Giant pyroelectricity in nanomembranes.

Pyroelectricity describes the generation of electricity by temporal temperature change in polar materials1-3. When free-standing pyroelectric materials approach the 2D crystalline limit, how pyroelectricity behaves remained largely unknown. Here, using three model pyroelectric materials whose bonding characters along the out-of-plane direction vary from van der Waals (In2Se3), quasi-van der Waals (CsBiNb2O7) to ionic/covalent (ZnO), we experimentally show the dimensionality effect on pyroelectricity and the relation between lattice dynamics and pyroelectricity. We find that, for all three materials, when the thickness of free-standing sheets becomes small, their pyroelectric coefficients increase rapidly. We show that the material with chemical bonds along the out-of-plane direction exhibits the greatest dimensionality effect. Experimental observations evidence the possible influence of changed phonon dynamics in crystals with reduced thickness on their pyroelectricity. Our findings should stimulate fundamental study on pyroelectricity in ultra-thin materials and inspire technological development for potential pyroelectric applications in thermal imaging and energy harvesting.

Reversible and rapid calcium intercalation into molybdenum vanadium oxides.

Looming concerns regarding scarcity, high prices, and safety threaten the long-term use of lithium in energy storage devices. Calcium has been explored in batteries because of its abundance and low cost, but the larger size and higher charge density of calcium ions relative to lithium impairs diffusion kinetics and cyclic stability. In this work, an aqueous calcium-ion battery is demonstrated using orthorhombic, trigonal, and tetragonal polymorphs of molybdenum vanadium oxide (MoVO) as a host for calcium ions. Orthorhombic and trigonal MoVOs outperform the tetragonal structure because large hexagonal and heptagonal tunnels are ubiquitous in such crystals, providing facile pathways for calcium-ion diffusion. For trigonal MoVO, a specific capacity of ∼203 mAh g-1 was obtained at 0.2C and at a 100 times faster rate of 20C, an ∼60 mAh g-1 capacity was achieved. The open-tunnel trigonal and orthorhombic polymorphs also promoted cyclic stability and reversibility. A review of the literature indicates that MoVO provides one of the best performances reported to date for the storage of calcium ions.

Facile Magnetite Coating for Stable High-Voltage Cycling of Nickel-Rich Cathodes in Conventional Liquid and All-Solid-State Lithium-Ion Batteries.

The instability of Nickel (Ni)-rich cathodes at high voltage is a critical bottleneck toward developing superior lithium-ion batteries. This instability is driven by cathode-electrolyte side reactions, causing rapid degradation, and compromising the overall cycle life. In this study, a protective coating using dispersed "magnetite (FeO.Fe2O3)" nanoparticles is used to uniformly decorate the surface of LiNi0.8Co0.1Mn0.1O2 (NMC 811) microparticles. The modified cathode delivers significant improvement in electrochemical performance at high voltage (≈4.6 V) by suppressing deleterious electrode-electrolyte interactions. A notably higher cycle stability, rate performance, and overall energy density is realized for the coated cathode in a conventional liquid electrolyte battery. When deployed in pellet-stacked solid-state cells with Li6PS5Cl as the electrolyte, the magnetite-coated NMC 811 showed strikingly superior cycling stability than its uncoated counterpart, proving the versatility of the chemistry. The facile surfactant-assisted coating process developed in this work, in conjunction with the affordability, abundance, and nontoxic nature of magnetite makes this a promising approach to realize commercially viable high voltage Ni-rich cathodes that exhibit stable performance in liquid as well as solid-state lithium-ion batteries.

Toward Practical Alloy Anode Based Solid State Batteries.

Alloy-based anodes are regarded as safer and higher capacity alternatives to lithium metal and commercial graphite anodes respectively. However, their commercialization is hindered by poor stability and irreversible loss of active material during cycling. Combining non-flammable and electrochemically stable solid-state electrolytes with high-capacity alloy anodes has chemo-mechanical benefits that can address these long-standing issues. The distinctive interfacial characteristics of solid-state electrolytes reduce the impact of volume variation and dynamic reconstruction of the solid-electrolyte-interphase, thereby realizing the best of both worlds. In this perspective, the interfacial underpinnings for alloy anode based solid-state batteries that are crucial for their success are discussed. The goal is to update the audience with key recent findings that can lay the foundation for future research work in this area. The relevant steps toward commercialization of alloy anode based solid-state batteries are also discussed, starting from bulk and interface architectures to electrode composite preparation and final cell assembly.

