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At least 1,369 records · Page 76

Ultra-low-density digitally architected carbon with a strutted tube-in-tube structure

Porous materials with engineered stretching-dominated lattice designs, which offer attractive mechanical properties with ultra-light weight and large surface area for wide-ranging applications, have recently achieved near-ideal linear scaling between stiffness and density. Here, rather than optimizing the microlattice topology, we explore a different approach to strengthen low-density structural materials by designing tube-in-tube beam structures. We develop a process to transform fully dense, three-dimensional printed polymeric beams into graphitic carbon hollow tube-in-tube sandwich morphologies, where, similar to grass stems, the inner and outer tubes are connected through a network of struts. Compression tests and computational modelling show that this change in beam morphology dramatically slows down the decrease in stiffness with decreasing density. In situ pillar compression experiments further demonstrate large deformation recovery after 30–50% compression and high specific damping merit index. Lastly, our strutted tube-in-tube design opens up the space and realizes highly desirable high modulus–low density and high modulus–high damping material structures.

36 MATERIALS SCIENCE↗

Relation between interfacial shear and friction force in 2D materials

Understanding the interfacial properties between an atomic layer and its substrate is of key interest at both the fundamental and technological levels. From Fermi level pinning to strain engineering and superlubricity, the interaction between a single atomic layer and its substrate governs electronic, mechanical and chemical properties. Here, we measure the hardly accessible interfacial transverse shear modulus of an atomic layer on a substrate. By performing measurements on bulk graphite, and on epitaxial graphene films on SiC with different stacking orders and twisting, as well as in the presence of intercalated hydrogen, we find that the interfacial transverse shear modulus is critically controlled by the stacking order and the atomic layer–substrate interaction. Importantly, we demonstrate that this modulus is a pivotal measurable property to control and predict sliding friction in supported two-dimensional materials. The experiments demonstrate a reciprocal relationship between friction force per unit contact area and interfacial shear modulus. As a result, the same relationship emerges from simulations with simple friction models, where the atomic layer– substrate interaction controls the shear stiffness and therefore the resulting friction dissipation.

36 MATERIALS SCIENCE↗

Li + (ionophore) nanoclusters engineered aqueous/non-aqueous biphasic electrolyte solutions for high-potential lithium-based batteries

The use of aqueous/non-aqueous biphasic electrolyte solutions in Li-based battery systems circumvents the limitations of poor reductive stability of aqueous electrolyte solutions, broadening their electrochemical stability window. However, aqueous/non-aqueous electrolytes suffer from biphasic mixing and high impedance when Li ions cross the biphasic interface. Here we propose the use of 12-crown-4 (12C4) and tetraglyme (G4) as lithium ionophores to form Li + (ionophore) nanoclusters in both non-aqueous and aqueous phases to overcome the interface challenges in biphasic electrolytes. The Li + (ionophore) nanoclusters have the H 2 O-excluding inner Li + solvation structure in non-polar 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), allowing fast charge transport across the biphasic interface without solvent mixing or water shuttling. Further, a tailored electrolyte formulation comprising the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, 12C4, TTE and H 2 O solvents (labelled LiTFSI-12C4@TTE/H 2 O) demonstrates low impedance (2.7 Ω cm -2 ) at the TTE/H 2 O interface and enabling 2,000 cycles of prelithiated graphite||LiFePO 4 coin cells at 850 mA g -1 with an average Coulombic efficiency of 99.8%. Single-layer 22.5 mAh Li||LiMn 2 O 4 pouch cells using LiTFSI-12C4@TTE/H 2 O electrolyte with G4 delivered a stable discharge capacity of about 1.3 mAh cm -2 for 80 cycles at 0.5 mA cm -2 .

