Production of phosphorene nanoribbons.

Phosphorene is a mono-elemental, two-dimensional (2D) substance with outstanding, highly directional properties and a bandgap that depends on the number of layers of the material1-8. Nanoribbons, meanwhile, combine the flexibility and unidirectional properties of one-dimensional nanomaterials, the high surface area of 2D nanomaterials and the electron-confinement and edge effects of both. The structures of nanoribbons can thus lead to exceptional control over electronic band structure, the emergence of novel phenomena and unique architectures for applications5,6,9-24. Phosphorene's intrinsically anisotropic structure has motivated numerous theoretical calculations of phosphorene nanoribbons (PNRs), predicting extraordinary properties5,6,12-24. So far, however, discrete PNRs have not been produced. Here we present a method for creating quantities of high-quality, individual PNRs by ionic scissoring of macroscopic black phosphorus crystals. This top-down process results in stable liquid dispersions of PNRs with typical widths of 4-50 nm, predominantly single-layer thickness, measured lengths of up to 75 µm and aspect ratios of up to 1,000. The nanoribbons are atomically flat single crystals, aligned exclusively in the zigzag crystallographic orientation. The ribbons have remarkably uniform widths along their entire lengths, and are extremely flexible. These properties-together with the ease of downstream manipulation via liquid-phase methods-should enable the search for predicted exotic states6,12-14,17-19,21, and an array of applications in which PNRs have been predicted to offer transformative advantages. These applications range from thermoelectric devices to high-capacity fast-charging batteries and integrated high-speed electronic circuits6,14-16,20,23,24.

Nanoscale Ultrafine Zinc Metal Anodes for High Stability Aqueous Zinc Ion Batteries.

Aqueous Zn batteries (AZBs) are a promising energy storage technology, due to their high theoretical capacity, low redox potential, and safety. However, dendrite growth and parasitic reactions occurring at the surface of metallic Zn result in severe instability. Here we report a new method to achieve ultrafine Zn nanograin anodes by using ethylene glycol monomethyl ether (EGME) molecules to manipulate zinc nucleation and growth processes. It is demonstrated that EGME complexes with Zn2+ to moderately increase the driving force for nucleation, as well as adsorbs on the Zn surface to prevent H-corrosion and dendritic protuberances by refining the grains. As a result, the nanoscale anode delivers high Coulombic efficiency (ca. 99.5%), long-term cycle life (over 366 days and 8800 cycles), and outstanding compatibility with state-of-the-art cathodes (ZnVO and AC) in full cells. This work offers a new route for interfacial engineering in aqueous metal-ion batteries, with significant implications for the commercial future of AZBs.

Disentangling water, ion and polymer dynamics in an anion exchange membrane.

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH- ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100-103 ps) to disentangle the water, polymer relaxation and OH- diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.

The local ordering of polar solvents around crystalline carbon nitride nanosheets in solution.

The crystalline graphitic carbon nitride, poly-triazine imide (PTI) is highly unusual among layered materials since it is spontaneously soluble in aprotic, polar solvents including dimethylformamide (DMF). The PTI material consists of layers of carbon nitride intercalated with LiBr. When dissolved, the resulting solutions consist of dissolved, luminescent single to multilayer nanosheets of around 60-125 nm in diameter and Li+ and Br- ions originating from the intercalating salt. To understand this unique solubility, the structure of these solutions has been investigated by high-energy X-ray and neutron diffraction. Although the diffraction patterns are dominated by inter-solvent correlations there are clear differences between the X-ray diffraction data of the PTI solution and the solvent in the 4-6 Å-1 range, with real space differences persisting to at least 10 Å. Structural modelling using both neutron and X-ray datasets as a constraint reveal the formation of distinct, dense solvation shells surrounding the nanoparticles with a layer of Br-close to the PTI-solvent interface. This solvent ordering provides a configuration that is energetically favourable underpinning thermodynamically driven PTI dissolution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Amphoteric dissolution of two-dimensional polytriazine imide carbon nitrides in water.

Crystalline two-dimensional carbon nitrides with polytriazine imide (PTI) structure are shown to act amphoterically, buffering both HCl and NaOH aqueous solutions, resulting in charged PTI layers that dissolve spontaneously in their aqueous media, particularly for the alkaline solutions. This provides a low energy, green route to their scalable solution processing. Protonation in acid is shown to occur at pyridinic nitrogens, stabilized by adjacent triazines, whereas deprotonation in base occurs primarily at basal plane NH bridges, although NH2 edge deprotonation is competitive. We conclude that mildly acidic or basic pHs are necessary to provide sufficient net charge on the nanosheets to promote dissolution, while avoiding high ion concentrations which screen the repulsion of like-charged PTI sheets in solution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Single Crystal, Luminescent Carbon Nitride Nanosheets Formed by Spontaneous Dissolution.

