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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Coupling between interfacial charge and mechanical deformation at high temperatures in ceramics. Final report

Basic research, under this project, has led to new fundamental discoveries in the effect of electric field (and temperature) on diffusion kinetics, electroluminescence and electronic conductivity in ceramic materials. For example, yttria stabilized zirconia sinters in just seconds well below 1000°C, while, at the same time, exhibiting a highly non-linear rise in conductivity, and intense electroluminescence. The phenomenon has been shown to occur in nearly all ceramics whether they are ionic or electronic conductors, or insulators. The rise in conductivity leads to Joule heating but in-situ measurements with a platinum standard at APS and Brookhaven (NSLS-II) have shown that the temperatures are much below what would have been needed to sinter in a few seconds. We have explored the hypothesis that huge concentrations of Frenkel pairs of vacancies and interstitials are produced. While these point defects accelerate sintering (by the interstitials being transported to the pores and the vacancies to the grain boundaries), they may also produce electron-hole pairs which can impart high electrical conductivity or recombine to emit photons. Many measurements, including in-situ measurements of lattice expansion are consistent with this hypothesis. However, the energy barrier for generating Frenkels in zirconia for example is much larger than can be expected at temperature and electrical fields in these experiments. Most recent work suggests that short wavelength phonons play a critical role in the genesis of the “flash” phenomenon. For example, the Debye temperature has been shown to be the lower bound for initiating flash. Molecular dynamics simulations have shown that large concentrations of Frenkel pairs can form under the proliferation of “optical” phonons at the edge of the Brillouin zone, that is with a wavelength at or below the lattice parameter. This project has led to the development of new experimental techniques as well as a software hardware interface for process and control and data analysis in real time, with a time scale of less than one second. This approach spells a new paradigm in materials science research. It potential impact on high rate manufacturing is self evident.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Origin of Intrinsically Low Thermal Conductivity in a Garnet-Type Solid Electrolyte: Linking Lattice and Ionic Dynamics with Thermal Transport

Understanding thermal transport in solid electrolytes is essential for improving the performance, reliability, and safety of all-solid-state batteries. Garnet-type lithium-ion conductors are promising candidates for solid electrolytes, yet their thermal-transport mechanisms remain poorly understood. Here, we connect the lattice and ion dynamics of single-crystal garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 to its intrinsically low thermal conductivity. Our study reveals that the single crystals grown by the floating-zone method exhibit remarkably low glasslike thermal conductivity. Using first-principles calculations and inelastic-neutron-scattering measurements, we identify both the acoustic and numerous optical phonon modes, which stem from the complex crystal structure of the material. Notably, a low-energy optical branch exhibits an avoided crossing with acoustic phonons near 7 meV. These optical modes can enhance the scattering of heat-carrying acoustic phonons and reduce thermal conductivity. Furthermore, the calculated Grüneisen parameters are large, especially for the vibrational modes around 6 meV, indicating strong anharmonicity, with a noticeable contribution from lithium-ion vibrations. A two-channel thermal-transport model is employed to describe the weak temperature dependence of the thermal conductivity, which can be attributed to the substantial contribution of diffuson transport facilitated by the abundance of optical phonons and intrinsic anharmonicity. These results offer valuable insights into the thermal transport in a broad class of ionic conductors of interest for energy conversion and storage applications.

Ab initio calculations↗
DOE OSTI2022

Mechanical, Microstructural, and Electrochemical Characterization of NaSICON Sodium Ion Conductors [Poster]

