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At least 1,639 records · Page 91
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)-Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands

Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers (HCPs), formulated as [Ln{sub 2}Ag(hma){sub 2}(ina)(H{sub 2}O){sub 2}]{sub n} nH{sub 2}O [Ln=La(1), Pr(2), Nd(3); Hina=isonicotinic acid, H{sub 3}hma=hemimellitic acid], have been synthesized under hydrothermal conditions. Single-crystal and powder X-ray diffractions confirm that they are isostructural, which features a three-dimensional (3D) pillared-layer heterometallic structure built upon the strictly alternate arrangement of lanthanide-organic layers and [Ag(ina)] pillars. The layers and pillars are connected to each other by Ln-O and Ag-O coordination bonds. The photoluminescent property of the Nd derivative (3) has also been investigated. - Graphical abstract: Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers have been synthesized and structurally characterized. Highlights: Black-Right-Pointing-Pointer Three 3D pillared-layer 4d-4f HCPs were synthesized by hydrothermal reactions. Black-Right-Pointing-Pointer The synergistic coordination strategy was employed. Black-Right-Pointing-Pointer It opens new perspective for the construction of structurally diversified 4d-4f HCPs.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis and crystal structure of Mg{sub 0.5}NbO{sub 2}: An ion-exchange reaction with Mg{sup 2+} between trigonal [NbO{sub 2}]{sup -} layers

A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2} through a cation-exchange reaction with Mg{sup 2+} at 450-550 Degree-Sign C. This is the first example of a topotactic reaction with an aliovalent cation between trigonal [NbO{sub 2}]{sup -} layers. It is proposed to be isostructural with LiNbO{sub 2} (space group; P6{sub 3}/mmc) with lattice parameters of a=2.9052(6) A, c=10.625(15) A. The lattice parameters and formation energy of Mg{sub 0.5}NbO{sub 2} crystallized in LiNbO{sub 2} form and other layered CaNb{sub 2}O{sub 4} one were calculated by density functional theory. - Graphical abstract: A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2} through a cation-exchange reaction with Mg{sup 2+} at 450-550 Degree-Sign C. It is isostructural with LiNbO{sub 2} with lattice parameters of a=2.9052(6) A, c=10.625(15) A. Mg{sup 2+} are described in spheres located between [NbO{sub 2}]{sup -} trigonal layers and its occupancy is 0.5. Highlights: Black-Right-Pointing-Pointer A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2}. Black-Right-Pointing-Pointer Cation-exchange reaction converted two monovalent Li{sup +} into one divalent Mg{sup 2+} at 450-550 Degree-Sign C. Black-Right-Pointing-Pointer Mg{sub 0.5}NbO{sub 2} was isostructural with LiNbO{sub 2} (space group; P6{sub 3}/mmc). Black-Right-Pointing-Pointer Its lattice parameters were a=2.9052(6) A and c=10.625(15) A. Black-Right-Pointing-Pointer Synthesized Mg{sub 0.5}NbO{sub 2} was calculated to be thermodynamically more favorable.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis and single crystal structure refinement of the one-layer hydrate of sodium brittle mica

A sodium brittle mica with the ideal composition [Na{sub 4}]{sup inter}[Mg{sub 6}]{sup oct}[Si{sub 4}Al{sub 4}]{sup tet}O{sub 20}F{sub 4} was synthesized via melt synthesis in a gas tight crucible. This mica is unusual inasmuch as the known mica structure holds only room for two interlayer cations per unit cell and inasmuch as it readily hydrates despite the high layer charge while ordinary micas and brittle micas are non-swelling. The crystal structure of one-layer hydrate sodium brittle mica was determined and refined from single crystal X-ray data. Interlayer cations reside at the center of the distorted hexagonal cavities and are coordinated by the three inner basal oxygen atoms. The coordination of the interlayer cation is completed by three interlayer water molecules residing at the center of the interlayer region. The relative position of adjacent 2:1-layers thus is fixed by these octahedrally coordinated interlayer cations. Pseudo-symmetry leads to extensive twinning. In total five twin operations generate the same environment for the interlayer species and are energetically degenerate. - Graphical abstract: The sodium brittle mica has been successfully synthesized by melt synthesis and the crystal structure of the one-layer hydrate of sodium brittle mica was determined from single crystal X-ray diffraction data. Highlights: Black-Right-Pointing-Pointer Melt synthesis yielded coarse grained sodium brittle mica which showed little disorder. Black-Right-Pointing-Pointer Sodium brittle mica hydrated completely to the state of one-layer hydrate. Black-Right-Pointing-Pointer Structure of one-layer hydrate of sodium brittle mica could therefore be determined and refined. Black-Right-Pointing-Pointer Arrangement of upper and lower tetrahedral sheet encompassing interlayer cation were clarified.