Physicochemically Interlocked Sulfur Covalent Triazine Framework for Lithium-Sulfur Batteries with Exceptional Longevity.

An electronically conjugated functional triazine framework is used to synthesize a physicochemically interlocked sulfur cathode that delivers high energy density coupled with exceptional cycle life in lithium-sulfur batteries. Conventional melt-diffusion strategies to impregnate sulfur in the cathode offer poor cycle life due to physical mixing with weak interactions. By contrast, in this approach, sulfur is physicochemically entrapped within a nanoporous and heteroatom doped high surface area covalent triazine framework, resulting in outstanding electrochemical performance (≈89% capacity retention after 1000 cycles, the energy density of ≈2,022 Wh kg-1 sulfur and high-rate capability up to 12 C). The overall structural characteristics and interactions of sulfur with the covalent triazine framework are explored in detail to explain the intriguing properties of the sulfur cathode.

In situ healing of dendrites in a potassium metal battery.

The use of potassium (K) metal anodes could result in high-performance K-ion batteries that offer a sustainable and low-cost alternative to lithium (Li)-ion technology. However, formation of dendrites on such K-metal surfaces is inevitable, which prevents their utilization. Here, we report that K dendrites can be healed in situ in a K-metal battery. The healing is triggered by current-controlled, self-heating at the electrolyte/dendrite interface, which causes migration of surface atoms away from the dendrite tips, thereby smoothening the dendritic surface. We discover that this process is strikingly more efficient for K as compared to Li metal. We show that the reason for this is the far greater mobility of surface atoms in K relative to Li metal, which enables dendrite healing to take place at an order-of-magnitude lower current density. We demonstrate that the K-metal anode can be coupled with a potassium cobalt oxide cathode to achieve dendrite healing in a practical full-cell device.

Graphene's Partial Transparency to van der Waals and Electrostatic Interactions.

Graphene is the thinnest known two-dimensional (2D) material. This thinness is responsible for graphene's well-known optical transparency. In addition to being transparent to light, its extreme thinness and nonpolar nature also render graphene partially transparent to van der Waals and electrostatic interactions. This enables media present on opposite sides of a graphene sheet to sense or feel each other and be influenced by each other. Such crosstalk between materials separated by an impermeable barrier is impossible for typical barrier or coating materials that are usually thick enough to completely screen out such interactions. In this article, we review graphene's partial transparency to atomic interactions at the liquid-solid, solid-solid, and liquid-liquid interfaces. We compare graphene with other 2D materials such as hexagonal boron nitride and show that the extent of graphene's transparency is strongly dependent on the nature and interaction range of the materials placed on opposite sides of the graphene layer. We end with recommendations for future research to better understand the underlying science and to develop practical applications of this exciting phenomena.

Effects of adatom and gas molecule adsorption on the physical properties of tellurene: a first principles investigation.

Tellurene is a new member of the two-dimensional (2D) materials' family, whose existence has been recently confirmed by first principles calculation and experimental work. Tellurene is also the first 2D mono-elemental material of group-VI predicted by scientists, and investigations of its basic properties are still in their infancy. In this study, we use first principles calculation based on density functional theory to investigate the adsorption of nineteen typical adatoms (Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Ag, Au, Pd, Pt, B, N, O, Si, Cl, and Al), and five typical gas molecules (H2, O2, H2O, NO2, and NH3) on α-phase as well as ß-phase tellurene sheets. Our calculations shows that most adatoms are chemisorbed on tellurene sheets with large adsorption energies. Moreover, some of the adatoms are observed to give rise to distinct structural deformations and even local reconstructions. We report that a variety of electronic states are induced by the adatoms, which implies that different electronic structures can be engineered by the adsorption of adatoms. In fact, n-type doping, p-type doping, half-metal, and spin-gapless semiconductor features can be acquired by doping adatoms on tellurene sheets. Our calculations also show that the five gas molecules are all physisorbed on tellurene sheets, and no splitting behaviors are observed. Therefore, the adsorption of the five gas molecules has a weak effect on the electronic properties of tellurene. To conclude, our results indicate that adatom engineering may be used to greatly expand the potential applications of 2D tellurene.

Vertically Oriented Arrays of ReS2 Nanosheets for Electrochemical Energy Storage and Electrocatalysis.