25 ENERGY STORAGE↗

Moiré nematic phase in twisted double bilayer graphene

Graphene moiré superlattices display electronic flat bands. At integer fillings of these flat bands, energy gaps due to strong electron-electron interactions are generally observed. However, the presence of other correlation-driven phases in twisted graphitic systems at non-integer fillings is unclear. Here, we report the existence of threefold rotational symmetry breaking in twisted double bilayer graphene. Using spectroscopic imaging over large and uniform areas to characterize the direction and degree of C 3 symmetry breaking, we find it to be prominent only at energies corresponding to the flat bands and nearly absent in the remote bands. We demonstrate that the magnitude of the rotational symmetry breaking does not depend on the degree of the heterostrain or the displacement field, being instead a manifestation of an interaction-driven electronic nematic phase. We show that the nematic phase is a primary order that arises from the normal metal state over a wide range of doping away from charge. Furthermore, our modelling suggests that the nematic instability is not associated with the local scale of the graphene lattice, but is an emergent phenomenon at the scale of the moiré lattice.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electrochemical ion insertion from the atomic to the device scale

Electrochemical ion insertion involves coupled ion–electron transfer reactions, transport of guest species and redox of the host. The hosts are typically anisotropic solids with 2D conduction planes but can also be materials with 1D or isotropic transport pathways. These insertion compounds have traditionally been studied in the context of energy storage but also find extensive applications in electrocatalysis, optoelectronics and computing. Recent developments in operando, ultrafast and high-resolution characterization methods, as well as accurate theoretical simulation methods, have led to a renaissance in the understanding of ion-insertion compounds. In this Review, we present a unified framework for understanding insertion compounds across timescales and length scales ranging from atomic to device levels. Using graphite, transition metal dichalcogenides, layered oxides, oxyhydroxides and olivines as examples, we explore commonalities in these materials in terms of point defects, interfacial reactions and phase transformations. We illustrate similarities in the operating principles of various ion-insertion devices, ranging from batteries and electrocatalysts to electrochromics and thermal transistors, with the goal of unifying research across disciplinary boundaries.

36 MATERIALS SCIENCE↗

Two-dimensional diamonds from sp 2 -to- sp 3 phase transitions

The ability to change material properties through phase engineering has long been sought, with the goal of ad hoc tunability of the physical and chemical properties of the transformed phases. The synthesis and study of graphene have made it possible to explore the mechanisms of 2D phase transformations, opening up paths towards the formation of 2D diamond and diamond thin films. This Review examines the state-of-the-art phase transformations in 2D graphitic systems and beyond. The theoretical models formulated to describe the sp2-to-sp3 transitions from graphene to 2D diamond and the experimental processes developed to induce the transition to 2D diamond are discussed, focusing on the transformations induced by chemical functionalization and pressure. The effects of different structural and environmental factors on the evolution of the phase transformations and on the properties of the transformed diamond phases are explored. Without comprehensively reviewing phase transitions in all 2D materials, we briefly mention hexagonal boron nitride, phosphorene, transition metal dichalcogenides and MXenes systems. Lastly, the Review delves into the technologies and applications of phase transformations in 2D materials and the opportunities for this field.

36 MATERIALS SCIENCE↗

A disordered rock salt anode for fast-charging lithium-ion batteries

Rechargeable lithium-ion batteries with high energy density that can be safely charged and discharged at high rates are desirable for electrified transportation and other applications. However, the sub-optimal intercalation potentials of current anodes result in a trade-off between energy density, power and safety. In this paper we report that disordered rock salt Li 3+ x V 2 O 5 can be used as a fast-charging anode that can reversibly cycle two lithium ions at an average voltage of about 0.6 volts versus a Li/Li + reference electrode. The increased potential compared to graphite reduces the likelihood of lithium metal plating if proper charging controls are used, alleviating a major safety concern (short-circuiting related to Li dendrite growth). In addition, a lithium-ion battery with a disordered rock salt Li 3 V 2 O 5 anode yields a cell voltage much higher than does a battery using a commercial fast-charging lithium titanate anode or other intercalation anode candidates (Li 3 VO 4 and LiV 0.5 Ti 0.5 S 2 ). Further, disordered rock salt Li 3 V 2 O 5 can perform over 1,000 charge–discharge cycles with negligible capacity decay and exhibits exceptional rate capability, delivering over 40 per cent of its capacity in 20 seconds. We attribute the low voltage and high rate capability of disordered rock salt Li 3 V 2 O 5 to a redistributive lithium intercalation mechanism with low energy barriers revealed via ab initio calculations. This low-potential, high-rate intercalation reaction can be used to identify other metal oxide anodes for fast-charging, long-life lithium-ion batteries.

