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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 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Polymer Solar Cells with 18.74% Efficiency: From Bulk Heterojunction to Interdigitated Bulk Heterojunction

The most popular approach to fabricating organic solar cells (OSCs) is solution processing a mixture of donor (D) and acceptor (A) materials into an active layer with a bulk heterojunction (BHJ) nanostructure. In this work, it is demonstrated that the interdigitated heterojunction (IHJ) is a more suitable nanostructure of the active layer for high-performance OSCs whereas it is a long standing challenge to realize well-defined IHJ structures. Here, a facile and versatile sequential solution processing method is developed to produce an IHJ nanostructure with power conversion efficiency reaching 18.74% (18.10% for BHJ the counterpart) by fabricating a donor film with nanopores created by a wax additive, sequentially casting the acceptor on top of infiltrating the nanopores. Compared to the BHJ, the IHJ structure with an interpillar distance within the exciton diffusion length can afford a large bulk D/A interface for efficient exciton dissociation with a minimized charge recombination while free electrons and holes can transport to the respective electrodes through more straightforward pathways, thus enhance performance. Furthermore, the D or A phase in the IHJ device contacts with only one electrode, which can prevent shunting between the anode and cathode and facilitate the industrial mass production of OSCs.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Uniaxial, Pure Bending, and Column Buckling Experiments on Superelastic NiTi Rods and Tubes

Many existing shape memory alloy (SMA) devices consist of slender beams and frames. To better understand SMA beam behavior, we experimentally examined the isothermal, room temperature response of superelastic NiTi rods and tubes, of similar outer diameters, subjected to four different modes of loading. Pure tension, pure compression, and pure bending experiments were first performed to establish and compare the baseline uniaxial and bending behaviors of rods and tubes. Column buckling experiments were then performed on rod and tube columns of several slenderness ratios to investigate their mechanical responses, phase transformation kinetics under combined uniaxial and bending deformation, and the interaction between material and structural instabilities. In all experiments, stereo digital image correlation measured local displacement fields in order to capture phenomena such as strain localization and propagating phase boundaries. Superelastic mechanical behavior and the nature of stress-induced phase transformation were found to be strongly affected by specimen geometry and the deformation mode. Under uniaxial tension, both the rod and tube had well-defined loading and unloading plateaus in their superelastic responses, during which stress-induced phase transformation propagated along the length of the specimen in the form of a high/low strain front. Due to the dependence of strain localization on kinematic compatibility, the high/low strain front morphologies differed between the rod and tube: for the rod, the high/low strain front consisted of a diffuse “neck”, while the high/low strain front in the tube consisted of distinct, criss-crossing “fingers.” During uniaxial compression, both cross-sectional forms exhibited higher transformation stresses and smaller transformation strains than uniaxial tension, highlighting the now well-known tension-compression asymmetry of SMAs. Additionally, phase transformation localization and propagation were absent under compressive loading. During pure bending, the moment-curvature response of both forms exhibited plateaus and strain localization during forward and reverse transformations. Rod specimens developed localized, high-curvature regions that propagated along the specimen axis and caused shear strain near the high/low curvature interface; whereas, the tube specimens exhibited finger/wedge-like high strain regions over the tensile side of the tube which caused nonlinear strain profiles through the thickness of the specimen that did not propagate. Here, it was therefore found that classical beam theory assumptions did not hold in the presence of phase transformation localization (although, the assumptions did hold on average for the tube). During column buckling, the structures were loaded into the post-buckling regime yet recovered nearly-straight forms upon unloading. Strain localization was observed only for high aspect ratio (slender) tubes, but the mechanical responses were similar to that of rods of the same slenderness ratio. Also, an interesting “unbuckling” phenomenon was discovered in certain low aspect ratio (stout) columns, where late post-buckling straightening was observed despite continuous monotonic loading. Thus, these behaviors are some of the challenging phenomena which must be captured when developing SMA constitutive models and executing structural simulations.

