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At least 721 records · Page 40

Development, Characterization, and Testing of Solid-State Electrolytes for Batteries

Traditional liquid electrolytes used in lithium (Li) metal batteries (LMBs) have severe safety issues, poor power density, as well as thermal and electrochemical instability that prevents their scaling to newer applications, such as electric vehicles. Using sulfide-based solid-state electrolytes (SSEs) is a viable method to address many of the issues that plague LMBs. However, the key issue preventing the expansion of sulfide-based SSEs is an interplay between poor interfacial stability with the electrodes and massive external stack pressure required to maintain electrode-electrolyte contact. The need for extensive pressure requires large system-level (i.e., battery pack used in an electric vehicle) housing that causes a disconnect between performance at a smaller scale and actual application. Secondary prevention to sulfide-based SSE adoption are difficulties in manufacturing, as toxic deterioration occurs when these materials are exposed to humidity, as well as drastic reduction in SSE performance at low temperature. This work hypothesizes that unique interfacial designs of electrodes and the modification of the sulfide-based SSE will enable reduction of necessary external cell pressure, and therefore support the design of practical LMBs. This will be done through collaboration within Idaho National Laboratory (INL), where manufacturing practices will be parameterized to produce low defect, low porosity SSEs with slight modifications. Next, artificial interfaces will be produced on electrodes to observe the conformality and mass transport properties between the modified SSE and pre-treated anode. External pressure on Li-metal cells will also be parameterized to reduce interfacial impedance while a reduction in the pressure will allot reasonable housing design for larger scale applications. Focus on novelty in this work occurs by modifications to the solid-solid interfaces between electrolyte and electrode, done through doping of the electrolyte and production of artificial interfaces on the Li-metal anode. The modifications at these interfaces, in addition to modified external pressure could identify and address the poor interfacial impedance that hinders high performance SSEs. Fundamental understanding on how to reduce the key hindrances of all-solid-state batteries (ASSBs) will support the advancement for larger scale production and performance, of which will be held in perspective for future works. Beyond battery development, the knowledge gained from process control and defect analysis is applicable to other ceramic systems, such as nuclear fuel coatings and high temperature electrolyzers.

25 ENERGY STORAGE↗

Interfacial Inversion of Stealth Surfactants

Amphiphilic macromolecular surfactants segregate to liquid–liquid interfaces, thereby reducing the interfacial tension and free energy. Here, we investigated “stealth surfactants” in the form of core–shell bottlebrush polymers comprised of pH-responsive diblock copolymer side chains forming a hydrophilic core and a hydrophobic shell, enabling solubility in oil. At liquid–liquid interfaces, these polymers undergo a structural “inversion”, with hydrophilic blocks segregating into the aqueous phase and hydrophobic blocks residing in the oil phase. The reconfiguration kinetics and surfactant properties are influenced by multiple factors, including the molecular weights of the backbone and side chain components, the hydrophilic-to-hydrophobic balance of the side chains, and the pH of the aqueous phase. An observed nonmonotonic dependence of interfacial tension with time is attributed to a progressive structural inversion, where the projected area of the macromolecule onto the interface decreases. To validate this inversion hypothesis, interfacial properties were characterized by sum-frequency generation vibrational spectroscopy, which revealed configurational changes of the core–shell bottlebrush polymers at the fluid interface and revealed a pH-dependent interfacial coverage. Coarse-grained molecular dynamics simulations supported these experimental findings, showing that the pH-responsive core and hydrophobic shell assume a time-averaged configuration with orientations parallel and perpendicular to the plane of the interface, respectively. These findings open routes to design multistimuli-responsive polymeric surfactants and compatibilizers, expanding their potential applications in advanced interfacial systems.

