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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 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Kinetic Effects of Anion Clusters on the Interfacial Stability between Solid-State Electrolyte and Metal Anode

The success of all-solid-state batteries (ASSBs) depends on the solid-state electrolyte (SSE) exhibiting high interfacial stability and room-temperature ionic conductivity. However, the current SSEs, especially those with practical ionic conductivities (≥10 –3 S/cm) at room temperature, often develop unstable interfaces at the metal anode, in some cases with even greater severity than with liquid organic electrolytes. Despite persistent efforts, achieving interfacial stability and sufficient ionic conductivity simultaneously represents one of the greatest challenges in ASSBs. The current approaches focus on stabilizing the interface by incorporating secondary interlayers or introducing coatings by surface engineering. The method is often material-specific, and the added interlayers often deteriorate during cycling. In this work, using phase analysis and explicit interface modeling, we demonstrate a strategy to kinetically stabilize the interface between the SSE and metal anode by incorporating selected monoanion clusters in the SSE; they can effectively lower or even halt the reduction kinetics at the interface by promoting on-site formation of interphases that are highly electron insulating. The study provides insight into the kinetic effects to achieve SSEs with superior properties in bulk and at the interface.

25 ENERGY STORAGE↗
DOE OSTI2026

Two-population Rouse models for polymer segmental dynamics in nanocomposites

Segmental dynamics of polymer chains in a model nanocomposite of poly(ethylene oxide) and silica nanoparticles (NPs) was investigated using quasielastic neutron scattering. The dynamics can be accurately described with the Rouse model. The bulklike polymer far from the NP surface behaves as the neat polymer. However, the slower polymer in the interface close to the NP surface is described either with a second Rouse population with different relaxation time or using the suppressed Rouse model. These simple two-population models accurately reproduce the experimental data, with the suppressed Rouse model describing topological constraints, on average, every 12 beads with an interfacial thickness up to 13.5 beads, and the effect of the interface extending to a layer of thickness comparable to the end-to-end distance of the polymer. This modeling provides an explanation for the observed reinforcement in PNC even at low loadings, consistent with current understanding of the relevance of the interphase.

Composite materials↗
DOE OSTI2022

Modeling and Analysis of a Polyphase Wireless Power Transfer System for EV Charging Applications

Extreme fast charging is an emerging technology targeting to significantly decrease charging times of electric vehicles to 10–20 minutes, similar to an interstate gas refueling practice. High-power wireless power transfer (WPT) systems with polyphase electromagnetic couplers can be an attractive solution for these applications due to the very high surface power density of polyphase coils with reduced ripple current characteristics on both the primary and secondary sides that result in more compact designs with reduced dc bus bar capacitor requirements. In addition, WPT systems offer automated charging process, which can be an enabling technology for connected and automated vehicles, with high-efficiency, convenience, safety, and flexibility. This study presents a matrix representation of a mathematical model for a three-phase WPT system with series-series connected three-phase resonant compensation networks. Nonzero interphase mutual inductances between the same side phase windings are considered for tuning to obtain a circuit model for parametric sensitivity. Simulation and experimental results presented for a 50-kW experimental prototype to demonstrate the operation of the polyphase WPT system.

Zeng, Rong↗
DOE OSTI2022

Stress rupture of SiC/SiC composite tubes under high-temperature steam

SiC-fiber–reinforced SiC matrix composite cladding for light water reactor fuel elements must withstand high-temperature steam oxidation in a loss-of-coolant accident scenario (LOCA). Current composite designs include an outer monolithic SiC layer, in part, to increase steam oxidation resistance. However, it is not clear how such a structure would behave under high-temperature steam in the case when the monolithic layer cracks and carbon interphases and SiC fibers are exposed to the environment. To fill this knowledge gap, stress-rupture tests of prototypic SiC composite cladding at 1000°C under steam and inert environments were conducted. The applied stress was ~120 MPa, which was beyond the initial cracking stress. The failure lifetime under steam was 400–1300 s, while 75% of the composite specimens did not fail after 3 h of total exposure under inert gases. Microstructural observations suggest that steam oxidation activated slow crack growth in the fibers, which led to failure of the composite. The results from this study suggest that stress rupture in steam environments could be a limiting factor of the cladding under reactor LOCA conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Optimization of a Cyclone Using Multiphase Flow Computational Fluid Dynamics

