Homogenizing Zn Deposition in Hierarchical Nanoporous Cu for a High-Current, High Areal-Capacity Zn Flow Battery.

A Zn anode can offset the low energy density of a flow battery for a balanced approach toward electricity storage. Yet, when targeting inexpensive, long-duration storage, the battery demands a thick Zn deposit in a porous framework, whose heterogeneity triggers frequent dendrite formation and jeopardizes the stability of the battery. Here, Cu foam is transferred into a hierarchical nanoporous electrode to homogenize the deposition. It begins with alloying the foam with Zn to form Cu5 Zn8 , whose depth is controlled to retain the large pores for a hydraulic permeability ≈10-11  m2 . Dealloying follows to create nanoscale pores and abundant fine pits below 10 nm, where Zn can nucleate preferentially due to the Gibbs-Thomson effect, as supported by a density functional theory simulation. Morphological evolution monitored by in situ microscopy confirms uniform Zn deposition. The electrode delivers 200 h of stable cycles in a Zn-I2 flow battery at 60 mAh cm-2 and 60 mA cm-2 , performance that meets practical demands.

Salt-Assisted Selective Growth of H-phase Monolayer VSe2 with Apparent Hole Transport Behavior.

Vanadium diselenide (VSe2) exhibits versatile electronic and magnetic properties in the trigonal prismatic (H-) and octahedral (T-) phases. Compared to the metallic T-phase, the H-phase with a tunable semiconductor property is predicted to be a ferrovalley material with spontaneous valley polarization. Herein we report an epitaxial growth of the monolayer 2D VSe2 on a mica substrate via the chemical vapor deposition (CVD) method by introducing salt in the precursor. Our first-principles calculations suggest that the monolayer H-phase VSe2 with a large lateral size is thermodynamically favorable. The honeycomb-like structure and the broken symmetry are directly observed by spherical aberration-corrected scanning transmission electron microscopy (STEM) and confirmed by giant second harmonic generation (SHG) intensity. The p-type transport behavior is further evidenced by the temperature-dependent resistance and field-effect device study. The present work introduces a new phase-stable 2D transition metal dichalcogenide, opening the prospect of novel electronic and spintronics device design.

Sodiophilically Graded Gold Coating on Carbon Skeletons for Highly Stable Sodium Metal Anodes.

Metallic sodium (Na) is an appealing anode material for high-energy Na batteries. However, Na metal suffers from low coulombic efficiencies and severe dendrite growth during plating/stripping cycles, causing short circuits. As an effective strategy to improve the deposition behavior of Na metal, a 3D carbon foam is developed that is sputter-coated with gold nanoparticles (Au/CF), forming a functional gradient through its thickness. The highly porous Au/CF host is proven to have gradually varying sodiophilicity, which in turn facilitates initially preferential Na deposition on the gold-rich, sodiophilic region in a "bottom-up growth" mode, leading to uniform plating over the entire Au/CF host. This finding contrasts with dendrite formation in the pristine CF host, as proven by in situ microscopy. The Na-predeposited Au/CF (Na@Au/CF) composite anode operates steadily for 1000 h at a low overpotential of ≈20 mV at 2 mA cm-2 in a symmetric cell. When the composite anode is coupled with a Na3 V2 (PO4 )2 F3 cathode, the full cell has a high capacity of 102.1 mAh g-1 after 500 cycles at 2 C. The sodiophilicity gradient design that is explored in this study offers new insight into developing porous Na metal hosts with highly stable plating/stripping performance for next-generation Na batteries.

Molybdenum Disulfide Based Nanomaterials for Rechargeable Batteries.

The rapid development of electrochemical energy storage systems requires new electrode materials with high performance. As a two-dimensional material, molybdenum disulfide (MoS2 ) has attracted increasing interest in energy storage applications due to its layered structure, tunable physical and chemical properties, and high capacity. In this review, the atomic structures and properties of different phases of MoS2 are first introduced. Then, typical synthetic methods for MoS2 and MoS2 -based composites are presented. Furthermore, the recent progress in the design of diverse MoS2 -based micro/nanostructures for rechargeable batteries, including lithium-ion, lithium-sulfur, sodium-ion, potassium-ion, and multivalent-ion batteries, is overviewed. Additionally, the roles of advanced in situ/operando techniques and theoretical calculations in elucidating fundamental insights into the structural and electrochemical processes taking place in these materials during battery operation are illustrated. Finally, a perspective is given on how the properties of MoS2 -based electrode materials are further improved and how they can find widespread application in the next-generation electrochemical energy-storage systems.