25 ENERGY STORAGE↗

Ligand-channel-enabled ultrafast Li-ion conduction

Li-ion batteries (LIBs) for electric vehicles and aviation demand high energy density, fast charging and a wide operating temperature range, which are virtually impossible because they require electrolytes to simultaneously have high ionic conductivity, low solvation energy and low melting point and form an anion-derived inorganic interphase. We report guidelines for designing such electrolytes by using small-sized solvents with low solvation energy. The tiny solvent in the secondary solvation sheath pulls out the Li + in the primary solvation sheath to form a fast ion-conduction ligand channel to enhance Li + transport, while the small-sized solvent with low solvation energy also allows the anion to enter the first Li + solvation shell to form an inorganic-rich interphase. The electrolyte-design concept is demonstrated by using fluoroacetonitrile (FAN) solvent. The electrolyte of 1.3 M lithium bis(fluorosulfonyl)imide (LiFSI) in FAN exhibits ultrahigh ionic conductivity of 40.3 mS cm -1 at 25 °C and 11.9 mS cm -1 even at -70 °C, thus enabling 4.5-V graphite||LiNi 0.8 Mn 0.1 Co 0.1 O 2 pouch cells (1.2 Ah, 2.85 mAh cm -2 ) to achieve high reversibility (0.62 Ah) when the cells are charged and discharged even at -65 °C. The electrolyte with small-sized solvents enables LIBs to simultaneously achieve high energy density, fast charging and a wide operating temperature range, which is unattainable for the current electrolyte design but is highly desired for extreme LIBs. This mechanism is generalizable and can be expanded to other metal-ion battery electrolytes.

25 ENERGY STORAGE↗

An investigation of the long-range and local structure of sub-stoichiometric zirconium carbide sintered at different temperatures

ZrC 1-x (sub-stoichiometric zirconium carbide), a group IV transition metal carbide, is being considered for various high temperature applications. Departure from stoichiometry changes the thermo-physical response of the material. Reported thermo-physical properties exhibit, in some cases, a degree of scatter with one likely contributor to this being the uncertainty in the C/Zr ratio of the samples produced. Conventional, methods for assigning C/Zr to samples are determined either by nominal stochiometric ratios or combustion carbon analysis. In this study, a range of stoichiometries of hot-pressed ZrC 1-x were examined by SEM, XRD, Raman spectroscopy and static 13 C NMR spectroscopy and used as a basis to correct the C/Zr. Graphite, amorphous, and ZrC 1-x carbon signatures are observed in the 13 C NMR spectra of samples and are determined to vary in intensity with sintering temperature and stoichiometry. In this study a method is outlined to quantify the stoichiometry of ZrC 1-x and free carbon phases, providing an improvement over the sole use and reliance of widely adopted bulk carbon combustion analysis. We report significantly lower C/Zr values determined by 13 C NMR analysis compared with carbon analyser and nominal methods. Furthermore, the location of carbon disassociated from the ZrC 1-x structure is analysed using SEM and Raman spectroscopy.

36 MATERIALS SCIENCE↗

A magnetic sensor using a 2D van der Waals ferromagnetic material

Two-dimensional (2D) van der Waals ferromagnetic materials are emerging as promising candidates for applications in ultra-compact spintronic nanodevices, nanosensors, and information storage. Our recent discovery of the strong room temperature ferromagnetism in single layers of VSe2 grown on graphite or MoS2 substrate has opened new opportunities to explore these ultrathin magnets for such applications. In this paper, we present a new type of magnetic sensor that utilizes the single layer VSe2 film as a highly sensitive magnetic core. The sensor relies in changes in resonance frequency of the LC circuit composed of a soft ferromagnetic microwire coil that contains the ferromagnetic VSe2 film subject to applied DC magnetic fields. We define sensitivity as the slope of the characteristic curve of our sensor, df0/dH, where f0 is the resonance frequency and H is the external magnetic field. The sensitivity of the sensor reaches a large value of 16×106Hz/Oe, making it a potential candidate for a wide range of magnetic sensing applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Towards developing robust solid lubricant operable in multifarious environments

