-independent scalable high-performance Li-S batteries with high areal sulfur loading via electron-enriched carbon framework

Abstract Increasing the energy density of lithium-sulfur batteries necessitates the maximization of their areal capacity, calling for thick electrodes with high sulfur loading and content. However, traditional thick electrodes often lead to sluggish ion transfer kinetics as well as decreased electronic conductivity and mechanical stability, leading to their thickness-dependent electrochemical performance. Here, free-standing and low-tortuosity N, O co-doped wood-like carbon frameworks decorated with carbon nanotubes forest (WLC-CNTs) are synthesized and used as host for enabling scalable high-performance Li-sulfur batteries. EIS-symmetric cell examinations demonstrate that the ionic resistance and charge-transfer resistance per unit electro-active surface area of S@WLC-CNTs do not change with the variation of thickness, allowing the thickness-independent electrochemical performance of Li-S batteries. With a thickness of up to 1200 µm and sulfur loading of 52.4 mg cm −2 , the electrode displays a capacity of 692 mAh g −1 after 100 cycles at 0.1 C with a low E/S ratio of 6. Moreover, the WLC-CNTs framework can also be used as a host for lithium to suppress dendrite growth. With these specific lithiophilic and sulfiphilic features, Li-S full cells were assembled and exhibited long cycling stability.

36 MATERIALS SCIENCE↗

Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

The biggest obstacle to the widespread implementation of polymer electrolyte membrane fuel cells (PEMFCs) is their cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited on a rotating disk electrode (RDE) is rarely realized in a membrane electrode assembly (MEA), which is a long-standing challenge for PEMFCs and a cause of low catalyst utilization. To translate the high RDE performance of a catalyst into a MEA, the design of an ideal ionomer/catalyst interface is proposed: a thin, conformal ionomer film covers the maximum surface of a Pt nanoparticle and thus simultaneously maximizes catalyst utilization, (i.e., high mass activity and electrochemically active surface area) and O 2 diffusion rate (i.e., high current density performance) without compromising proton conduction. Building such an interface is a long-standing challenge due to the lack of interaction between the ionomer and catalyst particles, resulting in large ionomer agglomerates and inhomogeneous ionomer coverage over the catalyst nanoparticle, with consequent poor fuel cell performance. In this work, this ionomer/catalyst interface has been engineered, utilizing the electrostatic attraction between positively charged catalyst and negatively charged ionomer particles in a catalyst ink and preserved in a solid catalyst layer. As a result, this interface leads to previously unachieved proton exchange membrane fuel cell performance in terms of both catalyst utilization (75% vs. 45%) and peak/rated power density (i.e., 1.430/0.930 W cm -2 , H 2 /air, cathode Pt loading: 0.1 mgPt cm -2 ) for pure Pt catalysts, even better than those of Pt alloy catalysts. This work demonstrates the formation of an interface in the liquid phase (using ultra-small-angle X-ray scattering in combination with cryo-TEM, isothermal–titration–calorimetry) and the preservation of the interface in the solid catalyst layer (using TEM) and estimates the effective coverage and thickness of the ionomer film (using limiting current density, RDE and fuel cell performance).

25 ENERGY STORAGE↗

Unraveling membrane electrode assembly design for electrochemical conversion of carbon dioxide to formate/formic acid

This work presents a one-dimensional continuum modeling approach to investigate various cell architectures used for electrochemical conversion of CO 2 to formate/formic acid. Ion transport is simulated by a system of generalized modified Poisson–Nernst–Planck (GMPNP) equations that reflect the reactive transport phenomena including steric effects as the electrolyte solutions become concentrated. In the cathode catalyst layer, ionic current contributions from both the supporting electrolyte and solid-state ionomer are considered. Voltage and CO 2 utilization breakdowns are utilized to deconvolute the impacts of the cell architecture. The origins of (bi)carbonate formation in the cathode are explored, as the subsequent decrease in CO 2 availability is a key reason for low faradaic efficiencies to formate/formic acid. In addition, the role of a supporting electrolyte (KOH) is investigated to understand its tradeoffs: while the K + ions can improve both conductivity and electrochemically active surface area in the cathode, the presence of OH − ions raises the pH and leads to deleterious formation of (bi)carbonates. To this end, we also present parametric studies on the concentration and flow rate of supplied KOH to the cell, to establish a path towards eliminating the need for a supporting electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Harnessing emergent multiple scattering resonances in a photonic glass structure for photoelectrochemical energy conversion

Light trapping nanostructures are often necessary to improve carrier collection yields in semiconductor photoelectrodes with intrinsically poor electron transport. Photonic crystal templates can generate tailorable light trapping via periodic and precise nanostructure, though this is not a scalable strategy for photoelectrochemical (PEC) applications. It is therefore critical to identify alternative mechanisms for light trapping that tolerate disorder. Light trapping in disordered media is generated by the diffusive transport caused by multiple scattering. In some cases, multiple scattering can generate resonances that resemble those observed in photonic crystals. While resonant multiple scattering is a disorder tolerant light trapping mechanism, it is unclear if the effect is sufficiently adaptable, or even useful, for PEC applications. Here, we describe a photonic omission glass, a nanostructure that can controllably induce resonances in multiple scattering transport. We characterized the emergence of these resonances after coating a disordered SiO 2 colloidal structure with a layer of TiO 2 , which functions both as dielectric contrast and as a light absorbing semiconductor. We show in finite element simulations and spectroscopic characterization that the resonant multiple scattering effect improves light trapping near the interface between the structure and the bulk electrolyte. This effect, coupled with the increased electrochemically active surface area, results in a hierarchically structured TiO 2 photoanode with orders of magnitude higher photocurrents compared to an equivalent planar photoanode for PEC reactions such as alkaline water oxidation. We show that controlling this resonant multiple scattering effect can be advantageous for improving PEC energy conversion in disordered photoelectrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