The U.S. Department of Energy National Energy Technology Laboratory's (NETL) 50 kW th chemical looping reactor (CLR) has an underperforming cyclone, which was designed using empirical correlations. To improve the performance of this cyclone using computational fluid dynamics (CFD)-based modeling simulations, four critical design parameters including the vortex tube radius and length, barrel radius, and the inlet width and height were optimized. Here, NETL's open source multiphase flow with interphase exchange (MFiX) CFD code has been used to model a series of cyclones by systematically varying the geometric design parameters. To perform the optimization process, the surrogate modeling and sensitivity analysis followed by the optimization capability in nodeworks was used. The basic methodology for the process is to employ a statistical design of experiments (DOE) method to generate sampling simulations that fill the design space. Corresponding CFD models are then created, executed, and postprocessed. A response surface is created to characterize the relationship between input parameters and the quantities of interest (QoI). Finally, the CFD-surrogate is used by an optimization method to find the optimal design condition based on the objective and constraints prescribed. The resulting optimal cyclone has a larger diameter and longer vortex tube, a larger diameter barrel, and a taller and narrower solids inlet. The improved design has a predicted pressure drop 11 times lower than the original design while reducing the mass loss by a factor of 2.3.

42 ENGINEERING↗
DOE OSTI2022

In-situ visualization of the transition metal dissolution in layered cathodes

Transition metal dissolution in layered cathodes is one of the most intractable issues that deteriorates the battery performance and lifetime. It not only aggravates the structure degradation in cathode, but also damages the solid electrolyte interphase in anode and even induce the formation of lithium dendrites. In this work, we investigate the dissolution behaviors of polycrystalline and single-crystalline layered cathode via operando X-ray imaging techniques. The described cathode particle morphology appears to have a significant impact on the evolution of the dissolution dynamics. As a mitigation strategy, we reveal that doping with trace amount of Zr in the layered cathode could improve its robustness against the transition metal dissolution. Our finding provides valuable insights for designing the next-generation highly-stable layered battery cathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Manufacturing Cathodes via Dry-Processing for Lithium-Ion Batteries

Conventional lithium-ion battery (LIB) electrodes are prepared through a wet slurry process with n-methyl pyrrolidone solvent, especially for cathodes. The wet slurry process encounters several disadvantages such as binder migration, electrode cracking in thick electrodes, energy intense heat-dry NMP solvent removal, and costly NMP recovery. The cost and energy consumption of coating and drying of electrode are about 11.5 % and > 46 % in LIB manufacturing, respectively. Thereby, it is essential to develop a facile roll-to-roll solvent-free LIB electrode processing for reducing the cost and energy consumption. Recently, the Maxwell-type dry processing (DP) shines new lights on LIB manufacturing, which mainly bases on dry mixing (DM) of electrode component powder followed by calendering into electrode films and laminating onto current collectors, realizing the rapid manufacturing of LIB electrodes in a powder-to-film manner for industries. This report shares some recent progress on the DP from our group. We aim to further advance the manufacturing science of DP by correlating the processing conditions with electrode properties and performance. Particularly, we investigate the effect of DM, and compression on the polytetrafluoroethylene (PTFE) binder fiberization, porosity, mechanical properties, electrical conductivity and electrochemical behaviors of electrodes. The DM study suggests that PTFE fiberization heavily relies on the degree of DM. Insufficient DM results in poor PTFE fiberization while outrageous DM damages the formed PTFE fibers. Both negatively affect the mechanical behaviors of the electrodes and their rate capability. However, moderate DM is highly beneficial. In addition, our study of the porosity impact reveals that LiNi0.8Mn0.1Co0.1O2 (NMC) secondary particles can be broken into primary particles due to compression, especially at low porosity. Those fractured NMC secondary particles exhibit lower modulus. We propose that a moderate porosity of around 32% favors the electronic conductivity, charge transfer impedance and rate capability. The study of the cathodic electrolyte interphase layer of PTFE-based DPed electrode confirms that side reactions of PTFE binder due to the formation of LiF in LiClO4-based electrolyte.