Abstract Conventional solid lubricants such as MoS 2 , graphite, or diamond-like carbon films demonstrate excellent tribological performance but only in specific environments due to their inherent materials properties. This limitation prohibits using these solid lubricants in environments that change dynamically. This study presents the results of a novel solid lubricant that was developed using a combination of solution-processed 2D-molybdenum disulfide and graphene-oxide (GO) that can be deposited on to stainless steel substrates using a simple spray-coating technique and show exceptional performance in multifarious environments namely, ambient (humid) atmosphere, dry nitrogen, and vacuum. The tribological performance of the coatings was evaluated using a ball-on-disc sliding test and demonstrated an excellent wear/friction performance in all environments and coating survived even after 44 km of linear sliding. Transmission electron microscopy and Raman spectroscopy analysis of the tribolayers suggested in-operando friction-induced re-orientation of MoS 2 layers that were protected by GO layers and, an absence of MoO x peaks indicate a strong resistance to intercalation with moisture and oxygen. The simplicity and robustness of the hybrid MoS 2 –GO solid lubricant in mitigating wear-friction behavior of steel-on-steel tribopair in a multifarious environment is a game-changing and is promising for various applications.

36 MATERIALS SCIENCE↗

Artificial intelligence inferred microstructural properties from voltage–capacity curves

Abstract The quantification of microstructural properties to optimize battery design and performance, to maintain product quality, or to track the degradation of LIBs remains expensive and slow when performed through currently used characterization approaches. In this paper, a convolution neural network-based deep learning approach (CNN) is reported to infer electrode microstructural properties from the inexpensive, easy to measure cell voltage versus capacity data. The developed framework combines two CNN models to balance the bias and variance of the overall predictions. As an example application, the method was demonstrated against porous electrode theory-generated voltage versus capacity plots. For the graphite|LiMn $$_2$$ 2 O $$_4$$ 4 chemistry, each voltage curve was parameterized as a function of the cathode microstructure tortuosity and area density, delivering CNN predictions of Bruggeman’s exponent and shape factor with 0.97 $$R^2$$ R 2 score within 2 s each, enabling to distinguish between different types of particle morphologies, anisotropies, and particle alignments. The developed neural network model can readily accelerate the processing-properties-performance and degradation characteristics of the existing and emerging LIB chemistries.

25 ENERGY STORAGE↗

Advancing neutron diffraction for accurate structural measurement of light elements at megabar pressures

Over the last 60 years, the diamond anvil cell (DAC) has emerged as the tool of choice in high pressure science because materials can be studied at megabar pressures using X-ray and spectroscopic probes. In contrast, the pressure range for neutron diffraction has been limited due to low neutron flux even at the strongest sources and the resulting large sample sizes. Here, we introduce a neutron DAC that enables break-out of the previously limited pressure range. Key elements are ball-bearing guides for improved mechanical stability, gem-quality synthetic diamonds with novel anvil support and improved in-seat collimation. We demonstrate a pressure record of 1.15 Mbar and crystallographic analysis at 1 Mbar on the example of nickel. Additionally, insights into the phase behavior of graphite to 0.5 Mbar are described. These technical and analytical developments will further allow structural studies on low-Z materials that are difficult to characterize by X-rays.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Phase engineering of layered anode materials during ion-intercalation in Van der Waal heterostructures

Transition metal dichalcogenides (TMDs) are a class of 2D materials demonstrating promising properties, such as high capacities and cycling stabilities, making them strong candidates to replace graphitic anodes in lithium-ion batteries. However, certain TMDs, for instance, MoS 2 , undergo a phase transformation from 2H to 1T during intercalation that can affect the mobility of the intercalating ions, the anode voltage, and the reversible capacity. In contrast, select TMDs, for instance, NbS 2 and VS 2 , resist this type of phase transformation during Li-ion intercalation. This manuscript uses density functional theory simulations to investigate the phase transformation of TMD heterostructures during Li-, Na-, and K-ion intercalation. The simulations suggest that while stacking MoS 2 layers with NbS 2 layers is unable to limit this 2H → 1T transformation in MoS 2 during Li-ion intercalation, the interfaces effectively stabilize the 2H phase of MoS 2 during Na- and K-ion intercalation. However, stacking MoS 2 layers with VS 2 is able to suppress the 2H → 1T transformation of MoS 2 during the intercalation of Li, Na, and K-ions. The creation of TMD heterostructures by stacking MoS 2 with layers of non-transforming TMDs also renders theoretical capacities and electrical conductivities that are higher than that of bulk MoS 2 .

