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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Site Disorder Drives Cyanide Dynamics and Fast Ion Transport in Li 6 PS 5 CN

Halide argyrodite solid-state electrolytes of the general formula Li 6 PS 5 X exhibit complex static and dynamic disorder that plays a crucial role in ion transport processes. Here, we unravel the rich interplay between site disorder and dynamics in the plastic crystal argyrodite Li 6 PS 5 CN and the impact on ion diffusion processes through a suite of experimental and computational methodologies, including temperature-dependent synchrotron powder X-ray diffraction, AC electrochemical impedance spectroscopy, 7 Li solid-state NMR, and machine learning-assisted molecular dynamics simulations. Sulfide and (pseudo)halide site disorder between the two anion sublattices unilaterally improves long-range lithium diffusion irrespective of the (pseudo)halide identity, which demonstrates the importance of site disorder in dictating bulk ionic conductivity in the argyrodite family. Furthermore, we find that anion site disorder modulates the presence and time scales of cyanide rotational dynamics. Ordered configurations of anions enable fast, quasi-free rotations of cyanides that occur on time scales of 10 11 Hz at T = 300 K. In contrast, we find that cyanide dynamics are slow or frozen in Li 6 PS 5 CN when site disorder between the cyanide and sulfide sublattices is present at T = 300 K. We rationalize the observed differences in cyanide dynamics in the context of elastic dipole interactions between neighboring cyanide anions and local strain induced by the configurations of site disorder that may impact the energetic landscape for cyanide rotational dynamics. Through this study, we find that anion disorder plays a decisive role in dictating the extent and time scales of both lithium ion and cyanide dynamics in Li 6 PS 5 CN.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Quantitative Analysis of Origin of Lithium Inventory Loss and Interface Evolution over Extended Fast Charge Aging in Li Ion Batteries

During the extreme fast charging (XFC) of lithium-ion batteries, lithium inventory loss (LLI) and reaction mechanisms at the anode/electrolyte interface are crucial factors in performance and safety. Determining the causes of LLI and quantifying them remain an essential challenge. We present mechanistic research on the evolution and interactions of aging mechanisms at the anode/electrolyte interface. We used NMC 532 /graphite pouch cells charged at rates of 1, 6, and 9 C up to 1000 cycles for our investigation. The cell components were characterized after cycling using electrochemical measurements, inductively coupled plasma optical emission spectroscopy, 7 Li solid-state nuclear magnetic resonance spectroscopy, and high-performance liquid chromatography/mass spectrometry. The results indicate that cells charged at 1 C exhibit no Li plating, and the increase of SEI thickness is the dominant source of the Li loss. In contrast, Li loss in cells charged at 9 C is related to the formation of the metallic plating layers (42%) the SEI layer (38.1%) and irreversible intercalation into the bulk graphite (19%). XPS analysis suggests that the charging rate has little influence on the evolution of SEI composition. The interactions between competing aging mechanisms were evaluated by a correlation analysis. In conclusion, the quantitative method established in this work provides a comprehensive analytical framework for understanding the synergistic coupling of anodic degradation mechanisms, forecasting SEI failure scenarios, and assessing the XFC lithium-ion battery capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2023

Interaction of methanol with a layered α-Sn(IV) phosphate on its surface: A solid-state NMR study

Here, a layered crystalline phosphate, α-Sn(HPO 4 ) 2 ·H 2 O, treated with CD 3 OD was characterized by the 31 P, 119 Sn, 1 H and 2 H solid-state NMR techniques. The 2 H solid-echo MAS NMR spectra of the product have unexpectedly revealed deuterated hydronium ions on the surface of this material instead of intercalated methanol. According to the 13 C NMR and GC–MS studies, these ions are formed by water molecules following a dehydration of the methanol-d 4 to yield deuterated dimethyl ether.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Insights into palladium poisoning of Cu/SSZ-13 selective catalytic reduction catalysts

