Observation of Flat Bands in Gated Semiconductor Artificial Graphene.

Flat bands near M points in the Brillouin zone are key features of honeycomb symmetry in artificial graphene (AG) where electrons may condense into novel correlated phases. Here we report the observation of van Hove singularity doublet of AG in GaAs quantum well transistors, which presents the evidence of flat bands in semiconductor AG. Two emerging peaks in photoluminescence spectra tuned by backgate voltages probe the singularity doublet of AG flat bands and demonstrate their accessibility to the Fermi level. As the Fermi level crosses the doublet, the spectra display dramatic stability against electron density, indicating interplays between electron-electron interactions and honeycomb symmetry. Our results provide a new flexible platform to explore intriguing flat band physics.

Poly(methyl methacrylate)-Assisted Exfoliation of Graphite and Its Use in Acrylonitrile-Butadiene-Styrene Composites.

One of the applications of graphene in which its scalable production is of utmost importance is the development of polymer composites. Among the techniques used to produce graphene flakes, the liquid-phase exfoliation (LPE) of graphite stands out due to its versatility and scalability. However, solvents suitable for the LPE process are generally toxic and have a high boiling point, making the processing challenging. The use of low boiling point solvents could be convenient for the processing, due to the easiness of their removal. In this study, the use of poly(methyl methacrylate) (PMMA) as a stabilizing agent is proposed for the production of graphene flakes in a low boiling point solvent, that is, acetone. The graphene dispersions produced in the mixture acetone-PMMA have higher concentration, +175 %, and contain a higher percentage of few-layer graphene flakes (<5 layers), that is, +60 %, compared to the dispersions prepared in acetone. The as-produced graphene dispersions are used to develop graphene/acrylonitrile-butadiene-styrene composites. The mechanical properties of the pristine polymer are improved, that is, +22 % in the Young's modulus, by adding 0.01 wt. % of graphene flakes. Moreover, a decrease of ≈20 % in the oxygen permeability is obtained by using 0.1 wt. % of graphene flakes filler, compared to the unloaded matrix.

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis.

Among the large family of transition metal dichalcogenides, recently ReS2 has stood out due to its nearly layer-independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in-plane anisotropy, and the presence of active sites at its surface makes ReS2 interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time-consuming and complex, therefore limiting its large-scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS2 at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution-based synthesis with surface functionalization strategies, the feasibility of colloidal ReS2 nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD-grown ReS2 and MoS2 . In addition, the integration of the ReS2 nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof-of-principle devices show an electrocatalytic overpotential competitive with devices based on ReS2 produced by CVD, and even with MoS2 , WS2 , and MoSe2 electrocatalysts.

WS2-Graphite Dual-Ion Batteries.

A novel WS2-graphite dual-ion battery (DIB) is developed by combining a conventional graphite cathode and a high-capacity few-layer WS2-flake anode. The WS2 flakes are produced by exploiting wet-jet milling (WJM) exfoliation, which allows large-scale and free-material loss production (i.e., volume up to 8 L h-1 at concentration of 10 g L-1 and exfoliation yield of 100%) of few-layer WS2 flakes in dispersion. The WS2 anodes enable DIBs, based on hexafluorophosphate (PF6-) and lithium (Li+) ions, to achieve charge-specific capacities of 457, 438, 421, 403, 295, and 169 mAh g-1 at current rates of 0.1, 0.2, 0.3, 0.4, 0.8, and 1.0 A g-1, respectively, outperforming conventional DIBs. The WS2-based DIBs operate in the 0 to 4 V cell voltage range, thus extending the operating voltage window of conventional WS2-based Li-ion batteries (LIBs). These results demonstrate a new route toward the exploitation of WS2, and possibly other transition-metal dichalcogenides, for the development of next-generation energy-storage devices.

Liquid-Phase Exfoliated Indium-Selenide Flakes and Their Application in Hydrogen Evolution Reaction.

Single- and few-layered InSe flakes are produced by the liquid-phase exfoliation of ß-InSe single crystals in 2-propanol, obtaining stable dispersions with a concentration as high as 0.11 g L-1 . Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as-produced InSe flakes. It is demonstrated that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few micrometers, and thicknesses ranging from 1 to 20 nm, with a maximum population centered at ≈5 nm, corresponding to 4 Se-In-In-Se quaternary layers. It is also shown that no formation of further InSe-based compounds (such as In2 Se3 ) or oxides occurs during the exfoliation process. The potential of these exfoliated-InSe few-layer flakes as a catalyst for the hydrogen evolution reaction (HER) is tested in hybrid single-walled carbon nanotubes/InSe heterostructures. The dependence of the InSe flakes' morphologies, i.e., surface area and thickness, on the HER performances is highlighted, achieving the best efficiencies with small flakes offering predominant edge effects. The theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes.