Discovering a First-Order Phase Transition in the Li-CeO2 System.

An in-depth understanding of (de)lithiation induced phase transition in electrode materials is crucial to grasp their structure-property relationships and provide guidance to the design of more desirable electrodes. By operando synchrotron XRD (SXRD) measurement and Density Functional Theory (DFT) based calculations, we discover a reversible first-order phase transition for the first time during (de)lithiation of CeO2 nanoparticles. The LixCeO2 compound phase is identified to possess the same fluorite crystal structure with FM3M space group as that of the pristine CeO2 nanoparticles. The SXRD determined lattice constant of the LixCeO2 compound phase is 0.551 nm, larger than that of 0.541 nm of the pristine CeO2 phase. The DFT calculations further reveal that the Li induced redistribution of electrons causes the increase in the Ce-O covalent bonding, the shuffling of Ce and O atoms, and the jump expansion of lattice constant, thereby resulting in the first-order phase transition. Discovering the new phase transition throws light upon the reaction between lithium and CeO2, and provides opportunities to the further investigation of properties and potential applications of LixCeO2.

Multilayer Graphene Enables Higher Efficiency in Improving Thermal Conductivities of Graphene/Epoxy Composites.

The effects of number of graphene layers (n) and size of multilayer graphene sheets on thermal conductivities (TCs) of their epoxy composites are investigated. Molecular dynamics simulations show that the in-plane TCs of graphene sheets and the TCs across the graphene/epoxy interface simultaneously increase with increasing n. However, such higher TCs of multilayer graphene sheets will not translate into higher TCs of bulk composites unless they have large lateral sizes to maintain their aspect ratios comparable to the monolayer counterparts. The benefits of using large, multilayer graphene sheets are confirmed by experiments, showing that the composites made from graphite nanoplatelets (n > 10) with over 30 µm in diameter deliver a TC of ∼1.5 W m(-1) K(-1) at only 2.8 vol %, consistently higher than those containing monolayer or few-layer graphene at the same graphene loading. Our findings offer a guideline to use cost-effective multilayer graphene as conductive fillers for various thermal management applications.

Detecting Arbitrary DNA Mutations Using Graphene Oxide and Ethidium Bromide.

We propose a simple and fast method for detecting arbitrary DNA mutations. Single-stranded DNA probes labeled with fluorescein amidite (FAM-ssDNA), ethidium bromide (EB), and graphene oxide (GO) are employed in the sensing system. The detection is achieved in two steps. In the first step, the sensing system contains FAM-ssDNA probes and EB molecules. It exhibits different fluorescence emissions in the presence of perfectly matched, mismatched, and random DNA sequences. With the addition of GO in the second step, the fluorescence signal for perfectly matched and random DNA does not vary greatly, which, however, experiences a significant change for mismatched DNA targets. The signal ratio before and after the addition of GO can clearly distinguish mutations from normal and random DNA sequences. The detection method works well regardless of the mutation positions and only requires "mix-and-detect" steps, which are completed within 15 min.

Mesoporous ZnCo2O4 nanoflakes grown on nickel foam as electrodes for high performance supercapacitors.

ZnCo2O4 nanoflakes, as electrodes for supercapacitors, are grown on a cellular nickel foam using a cost-effective hydrothermal procedure. The mesoporous ZnCo2O4 nanoflakes have large electroactive surface areas with strong adhesion to the Ni foam, allowing fast ion and electron transport. The nanoarchitecture electrodes deliver an excellent specific capacitance of 1220 F g(-1) at a current density of 2 A g(-1) in a 2 M KOH aqueous solution and a long-term cyclic stability of 94.2% capacitance retention after 5000 cycles. The fabrication strategy is facile, cost-effective, and can offer great promise for large-scale supercapacitor applications.

Graphene oxide-based amplified fluorescent biosensor for Hg(2+) detection through hybridization chain reactions.

We report a graphene oxide (GO)-based fluorescent sensor for Hg(2+) detection in aqueous solutions by using hybridization chain reactions (HCRs). GO is used as an adsorption material for capturing single-stranded DNA and an efficient fluorescence quencher for reducing the background signal. In the detection strategy, two hairpin probes and a helper DNA are employed. Without Hg(2+), they are adsorbed by the GO and the fluorescence of one of the hairpin probes is quenched. In the presence of Hg(2+), the HCRs between the two hairpin probes are initiated by Hg(2+) with the aid of the helper DNA through T-Hg(2+)-T coordination chemistry. The double-stranded DNA products of the HCRs are released by the GO and the fluorescence is recovered. The detection limit of the sensing method is 0.3 nM, which is sufficiently sensitive for practical applications. The sensing system also exhibits high selectivity against other divalent metal ions, and the application of the sensor for drinking water shows that the proposed method works well for real samples.