Stealth surfactants↗

Understanding of three different polyvinylpyrrolidone (PVP) based battery binders blends on graphene surfaces from first principles via DFT simulations

Binders play a crucial role in binding electrodes, current collectors, and conductive agents during battery manufacturing. The selection of the binders and their blends considerably affect various properties such as mechanical durability, adhesion performance, ionic/electronic conductivities, and solid electrolyte interface stability for lithium-ion batteries. In this work, polyvinylidene di-fluoride (PVDF), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP), and lithiated polyacrylic acid (Li-PAA) were selected as the model binders, and their blends were studied on graphene surfaces. Further, among them, PVDF is hardly soluble in water unlike the other binders, so in practice, the blend of PVP:PVDF is not thought to be a proper combination. However, the PVP:PVDF binder has also been included because the purpose of this work is to calculate several electronic properties such as binding energies, intermolecular interaction energies, bond critical points, electron density, and the Laplacian of electron density at critical bonding regions of all these blends at the molecular level via density functional theory (DFT) simulations in order to evaluate and compare how is the interaction strength and bonding type of three different lithium-ion batteries (LIBs) binder blends on graphene surfaces. Most stable binder pairs and their binding mechanisms on graphene surfaces were studied. The delocalization of lithium in Li-PAA was studied with the presence of water.

25 ENERGY STORAGE↗

Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal

Li 7 La 3 Zr 2 O 12 (LLZO) garnet-based oxides are a promising class of solid electrolytes used as the separator in all-solid-state batteries (ASSBs). While LLZO is considered to have a wide electrochemical stability window, its intrinsic stability in contact with lithium metal is not sufficiently well understood, and there is still a debate on the key question of whether LLZO does or does not form passivation layers before and during cycling. Utilizing both in situ and operando X-ray photoelectron spectroscopy techniques, in this work we reveal the presence of a kinetic barrier to the reduction of LLZO by Li metal, with the extent of oxygen-deficient interphase (ODI) formation depending sensitively on the energetics of Li metal arriving at the Li vertical bar LLZO interface. Despite the clear presence of a kinetic barrier to reduction, the electrochemical response of the Li vertical bar LLZO interface is unchanged by the presence of the ODI, indicating that ODI formation during electrochemical cycling does not hinder charge transfer across the Li vertical bar LLZO interface. Overall, these results reveal that the reactivity of LLZO with Li metal depends not only on the material properties of the adjoining phases (i.e., surface purity and active contact) and their resulting thermodynamic stability but also on the energy input at the interface and the resulting reaction kinetics. Furthermore, the presence of a kinetic barrier to reduction highlights the additional complexities governing the reactivity of solid-state interfaces in ASSBs and underscores the importance of operando characterization of interfacial stability to design more robust, high-performance protection strategies for solid electrolytes in contact with reactive electrodes.

25 ENERGY STORAGE↗

Emergent ferromagnetism and insulator-metal transition in δ-doped ultrathin ruthenates

Abstract Heterostructures of complex transition metal oxides are known to induce extraordinary emergent quantum states that arise from broken symmetry and other discontinuities at interfaces. Here we report the emergence of unusual, thickness-dependent properties in ultrathin CaRuO 3 films by insertion of a single isovalent SrO layer (referred to as δ-doping). While bulk CaRuO 3 is metallic and nonmagnetic, films thinner than or equal to ~15-unit cells (u.c.) are insulating though still nonmagnetic. However, δ-doping to middle of such CaRuO 3 films induces an insulator-to-metal transition and unusual ferromagnetism with strong magnetoresistive behavior. Atomically resolved imaging and density-functional-theory calculations reveal that the whole δ-doped film preserves the bulk-CaRuO 3 orthorhombic structure, while appreciable structural and electronic changes are highly localized near the SrO layer. The results highlight delicate nature of magnetic instability in CaRuO 3 and subtle effects that can alter it, especially the role of A-site cation in electronic and magnetic structure additional to lattice distortion in ruthenates. It also provides a practical approach to engineer material systems via highly localized modifications in their structure and composition that may offer new routes to the design of oxide electronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Extending the capillary wave model to include the effect of bending rigidity: X-ray reflectivity and diffuse scattering