The DOE Office of Electricity views sodium batteries as a priority in pursuing a safe, resilient, and reliable grid. Improvements in solid-state electrolytes are key to realizing the potential of these large-scale batteries. NaSICON structure consists of SiO 4 or PO 4 tetrahedra sharing common corners with ZrO 6 octahedra. Structure forms “tunnels” in three dimensions that can transport interstitial sodium ion. 3D structure provides higher ionic conductivity than other conductors (β’’-alumina), particularly at low temperature. Lower temperature (cheaper) processing compared to β’’-alumina. Our objective was to identify fundamental structure-processing-property relationships in NaSICON solid electrolytes to inform design for use in sodium batteries. In this work, the mechanical properties of NaSICON sodium ion conductors are affected by sodium conduction. Electrochemical cycling can alter modulus and hardness in NaSICON. Excessive cycling can lead to secondary phases and/or dendrite formation that change mechanical properties in NaSICON. Mechanical and electrochemical properties can be correlated with topographical features to further inform design decisions

25 ENERGY STORAGE↗
DOE OSTI2022

High-Temperature 2D Optical Relaxation Visualizes Enhanced Oxygen Exchange Kinetics at Metal-Mixed Conducting Oxide Interfaces

Solid-state heterointerfaces are of interest for emergent local behavior that is distinct from either bulk parent compound. One technologically relevant example is the case of mixed ionic/electronic conductor (MIEC)–metal interfaces, which play an important role in electrochemistry. Metal–MIEC composite electrodes can demonstrate improved catalytic activity vs single-phase MIECs, improving fuel cell efficiency. Similarly, MIEC surface reaction kinetics are often evaluated using techniques that place metal current collectors in contact with the surface under evaluation, potentially altering the response vs the native surface. Here, techniques enabling direct and local in situ observation of the behavior at and around such heterointerfaces are needed. Here, we develop a spatially resolved optical transmission relaxation (2D-OTR) method providing continuous evaluation of local, high-temperature, controlled atmosphere defect kinetics across a ~1 cm2 sample area simultaneously in a contact-free manner. We apply it to observe the spatial variance of oxygen incorporation and evolution rates at ~525–620 °C, in response to step changes in oxygen partial pressure, on MIEC SrTi 0.65 Fe 0.35 O 3–x films as a function of distance from porous Pt and Au layers. Using this model geometry, we find significant enhancements in kinetics adjacent to the metals that decay over a few millimeter distance. To extract kinetic parameters, we fit the short-term optical data (initial portion of relaxations) with an exponential decay function appropriate for surface-exchange-limited kinetics, yielding apparent surface exchange coefficients (k chem ) with spatial resolution, decreasing with distance from the metal. To understand the kinetic processes governing the complete (long-term) optical relaxations, we performed COMSOL simulations, which demonstrated that a combination of laterally varying k chem and in-plane diffusion controls the observed kinetics over the full time range. Further support for spatially varying kchem comes from demonstrations of changing surface and bulk chemistry vs distance from the metal–MIEC interface, by X-ray photoelectron and optical absorption spectroscopies, respectively. Although microporous Pt and Au are not excellent electrodes in isolation, both metals exert a synergistic effect on the oxygen surface exchange rate in the presence of the mixed conducting film.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High-Speed Ionic Synaptic Memory Based on 2D Titanium Carbide MXene

Synaptic devices with linear high-speed switching can accelerate learning in artificial neural networks (ANNs) embodied in hardware. Conventional resistive memories however suffer from high write noise and asymmetric conductance tuning, preventing parallel programming of ANN arrays. Electrochemical random-access memories (ECRAMs), where resistive switching occurs by ion insertion into a redox-active channel, aim to address these challenges due to their linear switching and low noise. ECRAMs using 2D materials and metal oxides however suffer from slow ion kinetics, whereas organic ECRAMs enable high-speed operation but face challenges toward on-chip integration due to poor temperature stability of polymers. Here, ECRAMs using 2D titanium carbide (Ti 3 C 2 T x ) MXene that combine the high speed of organics and the integration compatibility of inorganic materials in a single high-performance device are demonstrated. These ECRAMs combine the speed, linearity, write noise, switching energy, and endurance metrics essential for parallel acceleration of ANNs, and importantly, they are stable after heat treatment needed for back-end-of-line integration with Si electronics. The high speed and performance of these ECRAMs introduces MXenes, a large family of 2D carbides and nitrides with more than 30 stoichiometric compositions synthesized to date, as promising candidates for devices operating at the nexus of electrochemistry and electronics.