36 MATERIALS SCIENCE↗
DOE OSTI2014

One-step synthesis of layered yttrium hydroxides in immiscible liquid–liquid systems: Intercalation of sterically-bulky hydrophobic organic anions and doping of europium ions

Inorganic–organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid–liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu{sup 3+} ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect. - Graphical abstract: The Eu{sup 3+}-doped layered yttrium hydroxide exhibits intense red photoluminescence after intercalation of benzoate ions. Display Omitted - Highlights: • Immiscible biphasic liquid systems were introduced to synthesize layered yttrium hydroxides. • The temperature of the biphasic systems does not exceed 80 °C in one step of the synthesis. • Hydrophobic organic anions were intercalated between the hydroxide layers in one pot. • Structure and morphology of the hydroxides were modulated by changing the kind of organic anions. • Eu{sup 3+}-doping led to red luminescence from the hydroxides in association with the intercalated organic anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Atomic and molecular layer deposition for surface modification

Atomic and molecular layer deposition (ALD and MLD, respectively) techniques are based on repeated cycles of gas–solid surface reactions. A partial monolayer of atoms or molecules is deposited to the surface during a single deposition cycle, enabling tailored film composition in principle down to molecular resolution on ideal surfaces. Typically ALD/MLD has been used for applications where uniform and pinhole free thin film is a necessity even on 3D surfaces. However, thin – even non-uniform – atomic and molecular deposited layers can also be used to tailor the surface characteristics of different non-ideal substrates. For example, print quality of inkjet printing on polymer films and penetration of water into porous nonwovens can be adjusted with low-temperature deposited metal oxide. In addition, adhesion of extrusion coated biopolymer to inorganic oxides can be improved with a hybrid layer based on lactic acid. - Graphical abstract: Print quality of a polylactide film surface modified with atomic layer deposition prior to inkjet printing (360 dpi) with an aqueous ink. Number of printed dots illustrated as a function of 0, 5, 15 and 25 deposition cycles of trimethylaluminum and water. - Highlights: • ALD/MLD can be used to adjust surface characteristics of films and fiber materials. • Hydrophobicity after few deposition cycles of Al{sub 2}O{sub 3} due to e.g. complex formation. • Same effect on cellulosic fabrics observed with low temperature deposited TiO{sub 2}. • Different film growth and oxidation potential with different precursors. • Hybrid layer on inorganic layer can be used to improve adhesion of polymer melt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the V atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.

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

Numerical simulations of sand migration during gas production in hydrate-bearing sands interbedded with thin mud layers at site NGHP-02-16

The geomechanical behavior of gas hydrate-bearing sands during gas production is complex, involving changes in hydrate-dependent mechanical characteristics and also redistribution of stresses carried by the hydrate. When an interbedded mud layer is present, the complex response of the hydrate-bearing sediments is more pronounced because hydrate dissociation tends to occur preferentially in the sands adjacent to the hydrate-free mud layer, which can act as a heat source. This leads to non-uniform sediment deformation and potentially to shearing deformation along the sand/mud layers. In addition, since the hydrate-bearing sand permeability becomes far greater than the mud permeability with hydrate dissociation, a greater hydraulic gradient may exist along the interface between the sand/mud layers. These two behaviors may contribute to sand migration and thus a thorough study on the effect of a thin interbedded mud layer on the extent of sand migration is necessary. This paper presents numerical sand migration modeling of sand/mud interbedded hydrate-bearing sediments found at Site NGHP-02-16, one of 25 sites drilled as a part of National Gas Hydrate Program Expedition 02 (NGHP-02) in the offshore of India, subjected to depressurization. For a comparison and better understanding, simulation of homogeneous hydrate-bearing sediments is also conducted. It is found that greater sand migration occurs when the interbedded mud layer is present because of greater shearing deformation and greater pressure gradients at sand-mud interface.