A primary method for the production of 2D nanosheets is liquid-phase delamination from their 3D layered bulk analogues. Most strategies currently achieve this objective by significant mechanical energy input or chemical modification but these processes are detrimental to the structure and properties of the resulting 2D nanomaterials. Bulk poly(triazine imide) (PTI)-based carbon nitrides are layered materials with a high degree of crystalline order. Here, we demonstrate that these semiconductors are spontaneously soluble in select polar aprotic solvents, that is, without any chemical or physical intervention. In contrast to more aggressive exfoliation strategies, this thermodynamically driven dissolution process perfectly maintains the crystallographic form of the starting material, yielding solutions of defect-free, hexagonal 2D nanosheets with a well-defined size distribution. This pristine nanosheet structure results in narrow, excitation-wavelength-independent photoluminescence emission spectra. Furthermore, by controlling the aggregation state of the nanosheets, we demonstrate that the emission wavelengths can be tuned from narrow UV to broad-band white. This has potential applicability to a range of optoelectronic devices.

Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High-resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.

Controlled functionalisation of single-walled carbon nanotube network electrodes for the enhanced voltammetric detection of dopamine.

Voltammetric studies of dopamine (DA) oxidation on pristine and acid-treated single-walled carbon nanotube (SWNT) network electrodes were undertaken in order to investigate both the effect of network density and acid treatment times on the voltammetric characteristics for DA oxidation and the susceptibility of the electrodes to fouling. Through careful control of catalysed chemical vapour deposition growth parameters, multiply interconnected and randomly oriented SWNT networks of two significantly different densities were grown (high density, HD, coverage ≫10 µm length of SWNT per µm(-2) and low density, LD, coverage = 5 (±1) µmSWNTµm(-2)). Acid treatment was performed to provide materials with different electrochemical properties and SWNT coverage, as determined by field emission-scanning electron microscopy, atomic force microscopy and micro-Raman spectroscopy. A high concentration of DA (100 µM) was deliberately employed to accelerate the fouling phenomenon associated with DA oxidation in order to evaluate the lifetime of the electrodes. HD pristine SWNT networks were found to promote more facile electron transfer (ET) and were less susceptible to blocking, compared to LD pristine SWNT networks. Acid treatment resulted in both a further enhancement of the ET rate and a reduction in susceptibility towards electrode fouling. However, lengthy acid treatment detrimentally affected ET, due to a decrease in network density and significant damage to the SWNT network structure. These studies highlight the subtle interplay between SWNT coverage and degree of acid functionalisation when seeking to achieve the optimal SWNT electrode for the voltammetric detection of DA.

Electrochemical activation of pristine single walled carbon nanotubes: impact on oxygen reduction and other surface sensitive redox processes.

The effect of systematic anodic pre-treatments of pristine single walled carbon nanotube (SWNT) forests on the electrochemical response towards a variety of redox processes is investigated. An experimental arrangement is adopted whereby a microcapillary containing the solution of interest and a quasi reference-counter electrode is brought into contact with a small portion of the forest to enable measurements on the surface before and after controlled anodic polarisation (AP). AP of the surface is found to both improve the voltammetric response (faster apparent heterogeneous electron transfer kinetics) of surface sensitive redox processes, such as Fe(2+/3+), and enhance the electrocatalytic response of the SWNTs towards oxygen reduction; the extent of which can be carefully controlled via the applied anodic potential. AP is expected to remove any trace organic (atmospheric) contaminants that may accumulate on the forest over extended periods as well as allowing the controlled introduction of defects, as confirmed by micro-Raman spectroscopy.

The Influence of Cathode Degradation Products on the Anode Interface in Lithium-Ion Batteries.

Degradation of cathode materials in lithium-ion batteries results in the presence of transition metal ions in the electrolyte, and these ions are known to play a major role in capacity fade and cell failure. Yet, while it is known that transition metal ions migrate from the metal oxide cathode and deposit on the graphite anode, their specific influence on anode reactions and structures, such as the solid electrolyte interphase (SEI), is still quite poorly understood due to the complexity in studying this interface in operational cells. In this work we combine operando electrochemical atomic force microscopy (EC-AFM), electrochemical quartz crystal microbalance (EQCM), and electrochemical impedance spectroscopy (EIS) measurements to probe the influence of a range of transition metal ions on the morphological, mechanical, chemical, and electrical properties of the SEI. By adding representative concentrations of Ni2+, Mn2+, and Co2+ ions into a commercially relevant battery electrolyte, the impacts of each on the formation and stability of the anode interface layer is revealed; all are shown to pose a threat to battery performance and stability. Mn2+, in particular, is shown to induce a thick, soft, and unstable SEI layer, which is known to cause severe degradation of batteries, while Co2+ and Ni2+ significantly impact interfacial conductivity. When transition metal ions are mixed, SEI degradation is amplified, suggesting a synergistic effect on the cell stability. Hence, by uncovering the roles these cathode degradation products play in operational batteries, we have provided a foundation upon which strategies to mitigate or eliminate these degradation products can be developed.