25 ENERGY STORAGE↗

Ab initio structural dynamics of pure and nitrogen-containing amorphous carbon

Abstract Amorphous carbon (a-C) has attracted considerable interest due to its desirable properties, which are strongly dependent on its structure, density and impurities. Using ab initio molecular dynamics simulations we show that the sp 2 /sp 3 content and underlying structural order of a-C produced via liquid quenching evolve at high temperatures and pressures on sub-nanosecond timescales. Graphite-like densities ( $$\lesssim$$ ≲ 2.7 g/cc) favor the formation of layered arrangements characterized by sp 2 disordered bonding resembling recently synthesized monolayer amorphous carbon (MAC), while at diamond-like densities ( $$\gtrsim$$ ≳ 3.3 g/cc) the resulting structures are dominated by disordered tetrahedral sp 3 hybridization typical of diamond-like amorphous carbon (DLC). At intermediate densities the system is a highly compressible mixture of coexisting sp 2 and sp 3 regions that continue to segregate over 10’s of picoseconds. The addition of nitrogen (20.3%) (a-CN) generates major system features similar with those of a-C, but has the unexpected effect of reinforcing the thermodynamically disfavored carbon structural motifs at low and high densities, while inhibiting phase separation in the intermediate region. At the same time, no nitrogen elimination from the carbon framework is observed above $$\simeq$$ ≃ 2.8 g/cc, suggesting that nitrogen impurities are likely to remain embedded in the carbon structures during fast temperature quenches at high pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organic wastewater treatment by a single-atom catalyst and electrolytically produced H2O2

The presence of organic contaminants in wastewater poses considerable risks to the health of both humans and ecosystems. Although advanced oxidation processes that rely on highly reactive radicals to destroy organic contaminants are appealing treatment options, substantial energy and chemical inputs limit their practical applications. Here we demonstrate that Cu single atoms incorporated in graphitic carbon nitride can catalytically activate H 2 O 2 to generate hydroxyl radicals at pH 7.0 without energy input, and show robust stability within a filtration device. We further design an electrolysis reactor for the on-site generation of H 2 O 2 from air, water and renewable energy. Coupling the single-atom catalytic filter and the H 2 O 2 electrolytic generator in tandem delivers a wastewater treatment system. These findings provide a promising path toward reducing the energy and chemical demands of advanced oxidation processes, as well as enabling their implementation in remote areas and isolated communities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-particle chemical analysis reveals organic-rich detonation soot products

The detonation of high explosives produces a wide variety of particulate matter (PM) with distinct properties, not all of which are traditionally studied for chemical composition, formation processes, and forensic applications. We report particle-resolved measurements of Composition B detonation soot using soot particle aerosol mass spectrometry (SP-AMS), identifying carbonaceous species and metals not previously characterized on a single-particle basis. Results are combined with scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) to enhance source-dependent signatures. Black carbon, including graphitic carbon and detonation nanodiamonds, contributed 50.5-71.4% of PM 2.5 mass, while 22.5-43.4% was non-refractory organic carbon, a previously overlooked component that exhibited a complex and varying composition. Detonations were performed with and without PMMA confinement and under steady and overdriven conditions. Distinct particles enriched with polycyclic aromatic hydrocarbons (PAHs) were observed in experiments utilizing confinement, with quantities dependent on manufacturing method. SEM-EDS validated SP-AMS findings of metals internally mixed with carbonaceous species and extended the particle size range to 100 µm. This work makes detecting non-refractory organics using single-particle techniques more feasible for detonation forensics and understanding high-energy soot formation. While this analysis uses offline sample collection, SP-AMS could be deployed for in-situ measurements of detonation PM 2.5 transported in the atmosphere.

36 MATERIALS SCIENCE↗

Graphene nanoribbons for quantum electronics

Graphene nanoribbons (GNRs) are a family of one-dimensional (1D) materials with a graphitic lattice structure. GNRs possess high mobility and current-carrying capability, sizeable bandgap and versatile electronic properties, which make them promising candidates for quantum electronic applications. In the past 5 years, progress has been made towards atomically precise bottom-up synthesis of GNRs and heterojunctions that provide an ideal platform for functional molecular devices, as well as successful production of semiconducting GNR arrays on insulating substrates potentially useful for large-scale digital circuits. With further development, GNRs can be envisioned as a competitive candidate material in future quantum information sciences. In this Perspective, we discuss recent progress in GNR research and identify key challenges and new directions likely to develop in the near future.

36 MATERIALS SCIENCE↗