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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine-Free” SEI

Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid-electrolyte interphase (SEI) are ideal to enable sodium metal and anode-free cells. Herein we present advanced characterization of a novel fluorine-free electrolyte utilizing the [HCB 11 H 11 ] 1- anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm -2 and a high coulombic efficiency of 99.5 % in half-cell configurations. Additionally, surface characterization of electrodes post-operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine-free SEI. Furthermore, weak ion-pairing is identified as key towards the successful development of fluorine-free sodium electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Understanding LIB Battery Electrodes Through Classical Electrochemical Interface Theory

Classical models of the electrochemical interface can be applied to complex and dynamic electrodes to understand important mechanisms that are relevant to device-level phenomena like calendar aging or cycle life. Here, we show that negative alloy electrodes with wide electrochemical windows cannot be assumed to have static interfaces throughout all states of charge. Under high states of charge, the interface -including the solid electrolyte interphase - has characteristics that resemble a highly polarized electrode far from the point of zero charge. Under these conditions, the interface can be understood through the Helmholtz model. At lower states of charge, the interface capacitance decreases and the space charge layer length increases. This transformation resembles a metal electrode approaching the point of zero charge which is understood through the Gouy-Chapman-Stern-Grahame model of the electrochemical interface. This transformation happens at both silicon and carbon-coated silicon interfaces. From voltage-limited cycling experiments, in the limit of the diffuse double layer, the silicon electrode impedance rises significantly in the first few cycles. This rise is related to the continuous electrochemical reduction of electrolyte components from an interface that is not electronically screened from the electrolyte. In other words, an electrode interface for batteries should resemble a 'Helmholtz-like' structure.

anode↗
DOE OSTI2023

Gas-Liquid Flow Modeling for Renewable Fuels Production

Aerobic/anaerobic and gas fermentation pathways have emerged as promising new technologies for the generation of renewable fuels/chemicals from biomass derived sugars, and mixtures of greenhouse/energy rich gas streams (CO2/CH4/H2/CO) via microbial action. Example pathways include sugars-to-ethanol conversion, biomethanation (CO2/H2 to CH4), biogas upgrading, CO fermentation and wet-waste conversion. Gas and liquid phase transport, mass-transfer, and mixing physics at large length scales can significantly affect microbial conversion rates, particularly when the microbial reaction requires a narrow set of conditions. These phenomena are difficult to study in small-scale bench-top reactors that are typically well-mixed. Predictive computational fluid dynamics (CFD) based simulations can therefore aid in the scale-up, design and optimization of these reactors. This work presents multiphase Euler-Euler CFD simulations of at-scale (~500 m3) bioreactors. Our mathematical model treats the gas and liquid as interpenetrating phases. This approach reduces the computational complexity of tracking individual gas bubbles that are several orders of magnitude smaller than reactor dimensions. We solve the Reynolds averaged Navier-Stokes (RANS) multiphase equations that account for phase and chemical species transport, interphase mass and momentum transfer and uses a phenomenological model for gas uptake by microbes. We use a customized solver derived from open-source CFD toolbox, OpenFOAM [1], to perform these simulations, which has been validated against small-scale reactors in our previous work [2]. There is currently a knowledge-gap regarding bubble-size distributions when using gas mixtures with vastly different properties, which can have a significant impact overall mass-transfer. For example, hydrogen bubbles are more buoyant compared to other relatively heavier gases (CO2/CH4/CO), resulting in a large distribution of residence times and bubble sizes. This work therefore develops a deeper understanding of bubble dynamics and interphase mass transfer in such heterogenous gas mixtures through well-resolved computational models. We use a population balance model (PBM) for bubble-size-distribution modeling that is validated against small-scale experiments in our solver with an uncertainty quantification study for bubble coalescence and break-up model parameters. Results pertaining to multiple simulations of gas-fermentation reactors are presented where gas mixtures with varying compositions of CO2/CH4/CO/H2 are imposed at the sparger boundaries. The spatio-temporal variations in bubble-size distribution and mass transfer coefficient are analyzed for varying superficial velocities and gas-compositions for varying sizes of bubble-column and airlift reactors. This work will also examine the performance of different reactor designs, viz. bubble column reactor, airlift reactor with an internal draft tube, and a stirred-tank reactor with Rushton impellers. Reactor mass-transfer coefficient, gas hold-up, and dissolved gas distribution are critically analyzed among reactors, and sensitivity studies pertaining to gas flow rates and reactor geometry will be presented. [1] Weller, H., Tabor, G., Jasak, H. and Fureby, C., A tensorial approach to computational continuum mechanics using object-oriented techniques, Computers in physics, 12, 6, 620--631, 1998. [2] Rahimi, M., Sitaraman, H., Humbird, D. and Stickel, J., Computational fluid dynamics study of full-scale aerobic bioreactors: Evaluation of gas-liquid mass transfer, oxygen uptake, and dynamic oxygen distribution, Chemical Engineering Research and Design, 139: 283-295.