Here, the impacts of Pd poisoning to the activity, selectivity, and hydrothermal stability of Cu/SSZ-13 selective catalytic reduction (SCR) catalysts are reported. Pd lowers DeNOx efficiency of Cu/SSZ-13 via two mechanisms: (1) displacing SCR active sites in the form of isolated Pd-ions, and (2) catalyzing non-selective NH 3 oxidation in the form of PdO. The first mechanism works by the diffusion of isolated Pd-ions into chabazite cages to displace ZCu II OH SCR active species, and it occurs on Cu/SSZ-13 catalysts with and without external surface CuO clusters in similar fashion. In contrast, the second mechanism works differently with and without external surface CuO clusters. For Cu/SSZ-13 catalyst without external CuO clusters (i.e., primarily isolated Cu-ions), PdO leads to significant decrease of DeNOx efficiency at reaction temperatures above ~400°C due to its non-selective NH 3 oxidation activity at high temperatures. However, this poisoning effect becomes much less impactful on Cu/SSZ-13 catalyst containing CuO clusters. This is due to the formation of CuO-PdO solid solution via interactions between CuO and PdO, which reduces non-selective NH 3 oxidation potential. Furthermore, this solid solution formation even mitigates adverse effects caused by hydrothermal aging. Hence, the poisoning effects of Pd are closely related to Cu speciation and spatial distribution of a Cu/SSZ-13 catalyst. Finally, this study suggests a strategy in eliminating Pd poisoning, that is, the introduction of an oxide phase that effectively traps PdO but does not adversely influence SCR.

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

Supercritical water desalination and oxidation (SCWDO): Effectiveness on complex solutions, technoeconomic, and CO 2 impact for produced water treatment

The modern energy-economy is increasingly causing the production of highly saline brines, including from produced water. Supercritical water desalination can concentrate and extract minerals from these brines, but the effects of mixed salt interactions, organic degradation with additives, and the technology's economics are not well understood at supercritical condition. The present study evaluated and experimentally studied an integrated supercritical water desalination and oxidation (SCWDO) process for treating real-produced water samples from oil/natural gas field. The complex interactions between the various anions and cations in produced water were extensively evaluated. Most of the divalent and trivalent ions were extracted below 250 °C while the majority of the monovalent salt were removed between 380 to 410 °C. The treated real produced water was of drinking water quality, with <500 mg/l of total dissolved solid (TDS) and with 100% organics removal. Furthermore, the heat liberated during the organic oxidation could be utilized internally and for electricity generation for enhanced the energy efficiency and lower cost of produced water treatment. With system optimization, the proposed SCWDO process can essentially be made a net zero energy process. A novel process flow diagram for the commercial scale self-powered hybrid SCWDO technology was proposed as a cost-effective produced water treatment to mitigate the environmental crises. Techno-economic analysis showed that produced water treatment cost with SCWDO can be reduced to 2–3 $/m 3 and can be up to 60 % cheaper to traditional deep well reinjection. Additionally, the proposed SCWDO process could achieve net negative CO 2 emission.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Revealing the Anion–Solvent Interaction for Ultralow Temperature Lithium Metal Batteries

Anion solvation in electrolytes can largely change the electrochemical performance of the electrolytes, yet has been rarely investigated. Herein, three anions of bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), and derived asymmetric (fluorosulfonyl)(trifluoro-methanesulfonyl)imide (FTFSI) are systematically examined in a weakly Li + cation solvating solvent of bis(3-fluoropropyl)ether (BFPE). In-situ liquid secondary ion mass spectrometry demonstrates that FTFSI - and FSI - anions are associated with BFPE solvent, while weak TFSI - /BFPE cluster signals are detected. Molecular modeling further reveals that the anion–solvent interaction is accompanied by the formation of H-bonding-like interactions. Further, anion solvation enhances the Li + cation transfer number and reduces the organic component in solid electrolyte interphase, which enhances the Li plating/stripping Coulombic efficiency at a low temperature of -30 °C from 42.4% in TFSI-based electrolytes to 98.7% in 1.5 m LiFTFSI and 97.9% in LiFSI-BFPE electrolytes. The anion–solvent interactions, especially asymmetric anion solvation also accelerate the Li + desolvation kinetics. The 1.5 m LiFTFSI-BFPE electrolyte with strong anion–solvent interaction enables LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811)||Li (20 µm) full cell with stable cyclability even under -40 °C, retaining over 92% of initial capacity (115 mAh g -1 , after 100 cycles). The anion–solvent interactions insights allow to rational design the electrolyte for lithium metal batteries and beyond to achieve high performance.