Transition-metal dichalcogenide (TMD) nanolayers show potential as high-performance catalysts in energy conversion and storage devices. Synthetic TMDs produced by chemical-vapor deposition (CVD) methods tend to grow parallel to the growth substrate. Here, we show that with the right precursors and appropriate tuning of the CVD growth conditions, ReS2 nanosheets can be made to orient perpendicular to the growth substrate. This accomplishes two important objectives; first, it drastically increases the wetted or exposed surface area of the ReS2 sheets, and second, it exposes the sharp edges and corners of the ReS2 sheets. We show that these structural features of the vertically grown ReS2 sheets can be exploited to significantly improve their performance as polysulfide immobilizers and electrochemical catalysts in lithium-sulfur (Li-S) batteries and in hydrogen evolution reactions (HER). After 300 cycles, the specific capacity of the Li-S battery with vertical ReS2 catalyst is retained above 750 mA h g(-1), with only ∼0.063% capacity decay per cycle, much better than the baseline battery (without ReS2), which shows ∼0.184% capacity decay per cycle under the same test conditions. As a HER catalyst, the vertical ReS2 provides very small onset overpotential (<100 mV) and an exceptional exchange-current density (∼67.6 µA/cm(2)), which is vastly superior to the baseline electrode without ReS2.

Organic-Inorganic Heterointerfaces for Ultrasensitive Detection of Ultraviolet Light.

The performance of graphene field-effect transistors is limited by the drastically reduced carrier mobility of graphene on silicon dioxide (SiO2) substrates. Here we demonstrate an ultrasensitive ultraviolet (UV) phototransistor featuring an organic self-assembled monolayer (SAM) sandwiched between an inorganic ZnO quantum dots decorated graphene channel and a conventional SiO2/Si substrate. Remarkably, the room-temperature mobility of the chemical-vapor-deposition grown graphene channel on the SAM is an order-of-magnitude higher than on SiO2, thereby drastically reducing electron transit-time in the channel. The resulting recirculation of electrons (in the graphene channel) within the lifetime of the photogenerated holes (in the ZnO) increases the photoresponsivity and gain of the transistor to ∼10(8) A/W and ∼3 × 10(9), respectively with a UV to visible rejection ratio of ∼10(3). Our UV photodetector device manufacturing is also compatible with current semiconductor processing, and suitable for large volume production.

Cl-Doped ZnO Nanowire Arrays on 3D Graphene Foam with Highly Efficient Field Emission and Photocatalytic Properties.

An environmentally friendly, low-cost, and large-scale method is developed for fabrication of Cl-doped ZnO nanowire arrays (NWAs) on 3D graphene foam (Cl-ZnO NWAs/GF), and investigates its applications as a highly efficient field emitter and photocatalyst. The introduction of Cl-dopant in ZnO increases free electrons in the conduction band of ZnO and also leads to the rough surface of ZnO NWAs, which greatly improves the field emission properties of the Cl-ZnO NWAs/GF. The Cl-ZnO NWAs/GF demonstrates a low turn-on field (≈1.6 V µm(-1)), a high field enhancement factor (≈12844), and excellent field emission stability. Also, the Cl-ZnO NWAs/GF shows high photocatalytic efficiency under UV irradiation, enabling photodegradation of organic dyes such as RhB within ≈75 min, with excellent recyclability. The excellent photocatalytic performance of the Cl-ZnO NWAs/GF originates from the highly efficient charge separation efficiency at the heterointerface of Cl-ZnO and GF, as well as improved electron transport efficiency due to the doping of Cl. These results open up new possibilities of using Cl-ZnO and graphene-based hybrid nanostructures for various functional devices.

Mechanical degradation of graphene by epoxidation: insights from first-principles calculations.

Oxidation is a major cause for the degradation of materials including graphene, where epoxidation (forming the C-O-C bond) is very common. In addition, graphene oxide, in which the epoxy group is one of the two major functional groups (the other is hydroxy), is an important precursor material used for the bulk synthesis of graphene sheets. Information about the mechanical stabilities, non-linear elastic properties, and elastic limits under various strain components is invaluable for application of these nanomaterials. Here, we investigate the mechanical properties of the epoxidized graphene in ordered graphene oxide, namely C6O1, C6O2, and C6O3, representing the carbon : oxygen ratios of 6 : 1, 3 : 1, and 2 : 1, respectively, using first-principles calculations within the framework of density functional theory. We predict a reduction of Young's modulus of graphene by a factor of 20%, 23%, and 27% for C6O1, C6O2, and C6O3, respectively, indicating a monotonic degradation with respect to epoxidation. However, there is no clear trend for Poisson's ratio, implying that the local atomic configurations are dominant over oxygen concentrations in determining the Poisson ratio. Our computed high order elastic constants are good for the design of graphene oxide based flexible transparent electronics.

