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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Observations of the liquid/solid interface in low-gravity melting

Time-lapsed photography of the liquid/solid interface of a melting ice cylinder was taken on Skylab 3 over a period of three hours. The same experiment was simulated on earth such that morphological and thermodynamic differences could be noted. A study of the returned color film clearly shows the dominance of surface tension effects in low-gravity melting. In the Skylab experiment, the ends of the ice cylinder melted first with the water being driven by surface tension onto the cylindrical surfaces. At any time, the principle of minimum surface area governs the overall appearance of the water-ice globule which changed from a cylindrical to a spherical shape. The latent heat of melting in low-gravity is supplied only by radiation (81%) and conduction (19%); whereas in one-g, the convective (55%) and radiative (38%) mode of heat transfer dominates over the conductive portion (7%). Information is also provided on containerless melting and heat transfer in space in the absence of convective air currents.

Otto, G. H.↗
NASA NTRS1998

Simultaneous in situ Optical Monitoring Techniques during Crystal Growth of ZnSe by Physical Vapor Transport

ZnSe crystals grown in sealed ampoules by the physical vapor transport method were monitored in situ using three techniques, simultaneously. A Michelson interferometer was set-up to observe the growth rate and surface morphological evolution. An interference pattern (interferogram) is formed by the interaction between the reflection of a HeNe laser (632.8 nm wavelength) off the crystal-vapor interface and a reference beam from the same laser. Preliminary results indicate that the rate of growth/thermal-etching can be calculated using analog data acquisition and simple fringe counting techniques. Gross surface features may also be observed using a digital frame grabber and fringe analysis software. The second in situ technique uses optical absorption to determine the partial pressures of the vapor species. The Se2 and Zn vapor species present in the sealed ampoule absorb light at characteristic wavelengths. The optical absorption is determined by monitoring the light intensity difference between the sample and reference beams. The Se2 Partial pressure profile along the length of the ampoule was estimated from the vibronic absorption peaks at 340.5, 350.8, 361.3 and 379.2 nm using the Beer's law constants established in the calibration runs of pure Se. Finally, because the high temperature crystal growth furnace contains windows, in situ visual observation of the growing crystal is also possible. The use of these techniques not only permits in situ investigation of high temperature vapor growth of semiconductors, but also offers the potential for real time feed back on the growing crystal and allows the possibility of actively controlling the growth process.

Su, C.- H.↗
DOE OSTI2021

Formation of pyrophosphates across grain boundaries induces the formation of mismatched but oriented interfaces in silver phosphate polypods

The interfaces and their misfit defects determine the materials properties for a wide range of applications, such as electronic devices, photocatalysis, and mechanical engineering, etc. However, current understanding of atomic interfacial structures is limited. Here we discover a special interfacial structure, mismatched but oriented interface via two distinct facets. Transmission and scanning electron microscopy results suggest that, in Ag 3 PO 4 polypods structures, interfaces of {1 0 0} and {1 1 0}, ({1 0 0}/(1 1 0}), {1 0 0}/{1 1 1}, {1 1 0}/{1 1 1}, and {1 0 0}/{1 0 0}, etc., have a certain orientation relationship, corresponding to the energy minima and coincident site lattice of interfacial atoms as demonstrated by molecular dynamics simulations. Density functional theory demonstrates that the formation of pyrophosphate and/or phosphates rotation to bond across the interface compensate the lattice mismatch at the interfaces, as well as deformations of Ag-O bonds. Furthermore, our work opens up a new avenue for a much wider range of interfacial structures, allow for a higher diversity of structures, and shine light on tailoring crystal structures, morphologies, and the resulting properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Physics based Reliability Models for Supercritical CO 2 Turbomachinery Components