36 MATERIALS SCIENCE↗
NASA NTRS2016

Modeling Fatigue Damage Onset and Progression in Composites Using an Element-Based Virtual Crack Closure Technique Combined With the Floating Node Method

A new methodology is proposed to model the onset and propagation of matrix cracks and delaminations in carbon-epoxy composites subject to fatigue loading. An extended interface element, based on the Floating Node Method, is developed to represent delaminations and matrix cracks explicitly in a mesh independent fashion. Crack propagation is determined using an element-based Virtual Crack Closure Technique approach to determine mixed-mode energy release rates, and the Paris-Law relationship to obtain crack growth rate. Crack onset is determined using a stressbased onset criterion coupled with a stress vs. cycle curve and Palmgren-Miner rule to account for fatigue damage accumulation. The approach is implemented in Abaqus/Standard® via the user subroutine functionality. Verification exercises are performed to assess the accuracy and correct implementation of the approach. Finally, it was demonstrated that this approach captured the differences in failure morphology in fatigue for two laminates of identical stiffness, but with layups containing θdeg plies that were either stacked in a single group, or distributed through the laminate thickness.

De Carvalho, Nelson V.↗
NASA NTRS1999

The Isothermal Dendritic Growth Experiment (IDGE): USMP-4 One-Year-Report

Dendrites describe the tree-like crystal morphology commonly assumed in many material systems--particularly in metals and alloys that freeze from supercooled or supersaturated melts. There remains a high level of engineering interest in dendritic solidification because of the role of dendrites in the determination of cast alloy microstructures. Microstructure plays a key role in determining the physical properties of cast or welded products. In addition, dendritic solidification provides an example of non-equilibrium physics and is one of the simplest non-trivial examples of dynamic pattern formation, where an amorphous melt, under simple starting conditions, evolves into a complex ramified microstructure. Although it is well-known that dendritic growth is controlled by the transport of latent heat from the moving solid-melt interface as the dendrite advances into a supercooled melt, an accurate, and predictive model has not been developed. Current theories consider: 1) the transfer of heat or solute from the solid-liquid interface into the melt, and 2) the interfacial crystal growth and growth selection physics for the interface. However, the effects of gravity-induced convection on the transfer of heat from the interface prevent either element from being adequately tested solely under terrestrial conditions. The Isothermal Dendritic Growth Experiment (IDGE) constituted a series of three NASA-supported microgravity experiments, all of which flew aboard the space shuttle, Columbia. This experimental space flight series was designed and operated to grow and record dendrite solidification in the absence of gravity-induced convective heat transfer, and thereby produce a wealth of benchmark-quality data for testing solidification scaling laws. The data collection from the on-orbit phase of the IDGE flight series is now complete. We are currently completing analyses and moving towards final data archiving.

Glicksman, M. E.↗
DOE OSTI2024

High-pressure phase transition in 3-D printed nanolamellar high-entropy alloy by imaging and simulation insights

Abstract We report on the high-resolution imaging and molecular dynamics simulations of a 3D-printed eutectic high-entropy alloy (EHEA) Ni 40 Co 20 Fe 10 Cr 10 Al 18 W 2 consisting of nanolamellar BCC and FCC phases. The direct lattice imaging of 3D-printed samples shows the Kurdjumov–Sachs (K–S) orientation relation {111} FCC parallel to {110} BCC planes in the dual-phase lamellae. Unlike traditional iron and steels, this alloy shows an irreversible BCC-to-FCC phase transformation under high pressures. The nanolamellar morphology is maintained after pressure cycling to 30 GPa, and nano-diffraction studies show both layers to be in the FCC phase. The chemical compositions of the dual-phase lamellae after pressure recovery remain unchanged, suggesting a diffusion-less BCC–FCC transformation in this EHEA. The lattice imaging of the pressure-recovered sample does not show any specific orientation relation between the two resulting FCC phases, indicating that many grain orientations are produced during the BCC–FCC phase transformation. Molecular dynamics simulations on phase transformation in a nanolamellar BCC/FCC in K–S orientation show that phase transformation from BCC to FCC is completed under high pressures, and the FCC phase is retained on decompression aided by the stable interfaces. Our work elucidates the irreversible phase transformation under static compression, providing an understanding of the orientation relationships in 3-D printed EHEA under high pressures.