Illuminating Polysulfide Distribution in Lithium Sulfur Batteries; Tracking Polysulfide Shuttle Using Operando Optical Fluorescence Microscopy.

High-energy-density lithium sulfur (Li-S) batteries suffer heavily from the polysulfide shuttle effect, a result of the dissolution and transport of intermediate polysulfides from the cathode, into the electrolyte, and onto the anode, leading to rapid cell degradation. If this primary mechanism of cell failure is to be overcome, the distribution, dynamics, and degree of polysulfide transport must first be understood in depth. In this work, operando optical fluorescence microscope imaging of optically accessible Li-S cells is shown to enable real-time qualitative visualization of the spatial distribution of lithium polysulfides, both within the electrolyte and porous cathode. Quantitative determinations of spatial concentration are also possible at a low enough concentration. The distribution throughout cycling is monitored, including direct observation of polysulfide shuttling to the anode and consequent dendrite formation. This was enabled through the optimization of a selective fluorescent dye, verified to fluoresce proportionally with concentration of polysulfides within Li-S cells. This ability to directly and conveniently track the spatial distribution of soluble polysulfide intermediates in Li-S battery electrolytes, while the cell operates, has the potential to have a widespread impact across the field, for example, by enabling the influence of a variety of polysulfide mitigation strategies to be assessed and optimized, including in this work the LiNO3 additive.

Investigating the mechanism of phosphorene nanoribbon synthesis by discharging black phosphorus intercalation compounds.

Phosphorene nanoribbons (PNRs) can be synthesised in intrinsically scalable methods from intercalation of black phosphorus (BP), however, the mechanism of ribbonisation remains unclear. Herein, to investigate the point at which nanoribbons form, we decouple the two key synthesis steps: first, the formation of the BP intercalation compound, and second, the dissolution into a polar aprotic solvent. We find that both the lithium intercalant and the negative charge on the phosphorus host framework can be effectively removed by addition of phenyl cyanide to return BP and investigate whether fracturing to ribbons occurred after the first step. Further efforts to exfoliate mechanically with or without solvent reveal that the intercalation step does not form ribbons, indicating that an interaction between the amidic solvent and the intercalated phosphorus compound plays an important role in the formation of nanoribbons.

Comparison and reappraisal of carbon electrodes for the voltammetric detection of dopamine.

The electro-oxidation of dopamine (DA) is investigated on the unmodified surfaces of five different classes of carbon electrodes: glassy carbon (GC), oxygen-terminated polycrystalline boron-doped diamond (pBDD), edge plane pyrolytic graphite (EPPG), basal plane pyrolytic graphite (BPPG), and the basal surface of highly oriented pyrolytic graphite (HOPG), encompassing five distinct grades with step edge density and coverage varying by more than 2 orders of magnitude. Surfaces were prepared carefully and characterized by a range of techniques, including atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and Raman spectroscopy. Although pBDD was found to be the least susceptible to surface fouling (even at relatively high DA concentrations), the reaction showed sluggish kinetics on this electrode. In contrast, DA electro-oxidation at pristine basal plane HOPG at concentrations ≤100 µM in 0.15 M PBS, pH 7.2, showed fast kinetics and only minor susceptibility toward surface fouling from DA byproducts, although the extent of HOPG surface contamination by oxidation products increased substantially at higher concentrations (with the response similar on all grades, irrespective of step edge coverage). EPPG also showed a fast response, with little indication of passivation with repeated voltammetric cycling but a relatively high background signal due to the high capacitance of this graphite surface termination. Of all five carbon electrode types, freshly cleaved basal plane HOPG showed the clearest signal (distinct from the background) at low concentrations of DA (<10 µM) as a consequence of the low capacitance. Studies of the electrochemical oxidation of DA in the presence of the common interferents ascorbic acid (AA) and serotonin (5-HT), of relevance to neurochemical analysis, showed that the signals for DA were still clearly and easily resolved at basal plane HOPG surfaces. In the presence of AA, repetitive voltammetry caused products of AA electro-oxidation to adsorb onto the HOPG surface, forming a permselective film that allowed the electrochemical oxidation of DA to proceed unimpeded, while greatly inhibiting the electrochemical response of AA itself. The studies presented provide conclusive evidence that the pristine surface of basal plane HOPG is highly active for the detection of DA, irrespective of the step edge density and method of cleavage, and adds to a growing body of evidence that the basal plane of HOPG is a much more active electrode for many classes of electrode reactions than previously believed.