CSP plants using sCO 2 power cycle can potentially achieve high thermal conversion efficiency at low capital cost due to compact turbo-machinery and other components. An sCO 2 expander and improved heat exchanger is expected to provide a major stepping stone for achieving CSP power at $0.06/kW-hr LCOE, energy conversion efficiency > 50%, and total power block cost < $1,200/kW installed. Hybrid gas bearings (HGB) and Dry gas seals (DGS) are two key components that are critical for robust and efficient operation of future sCO 2 power cycles. From a system perspective, HGBs can provide substantial benefits (~3 to 5%) to the modular CSP operation, while use of DGSs limits the leakage losses as well as the windage losses in the generator and can increase overall generator efficiency by ~ 8%. The life limiting mechanisms of HGBs and DGSs in high pressure, high temperature sCO2 environment were not well understood and hence this program aims at developing physics-based performance prediction and life prediction models for these two components. The output of the performance models serves as input to the life models. The performance models were validated using experimental data and using data from literature. DGS and HGB models have shed light on some risks associated with its operation in sCO2 expander and will guide more robust designs tailored towards sCO 2 cycle applications. A DGS was tested in 1MWe sCO2 turbo expander to study its performance and validate the performance models. To understand the effect of high pressures, high temperatures and sCO 2 environment on crack initiation, crack propagation and LCF/HCF life of these components, a novel experimental setup was developed. The LCF test data was used to calibrate and validate the life prediction models. The effect of sCO 2 corrosion on the life of Ni-based super-alloys is quantified using long duration experiments. Advanced microstructure and spectroscopic analyses conducted shed light on some key differences between IN718 and IN617 in terms of oxidation morphology, chemical species diffusion and trapping, the formation of protective corrosion resistant layers and changes in surface properties. A novel crack initiation model was developed which takes into account strain distribution, temperature, hold times and activation energy at the gas-metal interface and predicts the number of cycles to initiate the crack in the Inconel alloy. An advanced 3D fracture mechanics-based crack propagation model was also developed which takes into account the transient loading mission of the component and predict how fast the crack will grow and what will be its final shape and size. High energy X-Ray tomography measurements were conducted to study and validate 3D morphology of crack growth inside the specimen. These two models along with chemical kinetics models obtained from corrosion tests can be combined to predict the total life of the component under given long term operating conditions. A Bayesian Hybrid Modeling (BHM) probabilistic framework was developed to quantify uncertainty in physics-based performance models and in crack initiation and crack propagation models, to calibrate the models and to validate the models with statistical confidence. Advanced coupled physics multi-phase flow models were developed to study condensation, boiling and phase change behavior of CO 2 under various sCO 2 turbomachinery and heat exchanger conditions. A novel experimental setup was also designed to observe phase change of CO 2 during its transition across liquid-gas-supercritical state lines.

14 SOLAR ENERGY↗
DOE OSTI2019

Physics based Reliability Models for Supercritical CO 2 Turbomachinery Components

CSP plants using sCO 2 power cycle can potentially achieve high thermal conversion efficiency at low capital cost due to compact turbo-machinery and other components. An sCO 2 expander and improved heat exchanger is expected to provide a major stepping stone for achieving CSP power at 0.06/kW-hr LCOE, energy conversion efficiency > 50 % ,and total power block cost< $1,200/kW installed. Hybrid gas bearings (HGB) and Dry gas seals (DGS) are two key components that are critical for robust and efficient operation of future sCO 2 power cycles. From a system perspective, HGBs can provide substantial benefits (~3 to 5%) to the modular CSP operation, while use of DGSs limits the leakage losses as well as the windage losses in the generator and can increase overall generator efficiency by ~ 8%. The life limiting mechanisms of HGBs and DGSs in high pressure, high temperature sCO 2 environment were not well understood and hence this program aims at developing physics-based performance prediction and life prediction models for these two components. The output of the performance models serves as input to the life models. The performance models were validated using experimental data and using data from literature. DGS and HGB models have shed light on some risks associated with its operation in sCO 2 expander and will guide more robust designs tailored towards sCO 2 cycle applications. A DGS was tested in 1MWe sCO 2 turbo expander to study its performance and validate the performance models. To understand the effect of high pressures, high temperatures and sCO 2 environment on crack initiation, crack propagation and LCF/HCF life of these components, a novel experimental setup was developed. The LCF test data was used to calibrate and validate the life prediction models. The effect of sCO 2 corrosion on the life of Ni-based super-alloys is quantified using long duration experiments. Advanced microstructure and spectroscopic analyses conducted shed light on some key differences between IN718 and IN617 in terms of oxidation morphology, chemical species diffusion and trapping, the formation of protective corrosion resistant layers and changes in surface properties. A novel crack initiation model was developed which takes into account strain distribution, temperature, hold times and activation energy at the gas-metal interface and predicts the number of cycles to initiate the crack in the Inconel alloy. An advanced 3D fracture mechanics-based crack propagation model was also developed which takes into account the transient loading mission of the component and predict how fast the crack will grow and what will be its final shape and size. High energy X-Ray tomography measurements were conducted to study and validate 3D morphology of crack growth inside the specimen. These two models along with chemical kinetics models obtained from corrosion tests can be combined to predict the total life of the component under given long term operating conditions. A Bayesian Hybrid Modeling (BHM) probabilistic framework was developed to quantify uncertainty in physics-based performance models and in crack initiation and crack propagation models, to calibrate the models and to validate the models with statistical confidence. Advanced coupled physics multi-phase flow models were developed to study condensation, boiling and phase change behavior of CO 2 under various sCO 2 turbomachinery and heat exchanger conditions. A novel experimental setup was also designed to observe phase change of CO 2 during its transition across liquid-gas-supercritical state lines.

