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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 379 records · Page 21

Designing Li 4 Ti 5 O 12 /LiMn 2 O 4 Cells: Negative-to-Positive Ratio and Electrolyte

Li 4 Ti 5 O12/LiMn2O 4 (LTO/LMO) system is a promising candidate for behind-the-meter storage (BTMS) applications due to its critical-material-free chemistry exhibiting good safety and long lifetime. In this paper we design LTO/LMO cells to mitigate their major degradation mechanism, loss of Li inventory, and improve their long-term cyclability. First, LMO electrodes with different loadings (2.61, 3.29, and 4.26 mAh cm -2 ) are paired with an LTO electrode (3.35 mAh cm -2 ) to create varying negative-to-positive ratios (N/P>1, =1, and <1). Additionally, conventional ethylene carbonate (EC)/ethyl methyl carbonate (EMC) mixture electrolyte and safety enhanced EC-only electrolyte are examined. We show that storing additional Li inventory in the cathode (i.e., using a thicker electrode and having N/P<1) is a convenient method to enhance the capacity retention of LTO/LMO cells, but only if the electrode utilization is not limited by the Li + ion transport. For systems that suffer from limited transport properties, prelithiating the anode will be more effective since LTO (~165 mAh g -1 LTO ) can store the same amount of capacity using less material compared to LMO (~100 mAh g -1 LMO ). In this work, we demonstrate how the electrolyte properties and the electrode thickness of LTO/LMO cells can be designed to enhance their performance.

25 ENERGY STORAGE↗

High capacity 3D structured tin-based electroplated Li-ion battery anodes

3D structured porous electrodes have been considered as a possible solution for accommodating the volume change of alloying lithium ion battery anode materials during cycling. However, lab-scale porous electrodes tend to be thin, and the loading of the activity materials is also small, the combination of which results in electrodes with impractically low areal and volumetric capacities. In this work, we develop a high areal and volumetric capacity 3D-structured Sn/C anode by using a two steps electroplating process. An electrode with a 20% v/v Sn loading exhibits a high volumetric/areal capacity of similar to 879 mA h/cm 3 /6.59 mA h/cm 2 after 100 cycles at 0.5 C and a good rate performance of about 750 mA h/cm 3 and 5.5 mA h/cm 2 (delithiation) at 10 C in a half-cell configuration. The 3D Sn/C anode also shows good compatibility with a commercial LCO cathode in a full cell configuration.

25 ENERGY STORAGE↗

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗

Low coordination number copper catalysts for electrochemical CO 2 methanation in a membrane electrode assembly

The electrochemical conversion of CO 2 to methane provides a means to store intermittent renewable electricity in the form of a carbon-neutral hydrocarbon fuel that benefits from an established global distribution network. The stability and selectivity of reported approaches reside below technoeconomic-related requirements. Membrane electrode assembly-based reactors offer a known path to stability; however, highly alkaline conditions on the cathode favour C-C coupling and multi-carbon products. In computational studies herein, we find that copper in a low coordination number favours methane even under highly alkaline conditions. Experimentally, we develop a carbon nanoparticle moderator strategy that confines a copper-complex catalyst when employed in a membrane electrode assembly. In-situ XAS measurements confirm that increased carbon nanoparticle loadings can reduce the metallic copper coordination number. At a copper coordination number of 4.2 we demonstrate a CO 2 -to-methane selectivity of 62%, a methane partial current density of 136 mA cm –2 , and > 110 hours of stable operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma dynamics on current-carrying magnetic flux tubes. II - Low potential simulation

The evolution of plasma in a current-carrying magnetic flux tube of variable cross section is investigated using a one-dimensional numerical simulation. The flux tube is narrow at the two ends and broad in the middle. The middle part of the flux tube is loaded with a hot, magnetically trapped population, and the two ends have a more dense, gravitationally bound population. A potential difference larger than the gravitational potential but less than the energy of the hot population is applied across the domain. The general result is that the potential change becomes distributed along the anode half of the domain, with negligible potential change on the cathode half. The potential is supported by the mirror force of magnetically trapped particles. The simulations show a steady depletion of plasma on the anode side of the flux tube. The current steadily decreases on a time scale of an ion transit time. The results may provide an explanation for the observed plasma depletions on auroral field lines carrying upward currents.