Densification of Alloying Anodes for High Energy Lithium-Ion Batteries: Critical Perspective on Inter- Versus Intra-Particle Porosity.

High Li-storage-capacity particles such as alloying-based anodes (Si, Sn, Ge, etc.) are core components for next-generation Li-ion batteries (LIBs) but are crippled by their intrinsic volume expansion issues. While pore pre-plantation represents a mainstream solution, seldom do this strategy fully satisfy the requirements in practical LIBs. One prominent issue is that porous particles reduce electrode density and negate volumetric performance (Wh L-1) despite aggressive electrode densification strategies. Moreover, the additional liquid electrolyte dosage resulting from porosity increase is rarely noticed, which has a significant negative impact on cell gravimetric energy density (Wh kg-1). Here, the concept of judicious porosity control is introduced to recalibrate existing particle design principles in order to concurrently boost gravimetric and volumetric performance, while also maintaining the battery's cycle life. The critical is emphasized but often neglected role that intraparticle pores play in dictating battery performance, and also highlight the superiority of closed pores over the open pores that are more commonly referred to in the literature. While the analysis and case studies focus on silicon-carbon composites, the overall conclusions apply to the broad class of alloying anode chemistries.

Piezoelectricity in chalcogenide perovskites.

Piezoelectric materials show potential to harvest the ubiquitous, abundant, and renewable energy associated with mechanical vibrations. However, the best performing piezoelectric materials typically contain lead which is a carcinogen. Such lead-containing materials are hazardous and are being increasingly curtailed by environmental regulations. In this study, we report that the lead-free chalcogenide perovskite family of materials exhibits piezoelectricity. First-principles calculations indicate that even though these materials are centrosymmetric, they are readily polarizable when deformed. The reason for this is shown to be a loosely packed unit cell, containing a significant volume of vacant space. This allows for an extended displacement of the ions, enabling symmetry reduction, and resulting in an enhanced displacement-mediated dipole moment. Piezoresponse force microscopy performed on BaZrS3 confirmed that the material is piezoelectric. Composites of BaZrS3 particles dispersed in polycaprolactone were developed to harvest energy from human body motion for the purposes of powering electrochemical and electronic devices.

Handheld Crop Pest Sensor Using Binary Catalyst-Loaded Nano-SnO2 Particles for Oxidative Signal Amplification.

In agriculture, pest management is a major challenge. Crop releases volatiles in response to the pest; hence, sensing these volatile signals at a very early stage will ease pest management. Here, binary catalyst-loaded SnO2 nanoparticles of <5 nm were synthesized for the repeated capture and oxidation of the signature volatile and its products to amplify the chemoresistive signal to detect concentrations as low as ≈120 ppb. The sensitivity may be due to the presence of the elements in the Sn-Fe-Pt bond evidenced by extended X-ray absorption fine-structure spectroscopy (EXAFS) that captures and oxidize the volatile without escaping. This strong catalyst may oxidize nontarget volatiles and can cause false signals; hence, a molecular sieve filter has been coupled to ensure high selectivity for the detection ofTuta absolutainfestation in tomato. Finally, with the support of a mobile power bank, the optimized sensor has been assembled into a lightweight handheld device.

Superhydrophobic graphene foams.

The static and dynamic wetting properties of a 3D graphene foam network are reported. The foam is synthesized using template-directed chemical vapor deposition and contains pores several hundred micrometers in dimension while the walls of the foam comprise few-layer graphene sheets that are coated with Teflon. Water contact angle measurements reveal that the foam is superhydrophobic with an advancing contact angle of ∼163 degrees while the receding contact angle is ∼143 degrees. The extremely water repellent nature of the foam is also confirmed when impacting water droplets are able to completely rebound from the surface. Such superhydrophobic graphene foams show potential in a variety of applications ranging from anti-sticking and self-cleaning to anti-corrosion and low-friction coatings.

Wetting transparency of graphene.