14 SOLAR ENERGY↗
DOE OSTI2022

Modeling Solution Drying by Moving a Liquid-Vapor Interface: Method and Applications

A method of simulating the drying process of a soft matter solution with an implicit solvent model by moving the liquid-vapor interface is applied to various solution films and droplets. For a solution of a polymer and nanoparticles, we observe “polymer-on-top” stratification, similar to that found previously with an explicit solvent model. Furthermore, “polymer-on-top” is found even when the nanoparticle size is smaller than the radius of gyration of the polymer chains. For a suspension droplet of a bidisperse mixture of nanoparticles, we show that core-shell clusters of nanoparticles can be obtained via the “small-on-outside” stratification mechanism at fast evaporation rates. “Large-on-outside” stratification and uniform particle distribution are also observed when the evaporation rate is reduced. Polymeric particles with various morphologies, including Janus spheres, core-shell particles, and patchy particles, are produced from drying droplets of polymer solutions by combining fast evaporation with a controlled interaction between the polymers and the liquid-vapor interface. Our results validate the applicability of the moving interface method to a wide range of drying systems. The limitations of the method are pointed out and cautions are provided to potential practitioners on cases where the method might fail.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Design Principles of Diketopyrrolopyrrole‐Thienopyrrolodione Acceptor 1 –Acceptor 2 Copolymers

Abstract The design principles of acceptor 1 –acceptor 2 copolymers featuring alternating diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) moieties are investigated. The investigated series of polymers is obtained by varying the aromatic linker between the two acceptor motifs between thiophene, thiazole, pyridine, and benzene. High electron affinities between 3.96 and 4.42 eV, facilitated by the synergy of the acceptor motifs are determined with optical gaps between 1.37 and 2.02 eV. Grazing incidence wide‐angle X‐ray scattering studies reveal a range of film morphologies after thermal annealing, including face‐on, end‐on and superstructure edge‐on‐like crystallites. Conversely, all materials form thin edge‐on layers on the polymer–air interface, as demonstrated by multi‐elemental near‐edge X‐ray absorption fine‐structure spectroscopy. The benefit of the electron‐deficient linkers thiazole and pyridine is evident: In organic field effect transistors, electron mobilities of up to 4.6 × 10 −2 cm 2 V −1 s −1 are obtained with outstanding on/off current ratios of 5 × 10 5 , facilitated by the absence of detectable hole transport in these materials. Viability for all‐polymer solar cells is assessed in active layer blends with the donor polymer PM6, yielding a maximum average power conversion efficiency of 4.8% and an open circuit voltage above 1 V.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Pitting Corrosion of 10Ni8CrMoV High-Strength Steel Induced by a Potential Perturbation