3-D Printing↗
NASA NTRS1990

Effect of thermosolutal convection on the solid-liquid interface in Pb-Au alloy

Liquid-solid interface distortion in the region of primary dendrite tips has been investigated in directionally solidified Pb-8 wt pct Au alloy. The distortions are caused by thermosolutal convection despite choice of growth conditions which should have been thermally and solutally stabilizing. The convection produces clustering of primary dendrites on a plane perpendicular to the growth direction. It produces a mushy zone, where the primary dendrites do not protrude with a uniform length, across the specimen cross section, resulting in large macrosegregation in the transverse direction. However, little macrosegregation is observed along the growth direction. The mushy zone, with uneven dendrite lengths, forms in the beginning of directional solidification. Its shape and dendrite distribution do not show much change during subsequent solidification. Tip morphologies of primary dendrites, within the dendrite clusters, appear to follow the morphological stability relationship.

Tewari, S. N.↗
DOE OSTI2022

High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode

The development of all-solid-state Li–S batteries has been greatly impeded by dendrite growth and dendrite penetration, which are both related to the Li metal anode. As a compromised alternative, we report lithium silicide (Li x Si) as a dendrite-free and high-capacity anode with Li source. Here, the as-synthesized Li x Si is relatively soft, highly electronically conductive, and with a high Li diffusivity. These distinctive properties make Li x Si anode viable as an “all-electrochem-active” electrode (consisted of 100 wt.% Li x Si). Compared with the typical composite electrode, the all-electrochem-active electrode not merely maximizes the electrode-level energy density but also minimizes the electrolyte-related interfacial degradation. Li x Si symmetric cell demonstrates a reversible cycling at 4 mA cm –2 for over 320 h. Stress change and morphological evolution of the Li x Si electrode are investigated upon dealloying/alloying. When paired with a S cathode (active mass loading of 3 mg cm –2 ), Li x Si–S full cell shows a good cycling behavior over 500 cycles and rate performance (69% capacity retained at 1.2C) even at 25 °C.

25 ENERGY STORAGE↗
DOE OSTI2022

Seeking regularity from irregularity: unveiling the synthesis–nanomorphology relationships of heterogeneous nanomaterials using unsupervised machine learning

Nanoscale morphology of functional materials determines their chemical and physical properties. However, despite increasing use of transmission electron microscopy (TEM) to directly image nanomorphology, it remains challenging to quantify the information embedded in TEM data sets, and to use nanomorphology to link synthesis and processing conditions to properties. We develop an automated, descriptor-free analysis workflow for TEM data that utilizes convolutional neural networks and unsupervised learning to quantify and classify nanomorphology, and thereby reveal synthesis–nanomorphology relationships in three different systems. While TEM records nanomorphology readily in two-dimensional (2D) images or three-dimensional (3D) tomograms, we advance the analysis of these images by identifying and applying a universal shape fingerprint function to characterize nanomorphology. After dimensionality reduction through principal component analysis, this function then serves as the input for morphology grouping through unsupervised learning. We demonstrate the wide applicability of our workflow to both 2D and 3D TEM data sets, and to both inorganic and organic nanomaterials, including tetrahedral gold nanoparticles mixed with irregularly shaped impurities, hybrid polymer-patched gold nanoprisms, and polyamide membranes with irregular and heterogeneous 3D crumple structures. In each of these systems, unsupervised nanomorphology grouping identifies both the diversity and the similarity of the nanomaterial across different synthesis conditions, revealing how synthetic parameters guide nanomorphology development. Our work opens possibilities for enhancing synthesis of nanomaterials through artificial intelligence and for understanding and controlling complex nanomorphology, both for 2D systems and in the far less explored case of 3D structures, such as those with embedded voids or hidden interfaces.