2D materials↗
DOE OSTI2022

Tension‐Induced Cavitation in Li‐Metal Stripping

Abstract Designing stable Li metal and supporting solid structures (SSS) is of fundamental importance in rechargeable Li‐metal batteries. Yet, the stripping kinetics of Li metal and its mechanical effect on the supporting solids (including solid electrolyte interface) remain mysterious to date. Here, through nanoscale in situ observations of a solid‐state Li‐metal battery in an electron microscope, two distinct cavitation‐mediated Li stripping modes controlled by the ratio of the SSS thickness ( t ) to the Li deposit's radius ( r ) are discovered. A quantitative criterion is established to understand the damage tolerance of SSS on the Li‐metal stripping pathways. For mechanically unstable SSS ( t / r < 0.21), the stripping proceeds via tension‐induced multisite cavitation accompanied by severe SSS buckling and necking, ultimately leading to Li “trapping” or “dead Li” formation; for mechanically stable SSS ( t / r > 0.21), the Li metal undergoes nearly planar stripping from the root via single cavitation, showing negligible buckling. This work proves the existence of an electronically conductive precursor film coated on the interior of solid electrolytes that however can be mechanically damaged, and it is of potential importance to the design of delicate Li‐metal supporting structures to high‐performance solid‐state Li‐metal batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A novel equivalent circuit for GDC-based solid oxide cells considering the variations of cell resistances under load

Regarding the mixed ionic-electronic conductive electrolytes, there are several constant assumptions about cell resistances and transference numbers. In this work, the charge transport frameworks of mixed conductive SOCs are comprehensively illustrated. And the independent external current density is introduced into the equivalent circuit for considering the variations of cell resistances under load. The updated expressions of cell resistances together with transference numbers are deduced rigorously based on the equivalent circuit. Electrolyte-supported NiO-GDC/GDC/LSCF cells are tested, and the experimental results validate the variations of cell resistances, especially for the polarization resistance. The comparisons show that electron hole resistances together with transference number calculated by the updated expressions are larger than those obtained by Liu’s method. More accurate transference number and cell resistances under load can be achieved by using the proposed method in this study.

25 ENERGY STORAGE↗
DOE OSTI2026

Additive-Induced Morphology Change of Polymer Film Enables Enhanced Charge Mobility and Faster Organic Electrochemical Transistor Switching

Conjugated polymers (CPs) play an important role in organic electrochemical transistors (OECTs) for bioelectronics and related applications, where they serve as channel materials. Currently, most successful polymers for CPs are re-engineered from traditional CPs by replacing hydrophobic alkyl side chains with hydrophilic ethylene glycol or ionic groups. Frustratingly, the enhanced ion transport often compromises the charge mobility of the original CP. In this work, we present an additive-mediated method to construct a modified poly(3-hexylthiophene) (P3HT) film to enable efficient ion migration. The additive is designed with a cleavable diazo group that releases nitrogen and 2-methoxyethanol, a volatile compound, to alter the P3HT film morphology. OECTs based on the film exhibit improved response times. Interestingly, the process also enhances the crystallinity of P3HT, leading to higher hole mobility compared with pristine P3HT. This study proposes an in situ strategy to achieve the functionality of the OMIEC via morphological regulation, offering a promising route to simultaneously enhance both ion accessibility and charge mobility.

Organic polymers↗
DOE OSTI2022

Understanding the Impact of Hydrogen Activation by SrCe 0.8 Zr 0.2 O 3-δ Perovskite Membrane Material on Direct Non-Oxidative Methane Conversion