Age of Flexible Electronics: Emerging Trends in Soft Multifunctional Sensors.

With the commercialization of first-generation flexible mobiles and displays in the late 2010s, humanity has stepped into the age of flexible electronics. Inevitably, soft multifunctional sensors, as essential components of next-generation flexible electronics, have attracted tremendous research interest like never before. This review is dedicated to offering an overview of the latest emerging trends in soft multifunctional sensors and their accordant future research and development (R&D) directions for the coming decade. First, key characteristics and the predominant target stimuli for soft multifunctional sensors are highlighted. Second, important selection criteria for soft multifunctional sensors are introduced. Next, emerging materials/structures and trends for soft multifunctional sensors are identified. Specifically, the future R&D directions of these sensors are envisaged based on their emerging trends, namely i) decoupling of multiple stimuli, ii) data processing, iii) skin conformability, and iv) energy sources. Finally, the challenges and potential opportunities for these sensors in future are discussed, offering new insights into prospects in the fast-emerging technology.

Anti-Fatigue Hydrogel Electrolyte for All-Flexible Zn-Ion Batteries.

Hydrogel electrolytes are widely explored in Zn metal batteries for application in wearable electronics. While extensive studies have been conducted on optimizing the chemical structure and boosting the tensile elasticity, the mechanical stability of the hydrogel under repeated deformation is largely overlooked, leading to unsatisfactory performance at large cycling capacity. This work systematically analyzes the compressive fatigue-resistance properties of the hydrogel electrolyte, revealing the critical roles of the salt and copolymer matrix on crack initiation and propagation. It shows that, on the premise of homogeneous Zn deposition, an improved anti-fatigue property is essential to achieve high-capacity Zn metal anodes. The optimal Zn(ClO4 )2 -polyacrylamide/chitosan hydrogel electrolyte (C-PAMCS) exhibits an unprecedented lifespan of 1500 h for Zn//Zn cells at a current density of 10 mA cm-2 and a high areal capacity of 10 mAh cm-2 . The potential application of C-PAMCS is exemplified in all-flexible Zn-ion batteries enabled by a flexible current collector consisting of a Ag nanowires embedded elastomer. This study provides the rationale under hydrogel electrolyte engineering toward advanced Zn-ion battereis and the application in flexible devices.

Mechanochromic Optical/Electrical Skin for Ultrasensitive Dual-Signal Sensing.

Following earlier research efforts dedicated to the realization of multifunctional sensing, recent developments of artificial skins endeavor to go beyond human sensory functions by integrating interactive visualization of strain and pressure stimuli. Inspired by the microcracked structure of spider slit organs and the mechanochromic mechanism of chameleons, this work aims to design a flexible optical/electrical skin (OE-skin) capable of responding to complex stimuli with interactive feedback of human-readable structural colors. The OE-skin consists of an ionic electrode combined with an elastomer dielectric layer, a chromotropic layer containing photonic crystals and a conductive carbon nanotube/MXene layer. The electrode/dielectric layers function as a capacitive pressure sensor. The mechanochromic photonic crystals of ferroferric oxide-carbon magnetic arrays embedded in the gelatin/polyacrylamide stretchable hydrogel film perceive strain and pressure stimuli with bright color switching outputs in the full visible spectrum. The underlying microcracked conductive layer is devoted to ultrasensitive strain sensing with a gauge factor of 191.8. The multilayered OE-skin delivers an ultrafast, accurate response for capacitive pressure sensing with a detection limit of 75 Pa and long-term stability of 5000 cycles, while visualizing complex deformations in the form of high-resolution spatial colors. These findings offer deep insights into the rational design of OE-skins as multifunctional sensing devices.

BN-PVDF/rGO-PVDF Laminate Nanocomposites for Energy Storage Applications.