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

High‐Efficiency Thin‐Film Superlattice Thermoelectric Cooler Modules Enabled by Low Resistivity Contacts

Abstract V‐telluride superlattice thin films have shown promising performance for on‐chip cooling devices. Recent experimental studies have indicated that device performance is limited by the metal/semiconductor electrical contacts. One challenge in realizing a low resistivity contact is the absence of fundamental knowledge of the physical and chemical properties of interfaces between metal and V‐telluride materials. This study presents a combination of experimental and theoretical efforts to understand, design, and harness low resistivity contacts to V‐tellurides. Ab initio calculations are used to explore the effects of interfacial structure and chemical compositions on the electrical contacts, and an ab initio based macroscopic model is employed to predict the fundamental limit of contact resistivity as a function of both carrier concentration and temperature. Under the guidance of theoretical studies, an experimental approach is developed to fabricate low resistivity metal contacts to V‐telluride thin film superlattices, achieving a 100‐fold reduction compared to previous work. Interfacial characterization and analysis using both scanning transmission electron microscopy and energy‐dispersive X‐ray spectroscopy show unusual interfacial morphology and the potential for further improvement in contact resistivity. Finally, the improved contacts are harnessed to realize an improved high‐performance thermoelectric cooling module.

He, Yuping↗
DOE OSTI2020

Electrical injection and transport in Teflon-diluted hole transport materials

Diluting small molecule organic semiconductor hole transport materials with Teflon AF (TAF) dramatically increases their thermal/morphological stability while counterintuitively also increasing the current density in hole-only diodes. Here, we explore the origin of this current enhancement in co-evaporated blends of TAF and N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD) and find that it results from improved hole injection and not from a mobility enhancement due to semiconductor dilution effects. Whereas electroabsorption measurements indicate that an interface dipole shift of up to 0.5 eV (depending on TAF concentration) aides hole injection at the indium-tin-oxide anode, time-of-flight and temperature-dependent current-voltage measurements show that the mobility of 25 vol% TAF:NPD blends decreases by roughly an order of magnitude relative to neat NPD despite having slightly lower energetic disorder. For comparison, diluting with 25 vol% high density polyethylene achieves a similar reduction in energetic disorder but only decreases the mobility by a factor of two. Furthermore, these results highlight the tradeoff between reducing energetic disorder and frustrating percolation in diluted organic semiconductors, and represent a step toward thermally-evaporated polymer-small molecule composites that maintain high mobility while offering improved morphological stability and lower refractive index for organic light emitting diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

VTO FY20Q4 quarterly report

Project Objective.This project has three objectives: (1) tuning microstructures of 3D-printed SSE separators,(2) determining material and processing compatibilities with cathode printing,and (3)3D printing of sintering-free SSE separators.Project Impact.All-solid-state lithium batteries are difficult to process due to the brittleness of ceramic materials, poor solid-solid contact, and electrolyte-electrode stability issues. As a result, the energy and power density and also cycling stability are far from satisfying. This project will address fabrication difficulties by using state-of-the-art 3D-printing techniques that can introduce 3D interfaces and architectures to enhance solid-solid contact and reduce charge transfer resistance. Success will benefit the DOE by establishing the best manufacturing methods for ASSBsto achieve VTO goals on the performance of beyond Li-ion batteries. Approach.The project employs 3D-printing techniques to manufacture SSEs and related components for ASSBs. The team starts with direct ink writing (DIW) to develop ink recipes with desired rheological properties and explore post-sintering approaches to achieve high densification. In parallel with DIW3D printing, the team also explores other 3D printing options, such as projection microstereolithography (PuSL). Both sintering and sintering-free approaches can gain benefit from 3D printing and therefore will be investigated.Out-Year Goals.The team will determine particle sizes and morphologies as well as post-processing conditions that deliver good ionic conductivity and charge transfer properties of LLZTO separators. They will examine co-sintering of LLZTO/cathode and determine the effects of material, particle size, surface coating, and sintering conditions.Collaborations.Microstructures, ionic conductivities, and mechanical properties will be provided to the LLNL simulation team, led by PI B. Wood, for establishing and validating phase-field modeling methods.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Influence of Solutocapillary Convection on Macrovoid Defect Formation in Polymeric Membranes