High-Power Collective Charging of a Solid-State Quantum Battery.

Quantum information theorems state that it is possible to exploit collective quantum resources to greatly enhance the charging power of quantum batteries (QBs) made of many identical elementary units. We here present and solve a model of a QB that can be engineered in solid-state architectures. It consists of N two-level systems coupled to a single photonic mode in a cavity. We contrast this collective model ("Dicke QB"), whereby entanglement is genuinely created by the common photonic mode, to the one in which each two-level system is coupled to its own separate cavity mode ("Rabi QB"). By employing exact diagonalization, we demonstrate the emergence of a quantum advantage in the charging power of Dicke QBs, which scales like sqrt[N] for N≫1.

3D Dirac Plasmons in the Type-II Dirac Semimetal PtTe_{2}.

Transition-metal dichalcogenides showing type-II Dirac fermions are emerging as innovative materials for nanoelectronics. However, their excitation spectrum is mostly unexplored yet. By means of high-resolution electron energy loss spectroscopy and density functional theory, here, we identify the collective excitations of type-II Dirac fermions (3D Dirac plasmons) in PtTe_{2} single crystals. The observed plasmon energy in the long-wavelength limit is ∼0.5 eV, which makes PtTe_{2} suitable for near-infrared optoelectronic applications. We also demonstrate that interband transitions between the two Dirac bands in PtTe_{2} give rise to additional excitations at ∼1 and ∼1.4 eV. Our results are crucial to bringing to fruition type-II Dirac semimetals in optoelectronics.

An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode.

We report an advanced lithium-ion battery based on a graphene ink anode and a lithium iron phosphate cathode. By carefully balancing the cell composition and suppressing the initial irreversible capacity of the anode in the round of few cycles, we demonstrate an optimal battery performance in terms of specific capacity, that is, 165 mAhg(-1), of an estimated energy density of about 190 Wh kg(-1) and a stable operation for over 80 charge-discharge cycles. The components of the battery are low cost and potentially scalable. To the best of our knowledge, complete, graphene-based, lithium ion batteries having performances comparable with those offered by the present technology are rarely reported; hence, we believe that the results disclosed in this work may open up new opportunities for exploiting graphene in the lithium-ion battery science and development.

On the Elusive Crystallography of Lithium-Rich Layered Oxides: Novel Structural Models.

Lithium-rich layered oxides (LRLOs) are one of the most attractive families among future positive electrode materials for the so-called fourth generation of lithium-ion batteries (LIBs). Their electrochemical performance is enabled by the unique ambiguous crystal structure that is still not well understood despite decades of research. In the literature, a clear structural model able to describe their crystallographic features is missing thereby hindering a clear rationalization of the interplay between synthesis, structure, and functional properties. Here, the structure of a specific LRLO, Li1.28 Mn0.54 Ni0.13 Co0.02 Al0.03 O2 , using synchrotron X-ray diffraction (XRD), neutron diffraction (ND), and High-Resolution Transmission Electron Microscopy (HR-TEM), is analyzed. A systematic approach is applied to model diffraction patterns of Li1.28 Mn0.54 Ni0.13 Co0.02 Al0.03 O2 by using the Rietveld refinement method considering the R 3 ¯ $\bar{3}$ m and C2/m unit cells as the prototype structures. Here, the relative ability of a variety of structural models is compared to match the experimental diffraction pattern evaluating the impact of defects and supercells derived from the R 3 ¯ $\bar{3}$ m structure. To summarize, two possible models able to reconcile the description of experimental data are proposed here for the structure of Li1.28 Mn0.54 Ni0.13 Co0.02 Al0.03 O2 : namely a monoclinic C2/m defective lattice (prototype Li2 MnO3 ) and a monoclinic defective supercell derived from the rhombohedral R 3 ¯ $\bar{3}$ m unit cell (prototype LiCoO2 ).

Prospects for hydrogen storage in graphene.