The surface roughness of a thin film at a liquid interface exhibits contributions of thermally excited fluctuations. This thermal roughness depends on temperature (𝑇), surface tension (𝛾), and elastic material properties, specifically the bending modulus (𝜅) of the film. A nonzero 𝜅 suppresses the thermal roughness at small length scales compared to an interface with zero 𝜅, as expressed by the power spectral density of the thermal roughness. The description of the x-ray scattering of the standard capillary wave model (CWM), which is valid for zero 𝜅, is extended to include the effect of 𝜅. The extended CWM (eCWM) provides a single analytical form for both the specular x-ray reflectivity (XRR) and the diffuse scattering around the specular reflection, and recovers the expression of the CWM at its zero 𝜅 limit. This theoretical approach enables the use of single-shot grazing incidence x-ray off-specular scattering (GIXOS) measurements for characterizing the structure of thin films on a liquid surface. The eCWM analysis approach decouples the thermal roughness factor from the surface scattering signal, providing direct access to the intrinsic surface-normal structure of the film and its bending modulus. Moreover, the eCWM facilitates the calculation of reflectivity at any desired resolution (pseudo-XRR approach). The transformation into pseudo-XRR provides the benefit of using widely available XRR software to perform GIXOS analysis. The extended range of the vertical scattering vector (𝑄 𝑧 ) available with the GIXOS pseudo-XRR approach allows for a higher spatial resolution than with conventional XRR. Experimental results are presented for various lipid systems, showing strong agreement between conventional specular XRR and pseudo-XRR methods. This agreement validates the proposed approach and highlights its utility for analyzing soft, thin films.

36 MATERIALS SCIENCE↗

Polymer-cement composites with adhesion and re-adhesion (healing) to casing capability for geothermal wellbore applications

Deterioration of cement/casing adhesion in wellbore scenarios can result in unwanted and potentially harmful leakage with the potential of serious repair costs. In this work, we explore the use of self-healing polymers added to conventional wellbore cements as a way to bring about self-healing and readhering (to steel casing) properties to the composite material. The polymers are pH resistant and seem to improve the cement integrity after exposure to typical chemical and thermal stresses encountered under geothermal wellbore conditions. We find that addition of about 10-15 wt% of polymer to the cement visually increases its resistance to fracturing from exposure to geothermal conditions, while the adhesive strength of cement/stainless steel increases with curing time for a period of about 10 days. Self-healing capability was demonstrated by permeability analysis showing that polymer-cement composites reduce flow by 50-70% at cement bulk and at the cement/steel interface. Use of atomistic simulations imply that these polymers have good wetting properties on the steel surfaces. Analysis of the interactions between steel/polymer and cement/polymer show that they are complementary, resulting in a wider range of bonding patterns. Cracks are likely to expose under-coordinated sites that result in more bonding interactions, which agrees well with the permeability measurements showing high degree of healed cracks and healed (cement-steel) interfacial gaps together with an overall increased in structural integrity of these advanced polymer-cement composite materials.

Rod, Kenton A.↗

In Situ Electrochemistry of Buried Interfaces in Metal Halide Perovskites: Probing Energy Bands, Halide Redox Activity, and Kinetics

Control over charge injection and extraction processes across buried interfaces is fundamental for all (opto)electronic multilayer device platforms, necessitating detailed understanding of local structural and chemical differences that promote defect formation, distort energetic band-edge alignments, and alter charge transport processes. Herein, the implementation of a low-cost electroanalytical methodologies’ tool suite is described to quantitatively characterize buried interfaces and redox reactions in printable, mixed electrical–ionic, and redox-active metal halide perovskites and a prototypical hole-transporting nickel oxide (NiO x ) thin film. The objective is to demonstrate the power of electrochemical methodologies to improve the nanoscale understanding of complex interfaces within optoelectronic devices by providing case studies on how to: i) differentiate between electronic and chemical properties in NiO x contacts; ii) measure changes in reversibility of halide redox reactions via NiO x surface states; iii) assess energy alignment and charge transport across (modified) buried interfaces; and iv) quantify defects at buried interfaces that change with modifiers and differences in perovskite processing, including increasing defect concentrations when films are slot-die-coated versus spin-cast. The collective approach addresses major challenges in understanding the precise energy landscape and interface reactivity under relevant electric fields that mimic operando conditions (away from equilibrium) and across length scales in thin film device formats.