The focus of this research project involved the dry-cast process for polymeric membrane formation, whereby evaporation of solvent from an initially homogeneous polymer/solvent/ nonsolvent solution results in phase separation and the formation of polymer-rich and polymer-lean phases. Under certain conditions the polymer-lean phase gives rise to very large and usually undesirable, tear-drop-shaped pores (size approx. 10 - 50 microns) termed macrovoids (MVs). Although in many cases the presence of MV pores has deleterious effects on membrane performance, there are a number of innovative applications where the presence of such pores is highly desirable. Although researchers have proposed a variety of mechanisms for MV formation over the past three decades, two main hypotheses are currently favored: one asserts that MV growth can be attributed solely to diffusion (the diffusive growth hypothesis), whereas the other states that solutocapillary convection (the SC hypothesis) at the MV interface contributes to growth. The overall goal of this research was to obtain a more comprehensive understanding of the fundamental mechanism of MV growth. This research incorporates a coupled modeling and experimental approach to test a solutocapillary convection hypothesis for the growth of macrovoid pores in polymeric membranes. Specifically, we utilized a modification of the first principles model developed by two of the PIs (ARG and WBK) for dry-cast CA membranes. For the experimental component, two separate and mutually complementary approaches were used to study MV growth. In the first, membranes cast in a zero-g environment aboard the NASA KC-135 aircraft were compared with those cast on the ground to assess the effect of the buoyancy force on membrane morphology and MV size and shape. In the second approach, videomicroscopy flow visualization (VMFV) was utilized to observe MV formation and growth in real time and to assess the effect of surface tension on the MV growth dynamics. As a result of these fundamental studies, our research group advanced a new hypothesis for MV pore development in polymeric membranes.

Greenberg, Alan R.↗
DOE OSTI2018

Metal–Organic Framework Thin Films on High-Curvature Nanostructures Toward Tandem Electrocatalysis

In tandem catalysis, two distinct catalytic materials are interfaced to feed the product of one reaction into the next one. This approach, analogous to enzyme cascades, can potentially be used to upgrade small molecules such as CO 2 to more valuable hydrocarbons. Here, we investigate the materials chemistry of metal-organic framework (MOF) thin films grown on gold nanostructured microelectrodes (AuNMEs), focusing on the key materials chemistry challenges necessary to enable the applications of these MOF/AuNME composites in tandem catalysis. We applied two growth methods—layer-by-layer and solvothermal —to grow a variety of MOF thin films on AuNMEs and then characterized them using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The MOF@AuNME materials were then evaluated for electrocatalytic CO 2 reduction. The morphology and crystallinity of the MOF thin films were examined, and it was found that MOF thin films were capable of dramatically suppressing CO production on AuNMEs and producing further-reduced carbon products such as CH 4 and C 2 H 4 . This work illustrates the use of MOF thin films to tune the activity of an underlying CO2RR catalyst to produce further-reduced products.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Novel High Efficient Organic Photovoltaic Materials