Hydrogen-based fuel cells are promising solutions for the efficient and clean delivery of electricity. Since hydrogen is an energy carrier, a key step for the development of a reliable hydrogen-based technology requires solving the issue of storage and transport of hydrogen. Several proposals based on the design of advanced materials such as metal hydrides and carbon structures have been made to overcome the limitations of the conventional solution of compressing or liquefying hydrogen in tanks. Nevertheless none of these systems are currently offering the required performances in terms of hydrogen storage capacity and control of adsorption/desorption processes. Therefore the problem of hydrogen storage remains so far unsolved and it continues to represent a significant bottleneck to the advancement and proliferation of fuel cell and hydrogen technologies. Recently, however, several studies on graphene, the one-atom-thick membrane of carbon atoms packed in a honeycomb lattice, have highlighted the potentialities of this material for hydrogen storage and raise new hopes for the development of an efficient solid-state hydrogen storage device. Here we review on-going efforts and studies on functionalized and nanostructured graphene for hydrogen storage and suggest possible developments for efficient storage/release of hydrogen under ambient conditions.

Correction: Tuning the morphology of sulfur-few layer graphene composites via liquid phase evaporation for battery application.

[This corrects the article DOI: 10.1039/D1NA00733E.].

Toward Sustainable Li-S Battery Using Scalable Cathode and Safe Glyme-Based Electrolyte.

The search for safe electrolytes to promote the application of lithium-sulfur (Li-S) batteries may be supported by the investigation of viscous glyme solvents. Hence, electrolytes using nonflammable tetraethylene glycol dimethyl ether added by lowly viscous 1,3-dioxolane (DOL) are herein thoroughly investigated for sustainable Li-S cells. The electrolytes are characterized by low flammability, a thermal stability of ∼200 °C, ionic conductivity exceeding 10-3 S cm-1 at 25 °C, a Li+ transference number of ∼0.5, electrochemical stability window from 0 to ∼4.4 V vs Li+/Li, and a Li stripping-deposition overpotential of ∼0.02 V. The progressive increase of the DOL content from 5 to 15 wt % raises the activation energy for Li+ motion, lowers the transference number, slightly limits the anodic stability, and decreases the Li/electrolyte resistance. The electrolytes are used in Li-S cells with a composite consisting of sulfur and multiwalled carbon nanotubes mixed in the 90:10 weight ratio, exploiting an optimized current collector. The cathode is preliminarily studied in terms of structure, thermal behavior, and morphology and exploited in a cell using standard electrolyte. This cell performs over 200 cycles, with sulfur loading increased to 5.2 mg cm-2 and the electrolyte/sulfur (E/S) ratio decreased to 6 µL mg-1. The above sulfur cathode and the glyme-based electrolytes are subsequently combined in safe Li-S batteries, which exhibit cycle life and delivered capacity relevantly influenced by the DOL content within the studied concentration range.

Influence of Ion Diffusion on the Lithium-Oxygen Electrochemical Process and Battery Application Using Carbon Nanotubes-Graphene Substrate.

Lithium-oxygen (Li-O2) batteries are nowadays among the most appealing next-generation energy storage systems in view of a high theoretical capacity and the use of transition-metal-free cathodes. Nevertheless, the practical application of these batteries is still hindered by limited understanding of the relationships between cell components and performances. In this work, we investigate a Li-O2 battery by originally screening different gas diffusion layers (GDLs) characterized by low specific surface area (<40 m2 g-1) with relatively large pores (absence of micropores), graphitic character, and the presence of a fraction of the hydrophobic PTFE polymer on their surface (<20 wt %). The electrochemical characterization of Li-O2 cells using bare GDLs as the support indicates that the oxygen reduction reaction (ORR) occurs at potentials below 2.8 V vs Li+/Li, while the oxygen evolution reaction (OER) takes place at potentials higher than 3.6 V vs Li+/Li. Furthermore, the relatively high impedance of the Li-O2 cells at the pristine state remarkably decreases upon electrochemical activation achieved by voltammetry. The Li-O2 cells deliver high reversible capacities, ranging from ∼6 to ∼8 mA h cm-2 (referred to the geometric area of the GDLs). The Li-O2 battery performances are rationalized by the investigation of a practical Li+ diffusion coefficient (D) within the cell configuration adopted herein. The study reveals that D is higher during ORR than during OER, with values depending on the characteristics of the GDL and on the cell state of charge. Overall, D values range from ∼10-10 to ∼10-8 cm2 s-1 during the ORR and ∼10-17 to ∼10-11 cm2 s-1 during the OER. The most performing GDL is used as the support for the deposition of a substrate formed by few-layer graphene and multiwalled carbon nanotubes to improve the reaction in a Li-O2 cell operating with a maximum specific capacity of 1250 mA h g-1 (1 mA h cm-2) at a current density of 0.33 mA cm-2. XPS on the electrode tested in our Li-O2 cell setup suggests the formation of a stable solid electrolyte interphase at the surface which extends the cycle life.