(spectro)electrochemistry↗

Strain Engineering: A Pathway for Tunable Functionalities of Perovskite Metal Oxide Films

Perovskite offers a framework that boasts various functionalities and physical properties of interest such as ferroelectricity, magnetic orderings, multiferroicity, superconductivity, semiconductor, and optoelectronic properties owing to their rich compositional diversity. These properties are also uniquely tied to their crystal distortion which is directly affected by lattice strain. Therefore, many important properties of perovskite can be further tuned through strain engineering which can be accomplished by chemical doping or simply element substitution, interface engineering in epitaxial thin films, and special architectures such as nanocomposites. In this review, we focus on and highlight the structure–property relationships of perovskite metal oxide films and elucidate the principles to manipulate the functionalities through different modalities of strain engineering approaches.

36 MATERIALS SCIENCE↗

Nanoscale Control of the Metal–Insulator Transition at LaAlO 3 /KTaO 3 Interfaces

Recent reports of superconductivity at KTaO 3 (KTO) (110) and (111) interfaces have sparked intense interest due to the relatively high critical temperature as well as other properties that distinguish this system from the more extensively studied SrTiO 3 (STO)-based heterostructures. Here, we report the reconfigurable creation of conducting structures at intrinsically insulating LaAlO 3 / KTO(110) and (111) interfaces. Devices are created using two distinct methods previously developed for STO-based heterostruc-tures: (1) conductive atomic-force microscopy lithography and (2) ultralow-voltage electron-beam lithography. At low temperatures, KTO(110)-based devices show superconductivity that is tunable by an applied back gate. A one-dimensional nanowire device shows single-electron-transistor (SET) behavior. A KTO(111)-based device is metallic but does not become superconducting. Finally, these reconfigurable methods of creating nanoscale devices in KTO-based heterostructures offer new avenues for investigating mechanisms of superconductivity as well as development of quantum devices that incorporate strong spin-orbit interactions, superconducting behavior, and nanoscale dimensions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

First-Principles Studies of Tritium Species Diffusivity Across the Interface of Nickel-Plated Zircaloy-4

In this study, we will calculate the 3H2 and 3H2O diffusion mechanism in the Ni coated layer and the dominant 3H species dissolution into the Zircaloy-4 getter. We will optimize the Ni/Zr interface and introduce Sn and O impurities. To achieve the objectives, we will perform the investigation by using spin-polarized density functional theory (DFT) methods to capture the effects of Ni magnetic properties on 3H diffusion. We will introduce NiO/Ni(OH) on the Ni side closer to the interface. Then, the 3H diffusion pathways and barriers from Ni side to the zircalory-4 will be explored. We will investigate how NiO/Ni(OH) affects the 3H diffusion across the interface.

Paudel, Hari P.↗

Cross-Cutting Metrology Tools for In Operando Characterization of Carrier Dynamics in Photovoltaic Devices (Final Technical Report)