Solar energy is a renewable, nonpolluting, and most abundant energy source for human exploration of a remote site or outer space. In order to generate appreciable electrical power in space or on the earth, it is necessary to collect sunlight from large areas and with high efficiency due to the low density of sunlight. Future organic or polymer (plastic) solar cells appear very attractive due to their unique features such as light weight, flexible shape, tunability of energy band-gaps via versatile molecular or supramolecular design, synthesis, processing and device fabrication schemes, and much lower cost on large scale industrial production. It has been predicted that supramolecular and nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration due to improved electronic ultrastructure and morphology in comparison to polymer composite system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel block copolymer system containing donor and acceptor blocks covalently attached. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (RO-PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (SF-PPV). The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block has a strong PL emission at around 560 nm, and acceptor block has a strong PL emission at around 520 nm, the PL emissions of final block copolymers are severely quenched. This verifies the expected electron transfer and charge separation due to interfaces of donor and acceptor nano phase separated blocks. The system therefore has potential for variety light harvesting applications, including high efficient photovoltaic applications.

Sun, Sam↗
DOE OSTI2019

Focus Issue: Understanding Water-Oxide Interfaces to Harness New Processes and Technologies. Introduction

Water interaction with metal oxides plays a fundamentally important role across environmental chemistry, geochemistry, catalysis, and in the control and performance of functional nanocrystalline oxides. Water is found virtually everywhere on Earth, from bulk fluid to trace molecules, and its interaction with natural and engineered materials often defines or at least influences a key part of their chemical and physical behavior. In turn, metal oxides play a dominant role as mineral particles across most natural environments, while comprising a compelling and versatile platform for the development of new functional materials with tailored properties that benefit society. Given the intrinsic correlation of their properties to water interactions, it is a common goal across materials and chemical sciences to develop a comprehensive understanding of water adsorption, water film formation, and water-mediated reactions on metal oxide surfaces. This is certainly true in heterogeneous catalysis and electrocatalysis, where water is omnipresent either as a reactant, a medium, an inhibitor or as a trace component in the feed. The effect of water on the morphological evolution during synthesis, particle assembly, and sintering is also important to the stability and functional properties of oxide nanostructures. Such processes are intimately related to how water molecules interact with their surfaces and affect local physical-chemical conditions.

Rosso, Kevin M.↗
DOE OSTI2024

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Utilizing the self-assembly of block copolymers with large Flory–Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air–polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. Here we further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Evidence for In-Plane Electrical Polarization in 3R-β’-In 2 Se 3 Thin Films Grown by Molecular Beam Epitaxy

β-In 2 Se 3 has been identified as a potential ferroelectric. This work describes the growth of β-In 2 Se 3 via molecular beam epitaxy along with a description of its properties, including the search for switchable polarization in 3R-β’-In2Se3. The thin-film morphology, crystal structure, and phase maps of β-In 2 Se 3 on Si(111) and Al 2 O 3 (0001) were evaluated by atomic force microscopy, X-ray diffraction, and Raman spectroscopy as a function of the atomic Se/In flux ratio and growth temperature. Smooth β-In 2 Se 3 thin films were successfully realized on Si(111) at a substrate temperature of 150 °C using a Se/In flux ratio of 5.7, as well as on Al 2 O 3 (0001) at 450 °C using a Se/In flux ratio of 5.5. Scanning transmission electron microscopy (STEM) confirms the 3R polytype of β-In 2 Se 3 in films on both substrates, with a minor disorder associated with the 2H polytype at the interface. Indications of in-plane Se atom displacements characteristic of the 3R-β’-In 2 Se 3 polytype were found by STEM and second harmonic generation analysis in films on Al 2 O 3 (0001), but not in films on Si(111). Furthermore, attempts at electrical polarization switching did not produce compelling evidence for ferroelectricity. Instead, electrical transport measurements demonstrated locally varying anisotropic responses with the applied electric fields along different in-plane directions, with some hysteresis associated with the trapping of charges.

36 MATERIALS SCIENCE↗
DOE OSTI2017

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi x Mn y Co 1–x–y O 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) to LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) was found to facilitate the diffusion of surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.

36 MATERIALS SCIENCE↗