Microglia Polarization and Antiglioma Effects Fostered by Dual Cell Membrane-Coated Doxorubicin-Loaded Hexagonal Boron Nitride Nanoflakes.

Microglial cells play a critical role in glioblastoma multiforme (GBM) progression, which is considered a highly malignant brain cancer. The activation of microglia can either promote or inhibit GBM growth depending on the stage of the tumor development and on the microenvironment conditions. The current treatments for GBM have limited efficacy; therefore, there is an urgent need to develop novel and efficient strategies for drug delivery and targeting: in this context, a promising strategy consists of using nanoplatforms. This study investigates the microglial response and the therapeutic efficacy of dual-cell membrane-coated and doxorubicin-loaded hexagonal boron nitride nanoflakes tested on human microglia and GBM cells. Obtained results show promising therapeutic effects on glioma cells and an M2 microglia polarization, which refers to a specific phenotype or activation state that is associated with anti-inflammatory and tissue repair functions, highlighted through proteomic analysis.

Tuning the morphology of sulfur-few layer graphene composites via liquid phase evaporation for battery application.

A comparative study on sulfur-based composite electrodes comprising different few-layer graphene contents prepared via a facile evaporation method is presented here. The active material production process employed here, exploring different sulfur-few layer graphene ratios, enabled tuning and optimization of the sample morphology, as confirmed via a scanning electron microscopy study. The results reveal that the graphene content is a crucial parameter yielding an optimized morphology of spherical particles composed of an elemental sulfur inner core covered by the carbonaceous compound. The electrodes are characterized in lithium metal half-cells in terms of cyclic voltammetry, galvanostatic cycling tests, rate capability and electrochemical impedance spectroscopy. Moreover, the lithium-ion diffusion coefficients of each sample are obtained by the Randles-Sevcik equation in order to evaluate the reliability of the electrochemical processes. The lithium metal half-cell with the sulfur carbon composite active material exploiting a spherical particle morphology delivers a high specific capacity of 950 mA h g-1 after 100 cycles at C/4 with a coulombic efficiency of 98%. An optimized sample, tuned in terms of sulfur content and morphology, shows superior performance, exhibiting capacities of 1128 mA h g-1 and 842 mA h g-1 over 80 cycles at C/4 and 2C, respectively.

Pushing Stoichiometries of Lithium-Rich Layered Oxides Beyond Their Limits.

Lithium-rich layered oxides (LRLOs) are opening unexplored frontiers for high-capacity/high-voltage positive electrodes in Li-ion batteries (LIBs) to meet the challenges of green and safe transportation as well as cheap and sustainable stationary energy storage from renewable sources. LRLOs exploit the extra lithiation provided by the Li1.2TM0.8O2 stoichiometries (TM = a blend of transition metals with a moderate cobalt content) achievable by a layered structure to disclose specific capacities beyond 200-250 mA h g-1 and working potentials in the 3.4-3.8 V range versus Li. Here, we demonstrate an innovative paradigm to extend the LRLO concept. We have balanced the substitution of cobalt in the transition-metal layer of the lattice with aluminum and lithium, pushing the composition of LRLO to unexplored stoichiometries, that is, Li1.2+x (Mn,Ni,Co,Al)0.8-x O2-δ. The fine tuning of the composition of the metal blend results in an optimized layered material, that is, Li1.28Mn0.54Ni0.13Co0.02Al0.03O2-δ, with outstanding electrochemical performance in full LIBs, improved environmental benignity, and reduced manufacturing costs compared to the state-of-the-art.

A Lithium-Sulfur Battery Using Binder-Free Graphene-Coated Aluminum Current Collector.

Lithium-sulfur battery of practical interest requires thin-layer support to achieve acceptable volumetric energy density. However, the typical aluminum current collector of Li-ion battery cannot be efficiently used in the Li/S system due to the insulating nature of sulfur and a reaction mechanism involving electrodeposition of dissolved polysulfides. We study the electrochemical behavior of a Li/S battery using a carbon-coated Al current collector in which the low thickness, the high electronic conductivity, and, at the same time, the host ability for the reaction products are allowed by a binder-free few-layer graphene (FLG) substrate. The FLG enables a sulfur electrode having a thickness below 100 µm, fast kinetics, low impedance, and an initial capacity of 1000 mAh gS -1 with over 70% retention after 300 cycles. The Li/S cell using FLG shows volumetric and gravimetric energy densities of 300 Wh L-1 and 500 Wh kg-1, respectively, which are values well competing with commercially available Li-ion batteries.