Direct non-oxidative methane conversion (DNMC) converts methane (CH 4 ) in one step to olefin and aromatic hydrocarbons and hydrogen (H 2 ) co-product. Membrane reactors comprising methane activation catalysts and H 2 -permeable membranes can enhance methane conversion by in situ H 2 removal via Le Chatelier's principle. Rigorous description of H 2 kinetic effects on both membrane and catalyst materials in the membrane reactor, however, has been rarely studied. In this work, we report the impact of hydrogen activation by hydrogen-permeable SrCe 0.8 Zr 0.2 O 3-δ (SCZO) perovskite oxide material on DNMC over an iron/silica catalyst. The SCZO oxide has mixed ionic and electronic conductivity and is capable of H 2 activation into protons and electrons for H 2 permeation. In the fixed-bed reactor packed with a mixture of SCZO oxide and iron/silica catalyst, stable and high methane conversion and low coke selectivity in DNMC was achieved by co-feeding of H 2 in methane stream. The characterizations show that SCZO activates H 2 to favor “soft coke” formation on the catalyst. The SCZO could absorb H 2 in situ to lower its local concentration to mitigate the reverse reaction of DNMC in the tested conditions. The co-existence of H 2 co-feed, SCZO oxide, and DNMC catalyst in the present study mimics the conditions of DNMC in the H 2 -permeable SCZO membrane reactor. The findings in this work offer the mechanistic understanding of and guidance for the design of H 2 -permeable membrane reactors for DNMC and other alkane dehydrogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Exploring Mixed Ionic–Electronic-Conducting PVA/PEDOT:PSS Hydrogels as Channel Materials for Organic Electrochemical Transistors

Here, we report the preparation and evaluation of PVA/PEDOT:PSS-conducting hydrogels working as channel materials for OECT applications, focusing on the understanding of their charge transport and transfer properties. Our conducting hydrogels are based on crosslinked PVA with PEDOT:PSS interacting via hydrogen bonding and exhibit an excellent swelling ratio of ~180–200% w/w. Our electrochemical impedance studies indicate that the charge transport and transfer processes at the channel material based on conducting hydrogels are not trivial compared to conducting polymeric films. The most relevant feature is that the ionic transport through the swollen hydrogel is clearly different from the transport through the solution, and the charge transfer and diffusion processes govern the low-frequency regime. In addition, we have performed in operando Raman spectroscopy analyses in the OECT devices supported by first-principle computational simulations corroborating the doping/de-doping processes under different applied gate voltages. The maximum transconductance (gm~1.05 μS) and maximum volumetric capacitance (C*~2.3 F.cm -3 ) values indicate that these conducting hydrogels can be promising candidates as channel materials for OECT devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Visualization of Solid-State Synthesis for Chalcogenide Na Superionic Conductors by in-situ Neutron Diffraction

Chalcogenide superionic sodium (Na) conductors are great potential as solid electrolytes (SEs) in all-solid-state Na batteries with advantages of high energy density and safety, and cost effectiveness. For solid Na-ion conductors, their crystal structures and ionically conductive properties are strongly influenced by the synthetic approaches and processing parameters. Thus, understanding the synthesis process is essential to control the structures and phases and thereby yields to Na-ion conductors with desirable properties. Thanks to the high-flux and deep-penetrating time-of-flight neutron diffraction (ND), we employed in situ experiments to track real-time structural changes of two chalcogenide SEs (Na 3 SbS 4 and Na 3 SbS 3.5 Se 0.5 ) during the solid-state synthesis. For these two conductors, the ND results reveal a fast one-step reaction for the synthesis and the molten process when heating up, and the recrystallization as well as the cubic-to-tetragonal phase transition up on cooling. Moreover, Se-doping is found to influence the reaction temperatures, lattice parameter and structure stability based on neutron experimental observations and theoretical simulation. This work presents a detailed structural study using in situ neutron diffraction technology for the solid synthesis process of chalcogenide Na-ion conductors, beneficial for the design and synthesis of new solid-state conductors.