We report that graphene coatings do not significantly disrupt the intrinsic wetting behaviour of surfaces for which surface-water interactions are dominated by van der Waals forces. Our contact angle measurements indicate that a graphene monolayer is wetting-transparent to copper, gold or silicon, but not glass, for which the wettability is dominated by short-range chemical bonding. With increasing number of graphene layers, the contact angle of water on copper gradually transitions towards the bulk graphite value, which is reached for ~6 graphene layers. Molecular dynamics simulations and theoretical predictions confirm our measurements and indicate that graphene's wetting transparency is related to its extreme thinness. We also show a 30-40% increase in condensation heat transfer on copper, as a result of the ability of the graphene coating to suppress copper oxidation without disrupting the intrinsic wettability of the surface. Such an ability to independently tune the properties of surfaces without disrupting their wetting response could have important implications in the design of conducting, conformal and impermeable surface coatings.

Graphene-enhanced environmentally-benign cutting fluids for high-performance micro-machining applications.

A canola-based cutting oil enhanced with graphene platelet (GPL) additives has been developed to fulfill the need for environmentally benign cutting oils for high performance micro-machining applications. Carboxyl-functionalized graphene platelets are used to enable stable GPL dispersion in the polar oil. Three oil formulations consisting of 0.05%, 0.10% and 0.15% GPL by weight are tested. The GPL-laden canola oil is first characterized based on its kinematic viscosity, thermal conductivity and coefficient of friction. Micro-turning tests are then performed to study the effect of GPL loading on the cutting temperature, cutting force, and the surface finish of the part. All tested loadings improve the cooling and lubricating properties of the canola oil. For cooling, this improvement is seen to increase with GPL loading. In the case of lubrication, there appears to be an optimal loading of around 0.10%. The presence of GPL also leads to a decrease in the surface roughness of the micro-machined surface but this improvement drops with increased GPL loading.

Machine Learning-Aided Band Gap Engineering of BaZrS3 Chalcogenide Perovskite.

The non-toxic and stable chalcogenide perovskite BaZrS3 fulfills many key optoelectronic properties for a high-efficiency photovoltaic material. It has been shown to possess a direct band gap with a large absorption coefficient and good carrier mobility values. With a reported band gap of 1.7-1.8 eV, BaZrS3 is a good candidate for tandem solar cell materials; however, its band gap is significantly larger than the optimal value for a high-efficiency single-junction solar cell (∼1.3 eV, Shockley-Queisser limit)─thus doping is required to lower the band gap. By combining first-principles calculations and machine learning algorithms, we are able to identify and predict the best dopants for the BaZrS3 perovskites for potential future photovoltaic devices with a band gap within the Shockley-Queisser limit. It is found that the Ca dopant at the Ba site or Ti dopant at the Zr site is the best candidate dopant. Based on this information, we report for the first time partial doping at the Ba site in BaZrS3 with Ca (i.e., Ba1-xCaxZrS3) and compare its photoluminescence with Ti-doped perovskites [i.e., Ba(Zr1-xTix)S3]. Synthesized (Ba,Ca)ZrS3 perovskites show a reduction in the band gap from ∼1.75 to ∼1.26 eV with <2 atom % Ca doping. Our results indicate that for the purpose of band gap tuning for photovoltaic applications, Ca-doping at the Ba-site is superior to Ti-doping at the Zr-site reported previously.

Electrocatalysts for Zinc-Air Batteries Featuring Single Molybdenum Atoms in a Nitrogen-Doped Carbon Framework.

Bifunctional catalysts can facilitate two different electrochemical reactions with conflicting characteristics. Here, a highly reversible bifunctional electrocatalyst for rechargeable zinc-air batteries (ZABs) is reported featuring a "core-shell structure" in which N-doped graphene sheets wrap around vanadium molybdenum oxynitride nanoparticles. Single Mo atoms are released from the particle core during synthesis and anchored to electronegative N-dopant species in the graphitic shell. The resultant Mo single-atom catalysts excel as active oxygen evolution reaction (OER) sites in pyrrolic-N and as active oxygen reduction reaction (ORR) sites in pyridinic-N environments. ZABs with such bifunctional and multicomponent single-atom catalysts deliver high power density (≈376.4 mW cm-2 ) and long cycle life of over 630 h, outperforming noble-metal-based benchmarks. Flexible ZABs that can tolerate a wide range of temperatures (-20 to 80 °C) under severe mechanical deformation are also demonstrated.