58 GEOSCIENCES↗
DOE OSTI2015

Crystallization study of amorphous sputtered NiTi bi-layer thin film

The crystallization of Ni-rich/NiTiCu bi-layer thin film deposited by magnetron sputtering from two separate alloy targets was investigated. To achieve the shape memory effect, the NiTi thin films deposited at room temperature with amorphous structure were annealed at 773 K for 15, 30, and 60 min for crystallization. Characterization of the films was carried out by differential scanning calorimetry to indicate the crystallization temperature, grazing incidence X-ray diffraction to identify the phase structures, atomic force microscopy to evaluate surface morphology, scanning transmission electron microscopy to study the cross section of the thin films. The results show that the structure of the annealed thin films strongly depends on the temperature and time of the annealing. Crystalline grains nucleated first at the surface and then grew inward to form columnar grains. Furthermore, the crystallization behavior was markedly affected by composition variations. - Highlights: • A developed bi-layer Ni45TiCu5/Ni50.8Ti was deposited on Si substrate and crystallized. • During crystallization, The Ni{sub 45}TiCu{sub 5} layer is thermally less stable than the Ni-rich layer. • The activation energy is 302 and 464 kJ/mol for Cu-rich and Ni-rich layer in bi-layer, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Surface modification induced phase transformation and structure variation on the rapidly solidified recast layer of titanium

In this study, neodymium-doped yttrium orthovanadate (Nd:YVO{sub 4}) as a laser source with different scanning speeds was used on biomedical Ti surface. The microstructural and biological properties of laser-modified samples were investigated by means of optical microscope, electron microscope, X-ray diffraction, surface roughness instrument, contact angle and cell cytotoxicity assay. After laser modification, the rough volcano-like recast layer with micro-/nanoporous structure and wave-like recast layer with nanoporous structure were generated on the surfaces of laser-modified samples, respectively. It was also found out that, an α → (α + rutile-TiO{sub 2}) phase transition occurred on the recast layers of laser-modified samples. The Ti surface becomes hydrophilic at a high speed laser scanning. Moreover, the cell cytotoxicity assay demonstrated that laser-modified samples did not influence the cell adhesion and proliferation behaviors of osteoblast (MG-63) cell. The laser with 50 mm/s scanning speed induced formation of rough volcano-like recast layer accompanied with micro-/nanoporous structure, which can promote cell adhesion and proliferation of MG-63 cell on Ti surface. The results indicated that the laser treatment was a potential technology to enhance the biocompatibility for titanium. - Highlights: • Laser induced the formation of recast layer with micro-/nanoporous structure on Ti. • An α → (α + rutile-TiO{sub 2}) phase transition was observed within the recast layer. • The Ti surface becomes hydrophilic at a high speed laser scanning. • Laser-modified samples exhibit good biocompatibility to osteoblast (MG-63) cell.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Room temperature multiferroic properties of (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film

Graphical abstract: - Highlights: • Chemical solution deposition of (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}–NiFe{sub 2}O{sub 4} double layered thin film. • Studies on structural, electrical and multiferroic properties. • NiFe{sub 2}O{sub 4} acts as both resistive buffer layer and magnetic source. - Abstract: (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film was prepared on a Pt(111)/Ti/SiO{sub 2}/Si(100) substrate by a chemical solution deposition method. X-ray diffraction and Raman scattering spectroscopy studies confirmed the formation of the distorted rhombohedral perovskite and the inverse spinel cubic structures for the (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film. The (Bi{sub 0.95}La{sub 0.05})(Fe{sub 0.97}Mn{sub 0.03})O{sub 3}/NiFe{sub 2}O{sub 4} double layered thin film exhibited well saturated ferromagnetic (2 M{sub r} of 18.1 emu/cm{sup 3} and 2H{sub c} of 0.32 kOe at 20 kOe) and ferroelectric (2P{sub r} of 60 μC/cm{sup 2} and 2E{sub c} of 813 kV/cm at 866 kV/cm) hysteresis loops with low order of leakage current density (4.5 × 10{sup −6} A/cm{sup 2} at an applied electric field of 100 kV/cm), which suggest the ferroelectric and ferromagnetic multi-layers applications in real devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene

We report two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for nonswollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation.