BIOMASS FUELS↗
DOE OSTI2022

Scaling CFB risers: Maintaining microstructure dynamics

Over the years there have been numerous approaches to develop a scaleup methodology for circulating fluidized beds. Many of these past approaches have relied on macroscopic definitions of similitude to define dimensionless groups such as Reynolds number, Froude number, density ratios, and dimensional ratios involving different length scales. These approaches have demonstrated various levels of success, but often fail when used outside the bounds of experimental datasets. The issue with these methods is that they rely on macroscopic similitude with the hopes that those conditions would provide microscopic similitude as it does in single phase systems where the Buckingham Pi techniques have given reasonable success. Two of the main reasons for failure are 1) changing fluidization regimes and 2) changing material properties that result in the material falling into a different Geldart group. Both are certain to change the microstructure (local instantaneous volume solids fraction) and changes to the microstructure affect the interphase transport properties of the reactor system, namely the mass transfer and heat transfer. Here, this work presents a new approach towards scaling based upon maintaining similitude at the microscale. It reviews a novel dimensionless flow regime map developed from analysis of the deterministic chaos parameters and higher order moments to ensure microstructure similitude. The work then examines four cases from the literature to assess the scaling approach used: (1) same particle-different scale risers for Geldart Group B particles, (2) Glicksman scaling of atmospheric circulating fluidized bed combustor, (3) same particle-different scale risers for Geldart Group A particles and (4) Glicksman scaling for pressurized gasification. General findings are that none of the scaling approaches produced directly applicable microstructure similar behavior based upon the chaotic and higher moment analysis. The positive take away is that the approach can define scale conditions that will provide similar microstructure that can be us to predict transport behavior.

42 ENGINEERING↗
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 OSTI2025

Investigation of kinetic inductance and microwave loss in thin-film TaC x N 1−x superconducting resonators

The promise of tantalum for realizing superconducting quantum devices has generated interest in its compound films, particularly nitrides. Among these, cubic-phase tantalum carbonitride (TaC x N 1−x ) offers reduced susceptibility to oxidation and a high critical temperature, yet its microwave properties remain largely unexplored. Here, in this study, we investigate plasma-enhanced atomic layer deposition of cubic-phase TaC x N 1−x thin films for superconducting microwave circuits. Structural and transport measurements reveal nanocrystalline morphology with sub-10 nm grains and superconductivity in the dirty limit. Coplanar waveguide resonators exhibit moderately high kinetic inductance (16.8 pH/sq for 30 nm films) with potential for enhancement through dimensional scaling. The films also support high internal quality factors exceeding 10 5 at 50 mK in the single-photon regime, comparable to granular aluminum. Loss analysis identifies the two-level systems as the dominant limiting mechanism, with potential for further reduction through interface engineering. These results establish atomic layer deposited TaC x N 1−x as a promising material for scalable, low-loss, high-inductance superconducting circuits.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Chemo‐Mechanics Interplay Dictates Interface Instability and Asymmetry in Plating and Stripping of Sodium Metal Electrodes