Tao, Runming↗
DOE OSTI2022

In situ x-ray photoelectron spectroscopy analysis of electrochemical interfaces in battery: Recent advances and remaining challenges

An in-depth understanding of charge transfer processes at the electrochemical interfaces is a critical knowledge gap impeding the design of energy storage materials. X-ray photoelectron spectroscopy plays an important role in analyzing electronic structures of heterogeneous interfaces, such as electrode-electrolyte interphases. Correspondingly, ex situ studies based on postmortem analysis of electrode materials using x-ray techniques are widely reported in the literature but often fail to capture intermediate and transient species, which are critical for a predictive understanding of the charge transfer process. The lack of extensive in situ/operando x-ray analysis of buried interfaces in energy storage systems can be mainly attributed to technical limitations, such as the requirement of high vacuum conditions. However, in the past decade, considerable efforts have been devoted to overcoming these technical barriers and enable investigation of the solid/solid and solid/liquid interfaces. This review catalogs some of the recent progresses and new experimental designs in the application of in situ and operando x-ray photoelectron spectroscopy toward characterizing interfacial processes and emergent properties, which can help build the design strategy for advanced batteries. The remaining challenges and future research directions are also discussed, as potential paths forward in this field.

Wi, Sungun↗
DOE OSTI2020

Deciphering atomistic mechanisms of the gas-solid interfacial reaction during alloy oxidation

Gas-solid interfacial reaction is critical to many technological applications from heterogeneous catalysis to stress corrosion cracking. A prominent question that remains unclear is how gas and solid interact beyond chemisorption to form a stable interphase for bridging subsequent gas-solid reactions. Here, we report real-time atomic-scale observations of Ni-Al alloy oxidation reaction from initial surface adsorption to interfacial reaction into the bulk. We found distinct atomistic mechanisms for oxide growth in O 2 and H 2 O vapor, featuring a “step-edge” mechanism with severe interfacial strain in O 2 , and a “subsurface” one in H 2 O. Ab initio density functional theory simulations rationalize the H 2 O dissociation to favor the formation of a disordered oxide, which promotes ion diffusion to the oxide-metal interface and leads to an eased interfacial strain, therefore enhancing inward oxidation. Our findings depict a complete pathway for the Ni-Al surface oxidation reaction and delineate the delicate coupling of chemomechanical effect on gas-solid interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Battery metal recycling by flash Joule heating

The staggering accumulation of end-of-life lithium-ion batteries (LIBs) and the growing scarcity of battery metal sources have triggered an urgent call for an effective recycling strategy. However, it is challenging to reclaim these metals with both high efficiency and low environmental footprint. We use here a pulsed dc flash Joule heating (FJH) strategy that heats the black mass, the combined anode and cathode, to >2100 kelvin within seconds, leading to ~1000-fold increase in subsequent leaching kinetics. There are high recovery yields of all the battery metals, regardless of their chemistries, using even diluted acids like 0.01 M HCl, thereby lessening the secondary waste stream. The ultrafast high temperature achieves thermal decomposition of the passivated solid electrolyte interphase and valence state reduction of the hard-to-dissolve metal compounds while mitigating diffusional loss of volatile metals. Life cycle analysis versus present recycling methods shows that FJH significantly reduces the environmental footprint of spent LIB processing while turning it into an economically attractive process

36 MATERIALS SCIENCE↗
DOE OSTI2025

Trapping and imaging dynamic battery nanointerfaces via electrified cryo-EM

The electrified interface between a liquid and a solid underpins diverse phenomena, from ion-transfer during battery operation to action potentials enabling biological communication. However, conventional tools are blind to the nanoscale dynamics of this metastable interface. Here, we leverage electrified cryo–electron microscopy (eCryo-EM), a technique that rapidly freezes and kinetically traps these dynamic, nonequilibrium states during battery operation for nanoscale characterization. Collective snapshots of the electrified interface at controlled time intervals quantifies early-stage growth kinetics of the solid electrolyte interphase (SEI), a passivation film that governs electron and ion transport. Unexpectedly, the diffusivity of charged species of the two SEI films with differing chemistry and performance are estimated to be within 10% of the other, indicated by the slope of their diffusion-limited SEI growth regimes. Instead, the slope of the reaction-limited SEI growth regimes differs by a factor of 3, suggesting that lowered reactivity of the high-performance electrolyte is largely responsible for its high coulombic efficiency.