Swift, Daniel W.↗

Mitigation of Shuttle Effect in Li–S Battery Using a Self-Assembled Ultrathin Molybdenum Disulfide Interlayer

Lithium–sulfur batteries are promising for low-cost and high-energy storage, but their applications are still limited by poor cycling stability owing to soluble lithium polysulfide shuttling during battery operation. Avoiding shuttle effect is challenging but it is essential to avoid active material loss and prevent performance decay. We use an ultrathin layer of MoS 2 with thickness of 10–40 nm, which is 1–2 orders of magnitude thinner than conventional interlayers, for Li–S batteries to mitigate polysulfide shuttling. The MoS2 layer formed by exfoliated nanoflakes is deposited by the scalable liquid-based self-assembly method. With less than 1% of additional weight in the cathode, the MoS 2 interlayer with complete coverage inhibits polysulfide diffusion across the separator and therefore remarkably improves the battery performances. Reversible specific capacity reaches 1010 and 600 mA h g –1 at 0.5 and 2C rates, respectively, which decay slowly over 400 cycles (0.11% per cycle). Moreover, the MoS 2 films with high density of catalytic active flake edges enable high areal sulfur loading up to 10 mg cm –2 and areal capacity up to 9.7 mA h cm –2 at a current density of 3.2 mA cm –2 .

25 ENERGY STORAGE↗

Application of a temporal multiscale method for efficient simulation of degradation in PEM Water Electrolysis under dynamic operating conditions

Hydrogen is emerging as a vital energy carrier, driven by the need to reduce carbon emissions. Proton Electrolyte Membrane Water Electrolysis (PEMWE) enables hydrogen production under fluctuating renewable power conditions but requires improved understanding and stability of the anode catalyst layer under dynamic operating conditions, especially with low noble metal loadings. Long-term degradation experiments are both time-consuming and costly; therefore, a systematic, model-aided approach is essential. In the present work, a temporal multiscale method is applied to reduce the computational effort of simulating long-term degradation processes in PEMWE, with an exemplary focus on catalyst dissolution. A mechanistic model incorporating the oxygen evolution reaction, catalyst dissolution, and hydrogen permeation from the cathode to the anode was hypothesized and implemented. In this way, the local periodicity of transport and reaction processes in dynamic PEMWE operation, which influence the gradual degradation of the catalyst layer, is captured. The temporal multiscale method significantly reduces the computational effort of simulation, decreasing processing time from hours to mere minutes. This efficiency gain is attributed to the limited evolution of Slow-Scale variables during each period of time P of the Fast-Scale variables. Consequently, simulation is required only until local periodicity is achieved within each Slow-Scale time step. Hence, the fully resolved dynamic problem is decoupled into these two scales, employing a heterogeneous multiscale technique. The developed approach effectively accelerates parameter estimation and predictive simulations, supporting systematic modeling of PEMWE degradation under dynamic conditions.

08 HYDROGEN↗

Incorporating Solvate and Solid Electrolytes for All‐Solid‐State Li 2 S Batteries with High Capacity and Long Cycle Life

Abstract The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN) 2 −LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li 2 S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g −1 at cycle 100 (330 mAh g −1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li 2 S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li 2 S loading, Li 2 S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.

Shin, Minjeong↗

Filamentation and Self-Focusing of Electron Beams in Vacuum and Gas Diodes

In this paper, we experimentally studied pulsed electron beams with a high local density. The conditions in which the energy density cumulation is observed during the interaction of electrons with the anode are shown to develop in vacuum and gas diodes at nanosecond and subnanosecond durations of a beam current pulse and a decrease in the interelectrode gap. The average electron energy in filamentation and self-focusing of an electron beam in a vacuum diode of an accelerator at a current of ~2 kA and a no-load voltage of ~400 kV was established to be 50–100 keV while the energy density was 10{sup 9}–10{sup 10} J/cm{sup 3}. It is confirmed that the beam current density in a gas diode can exceed 1 kA/cm{sup 2}. It is hypothesized that superdense electron beams in vacuum and gas diodes are formed as a result of avalanche multiplication of runaway electrons in the cathode–anode gap plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Interdigitated power connector

An electrical connector carries large amounts of electrical current between two circuit boards with low resistance and low self-inductance by means of an interdigitated anode and cathode, thereby providing low dynamic voltage loss. The connector also may include, near where power will be consumed, an interposer board with on-board capacitance to provide even lower dynamic voltage loss. The connector has application to delivering low-voltage, high-current power from a power supply on a first board to electronics on a second board: the low resistance provides low voltage drop for a load current that is constant, while the low inductance and the capacitors provide low voltage fluctuation for a load current that changes. These issues are of great importance, for example, in designing high-performance computers.