Understanding the nature of recombination and its dependence on defects and interfaces is essential for engineering materials and contacts for higher V oc and photovoltaic (PV) efficiency. Time-resolved photoluminescence (TRPL) has conventionally been used to evaluate recombination, but not all materials are strongly emissive or otherwise suitable. Time-resolved terahertz spectroscopy is a pump – probe method that presents valuable complementary information, wherein an optical pump pulse photoexcites carriers within the absorber and the transient photoconductivity is probed with a terahertz pulse. Until now, experimental constraints have prohibited the use of terahertz probes to interrogate full device stacks, and measurements were instead made on exfoliated films or films grown on unconventional substrates. However, interfaces are critical to the behavior of photoexcited carriers in solar cells, and the substrates themselves often influence the film growth and bulk properties. Therefore, it is important to probe the behavior of PV absorbers as close as possible to their normal operating conditions. Here we have developed cross-cutting metrology that enable in operando characterization of carrier dynamics and recombination mechanisms in working PV devices. Through a combination of complementary non-contact TRTS and TRPL experiments and modeling, we have obtained key parameters including photoexcited carrier bulk lifetime and interface and back surface recombination velocities with greater precision and accuracy than can be achieved with conventional TRPL alone. By varying pulsed photoexcitation conditions, the contributions of interface and bulk recombination mechanisms can be determined. We have developed and refined this characterization approach by investigating CdTe PVs, which is a well-established technology but with significant margin for further improvements in efficiency. Results were published in Journal of Applied Physics (DOI: 10.1063/5.0064730) and Proceedings of the IEEE PVSC (DOI: 10.1109/PVSC43889.2021.9518559). After validating the approach, we have applied it to correlate recombination rates to processing conditions and material properties, including composition and defects as well as interfaces and surface treatments. Such feedback can inform processing and design choices to enable higher PV efficiency, not only for CdTe, but also CdSe x Te 1-x , CIGS, perovskites, kesterites, and future technologies. A perspective on predicting solar cell performance from terahertz spectroscopy was published in Advanced Energy Materials (DOI: 10.1002/aenm.202102776). The cross-cutting metrology tools developed here will enable determination of the locus and mechanism of performance-limiting recombination in thin film PV devices. This feedback can guide the engineering of PV devices with higher V oc and efficiency, thereby leading to reductions in levelized cost of electricity to meet the SunShot 2030 target of $0.03/kWh for utility-scale PV. Lower costs will enable rapid expansion of renewable electricity generation that is nearly free of carbon emissions. Reducing carbon emissions of the electricity sector is one of the most important solutions to climate change. The project’s specific focus on CdTe PV can benefit First Solar, the US company that is the global leader in CdTe technology, through both technology and workforce development.

14 SOLAR ENERGY↗

Nanoscale control of LaAlO 3 /SrTiO 3 conductance beyond the polar catastrophe

Conductive atomic force microscope (c-AFM) lithography can be utilized to create a wide range of LaAlO 3 /SrTiO 3 (LAO/STO)-based nanoelectronic devices in a reconfigurable manner. Experiments were generally performed with intrinsically insulating LAO/STO heterostructures, with LAO thickness less than the critical value at which a polar catastrophe takes place [<4 unit cell (u.c.)]. Here, we use inductively coupled plasma reactive ion etching (ICPRIE) to fabricate c-AFM “canvases” on intrinsically conducting LAO/STO samples with ≥4 u.c. LAO. We observe that its interfacial two-dimensional electron gas (2DEG) can be pinched off and then switched back on by c-AFM lithography. Nanowires created with initially conductive LAO/STO interfaces have an order-of-magnitude longer lifetime in ambient conditions, when compared to an identically created 3.4 u.c. LAO/STO nanowire. We also demonstrate key nanoscale properties such as ballistic transport in a quasi-one-dimensional electron waveguide at a 5 u.c. LAO/STO interface. This approach frees c-AFM-written nanodevice designs from time constraints in air associated with <4 u.c. LAO/STO heterostructures.

36 MATERIALS SCIENCE↗

Controlling structure and interfacial interaction of monolayer TaSe2 on bilayer graphene

Abstract Tunability of interfacial effects between two-dimensional (2D) crystals is crucial not only for understanding the intrinsic properties of each system, but also for designing electronic devices based on ultra-thin heterostructures. A prerequisite of such heterostructure engineering is the availability of 2D crystals with different degrees of interfacial interactions. In this work, we report a controlled epitaxial growth of monolayer TaSe 2 with different structural phases, 1 H and 1 T , on a bilayer graphene (BLG) substrate using molecular beam epitaxy, and its impact on the electronic properties of the heterostructures using angle-resolved photoemission spectroscopy. 1 H -TaSe 2 exhibits significant charge transfer and band hybridization at the interface, whereas 1 T -TaSe 2 shows weak interactions with the substrate. The distinct interfacial interactions are attributed to the dual effects from the differences of the work functions as well as the relative interlayer distance between TaSe 2 films and BLG substrate. The method demonstrated here provides a viable route towards interface engineering in a variety of transition-metal dichalcogenides that can be applied to future nano-devices with designed electronic properties.