Pseudohexagonal Nb2O5 Anodes for Fast-Charging Potassium-Ion Batteries.

High-rate batteries will play a vital role in future energy storage systems, yet while good progress is being made in the development of high-rate lithium-ion batteries, there is less progress with post-lithium-ion chemistry. In this study, we demonstrate that pseudohexagonal Nb2O5(TT-Nb2O5) can offer a high specific capacity (179 mAh g-1 ∼ 0.3C), good lifetime, and an excellent rate performance (72 mAh g-1 at ∼15C) in potassium-ion batteries (KIBs), when it is composited with a highly conductive carbon framework; this is the first reported investigation of TT-Nb2O5 for KIBs. Specifically, multiwalled carbon nanotubes are strongly tethered to Nb2O5 via glucose-derived carbon (Nb2O5@CNT) by a one-step hydrothermal method, which results in highly conductive and porous needle-like structures. This work therefore offers a route for the scalable production of a viable KIB anode material and hence improves the feasibility of fast-charging KIBs for future applications.

Deploying Proteins as Electrolyte Additives in Li-S Batteries: The Multifunctional Role of Fibroin in Improving Cell Performance.

It is widely accepted that the commercial application of lithium-sulfur batteries is inhibited by their short cycle life, which is primarily caused by a combination of Li dendrite formation and active material loss due to polysulfide shuttling. Unfortunately, while numerous approaches to overcome these problems have been reported, most are unscalable and hence further hinder Li-S battery commercialization. Most approaches suggested also only tackle one of the primary mechanisms of cell degradation and failure. Here, we demonstrate that the use of a simple protein, fibroin, as an electrolyte additive can both prevent Li dendrite formation and minimize active material loss to enable high capacity and long cycle life (up to 500 cycles) in Li-S batteries, without inhibiting the rate performance of the cell. Through a combination of experiments and molecular dynamics (MD) simulations, it is demonstrated that the fibroin plays a dual role, both binding to polysulfides to hinder their transport from the cathode and passivating the Li anode to minimize dendrite nucleation and growth. Most importantly, as fibroin is inexpensive and can be simply introduced to the cell via the electrolyte, this work offers a route toward practical industrial applications of a viable Li-S battery system.

Black Phosphorus Degradation during Intercalation and Alloying in Batteries.

Numerous layered materials are being recognized as promising candidates for high-performance alkali-ion battery anodes, but black phosphorus (BP) has received particular attention. This is due to its high specific capacity, due to a mixed alkali-ion storage mechanism (intercalation-alloying), and fast alkali-ion transport within its layers. Unfortunately, BP based batteries are also commonly associated with serious irreversible losses and poor cycling stability. This is known to be linked to alloying, but there is little experimental evidence of the morphological, mechanical, or chemical changes that BP undergoes in operational cells and thus little understanding of the factors that must be mitigated to optimize performance. Here the degradation mechanisms of BP alkali-ion battery anodes are revealed through operando electrochemical atomic force microscopy (EC-AFM) and ex situ spectroscopy. Among other phenomena, BP is observed to wrinkle and deform during intercalation but suffers from complete structural breakdown upon alloying. The solid electrolyte interphase (SEI) is also found to be unstable, nucleating at defects before spreading across the basal planes but then disintegrating upon desodiation, even above alloying potentials. By directly linking these localized phenomena with the whole-cell performance, we can now engineer stabilizing protocols for next-generation high-capacity alkali-ion batteries.

Engineering Solution-Processed Non-Crystalline Solid Electrolytes for Li Metal Batteries.