Abstract The development of practical sodium (Na) metal batteries is hindered by key challenges including dendrite growth, dead metal formation, and unstable solid electrolyte interphase (SEI) growth. A fundamental understanding of the chemo‐mechanical interactions at the Na/SEI interface is critical for designing stable Na metal electrodes. In this work, the coupled electrochemical‐mechanical processes governing the morphological evolution and stability of Na metal during plating and stripping are investigated. The heterogeneous nature of transport and morphological interactions at the Na/SEI interface is revealed to result in nonuniform mechanical overpotentials and reaction fronts, eventually leading to Na filaments or pits. The spatio‐temporal evolution of stress heterogeneities during Na plating and stripping is shown to be asymmetric, manifesting in varying morphological nonuniformities and instability modes. The crucial role of external pressure in modulating the electrochemical‐transport interactions, the mechanical response of Na, and the localized reaction currents and stresses at the Na/SEI interface is demonstrated. At different external pressure conditions, the correlation between transport heterogeneities in the SEI and the onset and propagation of interface instability has been delineated. This work highlights the need for synergistic tailoring of external pressure and SEI heterogeneity toward achieving stable electrodeposition and dissolution in Na metal electrodes.

Singla, Aditya [School of Mechanical Engineering P↗
DOE OSTI2025

Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte

Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.

Wang, Yixian [Materials Science and Engineering Pr↗
DOE OSTI2022

Ionic Conductive and Highly-Stable Interface for Alkali Metal Anodes

Alkali metals are regarded as the most promising candidates for advanced anode for the next-generation batteries due to their high specific capacity, low electrochemical potential, and lightweight. However, critical problems of the alkali metal anodes, especially dendrite formation and interface stabilization, remain challenging to overcome. The solid electrolyte interphase (SEI) is a key factor affecting Li and Na deposition behavior and electrochemical performances. Herein, a facile and universal approach is successfully developed to fabricate ionic conductive interfaces for Li and Na metal anodes by modified atomic layer deposition (ALD). In this process, the Li metal (or Na metal) plays the role of Li (or Na) source without any additional Li (or Na) precursor during ALD. Moreover, the key questions about the influence of ALD deposition temperature on the compositions and structure of the coatings are addressed. The optimized ionic conductive coatings have significantly improved the electrochemical performances. In addition, the electrochemical phase-field model is performed to prove that the ionic conductive coating is very effective in promoting uniform electrodeposition. Further, this approach is universal and can be potentially applied to other different metal anodes. At the same time, it can be extended to other types of coatings or other deposition techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

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

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

Xia, Li [State Key Laboratory of Physical Chemistr↗
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 OSTI2025

Systematic feature design for cycle life prediction of lithium-ion batteries during formation

Optimization of the formation step in lithium-ion battery manufacturing is challenging due to limited physical understanding of solid-electrolyte interphase formation and the long testing time (∼100 days) for cells to reach the end of life. We propose a systematic feature-design framework that requires minimal domain knowledge for accurate cycle life prediction during formation. By only using two simple Q (V) features designed from our framework, extracted from formation data without any additional diagnostic cycles, we achieved an average of 9.87% error for cycle life prediction. Here, the physics-based investigation guided by the two designed features shows that the voltage ranges identified by our framework capture the effects of formation temperature and microscopic-particle resistance heterogeneity. By designing highly predictive, robust, and interpretable features, our approach can accelerate industrial battery formation research, leveraging the interplay between data-driven feature design and mechanistic understanding.

25 ENERGY STORAGE↗
DOE OSTI2020

Verification and Validation of MFiX-PIC

This work is aimed at verification and validation (V&V) of particle-in-cell (PIC) approach in the National Energy Technology Laboratory’s (NETL) Multiphase Flow with Interphase eXchanges (MFiX-PIC) which was officially released in April 2019. Under verification, the results from MFiX-PIC are compared with exact or analytical solutions, while experimental results are used for benchmarking under validation. The test suite consists of the following cases: Terminal velocity. Particle advection in time-varying flow field. Particle settling in a dense medium. Evaporation. Rayleigh-Taylor instability. Minimum fluidization. Mini-circulating fluidized bed. The cases reported in a format consistent with the existing Verification and Validation Manual (Musser et al., 2018) explore a wide range of flow velocities and concentration regimes. Only one case considered in this work verifies the implementation of heat and mass transfer routines in MFiX-PIC, while a few other studies are currently underway to further expand the validation space in reacting flows. This study highlights the need for a rigorous analysis to objectively quantify the effect of model parameters. In addition, there is a scarcity of high-quality experimental data in the literature suitable for validating PIC methodology. Future efforts would include performing experiments which provide results for a valuable database. While designing such experiments, particle count should be significant to have sufficient particles per parcel while maintaining an optimal parcel to cell volume ratio. Also, datasets should have objectively assessed experimental uncertainty whereby confidence interval in those measurements become more explicit.