36 MATERIALS SCIENCE↗

Constitutional under-potential plating (CUP) – New insights for predicting the morphological stability of deposited lithium anodes in lithium metal batteries

Lithium (Li) cycling in lithium metal batteries (LMBs) inevitably witnesses a non-planar Li/electrolyte interface (cellular/dendritic microstructure) affecting the performance, safety and reliability of LMBs. Herein, the “constitutional under-potential plating” (CUP) concept is presented for the first time to understand the evolution, formation and predict the morphological stability/instability of the Li/electrolyte interface. Here, the CUP condition, a measure of the driving force for interface perturbation, occurs when the true potential gradient at the interface is smaller than the equilibrium electrodeposition potential gradient at the Li/electrolyte interface resulting in the electrolyte ahead of the Li-electrolyte interface to be in an under-potential state. Detailed CUP criterion calculations conducted herein establishes the relationship of battery operating conditions (e.g. current density, potential gradient) with the electrolyte properties (e.g. Li-ion transference number and diffusion coefficient) predicting the morphological stability condition at the interface. In addition to the driving force for interface perturbation, the capillarity effect or the Gibbs Thomson effect, a measure of the resistance to perturbation of the perturbed interface is discussed for understanding the influence of interfacial energy/adhesion energy between the current collector and the deposited Li on the overall morphological stability of the Li/electrolyte interface, a critical criterion for the unwanted dendritic morphology.

25 ENERGY STORAGE↗

Discussion on molecular dynamics (MD) simulations of the asphalt materials

The application of asphalt materials in pavement engineering has been increasingly widespread and sophisticated over the past several decades. Variations in the properties of asphalt binder during mixing, transportation, and paving can affect the performance of asphalt pavement. However, the asphalt material is a non-homogeneous and complex organic substance, consisting of various molecules with widely various molecular weights, elemental compositions, and structures. This complexity leads to difficulties for researchers to clearly and immediately understand the properties of asphalt materials and their variations. The multi-scale research approach combines macroscopic experimental data and microscopic simulation results from a practical engineering perspective. It helps to improve the understanding of asphalt materials. The molecular dynamics (MD) simulation proposes a corresponding molecular model of asphalt material based on experimental data, and the simulation algorithm is able to derive properties similar to those of real asphalt. Here, this paper provides a comprehensive review of the current studies on MD simulation of asphalt materials, including modeling, properties, and multi-scale analysis. As a key part of the computational simulation, this paper discusses the typical asphalt binder and asphalt-aggregate interface models constructed by different groups, and also presents their differences from real samples and their feasibility based on fundamental properties. After the introduction of molecular models, the extensive work made by researchers based on molecular models is categorically reviewed and discussed. The strengths and weaknesses of MD simulation methods in the study of asphalt materials are also summarized in order to provide the reader with a more comprehensive understanding of the relevant contents and to guide subsequent research.

36 MATERIALS SCIENCE↗

Phase Separation, Capillarity, and Odd-Surface Flows in Chiral Active Matter

Active phase separations evade canonical thermodynamic descriptions and have thus challenged our understanding of coexistence and interfacial phenomena. Considerable progress has been made towards a nonequilibrium theoretical description of these traditionally thermodynamic concepts. Spatial parity symmetry is conspicuously assumed in much of this progress, despite the ubiquity of chirality in experimentally realized systems. Here, in this Letter, we derive a theory for the phase coexistence and interfacial fluctuations of a system that microscopically violates spatial parity. We find suppression of the phase separation as chirality is increased as well as the development of steady-state currents tangential to the interface dividing the phases. These odd flows are irrelevant to stationary interfacial properties, with stability, capillary fluctuations, and surface area minimization determined entirely by the capillary surface tension. Using large-scale Brownian dynamics simulations, we find excellent agreement with our theoretical scaling predictions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