25 ENERGY STORAGE↗
DOE OSTI2022

Argyrodite-type advanced lithium conductors and transport mechanisms beyond paddle-wheel effect

Abstract Development of next-generation solid-state Li-ion batteries requires not only electrolytes with high room-temperature (RT) ionic conductivities but also a fundamental understanding of the ionic transport in solids. In spite of considerable work, only a few lithium conductors are known with the highest RT ionic conductivities ~ 0.01 S/cm and the lowest activation energies ~0.2 eV. New design strategy and novel ionic conduction mechanism are needed to expand the pool of high-performance lithium conductors as well as achieve even higher RT ionic conductivities. Here, we theoretically show that lithium conductors with RT ionic conductivity over 0.1 S/cm and low activation energies ~ 0.1 eV can be achieved by incorporating cluster-dynamics into an argyrodite structure. The extraordinary superionic metrics are supported by conduction mechanism characterized as a relay between local and long-range ionic diffusions, as well as correlational dynamics beyond the paddle-wheel effect.

25 ENERGY STORAGE↗
DOE OSTI2025

The Dynamical Role of Optical Phonons and Sublattice Screening in a Solid-State Ion Conductor

Solid-state electrolytes (SSEs) require ionic conductivities that are competitive with liquid electrolytes to realize applications in all-solid-state batteries. Although candidate SSEs have been discovered, the underlying mechanisms enabling superionic conduction (>1 mS cm –1 ) remain elusive. In particular, the role of ultrafast lattice dynamics in mediating ion migration, which involves couplings between ions, phonons, and electrons, is rarely explored experimentally at their corresponding time scales. To investigate the complex contributions of coupled lattice dynamics on ion migration, we modulate the charge density occupations within the crystal framework and then measure the time-resolved change in impedance on picosecond time scales for a candidate SSE, Li 0.5 La 0.5 TiO 3 (LLTO). Upon perturbation, we observe enhanced ion migration at ultrafast time scales. The respective transients match the time scales of optical and acoustic phonon vibrations, suggesting their involvement in ion migration. We further computationally evaluate the effect of a charge transfer from the O 2p to the Ti 3d band on the electronic and physical structure of LLTO. We hypothesize that the charge-transfer excitation distorts the TiO 6 polyhedra by altering the local charge density occupancy of the hopping site at the migration pathway saddle point, thereby causing a reduction in the migration barrier for the Li + hop. We rule out the contribution of photogenerated electron carriers and laser heating. Overall, our investigation introduces a new spectroscopic tool to probe fundamental ion hopping mechanisms transiently at ultrafast time scales, which has previously only been achieved in a time-averaged manner or solely via computational methods.

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

High‐Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All‐Solid‐State Batteries

Abstract Superionic solid electrolytes (SEs) are essential for bulk‐type solid‐state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge‐transport properties, however a thorough understanding of how configurational entropy (ΔS conf ) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen‐rich lithium argyrodites with the general formula Li 5.5 PS 4.5 Cl x Br 1.5‐x (0≤x≤1.5). Using neutron powder diffraction and 31 P magic‐angle spinning nuclear magnetic resonance spectroscopy, the S 2− /Cl − /Br − occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li‐ion dynamics, leading to a room‐temperature ionic conductivity of 22.7 mS cm −1 (9.6 mS cm −1 in cold‐pressed state) for Li 5.5 PS 4.5 Cl 0.8 Br 0.7 (ΔS conf =1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li 5.5 PS 4.5 Cl 0.8 Br 0.7 SE allowed for stable cycling of single‐crystal LiNi 0.9 Co 0.06 Mn 0.04 O 2 (s‐NCM90) composite cathodes in SSB cells, emphasizing that dual‐substituted lithium argyrodites hold great promise in enabling high‐performance electrochemical energy storage.