25 ENERGY STORAGE↗
DOE OSTI2022

U(VI) binding onto electrospun polymers functionalized with phosphonate surfactants

We previously observed that phosphonate functionalized electrospun nanofibers can uptake U(VI), making them promising materials for sensing and water treatment applications. Here, we investigate the optimal fabrication of these materials and their mechanism of U(VI) binding under the influence of environmentally relevant ions (e.g., Ca 2+ and CO 3 2- ). We found that U(VI) uptake was greatest on polyacrylonitrile (PAN) functionalized with longer-chain phosphonate surfactants (e.g., hexa- and octadecyl phosphonate; HDPA and ODPA, respectively), which were better retained in the nanofiber after surface segregation. Subsequent uptake experiments to better understand specific solid-liquid interfacial interactions were carried out using 5 mg of HDPA-functionalized PAN mats with 10 μM U at pH 6.8 in four systems with different combinations of solutions containing 5 mM calcium (Ca 2+ ) and 5 mM bicarbonate (HCO 3 -). U uptake was similar in control solutions containing no Ca 2+ and HCO 3 - (resulting in 19 ± 3% U uptake), and in those containing only 5 mM Ca2+ (resulting in 20 ± 3% U uptake). A decrease in U uptake (10 ± 4% U uptake) was observed in experiments with HCO 3 -, indicating that UO 2 -CO 3 complexes may increase uranium solubility. Results from shell-by-shell EXAFS fitting, aqueous extractions, and surface-enhanced Raman scattering (SERS) indicate that U is bound to phosphonate as a monodentate inner sphere surface complex to one of the hydroxyls in the phosphonate functional groups. New knowledge derived from this study on material fabrication and solid-liquid interfacial interactions will help to advance technologies for use in the in-situ detection and treatment of U in water.

42 ENGINEERING↗
DOE OSTI2025

Spin squeezing in an ensemble of nitrogen–vacancy centres in diamond

Spin-squeezed states provide a seminal example of how the structure of quantum mechanical correlations can be controlled to produce metrologically useful entanglement. These squeezed states have been demonstrated in a wide variety of quantum systems ranging from atoms in optical cavities to trapped ion crystals. By contrast, despite their numerous advantages as practical sensors, spin ensembles in solid-state materials have yet to be controlled with sufficient precision to generate targeted entanglement such as spin squeezing. Here we report the experimental demonstration of spin squeezing in a solid-state spin system. Our experiments are performed on a strongly interacting ensemble of nitrogen–vacancy colour centres in diamond at room temperature, and squeezing (−0.50 ± 0.13 dB) below the noise of uncorrelated spins is generated by the native magnetic dipole–dipole interaction between nitrogen–vacancy centres. To generate and detect squeezing in a solid-state spin system, we overcome several challenges. First, we develop an approach, using interaction-enabled noise spectroscopy, to characterize the quantum projection noise in our system without directly resolving the spin probability distribution. Second, noting that the random positioning of spin defects severely limits the generation of spin squeezing, we implement a pair of strategies aimed at isolating the dynamics of a relatively ordered sub-ensemble of nitrogen–vacancy centres. Furthermore, our results open the door to entanglement-enhanced metrology using macroscopic ensembles of optically active spins in solids.

Atomic and molecular physics↗
DOE OSTI2021

Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading

The solid–electrolyte interphase (SEI), a layer formed on the electrode surface, is essential for electrochemical reactions in batteries and critically governs the battery stability. Active materials, especially those with extremely high energy density, such as silicon (Si), often inevitably undergo a large volume swing upon ion insertion and extraction, raising a critical question as to how the SEI interactively responds to and evolves with the material and consequently controls the cycling stability of the battery. Here, by integrating sensitive elemental tomography, an advanced algorithm and cryogenic scanning transmission electron microscopy, we unveil, in three dimensions, a correlated structural and chemical evolution of Si and SEI. Furthermore, corroborated with a chemomechanical model, we demonstrate progressive electrolyte permeation and SEI growth along the percolation channel of the nanovoids due to vacancy injection and condensation during the delithiation process. Consequently, the Si–SEI spatial configuration evolves from the classic ‘core–shell’ structure in the first few cycles to a ‘plum-pudding’ structure following extended cycling, featuring the engulfing of Si domains by the SEI, which leads to the disruption of electron conduction pathways and formation of dead Si, contributing to capacity loss. The spatially coupled interactive evolution model of SEI and active materials, in principle, applies to a broad class of high-capacity electrode materials, leading to a critical insight for remedying the fading of high-capacity electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Measurement of Mass-Temperature Distributions in the Core of Implosions on the National Ignition Facility (Full Technical Final Report)