Non-crystalline Li-ion solid electrolytes (SEs), such as lithium phosphorus oxynitride, can uniquely enable high-rate solid-state battery operation over thousands of cycles in thin film form. However, they are typically produced by expensive and low throughput vacuum deposition, limiting their wide application and study. Here, we report non-crystalline SEs of composition Li-Al-P-O (LAPO) with ionic conductivities > 10-7 S cm-1 at room temperature made by spin coating from aqueous solutions and subsequent annealing in air. Homogenous, dense, flat layers can be synthesized with submicrometer thickness at temperatures as low as 230 °C. Control of the composition is shown to significantly affect the ionic conductivity, with increased Li and decreased P content being optimal, while higher annealing temperatures result in decreased ionic conductivity. Activation energy analysis reveals a Li-ion hopping barrier of ≈0.4 eV. Additionally, these SEs exhibit low room temperature electronic conductivity (< 10-11 S cm-1) and a moderate Young's modulus of ≈54 GPa, which may be beneficial in preventing Li dendrite formation. In contact with Li metal, LAPO is found to form a stable but high impedance passivation layer comprised of Al metal, Li-P, and Li-O species. These findings should be of value when engineering non-crystalline SEs for Li-metal batteries with high energy and power densities.

Electrode Materials for Enhancing the Performance and Cycling Stability of Zinc Iodide Flow Batteries at High Current Densities.

Aqueous redox flow battery systems that use a zinc negative electrode have a relatively high energy density. However, high current densities can lead to zinc dendrite growth and electrode polarization, which limit the battery's high power density and cyclability. In this study, a perforated copper foil with a high electrical conductivity was used on the negative side, combined with an electrocatalyst on the positive electrode in a zinc iodide flow battery. A significant improvement in the energy efficiency (ca. 10% vs using graphite felt on both sides) and cycling stability at a high current density of 40 mA cm-2 was observed. A long cycling stability with a high areal capacity of 222 mA h cm-2 is obtained in this study, which is the highest reported areal capacity for zinc-iodide aqueous flow batteries operating at high current density, in comparison to previous studies. Additionally, the use of a perforated copper foil anode in combination with a novel flow mode was discovered to achieve consistent cycling at exceedingly high current densities of >100 mA cm-2. In situ and ex situ characterization techniques, including in situ atomic force microscopy coupled with in situ optical microscopy and X-ray diffraction, are applied to clarify the relationship between zinc deposition morphology on the perforated copper foil and battery performance in two different flow field conditions. With a portion of the flow going through the perforations, a significantly more uniform and compact zinc deposition was observed compared to the case where all of the flow passed over the surface of the electrode. Results from modeling and simulation support the conclusion that the flow of a fraction of electrolyte through the electrode enhances mass transport, enabling a more compact deposit.

Ex Situ Characterization of 1T/2H MoS2 and Their Carbon Composites for Energy Applications, a Review.

The growing interest in the development of next-generation net zero energy systems has led to the expansion of molybdenum disulfide (MoS2) research in this area. This activity has resulted in a wide range of manufacturing/synthesis methods, controllable morphologies, diverse carbonaceous composite structures, a multitude of applicable characterization techniques, and multiple energy applications for MoS2. To assess the literature trends, 37,347 MoS2 research articles from Web of Science were text scanned to classify articles according to energy application research and characterization techniques employed. Within the review, characterization techniques are grouped under the following categories: morphology, crystal structure, composition, and chemistry. The most common characterization techniques identified through text scanning are recommended as the base fingerprint for MoS2 samples. These include: scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Similarly, XPS and Raman spectroscopy are suggested for 2H or 1T MoS2 phase confirmation. We provide guidance on the collection and presentation of MoS2 characterization data. This includes how to effectively combine multiple characterization techniques, considering the sample area probed by each technique and their statistical significance, and the benefit of using reference samples. For ease of access for future experimental comparison, key numeric MoS2 characterization values are tabulated and major literature discrepancies or currently debated characterization disputes are highlighted.

Three-dimensional operando optical imaging of particle and electrolyte heterogeneities inside Li-ion batteries.

Understanding (de)lithiation heterogeneities in battery materials is key to ensure optimal electrochemical performance. However, this remains challenging due to the three-dimensional morphology of electrode particles, the involvement of both solid- and liquid-phase reactants and a range of relevant timescales (seconds to hours). Here we overcome this problem and demonstrate the use of confocal microscopy for the simultaneous three-dimensional operando measurement of lithium-ion dynamics in individual agglomerate particles, and the electrolyte in batteries. We examine two technologically important cathode materials: LixCoO2 and LixNi0.8Mn0.1Co0.1O2. The surface-to-core transport velocity of Li-phase fronts and volume changes are captured as a function of cycling rate. Additionally, we visualize heterogeneities in the bulk and at agglomerate surfaces during cycling, and image microscopic liquid electrolyte concentration gradients. We discover that surface-limited reactions and intra-agglomerate competing rates control (de)lithiation and structural heterogeneities in agglomerate-based electrodes. Importantly, the conditions under which optical imaging can be performed inside the complex environments of battery electrodes are outlined.