The increasing demand for high energy storage devices calls for concurrently enhanced dielectric constants and reduced dielectric losses of polymer dielectrics. In this work, we rationally design dielectric composites comprising aligned 2D nanofillers of reduced graphene oxide (rGO) and boron nitride nanosheets (BNNS) in a polyvinylidene fluoride (PVDF) matrix through a novel press-and-fold technique. Both nanofillers play different yet complementary roles: while rGO is designed to enhance the dielectric constant through charge accumulation at the interfaces with polymer, BNNS suppress the dielectric loss by preventing the mobility of free electrons. The microlaminate containing eight layers each of rGO/PVDF and BNNS/PVDF films exhibits remarkable dielectric performance with a dielectric constant of 147 and an ultralow dielectric loss of 0.075, due to the synergistic effect arising from the alternatingly electrically conductive and insulating films. Consequently, a maximum energy density of 3.5 J/cm3-about 18 times the bilayer composite counterpart-is realized. The high thermal conductivities of both nanofillers and their alignment endow the microlaminate with an excellent in-plane thermal conductivity of 6.53 Wm-1K-1, potentially useful for multifunctional applications. This work offers a simple but effective approach to fabricating a composite for high dielectric energy storage using two different 2D nanofillers.

Superinsulating BNNS/PVA Composite Aerogels with High Solar Reflectance for Energy-Efficient Buildings.

With the mandate of worldwide carbon neutralization, pursuing comfortable living environment while consuming less energy is an enticing and unavoidable choice. Novel composite aerogels with super thermal insulation and high sunlight reflection are developed for energy-efficient buildings. A solvent-assisted freeze-casting strategy is used to produce boron nitride nanosheet/polyvinyl alcohol (BNNS/PVA) composite aerogels with a tailored alignment channel structure. The effects of acetone and BNNS fillers on microstructures and multifunctional properties of aerogels are investigated. The acetone in the PVA suspension enlarges the cell walls to suppress the shrinkage, giving rise to a lower density and a higher porosity, accompanied with much diminished heat conduction throughout the whole product. The addition of BNNS fillers creates whiskers in place of disconnected transverse ligaments between adjacent cell walls, further ameliorating the thermal insulation transverse to the cell wall direction. The resultant BNNS/PVA aerogel delivers an ultralow thermal conductivity of 23.5 mW m-1 K-1 in the transverse direction. The superinsulating aerogel presents both an infrared stealthy capability and a high solar reflectance of 93.8% over the whole sunlight wavelength, far outperforming commercial expanded polystyrene foams with reflective coatings. The anisotropic BNNS/PVA composite aerogel presents great potential for application in energy-saving buildings.

Highly porous carbon nanofiber electrodes for vanadium redox flow batteries.

The electrochemical performance of carbon nanofiber (CNF) electrodes in vanadium redox flow batteries (VRFBs) is enhanced by optimizing the morphological and physical properties of low-cost electrospun CNFs. The surface area, porosity and electrical conductivity of CNFs are tailored by modifying the precursor composition, especially the sacrificing agent, Fe(acac)3, in the polymer precursor and carbonization temperature. A highly porous structure with a large surface area is generated by the catalytic growth of graphitic carbon spheres surrounding the iron nanoparticles which are removed by an acid etching process. The graphitic carbon layers formed at a high carbonization temperature improve the electrical conductivity of CNFs. The large surface area of 349 m2 g-1 together with the abundant mesopore-dominant structure leads to high wettability and high activity for redox reactions of the electrode, giving rise to enhanced electrochemical performance in VRFBs. It delivers an energy efficiency (EE) of 91.4% at a current density of 20 mA cm-2 and 79.3% at 100 mA cm-2, and maintains an average EE of 72.5% after 500 charge/discharge cycles at 100 mA cm-2.

Interdigitated Three-Dimensional Heterogeneous Nanocomposites for High-Performance Mechanochromic Smart Membranes.

Mechanochromic smart membranes capable of optical modulation have great potential in smart windows, artificial skins, and camouflage. However, the realization of high-contrast optical modulation based on light scattering activated at a low strain remains challenging. Here, we present a strategy for designing mechanochromic scattering membranes by introducing a Young's modulus mismatch between the two interdigitated polydimethylsiloxane phases with weak interfaces in a periodic three-dimensional (3D) structure. The refractive index-matched interfaces of the nanocomposite provide a high optical transparency of 93%. Experimental and computational studies reveal that the 3D heterogeneity facilitates the generation of numerous nanoscale debonds or "nanogaps" at the modulus-mismatching interfaces, enabling incident light scattering under tension. The heterogeneous scatterer delivers both a high transmittance contrast of >50% achieved at 15% strain and a maximum contrast of 82%. When used as a smart window, the membrane demonstrates effective diffusion of transmitting sunlight, leading to moderate indoor illumination by eliminating extremely bright or dark spots. At the other extreme, such a 3D heterogeneous design with strongly bonded interfaces can enhance the coloration sensitivity of mechanophore-dyed nanocomposites. This work presents insights into the design principles of advanced mechanochromic smart membranes.