Science & Technology - Other Topics↗
DOE OSTI2025

Highly textured metal anodes for stable aqueous batteries: Fabrication and characterization

We report a purely mechanical “cold-compression flow” method for fabricating Zn, Sn, and In substrates with tunable crystallographic textures. Using textured Zn as a model system, we investigate Zn electrocrystallization and demonstrate correlated growth of crystalline films with correlation lengths from tens to hundreds of micrometers. At 5 milliamperes per square centimeter (mA/cm 2 ), capacities between 20 and 82 milliampere hours per square centimeter (mA·hour/cm 2 ) are achieved depending on substrate texture level. At higher currents (40 mA/cm 2 ), capacities reach up to 604 mA·hour/cm 2 . Rotating disk electrode studies show that dominantly (002) textured Zn substrates exhibit enhanced corrosion resistance and reduced interphase passivation. We introduce an effective Damköhler number (Da*) to concisely describe morphological evolution during electrocrystallization across substrates with different textures. High-texture (002) Zn substrates substantially enhance performance in high-capacity (~20 mA·hour/cm 2 ) symmetric Zn||Zn cells and full cells (Zn||δ-MnO 2 and Zn||I 2 ), enabling fast-charging and prolonged energy storage in coin and pouch rechargeable Zn battery formats.

Science & Technology - Other Topics↗
DOE OSTI2026

Electrode-omics reveals epochs in silicon anode evolution underpinning electrochemomechanical resilience

Here, we advance electrode-omics to identify evolutionary bursts by which ethereal locally superconcentrated electrolytes (LSCEs) mitigate silicon anode degradation through its epochs of electrochemical and chemical reactions. Anode composites form initially at high potential from ethereal solvent and anion [bis(fluorosulfonyl)imide (FSI − )] redox. A first evolutionary burst at lower potential enriches composites with lithium alkoxides (LiO–R) and lithium oxide (Li 2 O) and depletes sulfur oxides (SO x ) species. As the cells are cycled, a second evolutionary burst takes place, where previously extinct SO x species reemerge concurrently with a loss of LiO–R and Li 2 O. This identifies reactions rooted in “SuFEx” chemistry, where oxoanionic LiO–R and Li 2 O species, electrochemically generated in the solid-electrolyte interphase, chemically react with FSI − in the electrolyte to form emergent species. This sequence of evolutionary bursts produces a mechanically resilient composite that reduces silicon anode cracking over hundreds of cycles, leading to overpotential increase of only ~0.01 volts after 200 cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Operando Acoustic Monitoring of SEI Formation and Long-Term Cycling in NMC/SiGr Composite Pouch Cells

Stable long-term cycling and solid-electrolyte-interphase (SEI) formation are key challenges in the design of Si/graphite composites as Li-ion battery (LIB) anode materials. Typically, these long-term cycling properties are examined in flooded half-cell settings making use of a Li-metal counter electrode and a Si/graphite working electrode. This form factor has the advantage of offering an unlimited supply of Li-ions and electrolyte, thus isolating performance degradation to the passivation of the working electrode. However, half-cell studies are ineffective in revealing performance and degradation mechanisms of the Si/graphite composite in a more commercially realistic full cell setting. This paper outlines an operando acoustic technique that can offer insights on SEI formation and capacity degradation of Si/graphite composites in a full cell setting. Through a combination of electrochemical and chemical analyses, we show that increasing passivation of the silicon particles in the Si/graphite composite anode is correlated with an increase in the acoustic time-of-flight shift. We further show that temporary loss of the acoustic signal during the first cycle is associated with significant gassing of the cell. The operando acoustic technique outlined here is low-cost, simple to setup and has the potential for localized resolution, indicating usefulness in commercial-scale Si/graphite cell quality control and diagnosis.

42 ENGINEERING↗
DOE OSTI2020

Influence of Binder Coverage on Interfacial Chemistry of Thin Film LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathodes

In this work, we explore the influence of binder coverage and chemistry on the interfacial properties of the textured Ni-rich cathode LiNi 0.6 Mn 0.2 Co 0.2 O 2 . We find that the formation of the cathode/electrolyte interphase (CEI) composition varies significantly for cathodes coated with either poly(vinylene fluoride) (PVDF), carboxymethyl cellulose (CMC), or lithium polyacrylate (LiPAA) after cycling to high upper cutoff voltages (4.5 V vs Li/Li). The PVDF-coated samples had a thinner CEI and twice the relative concentration of LiF and Li 2 CO 3 to Li x PO y F z species in the CEI compared to the uncoated sample. This correlated with significantly lower interfacial impedance (285 vs ~1700 Ohm-cm 2 ) and improved capacity retention between cycles of the PVDF-coated samples compared to the other binder compositions and the uncoated sample. CMC-coated samples performed worst, with a CEI comprised of greater amounts of Li x PO y F z . In addition, we find the choice of binder results in the selective protection or promotion of electrolyte reactions at the (104) surface of the 622 cathode. This suggests that the choice of binder can impact the surface chemistry and performance of high voltage cathodes and supports an avenue for interest in multifunctional binders for stabilizing the CEI.