Pitting corrosion of high-strength steel 10Ni8CrMoV under square wave polarization (SWP) in simulated deep-sea environment is investigated and the possible mechanism is proposed. The results show that potential perturbation generates periodic intensification effect on both anodic and cathodic processes by frequently breaking the electrode equilibrium state. The intensity of periodic intensification effect essentially depends on the concentration gradient of Fe{sup 2+} cations at the steel/solution interface which acts as the forced electrochemical oscillator. The concentration gradient and the resulting concentration polarization effect increase periodically with the increase in SWP potential range. The morphology observation of the pitting and electric charge calculation indicate that the periodic intensification effect can promote the initiation and growth of pits by enhancing the anodic dissolution even under cathodic protection, but it is ineffective below the hydrogen evolution potential. The decrease in either upper or lower potential can mitigate anodic dissolution. Through the statistical analysis of pitting size, it is found that the wide potential range tends to activate the metastable pitting formed under hydrostatic pressure, forming densely distributed pitting. Meanwhile, it is more favorable to the formation of fully grown pits with high size dispersion degree when the proportion of electric charge in the anodic process is higher.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Secondary-Phase Stochastics in Lithium-Ion Battery Electrodes

Lithium-ion battery electrodes exhibit complex interplay among multiple electrochemically coupled transport processes, which rely on the underlying functionality and relative arrangement of different constituent phases. The electrochemically inactive solid phases (e.g., conductive additive and binder, referred to as the secondary phase), while beneficial for improved electronic conductivity and mechanical integrity, may partially block the electrochemically active sites and introduce additional transport resistances in the pore (electrolyte) phase. In this work, the role of mesoscale interactions and inherent stochasticity in porous electrodes is elucidated in the context of short-range (interface) and long-range (transport) characteristics. The electrode microstructure significantly affects kinetically and transport-limiting scenarios and thereby the cell performance. The secondary-phase morphology is also found to strongly influence the microstructure-transport-kinetics interactions. Apropos, strategies have been proposed for performance improvement via electrode microstructural modifications.

25 ENERGY STORAGE↗
DOE OSTI2019

Electrochemical Properties and Challenges of Type II Silicon Clathrate Anode in Sodium Ion Batteries

The development of advanced anodes for low-cost room temperature sodium-ion batteries (SIBs) with high cycling stability is of great significance. Silicon clathrates are promising intercalation anodes due to their cage-like frameworks. It is predicted that the open cages can easily accommodate alkali ions with negligible volume changes. However, the complicated surface structure and chemical reactions make it challenging to understand the electrochemical performance of clathrate anodes in SIBs. In this paper, we evaluated the performance of type II clathrate anodes in SIBs. A slightly elevated testing temperature (45 degrees C) is shown to improve the cell capacity and rate performance due to the improved ionic conductivity. However, side reactions on the solid electrolyte interface (SEI) and loss of active material during the first sodiation process contribute to the low Coulombic efficiency during the first cycle. Analysis is supported by electrode morphology, elemental mapping, and X-ray photoelectron spectroscopy (XPS) on the clathrate electrodes at different electrochemical states. Na+ ion transport behavior between clathrate cages and surface in terms of migration barriers was also computed to explain the positive effect of higher cell testing temperature, and the low Coulombic efficiency of the first cycle.

25 ENERGY STORAGE↗
NASA NTRS1979

Survey of ion plating sources

Based on the type of evaporation source, gaseous media and mode of transport, the following is discussed: resistance, electron beam, sputtering, reactive and ion beam evaporation. Ionization efficiencies and ion energies in the glow discharge determine the percentage of atoms which are ionized under typical ion plating conditions. The plating flux consists of a small number of energetic ions and a large number of energetic neutrals. The energy distribution ranges from thermal energies up to a maximum energy of the discharge. The various reaction mechanisms which contribute to the exceptionally strong adherence - formation of a graded sustrate/coating interface are not fully understood, however the controlling factors are evaluated. The influence of process variables on the nucleation and growth characteristics are illustrated in terms of morphological changes which affect the mechanical and tribological properties of the coating.