Chemistry↗
DOE OSTI2025

Superionic Surface Li-Ion Transport in Carbonaceous Materials

Unlike Li-ion transport in the bulk of carbonaceous materials, little is known about Li-ion diffusion on their surface. Here, in this study, we have discovered an ultrafast Li-ion transport phenomenon on the surface of carbonaceous materials with limited reversible Li insertion capacity and high surface area. An ionic conductivity of 18.1 mS cm –1 at room temperature is observed in lithiated Ketjen black (KB), far exceeding those of most solid-state ion conductors. Theoretical calculations reveal low diffusion barriers for the surface Li species. As a result, lithiated KB functions effectively as an interlayer between Li and solid-state electrolytes (SSEs) to mitigate dendrite growth. Further, lithiated KB acts as a high-performance mixed ionic–electronic conductor and replaces solid electrolytes to enhance graphite anode performance, demonstrating full utilization with ∼85% capacity retention over 300 cycles. The discovery of this surface-mediated ultrafast Li-ion transport mechanism provides new directions for the design of solid-state ion conductors and solid-state batteries.

Li metal batteries↗
DOE OSTI2021

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li6PS5CN

Rapid advancements in safe and high-energy-density energy storage are predicated on identifying new solid-state ion conductors with low activation energies and high ionic conductivities for all-solid-state battery technologies. Halide argyrodites are among some of the top candidates for solid-state electrolytes, as they can achieve ionic conductivities that approach liquid electrolytes. Incorporating dynamic pseudohalide species in argyrodite solid electrolytes presents an exciting opportunity to exploit lattice dynamics as a design principle to modulate the ion conduction properties of solid-state ion conductors. In the present study, we have prepared the new argyrodite Li 6 PS 5 CN containing orientationally disordered cyanide ions. The new cyanide argyrodite Li 6 PS 5 CN exhibits an activation barrier to Li-ion transport of 471 ± 25 meV and a room-temperature ionic conductivity of 6(2) × 10 –5 S cm –1 in comparison to the activation barrier of 502 ± 16 meV and an ionic conductivity of 2.3(1) × 10 –4 S cm –1 measured for the bromide analogue Li 6 PS 5 Br. Structural studies of both compounds by high-resolution X-ray diffraction indicate that Li 6 PS 5 CN and Li 6 PS 5 Br adopt nearly identical crystal structures with similar lattice parameters, which indicates that lower activation barriers in Li 6 PS 5 CN arise due to the cyanide ion itself rather than due to changes in the geometry of conduction pathways in the local lithium environment. The orientational disorder of the quadrupolar cyanide ion in Li 6 PS 5 CN points to a complex interplay of lattice polarizability and molecular dynamics that lower the activation barrier for lithium-ion conductivity in the cyanide argyrodite.

25 ENERGY STORAGE↗
DOE OSTI2025

Understanding and design of interstitial oxygen conductors

Highly efficient oxygen-active materials that react with, absorb, and transport oxygen is essential for fuel cells, electrolyzers and related applications. While vacancy-mediated oxygen-ion conductors have long been the focus of research, they are limited by high migration barriers at intermediate temperatures (400–600 °C), which hinder their practical applications. In contrast, interstitial oxygen conductors exhibit significantly lower migration barriers enabling higher ionic conductivity at lower temperatures. This review systematically examines both well-established and recently identified families of interstitial oxygen-ion conductors, focusing on how their unique structural motifs such as corner-sharing polyhedral frameworks, isolated polyhedral, and cage-like architectures, facilitate low migration barriers through interstitial and/or interstitialcy diffusion mechanisms. A central discussion of this review focuses on the evolution of design strategies, from targeted donor doping, element screening, to physical-intuition descriptor material screening and machine learning approach, which leverage computational tools to explore vast chemical spaces in search for new interstitial conductors. The success of these strategies demonstrates that a significant, largely unexplored space remains for discovering high-performing interstitial oxygen conductors. Crucial features enabling high-performance interstitial oxygen diffusion include the availability of electrons for oxygen reduction and sufficient structural flexibility with accessible volume for interstitial accommodation and migration. This review concludes with a forward-looking perspective, proposing a knowledge-driven methodology that integrates current understanding with data-centric approaches to identify promising interstitial oxygen conductors outside traditional search paradigms. These approaches are expected to significantly accelerate the development of high-performance interstitial oxygen conductors for a variety of oxygen-active applications, ultimately paving the way for more efficient and sustainable energy technologies.

Interstitial oxygen conductors↗