Inertial confinement fusion plasmas are characterized by several kilo-electron-volt (keV) electron temperatures and ion and electron densities approaching 100 to 1000 times solid. In these implosions which simulate the dynamics of our sun, spectroscopic dopants can lead to detailed exploration of the plasma gradients that are not possible in other places. This is both in the central core pressure and temperature as well as any “mix” resultant from ablation and hydrodynamic interactions. This work will show new Bayesian atomic physics models applied to ICF plasmas to give both the temperature and density of the internal hot spot to better describe the physical nature of these implosions along with trying to spatially resolve the mix coming from the ablator region. The mission impact is to demonstrate this effect and to lead to a more quantitative description of mix in inertial confinement plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Origin of rate limitations in solid-state polymer batteries from constrained segmental dynamics within the cathode

Currently, one of the key challenges preventing the wide commercialization of polymer-based solid-state batteries is achieving high-rate capabilities. This work unravels chain structure and segmental dynamics in a polymer-based composite cathode consisting of LiFePO 4 (LFP), carbon, and poly(ethylene oxide) (PEO) with lithium bis(trifluoromethanesulfonyl)imide. Small-angle neutron scattering (SANS) data reveal that PEO chains are adsorbed on the surface of LFP particles during slurry processing to make the composite electrode. The strong interaction between LFP and PEO chains leads to greatly reduced segmental dynamics of PEO, as discovered by quasi-elastic neutron scattering (QENS). The reduced segmental dynamics results in 70% decreased Li + mobility of the polymer electrolyte in the composite cathode. The combined SANS and QENS study indicates that one of the key bottlenecks that limits the rate performance of PEO-based polymer batteries originates from molecular interactions within the cathode.

25 ENERGY STORAGE↗
DOE OSTI2020

Calculation of electron-ion temperature equilibration rates and friction coefficients in plasmas and liquid metals using quantum molecular dynamics

In this work, we discuss a method to calculate with quantum molecular dynamics simulations the rate of energy exchanges between electrons and ions in two-temperature plasmas, liquid metals, and hot solids. Promising results from this method were recently reported for various materials and physical conditions. Like other ab initio calculations, the approach offers a very useful comparison with the experimental measurements and permits an extension into conditions not covered by the experiments. The energy relaxation rate is related to the friction coefficients felt by individual ions due to their nonadiabatic interactions with electrons. Each coefficient satisfies a Kubo relation given by the time integral of the autocorrelation function of the interaction force between an ion and the electrons. These Kubo relations are evaluated using the output of quantum molecular dynamics calculations in which electrons are treated in the framework of finite-temperature density functional theory. The calculation presents difficulties that are unlike those encountered with the Kubo formulas for the electrical and thermal conductivities. In particular, the widely used Kubo-Greenwood approximation is inapplicable here. Indeed, the friction coefficients and the energy relaxation rate diverge in this approximation since it does not properly account for the electronic screening of electron-ion interactions. The inclusion of screening effects considerably complicates the calculations. We discuss the physically motivated approximations we applied to deal with these complications in order to investigate a widest range of materials and physical conditions. Unlike the standard method used for the electronic conductivities, the Kubo formulas are evaluated directly in the time domain and not in the energy domain, which spares one from needing to introduce an extraneous undetermined numerical parameter to account for the discrete character of the numerical density of states. We highlight interesting properties of the energy relaxation rate not shared by other electronic properties, in particular its self-averaging character. We then present a detailed parametric and convergence study with the numerical parameters, including the system size, the number of bands and k-points, and the physical approximations for the dielectric function and the exchange-correlation energy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Interaction energy and isosteric heat of adsorption between hydrogen and magnesium diboride

Hydrogen storage materials form a crucial research topic for future energy utilization employing hydrogen and among those of interest magnesium diboride (MgB 2 ) has shown its prevalence. In this study, a first-principles analytical adsorption model of one hydrogen molecule in the vicinity of various magnesium diboride crystal surfaces was developed in order to obtain surface thermodynamic properties as a function of molecular and lattice properties. Henry's law constant (K H ) and isosteric heat of adsorption (ΔH ads ) indicators of the affinity between a gaseous molecule and a solid surface are thus calculated. The results in this paper not only address questions pertaining to the first stage of hydrogen storage processes but also advance the understanding of physisorption thermodynamics of a neutral molecule (H 2 ) coming in contact with a layered metallic-like surface (MgB 2 ). Although the model is built from a framework of classical calculations, quantum effects are incorporated as the fractional charge of the ions on the free surfaces, which is essential for the calculation of analytic thermodynamic values that approximate calculations from other methods. To benchmark our theoretical models, periodic density functional calculations were performed to determine the interactions between H 2 and different MgB 2 surfaces from first-principles. By considering both the top and sublayers of MgB 2 in calculating interaction energy, we have analytically and computationally calculated the interaction energies of H 2 molecules and MgB 2 's terminated planes, and witnessed the strong dependence of interaction energies on surface charges. We have also observed a dipole flipping phenomenon which explains the discontinuity seen in the interaction energy graph of Mg(0001). Both analytical and computational results showed heat of adsorption at zero coverage varying at a very low range (<7 kJ mol -1 ).