2D nanosheets↗
DOE OSTI2019

Effect of the doping of PC61BM electron transport layer with carbon nanodots on the performance of inverted planar MAPbI3 perovskite solar cells

The doping effect of carbon nanodots (CNDs) in the PC61BM electron-transport layer on the performance of inverted planar MAPbI3 perovskite solar cells (PSCs) having two different kinds of the hole-transport layer, namely organic PEDOT:PSS and inorganic NiOx, was investigated. The CH3NH3PbI3 perovskite layer was deposited in air at 35% humidity. An average 11% and 12% enhancement of the power conversion efficiency (PCE) was achieved for 1 wt% CNDs doping in the PSCs with PEDOT:PSS and NiOx, respectively. This improvement is attributed to high electron density of CNDs resulting in a triple increase of the electrical conductivity of the PC61BM layer and passivation of the perovskite/PC61BM interface that is reflected by an increase of the open-circuit voltage. In line with this, parallel resistance and fill factor of the PSCs are also improved. Moreover, the energy-resolved electrochemical impedance spectroscopy revealed additional free-charge carriers in the PC61BM layer generated under illumination that were detected via the polaron states formation in the band gap with positive effect on the short-circuit current. All these factors contribute to the PCE improvement. Stability tests of the PSC with PEDOT:PSS under a continuous 24 hour 1.5 AM illumination showed a five times smaller final PCE decrease for the 1 wt% CNDs doping of the PC61BM layer comparing to the undoped counterpart. The passivation effect of CNDs, namely electron filling the traps formed by the photo-dimerization and photo-oxidation of PC61BM molecules, is responsible for this remarkable improvement of the short-term stability. © 2019 International Solar Energy Society.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Selective excitation of window and buffer layers in chalcopyrite devices and modules

Window and buffer layers in chalcopyrite devices are well known to affect junctions, conduction, and photo-absorption properties of the device. Some of these layers, particularly 'buffers,' which are deposited directly on top of the absorber, exhibit metastable effects upon exposure to light. Thus, to understand device performance and/or metastability, it is sometimes desirable to selectively excite different layers in the device stack. Absorption characteristics of various window and buffer layers used in chalcopyrite devices are measured. These characteristics are compared with emission spectra of common and available light sources that might be used to optically excite such layers. Effects of the window and buffer absorption on device quantum efficiency and metastability are discussed. For the case of bath-deposited Zn(O,S) buffers, we conclude that this layer is not optically excited in research devices or modules. Furthermore, this provides a complimentary mechanism to the chemical differences that may cause long time constants (compared to devices with CdS buffers) associated with reaching a stable 'light-soaked' state.

14 SOLAR ENERGY↗
DOE OSTI2023

Near-wall model for compressible turbulent boundary layers based on an inverse velocity transformation

In this work, a near-wall model, which couples the inverse of a recently developed compressible velocity transformation (Griffin et al., Proc. Natl Acad. Sci., vol. 118, 2021, p. 34) and an algebraic temperature–velocity relation, is developed for high-speed turbulent boundary layers. As input, the model requires the mean flow state at one wall-normal height in the inner layer of the boundary layer and at the boundary-layer edge. As output, the model can predict mean temperature and velocity profiles across the entire inner layer, as well as the wall shear stress and heat flux. The model is tested in an a priori sense using a wide database of direct numerical simulation high-Mach-number turbulent channel flows, pipe flows and boundary layers (48 cases, with edge Mach numbers in the range 0.77–11, and semi-local friction Reynolds numbers in the range 170–5700). The present model is significantly more accurate than the classical ordinary differential equation (ODE) model for all cases tested. The model is deployed as a wall model for large-eddy simulations in channel flows with bulk Mach numbers in the range 0.7–4 and friction Reynolds numbers in the range 320–1800. When compared to the classical framework, in the a posteriori sense, the present method greatly improves the predicted heat flux, wall stress, and temperature and velocity profiles, especially in cases with strong heat transfer. In addition, the present model solves one ODE instead of two, and has a computational cost and implementation complexity similar to that of the commonly used ODE model.