Spalvins, T.↗
NASA NTRS1989

Hydrogen-terminated silicon substrates for low-temperature molecular beam epitaxy

The preparation of hydrogen-terminated silicon surfaces for use as starting substrates for low-temperature MBE growth is examined in detail. The procedure involves the ex situ removal under nitrogen of residual oxide from a silicon substrate using a spin-clean with HF in ethanol, followed by the in situ low-temperature desorption (150 C) of physisorbed etch residues. The critical steps and the chemical basis for these steps are examined using X-ray photoelectron spectroscopy. Impurity residues at the epilayer-substrate interface following subsequent homoepitaxial growth are studied using AES, SIMS and TEM. Finally, scanning tunneling microscopy is used to examine the effect of cleaning methods on substrate morphology.

Grunthaner, P. J.↗
DOE OSTI2022

Local nm-Scale Imaging of Electrical Contact for Series Resistance Degradation of Silicon Solar Cells

We report on an electrical conduction mechanism for series resistance (Rs) degradation observed in a utility scale solar farm by nm-scale imaging of the local resistance at the Ag/Si interface of c-Si cell front metallization. Our previous work showed that the I-V measurement of individual cells demonstrated exclusively the cell Rs degradation, and the "beads pattern" of electroluminescence indicated the degradation at the Ag grid of front metallization. Scanning spreading resistance microscopy (SSRM) imaging, which is based on the contact mode of atomic force microscopy and taken on the cross-sections of Ag/Si contact, revealed the electrical conduction pathway of Ag particles in point or small area contact with Si cell emitter. The SSRM results illustrated that the number of electrical contacts in the degraded cell decreased largely compared with the unaffected cell, demonstrating the direct cause of the Rs degradation. This reduction in electrical contact in the degraded cell could be caused by a structural change in the Ag grid during long-term field service: The Ag particles in contact with Si aggregate into the Ag bulk and a highly resistive ceramic oxide is formed in a "belt" shape at the Ag/Si interface. This resistive belt with a thickness of ~1 m blocks the current conduction from cell emitter to the Ag grid. The degraded cell shows both a morphological and chemical difference in the screen-printed finger contact compared to the unaffected cell, which likely caused the different degradation susceptibility during the long-term field service. Our results demonstrate an example of the multi-scale characterization approach for understanding photovoltaic degradation mechanisms.

ENGINEERING,SOLAR ENERGY↗
NASA NTRS1982

Surface morphology of erbium silicide

The surface of rare-earth silicides (Er, Tb, etc.), formed by the reaction of thin-film metal layers with a silicon substrate, is typically dominated by deep penetrating, regularly shaped pits. These pits may have a detrimental effect on the electronic performance of low Schottky barrier height diodes utilizing such silicides on n-type Si. This study suggests that contamination at the metal-Si or silicide-Si interface is the primary cause of surface pitting. Surface pits may be reduced in density or eliminated entirely through either the use of Si substrate surfaces prepared under ultrahigh vacuum conditions prior to metal deposition and silicide formation or by means of ion irradiation techniques. Silicide layers formed by these techniques possess an almost planar morphology.

Lau, S. S.↗
DOE OSTI2019

Extended Cycling through Rigid Block Copolymer Electrolytes Enabled by Reducing Impurities in Lithium Metal Electrodes

Successful prevention of lithium dendrite growth would enable the use of lithium metal as an anode material in next-generation rechargeable batteries. Mechanically stiff block copolymer electrolytes have been shown to prolong the life of lithium metal cells by partially suppressing lithium dendrite growth. Yet, impurity particles that are invariably present in the lithium metal nucleate electrodeposition defects that eventually lead to short circuits. Here, we use X-ray tomography to study the morphology of electrodeposited lithium in symmetric cells containing a block copolymer electrolyte. An "electrochemical filtering" treatment was performed on these cells to reduce the concentration of impurity particles near the electrode-electrolyte interface, and cells were cycled to determine the effects of the treatment on lifetime. Depending on the treatment details, the average charge passed before failure was improved by 30-400%. For a cell in which the treatment was most effective, the cycle life was increased by more than an order of magnitude, and the measured number of deposition defects per area was negligible. Other treated cells, however, in which the treated lithium was imperfect, had a higher number of deposition defects per area compared to control cells. A majority of the deposition defects in treated cells were confined within the electrodes. In contrast, most of the deposition defects seen in the control cells were protrusions that invaded the electrolyte phase. The increased lifetime in these imperfectly treated cells was not due to a reduction in the number of deposition defects per area, but rather due to the differences in defect morphology. These findings motivate the development of deposition defect- and impurity-free lithium metal electrodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Janus bottlebrush compatibilizers