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

Shape Persistent, Highly Conductive Ionogels from Ionic Liquids Reinforced with Cellulose Nanocrystal Network

Abstract Shape‐persistent, conductive ionogels where both mechanical strength and ionic conductivity are enhanced are developed using multiphase materials composed of cellulose nanocrystals and hyperbranched polymeric ionic liquids (PILs) as a mechanically strong supporting network matrix for ionic liquids with an interrupted ion‐conducting pathway. The integration of needlelike nanocrystals and PIL promotes the formation of multiple hydrogen bonding and electrostatic ionic interaction capacitance, resulting in the formation of interconnected networks capable of confining a high amount of ionic liquid (≈95 wt%) without losing its self‐sustained shape. The resulting nanoporous and robust ionogels possess outstanding mechanical strength with a high compressive elastic modulus (≈5.6 MPa), comparable to that of tough, rubbery materials. Surprisingly, these rigid materials preserve the high ionic conductivity of original ionic liquids (≈7.8 mS cm −1 ), which are distributed within and supported by the nanocrystal network‐like rigid frame. On the one hand, such stable materials possess superior ionic conductivities in comparison to traditional solid electrolytes; on the other hand, the high compression resistance and shape‐persistence allow for easy handling in comparison to traditional fluidic electrolytes. The synergistic enhancement in ion transport and solid‐like mechanical properties afforded by these ionogel materials make them intriguing candidates for sustainable electrodeless energy storage and harvesting matrices.

Lee, Hansol↗
DOE OSTI2021

Multimodal imaging of oil-in-water bilgewater emulsion and biofilms

Bilgewater emulsions, consisting of oil and surfactant mixtures in water, affect many aquatic species. Thus development of methods and techniques to treat or mitigate the formation and undesired consequences of shipboard emulsions are urgently needed. This work presents new results of the evolution of the bilgewaer chemical and physical properties using in situ imaging. A Navy O/W emulsion consisting of three oils and a detergent mixture was used as the synthetic bilgewater model [1, 2]. Synthetic oil-in-water (O/W) emulsion droplets were seled in a vacuum compatible microfluidic sample holder and imaged using a suite of tools including scanning electron microscopy (SEM), time-of-flight secondary ion mass spectrometry (ToF-SIMS), confocal laser scanning microscopy, and optical microscopy, highlighting the advantage of multiscale analysis and its applications in waste reduction and treatment in the environment. The transferrable and vacuum compatible microfluidic interface, System for Analysis at the Liquid Vacuum Interface (SALVI), was used in this study. SALVI enabled surface analysis of liquids and liquid-solid interactions using ToF-SIMS and SEM [3, 4]. Its detection window is an aperture of 2 ?m in diameter open to vacuum, permitting direct detection of the liquid surface. Liquid is withheld by surface tension within the aperture. The interface is composed of a silicon nitride membrane and polydimethylsiloxane microchannel [3, 4]. A variety of samples including complex liquid mixtures, ionic liquids, single mammalian cells, live biofilms, and solid-electrolyte interface have been analyzed using in situ imaging [5, 6]. The feasibility of using SALVI for in situ SEM imaging of nanoparticles and colloids in liquid was recently demonstrated [7]. This paper shows new findings of multimodal imaging and analysis of synthesized emulsion particles in water. Figure 1 depicts a schematic of multimodal in situ imaging of bilgewater emulsion using SEM and ToF-SIMS. Furthermore, we study the interactions of microbes and bilgewater emulsion. Microbes play an important role in the ocean. We hypothesize that microbes release organics that can act as surfactants that affect bilgewater formation or weakening. We present the first systematic study of emulsions and biofilms and investigate the effects of biofilms on bilgewater emulsions. Pseudomonas was selected as a model strain. Biofilms were cultured in a microchannel to allow culture [8]. Once a thick layer of biofilms was formed, the medium solution was changed to a mixture consisting of 50 % bilgewater emulsion. Dispersed biofilms were collected at 24 hrs. and 48 hrs. after emulsions were introduced into the channel. Bilgewater emulsions, biofilms, and mixtures of bilgewater emulsions and biofilms were analyzed using multiple in situ and ex situ techniques as described earlier. Our findings indicate that biofilms change the chemical makeup of the emulsion surface compositions and emulsion droplet size distribution, confirming the hypothesis that extracellular polymeric substance (EPS) related components released from biofilms can function as surfactants and change the oil-in-water interfaces.