42 ENGINEERING↗
DOE OSTI2023

Bimolecular Reaction Mechanism in the Amido Complex-Based Atomic Layer Deposition of HfO 2

The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO 2 atomic layer deposition on a SiO 2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and density functional theory together show that the decomposition of the metal precursor on the stoichiometric SiO 2 surface in the first half-cycle of atomic layer deposition proceeds via a bimolecular reaction mechanism. The reaction leads to the formation of Hf-bonded methyl methylene imine and free dimethylamine. In addition, ligand exchange takes place involving the surface hydroxyls adsorbed at defect sites of the SiO 2 surface.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Layered Oxide Cathodes for Li-Ion Batteries: Oxygen Loss and Vacancy Evolution

Loss of oxygen in layered transition metal oxides is a major reason for the structural degradation and thus the fade of electrochemical performance in the cathodes for Li-ion batteries. Via in-situ transmission electron microscopy observations of LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA), we found that the oxygen loss in the layered cathode is a two-stage process with distinct release rates. The initial rapid oxygen loss generates a high concentration of oxygen vacancies that results in the formation of an amorphized, vacancy-containing rock-salt layer in the surface. In the second stage, the slower rate of oxygen loss allows recrystallization of this defective phase via coalescing of atomic oxygen vacancies, which results in the formation of a cavity-containing surface layer with a crystalline rock-salt structure over the layered phase in the bulk. Comparison of the in-situ results with electrochemically cycled NCA cathodes confirms this two-stage process of oxygen loss. Furthermore, these results provide unprecedented microscopic details regarding the structural degradation of layered oxides arising from oxygen loss and have broader implications in manipulating the oxygen activity in the electrode.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural Stability of Graphene-Supported Pt Layers: Diffusion Monte Carlo and Density Functional Theory Calculations

In this study, we used a combination of diffusion Monte Carlo and density functional theory calculations to investigate the stability and interlayer binding of various layered structures of Pt atoms adsorbed on graphene. Our findings show that vertically buckled Pt monolayer and bilayer with (111)-packing order are more energetically favorable than the corresponding buckled (100) or flat (100)-packing structures. This can be attributed to the significant lattice mismatch (>10%) between pristine graphene and a free-standing (100)-packing Pt layer. Additionally, our calculations reveal that among the (100)-packing Pt layers, an incommensurate structure with a Pt/C atomic ratio less than 1/2 may be more stable than the commensurate structures registered at the bridge sites, which aligns with recent experimental findings of incommensurate (100)-packing Pt layers on graphene. The interlayer binding between the Pt layer and graphene is found to be primarily driven by van der Waals interaction, except for the AA-stacked buckled-(100) Pt bilayer where the bottom Pt atoms show chemisorption to the graphene surface. In conclusion, this research offers a comprehensive examination of the stability and interlayer binding of metallic Pt layers, providing valuable insights for potential applications as a next-generation catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode

Layered lithium transition metal oxides (LTMO) are promising candidate cathode materials for next generation high energy density lithium ion battery. The challenge for using this category of cathode is the capacity and voltage fading, which is believed to be associated with the layered structure disordering, a process that is initiated from the surface or solid-electrolyte interface and facilitated by transition metal (TM) reduction and oxygen vacancy formation. However, the atomic level dynamic mechanism of such a layered structure disordering is still not fully clear. In this work, utilizing atomic resolution electron energy loss spectroscopy (EELS), we map, for the first time at atomic scale, the spatial evolution of Ni, Co and Mn in a cycled LiNi1/3M1/3Co1/3O2 layered cathode. In combination with atomic level structural imaging, we discovered the direct correlation of TM ions migration behavior with lattice disordering, featuring the residing of TM ions in the tetrahedral site and a sequential migration of Ni, Co, and Mn upon the increased lattice disordering of the layered structure. This work highlights that Ni ions, though acting as the dominant redox species in many LTMO, are labile to migrate to cause lattice disordering upon battery cycling; while the Mn ions are more stable as compared with Ni and Co and can act as pillar to stabilize layered structure. Direct visualization of the behavior of TM ions during the battery cycling provides insight for designing of cathode with structural stability and correspondingly a superior performance.

annular bright field image↗