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

The Impact of Different Substituents in Fluorinated Cyclic Carbonates in the Performance of High Voltage Lithium-Ion Battery Electrolyte

Ethylene carbonate (EC) has been used as the Solid-Electrolyte Interphase (SEI) former in the conventional electrolyte for decades. However, its low anodic stability leads to severe capacity decay during cycling under high voltage operation. Therefore, finding a viable electrolyte with high anodic stability and the ability to form robust SEI for high voltage lithium-ion batteries is of primary importance. In this study, a series of electrolytes containing various fluorinated cyclic carbonates as the SEI former have been designed, synthesized and evaluated. Linear sweep voltammetry study suggested that fluorinated cyclic carbonates generally possess higher anodic stability than EC. Based on the cycling performance of LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC532)/ graphite full cells, the electrolyte with DFEC/FEMC (1.0 M LiPF 6 ) inhibited the oxidation side reaction on the cathode and forms a vigorous SEI on the anode. The high voltage NMC532/Graphite cell utilizing the novel electrolyte exhibits excellent cycling durability under both room and elevated temperature. The superior performance of the DFEC based electrolyte was further unveiled by SEM, EDAX and XRD. Both the anode and cathode of the full cell employing DFEC based electrolyte retained their intrinsic structures after cycling while the electrodes cycled in conventional electrolyte showed severe degradation.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design

The severe volumetric changes in Si particles during the Li (de)alloying process cause expansion and contraction of the electrodes, which along with excessive electrolyte reduction and solid electrolyte interphase formation brings about rapid decay in cell capacity. In this work, we use operando electrochemical dilatometry to quantify the (de)lithiation-induced expansion/contraction of Si-based and graphite-rich electrodes during electrochemical cycling. We evaluate the relationship between electrode capacity and dilation and observe that by increasing the Si contribution to the electrode capacity, the swelling is aggravated upon lithiation. For silicon-rich anodes, the electrode dilation can be higher than 300%, and the expansion profile consists of a combination of slow swelling at low lithiation followed by an accelerated increase at higher lithium contents. We investigate how electrode properties, such as porosity, affect the dilation profile and quantify the irreversible expansion of the electrodes. Finally, we discuss some of the challenges associated with the dilatometry technique and suggest experimental approaches for obtaining consistent and reliable data.

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

Challenging Practices of Algebraic Battery Life Models through Statistical Validation and Model Identification via Machine-Learning

Various modeling techniques are used to predict the capacity fade of Li-ion batteries. Algebraic reduced-order models, which are inherently interpretable and computationally fast, are ideal for use in battery controllers, technoeconomic models, and multi-objective optimizations. For Li-ion batteries with graphite anodes, solid-electrolyte-interphase (SEI) growth on the graphite surface dominates fade. This fade is often modeled using physically informed equations, such as square-root of time for predicting solvent-diffusion limited SEI growth, and Arrhenius and Tafel-like equations predicting the temperature and state-of-charge rate dependencies. In some cases, completely empirical relationships are proposed. However, statistical validation is rarely conducted to evaluate model optimality, and only a handful of possible models are usually investigated. This article demonstrates a novel procedure for automatically identifying reduced-order degradation models from millions of algorithmically generated equations via bi-level optimization and symbolic regression. Identified models are statistically validated using cross-validation, sensitivity analysis, and uncertainty quantification via bootstrapping. On a LiFePO 4 /Graphite cell calendar aging data set, automatically identified models utilizing square-root, power law, stretched exponential, and sigmoidal functions result in greater accuracy and lower uncertainty than models identified by human experts, and demonstrate that previously known physical relationships can be empirically "rediscovered" using machine learning.

25 ENERGY STORAGE↗