42 ENGINEERING↗
DOE OSTI2022

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

A deep understanding of the interaction of the surface of cathode materials with solid electrolytes is crucial to design advanced solid-state batteries (SSBs). This is especially true for the new class of lithium metal chloride (Li-M-Cl) solid electrolytes which are receiving rapidly growing attention due to their very high oxidative stability (>4 V) in combination with good ionic conductivity that can enable long cell cycle life. While Li-M-Cl electrolytes typically contain resource-limited metals (M) such as indium or rare earths, work has focused on substituting M with more abundant elements such as zirconium. Via operando resistance measurements using intermittent current interruption we explore the dynamic evolution of the interphase at the surface of Ni-rich NCM85 or NCM111 cathode particles inside a working SSB with three different Li-(M 1 ,M 2 )-Cl catholytes (Li 3 InCl 6 , Li 2 Sc 1/3 In 1/3 Cl 4 and Li 5/2 Y 1/2 Zr 1/2 Cl 6 ) to reveal the impact of the cationic metal substitution on the interfacial chemistry. We show that the metal plays a critical role in determining high voltage stability, contrary to prior assumptions. Using a combination of cyclic voltammetry and ultraviolet photoelectron spectroscopy measurements of the electronic band structure to assess oxidative stability; coupled with DFT calculations and ToF-SIMS to evaluate products formed at the interface at different upper cutoff potentials and degrees of delithiation, we are able to differentiate between electrochemical and chemical degradation. We find that Li 2 Sc 1/3 In 1/3 Cl 4 yields the highest (and Li 3 InCl 6 the lowest) stability against electrochemical oxidation, while Li 5/2 Y 1/2 Zr 1/2 Cl 6 undergoes a detrimental chemical reaction with oxygen released from Ni-rich NCM85 at high potentials, resulting in fast capacity fading. Altogether, our work establishes a platform for the metrics and an approach that can be utilized to efficiently evaluate the stability of new halide SEs in SSB cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Computational Fluid Dynamics Analysis of a 12 MW Circulating Fluidized Bed Rise

A three-dimensional (3D) two fluid model (TFM) model of the 12 MW circulating fluidized bed (CFB) riser at Chalmers University was developed using the open-source Multiphase Flow with Interphase eXchanges (MFiX) Software Suite. The hydrodynamic behavior of the riser was validated by comparing axial pressure profiles from experimental measurements with the results from the simulations. Under some of the operating conditions where there was no external circulation of solids, the pressure profiles from the simulation matched well with the experimental measurements. For the cases where there was external circulation of solids, the pressure profiles with the monodisperse solid phase modeling underpredicted the solids concentration in the freeboard region. With the inclusion of polydispersity in the model, the predicted pressure profiles agreed well with the experimental measurements. A two-dimensional (2D) model of the riser was used to perform simulations of coal combustion. The predicted flue gas outlet compositions of oxygen and carbon dioxide compared reasonably to experiments. The experiments also reported some concentration of carbon monoxide which was overpredicted in the simulations. Additional experimental data such as axial oxygen concentration profile and pressure profiles were also compared with the experiment. It was observed that the oxygen concentration in the bottom bed from the simulations was higher than in the experiments, which suggested that most of the oxidation reactions occurred in the bottom bed. The concentration of volatiles and char in the simulations was lower in the bottom bed than in the experiments, which suggest that there is not sufficient penetration of the solid phase species into the bed.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2026

Stabilizing Cathode–Electrolyte Interphase of Nickel-Rich Single-Crystal Cathodes for Lithium-Ion Batteries

Nickel-rich single-crystal (SC) layered oxides are promising cathode candidates for next-generation lithium-ion batteries (LIBs) owing to their high energy density and structural robustness against intergranular cracking. However, their intrinsic surface reactivity with liquid electrolytes accelerates parasitic reactions at the cathode–electrolyte interphase (CEI), leading to transition-metal dissolution, gas generation, and impedance buildup. In this work, we synthesized SC-Li x Ni 0.9 Mn 0.05 Co 0.05 O 2 (NMC9055, 1 ≤ x ≤ 1.2) using a eutectic-assisted method and investigated interface stabilization strategies. A nickel-deficient Li x Ni 0.6 Mn 0.2 Co 0.2 O 2 (NMC622, 1 ≤ x ≤ 1.2) coating was applied via evaporation-based deposition to suppress CEI degradation pathways. Structural and compositional analyses confirmed uniform shell formation and preserved particle integrity. Half-cell electrochemical testing against lithium metal revealed ∼10% higher capacity retention and improved reversibility compared with pristine SC NMC9055, particularly under high-voltage operation. In conclusion, these results highlight the critical role of controlled surface chemistry in mitigating CEI instability in nickel-rich SC cathodes, offering a pathway toward enabling durable high-energy LIBs.