Coteus, Paul W.↗

Application of a dedicated micro-processor for automatic data acquisition of load strain and acoustic-emission data

This paper describes an automatic system for acquisition, logging and analysis of stress, strain and acoustic emission data. The complete system is a combination of several standard items of equipment and a newly developed intelligent data logger which has the capability to send data directly to a large scale computer for reduction and plotting. The data logging and all interfacing with peripheral equipment are accomplished using digital electronics. The heart of the system is a four-bit microprocessor and digital cassette tape unit. The system, which is controlled by instructions from a cathode ray tube terminal, has the capability to transmit data from the cassette unit to a large computer via a time sharing option. Typical results are presented for acoustic emission count rate and total count curves superimposed on stress-strain diagrams for boron/epoxy advanced composites.

Wilson, G. H.↗

A rejuvenation process to enhance the durability of low Pt loaded polymer electrolyte membrane fuel cells

Here, an effective method to enhance the durability of polymer electrolyte membrane fuel cells (PEMFCs) is reported. PEMFC performance loss is mitigated by exposing the electrodes of fuel cells to dry nitrogen gas periodically at high temperature. This method extends the lifetime of fuel cells significantly compared to their non-treated counterparts. The impact of treatment temperature and exposure time on PEMFC durability is reported, using potential cycling accelerated stress tests. The enhanced durability is attributed to the suppression of “ionomer relaxation” that occurs under the nearly water saturated operating conditions of a PEMFC cathode.

30 DIRECT ENERGY CONVERSION↗

High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Fuel cells for heavy-duty vehicles (HDVs) have attracted considerable attention because of their unique scalability, better fuel economy, the less demand for hydrogen refilling infrastructure. However, the potential application requires more stringent fuel cell durability up to 25,000 h. Membrane electrode assemblies (MEAs) made from platinum group metal (PGM) catalyst with relatively high loading 0.3 mgPt cm –2 play a crucial role in ensuring high-power and long-term durability. Integrating fine PGM nanoparticles and robust carbon support with strengthened interactions is critical for improving MEA performance and durability. Herein, a unique atomically dispersed and nitrogen coordinated single Mn site-rich carbon (M–N–C) support was developed for high content (40 wt%) platinum catalysts for the oxygen reduction reaction (ORR) cathode with reduced thickness. Compared with two controls studied in this work (e.g., a porous graphitic carbon-supported Pt and a commercial TKK Pt/C catalysts), the Pt (40 wt%)/Mn–N–C catalyst exhibited much enhanced catalytic activity and stability for the ORR in both aqueous acidic electrolyte and polymer electrolyte-based MEA. Here, we carefully elucidated the—role of the Mn–N–C support in promoting Pt catalyst concerning its high surface area, partially graphitic structure, and nitrogen dopants, providing better Pt nanoparticle dispersion, and strengthened interactions between Pt and carbon. Consequently, the MEA from the Pt (40 wt%)/Mn–N–C catalyst generated a 1.61 A cm –2 at 0.7 V based on HDV conditions (0.2 mgPt cm –2 and 250 kPa air). More importantly, the MEA is highly durable and can retain 1.31 A cm –2 at 0.7 V after 30,000 voltage cycles (~19% loss), surpassing the commercial Pt/C catalyst (loss of ~56%). Therefore, the Mn–N–C carbon-supported Pt catalyst holds a great promise to meet the challenging DOE target (1.07 A cm –2 at 0.7 V after 150,000 cycles) for HDVs.