Scalable anisotropic cooling aerogels by additive freeze-casting.

Cooling in buildings is vital to human well-being but inevitability consumes significant energy, adding pressure on achieving carbon neutrality. Thermally superinsulating aerogels are promising to isolate the heat for more energy-efficient cooling. However, most aerogels tend to absorb the sunlight for unwanted solar heat gain, and it is challenging to scale up the aerogel fabrication while maintaining consistent properties. Herein, we develop a thermally insulating, solar-reflective anisotropic cooling aerogel panel containing in-plane aligned pores with engineered pore walls using boron nitride nanosheets by an additive freeze-casting technique. The additive freeze-casting offers highly controllable and cumulative freezing dynamics for fabricating decimeter-scale aerogel panels with consistent in-plane pore alignments. The unique anisotropic thermo-optical properties of the nanosheets combined with in-plane pore channels enable the anisotropic cooling aerogel to deliver an ultralow out-of-plane thermal conductivity of 16.9 mW m-1 K-1 and a high solar reflectance of 97%. The excellent dual functionalities allow the anisotropic cooling aerogel to minimize both parasitic and solar heat gains when used as cooling panels under direct sunlight, achieving an up to 7 °C lower interior temperature than commercial silica aerogels. This work offers a new paradigm for the bottom-up fabrication of scalable anisotropic aerogels towards practical energy-efficient cooling applications.

Effects of stage, intercalant species and expansion technique on exfoliation of graphite intercalation compound into graphene sheets.

Graphite is composed of a series of stacked parallel graphene layers bonded by weak van der Waals forces. Although the weak interactions that hold the graphene sheets together allow them to slide readily over each other, the numerous weak bonds make it difficult to separate the sheets. A graphene sheet is a two-dimensional platelet consisting of a few graphene layers with an overall thickness in nanometer scale. Graphene sheets can be obtained from intercalation and subsequent exfoliation of graphite. To realize the expansion and exfoliation behaviors of graphite, graphite intercalation compound (GIC) is produced using an electrochemical method and three important factors, namely stage structure of GIC, intercalant species and expansion techniques, are taken into account. Graphene sheets produced from a lower stage FeCl3-GIC display the best exfoliation behavior in terms of specific surface area, total pore volume and expansion volume. Microwave irradiation gives rise to a more explosive expansion than heating in a furnace.

Beyond homogeneous dispersion: oriented conductive fillers for high κ nanocomposites.

Rational design of structures for regulating the thermal conductivities (κ) of materials is critical to many components and products employed in electrical, electronic, energy, construction, aerospace, and medical applications. As such, considerable efforts have been devoted to developing polymer composites with tailored conducting filler architectures and thermal conduits for highly improved κ. This paper is dedicated to overviewing recent advances in this area to offer perspectives for the next level of future development. The limitations of conventional particulate-filled composites and the issue of percolation are discussed. In view of different directions of heat dissipation in polymer composites for different end applications, various approaches for designing the micro- and macroscopic structures of thermally conductive networks in the polymer matrix are highlighted. Methodological approaches devised to significantly ameliorate thermal conduction are categorized with respect to the pathways of heat dissipation. Future prospects for the development of thermally conductive polymer composites with modulated thermal conduction pathways are highlighted.

Hierarchical crumpled NiMn2O4@MXene composites for high rate ion transport electrochemical supercapacitors.

MXenes have received great attention due to their excellent features such as metal-like electronic conductivity, hydrophilic surface groups, and high volumetric capacitance. However, many performances of MXenes are still unsatisfactory due to their low energy density and easy horizontal stacking. In this work, an NiMn2O4@MXene composite with a crumpled surface was fabricated by a hydrothermal method and a developed dip-coating method. The maximum specific capacitance of the electrode is about 1.52 times that of NiMn2O4. Besides, it delivers a retention rate of 93.3% after 4000 cycles due to the increased transport of ions and electrons by the crumpled surface. An asymmetrical device based on the crumpled NiMn2O4@MXene composite and AC was also assembled, which shows an ultra-high energy density. This work provides an effective strategy to solve the vertical stacking problem of MXenes, which can open new avenues for large-scale applications of MXenes in energy storage.