Sulfonated NbS2-based proton-exchange membranes for vanadium redox flow batteries.

In this work, novel proton-exchange membranes (PEMs) based on sulfonated poly(ether ether ketone) (SPEEK) and two-dimensional (2D) sulfonated niobium disulphide (S-NbS2) nanoflakes are synthesized by a solution-casting method and used in vanadium redox flow batteries (VRFBs). The NbS2 nanoflakes are produced by liquid-phase exfoliation of their bulk counterpart and chemically functionalized with terminal sulfonate groups to improve dimensional and chemical stabilities, proton conductivity (σ) and fuel barrier properties of the as-produced membranes. The addition of S-NbS2 nanoflakes to SPEEK decreases the vanadium ion permeability from 5.42 × 10-7 to 2.34 × 10-7 cm2 min-1. Meanwhile, it increases the membrane σ and selectivity up to 94.35 mS cm-2 and 40.32 × 104 S min cm-3, respectively. The cell assembled with the optimized membrane incorporating 2.5 wt% of S-NbS2 nanoflakes (SPEEK:2.5% S-NbS2) exhibits high efficiency metrics, i.e., coulombic efficiency between 98.7 and 99.0%, voltage efficiency between 90.2 and 73.2% and energy efficiency between 89.3 and 72.8% within the current density range of 100-300 mA cm-2, delivering a maximum power density of 0.83 W cm-2 at a current density of 870 mA cm-2. The SPEEK:2.5% S-NbS2 membrane-based VRFBs show a stable behavior over 200 cycles at 200 mA cm-2. This study opens up an effective avenue for the production of advanced SPEEK-based membranes for VRFBs.

Functionalized Metallic 2D Transition Metal Dichalcogenide-Based Solid-State Electrolyte for Flexible All-Solid-State Supercapacitors.

Highly efficient and durable flexible solid-state supercapacitors (FSSSCs) are emerging as low-cost devices for portable and wearable electronics due to the elimination of leakage of toxic/corrosive liquid electrolytes and their capability to withstand elevated mechanical stresses. Nevertheless, the spread of FSSSCs requires the development of durable and highly conductive solid-state electrolytes, whose electrochemical characteristics must be competitive with those of traditional liquid electrolytes. Here, we propose an innovative composite solid-state electrolyte prepared by incorporating metallic two-dimensional group-5 transition metal dichalcogenides, namely, liquid-phase exfoliated functionalized niobium disulfide (f-NbS2) nanoflakes, into a sulfonated poly(ether ether ketone) (SPEEK) polymeric matrix. The terminal sulfonate groups in f-NbS2 nanoflakes interact with the sulfonic acid groups of SPEEK by forming a robust hydrogen bonding network. Consequently, the composite solid-state electrolyte is mechanically/dimensionally stable even at a degree of sulfonation of SPEEK as high as 70.2%. At this degree of sulfonation, the mechanical strength is 38.3 MPa, and thanks to an efficient proton transport through the Grotthuss mechanism, the proton conductivity is as high as 94.4 mS cm-1 at room temperature. To elucidate the importance of the interaction between the electrode materials (including active materials and binders) and the solid-state electrolyte, solid-state supercapacitors were produced using SPEEK and poly(vinylidene fluoride) as proton conducting and nonconducting binders, respectively. The use of our solid-state electrolyte in combination with proton-conducting SPEEK binder and carbonaceous electrode materials (mixture of activated carbon, single/few-layer graphene, and carbon black) results in a solid-state supercapacitor with a specific capacitance of 116 F g-1 at 0.02 A g-1, optimal rate capability (76 F g-1 at 10 A g-1), and electrochemical stability during galvanostatic charge/discharge cycling and folding/bending stresses.

Controlled coupling of spin-resolved quantum Hall edge states.

We introduce and experimentally demonstrate a new method that allows us to controllably couple copropagating spin-resolved edge states of a two-dimensional electron gas (2DEG) in the integer quantum Hall regime. The scheme exploits a spatially periodic in-plane magnetic field that is created by an array of Cobalt nanomagnets placed at the boundary of the 2DEG. A maximum charge or spin transfer of 28±1% is achieved at 250 mK.