bilgewater, multimodal imaging, biofilms↗
DOE OSTI2023

Electrolyte design for Li-ion batteries under extreme operating conditions

The ideal electrolyte for the widely used LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811)||graphite lithium-ion batteries is expected to have the capability of supporting higher voltages (≥4.5 volts), fast charging (≤15 minutes), charging/discharging over a wide temperature range (±60 degrees Celsius) without lithium plating, and non-flammability. No existing electrolyte simultaneously meets all these requirements and electrolyte design is hindered by the absence of an effective guiding principle that addresses the relationships between battery performance, solvation structure and solid-electrolyte-interphase chemistry. Here we report and validate an electrolyte design strategy based on a group of soft solvents that strikes a balance between weak Li+-solvent interactions, sufficient salt dissociation and desired electrochemistry to fulfil all the aforementioned requirements. Remarkably, the 4.5-volt NMC811||graphite coin cells with areal capacities of more than 2.5 milliampere hours per square centimetre retain 75 per cent (54 per cent) of their room-temperature capacity when these cells are charged and discharged at -50 degrees Celsius (-60 degrees Celsius) at a C rate of 0.1C, and the NMC811||graphite pouch cells with lean electrolyte (2.5 grams per ampere hour) achieve stable cycling with an average Coulombic efficiency of more than 99.9 per cent at -30 degrees Celsius. The comprehensive analysis further reveals an impedance matching between the NMC811 cathode and the graphite anode owing to the formation of similar lithium-fluoride-rich interphases, thus effectively avoiding lithium plating at low temperatures. Additionally, this electrolyte design principle can be extended to other alkali-metal-ion batteries operating under extreme conditions.

25 ENERGY STORAGE↗
DOE OSTI2021

Degradation-resistant TiO 2 @Sn anodes for high-capacity lithium-ion batteries

As the demand for higher-performance batteries has increased, so has the body of research on theoretical high-capacity anode materials. However, the research has been hindered because the high-capacity anode material properties and interactions are not well understood, largely due to the difficulty of observing cycling in situ. Using electrochemical scanning transmission electron microscopy (ec-STEM), we report the real-time observation and electrochemical analysis of pristine tin (Sn) and titanium dioxide-coated Sn (TiO 2 @Sn) electrodes during lithiation/delithiation. As expected, we observed a volume expansion of the pristine Sn electrodes during lithiation, but we further observed that the expansion was followed by Sn detachment from the current collector. Remarkably, although the TiO 2 @Sn electrodes also exhibited similar volume expansion during lithiation, they showed no evidence of Sn detachment. We found that the TiO 2 surface layer acted as an electrochemically activated artificial solid-electrolyte interphase that serves to conduct Li ions. As a physical coating, it mechanically prevented Sn detachment following volume changes during cycling, providing significant degradation resistance and 80% Coulombic efficiency for a complete lithiation/delithiation cycle. Interestingly, upon delithiation, TiO 2 @Sn electrode displayed a self-healing mechanism of small pore formation in the Sn particle followed by agglomeration into several larger pores as delithiation continued.

25 ENERGY STORAGE↗
DOE OSTI2021

Role of Polysulfide Anions in Solid-Electrolyte Interphase Formation at the Lithium Metal Surface in Li–S Batteries

Delineating intricate interactions between highly reactive Li-metal electrodes and the diverse constituents of battery electrolytes has been a long-standing scientific challenge in materials design for advanced energy storage devices. Here, we isolated lithium polysulfide anions (LiS 4 - ) from an electrolyte solution based on their mass-to-charge ratio and deposited them on Li-metal electrodes under clean vacuum conditions using ion soft landing (ISL), a highly controlled interface preparation technique. The molecular level precision in the construction of these model interfaces with ISL, coupled with in situ x-ray photoelectron spectroscopy and ab initio theoretical calculations, allowed us to obtain unprecedented insight into the parasitic reactions of well-defined polysulfides on Li-metal electrodes. Our study reveals that the oxide-rich surface layer, which is amenable to direct electron exchange, drives multielectron sulfur oxidation (S o → S 6+ ) processes. Furthermore, our results have substantial implications for the rational design of future Li-S batteries with improved efficiency and durability.

25 ENERGY STORAGE↗