25 ENERGY STORAGE↗

Designing Low Tortuosity Electrodes through Pattern Optimization for Fast-Charging

The development of fast-charging technologies is crucial for expediting the progress and promotion of electric vehicles. In addition to innovative material exploration, reduction in the tortuosity of electrodes is a favored strategy to enhance the fast-charging capability of lithium-ion batteries by optimizing the ion-transfer kinetics. To realize the industrialization of low-tortuosity electrodes, a facile, cost-effective, highly controlled, and high-output continuous additive manufacturing roll-to-roll screen printing technology is proposed to render customized vertical channels within electrodes. Extremely precise vertical channels are fabricated by applying the as-developed inks, using LiNi 0.6 Mn 0.2 Co 0.2 O 2 as the cathode material. Additionally, the relationship between the electrochemical properties and architecture of the channels, including the pattern, channel diameter, and edge distance between channels, is revealed. The optimized screen-printed electrode exhibited a seven-fold higher charge capacity (72 mAh g -1 ) at a current rate of 6 C and superior stability compared with that of the conventional bar-coated electrode (10 mAh g -1 , 6 C) at a mass loading of 10 mg cm -2 . Finally, this roll-to-roll additive manufacturing can potentially be applied to various active materials printing to reduce electrode tortuosity and enable fast charging in battery manufacturing.

42 ENGINEERING↗

PILBCP-IL Composite Ionomers for High Current Density Performance

Wide-spread commercialization of fuel cell electric vehicles using proton exchange membrane fuel cell (PEMFC) power sources requires that several existing limitations be addressed. These include: (1) a reduction in platinum (Pt) loading in the catalytic electrodes, (2) improvements in reactant and electronic mobility throughout the catalytic electrodes, (3) reduction in the reliance on materials derived from polluting “forever chemicals”, and (4) a significant improvement in the operational longevity of catalytic electrode components. In this project, a team of two universities, Drexel University and Texas A&M University, one national lab, National Renewable Energy Laboratory, and one company, General Motors, collaborated to develop a new cathode ionomer chemistry that would address these limitations and result in an improvement in performance over existing ionomer materials. The key technology developed through this collaborative project was a composite cathode ionomer encompassing an ionic liquid interlayer between Pt catalysts and a sulfonated polymerized ionic liquid block co-polymer (S-PILBCP) that possess the orthogonal properties of protonic conductivity and ionic liquid enhanced kinetics and durability (see schematic in Figure 1). The composite S-PILBCP ionomer eliminates many of the existing issues with perfluorosulfonic acid-based ionomers including active site blocking by sulfonate specific adsorption, restricted O 2 transport through ionomer films, limited humidity tolerance and active area loss for carbon pore confined catalyst particles, and use of polluting “forever chemicals”. Following successful integration of the developed composite ionic liquid into a PEMFC cathode catalyst layer, we demonstrate enhanced performance over Nafion containing cathodes with Pt/C and PtCo/C at both low and high current density. The performance with our composite S-PILBCP ionomer meets the Department of Energy (DOE) targets for light duty vehicle applications

08 HYDROGEN↗

Effect of Catalyst and Catalyst Layer Composition on Catalyst Support Durability

Polymer electrolyte membrane fuel cells (PEMFCs) are efficient, zero-emission engines for the automotive sector. However, cost and durability are major barriers for the commercialization of PEMFCs. Degradation of the carbon support in the cathode catalyst layer due to high potential excursions caused by unmitigated events like H 2 starvation, or start-up/shutdown are still a major durability issue in PEMFCs. Catalyst support durability was studied by accelerated stress tests (ASTs) that included repeated potential cycling from 1.0 to 1.5 V. The effect of catalyst layer composition on carbon corrosion was studied using membrane electrode assemblies with different catalysts (Pt, PtCo), catalyst composition (catalyst wt.%, supports), ionomer composition (loading, and equivalent weights). The corrosion of the carbon support is similar between Pt and PtCo catalysts. However, the performance degradation rate is higher for the alloy catalysts due to differences in catalyst particle size and the transition metal’s leaching accelerating the performance degradation. The carbon loss is lower for catalysts with lower initial carbon loading (or higher catalyst wt.%), which is better for durability. However, the cumulative loss of carbon is identical for electrodes with the same catalyst support irrespective of catalyst and ionomer composition in the catalyst layer.

25 ENERGY STORAGE↗