Bottlebrush random copolymers (BRCPs), consisting of a random distribution of two homopolymer chains along a backbone, can segregate to the interface between two immiscible homopolymers. BRCPs undergo a reconfiguration, where each block segregates to one of the homopolymer phases, adopting a Janus-type structure, reducing the interfacial tension and promoting adhesion between the two homopolymers, thereby serving as a Janus bottlebrush copolymer (JBCP) compatibilizer. Here, we synthesized a series of JBCPs by copolymerizing deuterated or hydrogenated polystyrene (DPS/PS) and poly(tert-butyl acrylate) (PtBA) macromonomers using ruthenium benzylidene-initiated ring-opening metathesis polymerization (ROMP). Subsequent acid-catalyzed hydrolysis converted the PtBA brushes to poly(acrylic acid) (PAA). The JBCPs were then placed at the interface between DPS/PS homopolymers and poly(2-vinyl pyridine) (P2VP) homopolymers, where the degree of polymerization of the backbone (N BB ) and the grafting density (GD) of the JBCPs were varied. Neutron reflectivity (NR) was used to determine the interfacial width and segmental density distributions (including PS homopolymer, PS block, PAA block and P2VP homopolymer) across the polymer-polymer interface. Our findings indicate that the star-like JBCP with N BB = 6 produces the largest interfacial broadening. Increasing N BB to 100 (rod-like shape) and 250 (worm-like shape) reduced the interfacial broadening due to a decrease in the interactions between blocks and homopolymers by stretching of blocks. Decreasing the GD from 100% to 80% at N BB = 100 caused an increase the interfacial width, yet further decreasing the GD to 50% and 20% reduced the interfacial width, as 80% of GD may efficiently increase the flexibility of blocks and promote interactions between homopolymers, while maintaining relatively high number of blocks attached to one molecule. The interfacial conformation of JBCPs was further translated into compatibilization efficiency. Thin film morphology studies showed that only the lower N BB values (N BB = 6 and N BB = 24) and the 80% GD of N BB = 100 had bicontinuous morphologies, due to a sufficient binding energy that arrested phase separation, supported by mechanical testing using asymmetric double cantilever beam (ADCB) tests. These provide fundamental insights into the assembly behavior of JBCPs compatibilizers at homopolymer interfaces, opening strategies for the design of new BCP compatibilizers.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2 ) at a potential of 0 V vs. RHE (j 0 ) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.

42 ENGINEERING↗
DOE OSTI2018

From Microparticles to Nanowires and Back: Radical Transformations in Plated Li Metal Morphology Revealed via in Situ Scanning Electron Microscopy

We report that Li metal is the preferred anode material for all-solid-state Li batteries. However, a stable plating and stripping of Li metal at the anode–solid electrolyte interface remains a significant challenge particularly at practically feasible current densities. This problem usually relates to high and/or inhomogeneous Li-electrode–electrolyte interfacial impedance and formation and growth of high-aspect-ratio dendritic Li deposits at the electrode–electrolyte interface, which eventually shunt the battery. To better understand details of Li metal plating, we use operando electron microscopy and Auger spectroscopy to probe nucleation, growth, and stripping of Li metal during cycling of a model solid-state Li battery as a function of current density and oxygen pressure. We find a linear correlation between the nucleation density of Li clusters and the charging rate in an ultrahigh vacuum, which agrees with a classical nucleation and growth model. Moreover, the trace amount of oxidizing gas (≈10 –6 Pa of O 2 ) promotes the Li growth in a form of nanowires due to a fine balance between the ion current density and a growth rate of a thin lithium-oxide shell on the surface of the metallic Li. Interestingly, increasing the partial pressure of O 2 to 10 –5 Pa resumes Li plating in a form of 3D particles. In conclusion, our results demonstrate the importance of trace amounts of preexisting or ambient oxidizing species on lithiation processes in solid-state batteries.

25 ENERGY STORAGE↗