Coating processes↗
DOE OSTI2025

Monofluorinated acetal electrolyte for high-performance lithium metal batteries

High degree of fluorination for ether electrolytes has resulted in improved cycling stability of lithium metal batteries due to stable solid electrolyte interphase (SEI) formation and good oxidative stability. However, the sluggish ion transport and environmental concerns of high fluorination degree drive the need to develop less fluorinated structures. Here, we depart from the traditional ether backbone and introduce bis(2-fluoroethoxy)methane (F2DEM), featuring monofluorination of the acetal backbone. High coulombic efficiency and stable long-term cycling in Li||Cu half cells can be achieved with F2DEM even under fast Li metal plating conditions. The performance of F2DEM is further compared with diethoxymethane (DEM) and 2-[2-(2,2-difluoroethoxy)ethoxy]-1,1,1-trifluoroethane (F5DEE). A significantly lower overpotential is observed with F2DEM, which improves energy efficiency and enables its application in high-rate conditions. Comparative studies of F2DEM with DEM and F5DEE in anode-free lithium iron phosphate (LiFePO4) LFP pouch cells and high-loading LFP coin cells further show improved capacity retention of F2DEM electrolyte, demonstrating its practical applicability. More importantly, we also extensively investigate the underlying mechanism for the superior performance of F2DEM through various techniques, including X-ray photoelectron spectroscopy, scanning electron microscopy, cryogenic electron microscopy, focused ion beam, electrochemical impedance spectroscopy, and titration gas chromatography. Overall, F2DEM facilitates improved Li deposition morphology with reduced amount of dead Li. This enables F2DEM to show superior performance, especially under higher charging and slower discharging rate conditions.

25 ENERGY STORAGE↗
DOE OSTI2026

Multiscale Cryo Electron Microscopy Reveals Interfacial Degradation and Stabilization in Battery Electrodes

Electrochemical interfaces are dynamic systems, evolving based on their local environment and reactant surface structures. The electrode-electrolyte interface in Li-ion batteries can be protective, limiting parasitic reactions with the electrolyte to passivate the surface [1]. Additionally, this interphase has an impact on the Li-ion transport through that layer based on its composition, bonding environment, and thickness. These parameters are challenging to collect and may vary depending on the electrode surface site investigated relative to its spatial position in a coin cell. This study will detail a multiscale cryogenic electron microscopy approach where millimeter-scale cross-sections through the coin cell batteries were made using a cryogenic stage within a fs-laser plasma focused ion beam (laser PFIB) with complementary energy dispersive X-ray spectroscopy able to detect variations in the composition at electrode interfaces [2]. Microscale cross-sectioning and lamella sample preparation of battery electrodes was conducted at the Center for Integrated Nanotechnologies using a Ga-ion focused ion beam (FIB) with air-free and cryo-transfer [3], followed by nanoscale mapping of composition and bonding within the CEI through cryo-scanning transmission electron microscopy (cryo-STEM) electron energy loss spectroscopy [4]. This multiscale approach enabled identification of millimeter-scale features of a battery stack with visualization of degradation in electrodes such as cracks in cathode particles, gas evolution, and SEI evolution; microscale interfacial characteristics, such as heterogeneity in the SEI or barrier layer and identification of electrolyte networks to the electrode surfaces; and nanoscale measurement of the CEI thickness, mapping of transition metal bonding within the cathode particles to identify loss of active materials, and identification of beneficial electrolyte additives incorporated into the CEI structure. This multiscale approach allows for a statistical understanding of the primary mechanisms and parasitic degradation pathways that impact performance by limiting the ion transport pathways within Li+ batteries.

36 MATERIALS SCIENCE↗