Acidity-Aided Surface Modification Strategy to Enhance In Situ MnO2 Deposition for High Performance Zn-MnO2 Battery Prototypes.

Zn-MnO2 batteries offer cost-effective, eco-friendly, and efficient solutions for large-scale energy storage applications. However, challenges, like irreversible cathode reactions, prolonged cyclability, and electrolyte stability during high-voltage operations limit their broader application. This study provides insight into the charge-discharge process through in situ deposition of active ß-MnO2 nanoflakes on a carbon-based current collector. The study elucidates the effect of pH and electrolyte concentration on chemical conversion reactions with Zn, in particular focus on their impact on the two-electron MnO2/Mn2+ reaction crucial for high voltage operation. The electrolyte, characterized by being relatively lean in Mn2+ and with a targeted low pH, enables extended cycling. This research achieves greater cycling durability by integrating a carbon-based cathode current collector with high density of structural defects in combination with cell architectures suitable for large-scale energy storage. A flooded stack-type Zn-MnO2 battery prototype employing the optimized electrolyte demonstrates a high discharge voltage (≈2 V) at a substantial discharge current rate of 10 mA cm-2. The battery exhibits an impressive areal capacity of ≈2 mAh cm-2, maintaining ≈100% capacity retention over 400 cycles. This research establishes a promising practical, and cost-effective cathode-free design for Zn-MnO2 batteries, that minimizes additional processing and assembly costs.

Customized Production of Holey Graphene Oxides via a Continuous Flow Process.

Continuous flow manufacturing is an innovative technology mainly applied in the chemical and pharmaceutical industries that is progressively being adapted to the manufacturing of nanomaterials to overcome the challenge of reproducing a product with consistent characteristics at a large scale. Here, a flow photochemical system is designed and prototyped for the synthesis of holey graphene oxides (hGOs). Compared to existing methods for the synthesis of hGO, the process is fast, highly scalable, and controllable. Through a combination of rigorous data analysis using machine learning algorithms on transmission electron microscope images and systematic studies of process parameters, it is demonstrated that characteristics of the produced hGO (i.e., porosity and pore size) are remarkably reproducible to the extent that it can be predicted by empirical models of processing-property correlations. Depending on the tailored nanopore structures, the synthesized hGOs out-performed GO in a range of applications that can benefit from the nanoporous two-dimensional (2D) sheets such as in supercapacitors, gas adsorption, and nanofiltration membranes. These results are significant in offering new perspectives on the low-cost industrialization of 2D nanomaterials.

Nematic to Cholesteric Transformation in the Cellulose Nanocrystal Droplet Phase.

Nucleation, growth, and transformation of chirality in nanomaterial systems is a growing research topic with broad interest in tunable and configurable chiroptical materials. Similar to other one-dimensional nanomaterials, cellulose nanocrystals (CNCs), which are nanorods of naturally abundant biopolymer cellulose, display chiral or cholesteric liquid crystal (LC) phases in the form of tactoids. However, the nucleation and growth of the cholesteric CNC tactoids to equilibrium chiral structures and their morphological transformations are yet to be critically assessed. We noticed that the onset of liquid crystal formation in CNC suspensions is characterized by the nucleation of a nematic tactoid that grows in volume and spontaneously transforms into a cholesteric tactoid. The cholesteric tactoids merge with the neighboring tactoids to form bulk cholesteric mesophases with various configurational palettes. We applied scaling laws from the energy functional theory and found suitable agreement with the morphological transformation of the tactoid droplets monitored for their fine structure and orientation by quantitative polarized light imaging.

High Performance Lithium-Ion Batteries Using Layered 2H-MoTe2 as Anode.

The major challenges faced by candidate electrode materials in lithium-ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe2 ) has emerged as a new material for energy storage applications. Though 2H-MoTe2 with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi-metallic phase, its application as an anode in LIB has been elusive. Here, 2H-MoTe2 , prepared by a solid-state synthesis route, has been employed as an efficient anode with remarkable Li+ storage capacity. The as-prepared 2H-MoTe2 electrodes exhibit an initial specific capacity of 432 mAh g-1 and retain a high reversible specific capacity of 291 mAh g-1 after 260 cycles at 1.0 A g-1 . Further, a full-cell prototype is demonstrated by using 2H-MoTe2 anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg-1 (based on the MoTe2 mass) and capacity retention of 80% over 100 cycles. Synchrotron-based in situ X-ray absorption near-edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.

Capture of Perfluorooctanoic Acid Using Oil-Filled Graphene Oxide-Silica Hybrid Capsules.

Fluorinated hydrocarbon (FHC) contamination has attracted global attention recently because of persistence within the environment and ecosystems of many types of FHC. The surfactant perfluorooctanoic acid (PFOA) is particularly commonly found in contaminated sites, and thus, urgent action is needed for its removal from the environment. In this study, water dispersible hybrid capsules were successfully prepared from an oil-in-water emulsion stabilized by graphene oxide and including a silicate precursor to grow a strong, mesoporous capsule shell surrounding the droplets. These capsules were decorated with amine groups to present a positively charged outer corona that attracts negative PFOA molecules. The aminated capsules were effectively applied as a novel technology to adsorb and sequester PFOA contamination in water. It was confirmed that PFOA removal by the capsules was pH and PFOA concentration dependent, with adsorption efficiencies of >60 mg g-1 under ideal conditions. PFOA removal kinetics followed using high-performance liquid chromatography and liquid chromatography-mass spectrometry showed that capture of PFOA by the capsules reached a maximum of >99.9% in 2-3 days.

Ion and organic transport in Graphene oxide membranes: Model development to difficult water remediation applications.

The role of steric hindrance and charge interactions in governing ionic transport through reduced graphene oxide (rGO) and commercial (DOW-Filmtec NF270) membranes was elucidated by a comprehensive study of experimental and established mathematical analysis based on Nernst-Planck equation. A charge-dominated salt exclusion mechanism was observed for the rGO membranes, which exhibited retention from low (7%) to moderate (70%) extent depending on the nature of ions (5 mM). Swelling of GO (1.2 nm interlayer distance) in water beyond the hydrated diameter of ions was attributed as a primary cause for lowering steric hindrance effects. The influence of parameters affecting charge interactions, such as pH and ionic strength, on the extent of salt rejection was modelled. The potential impact of the membrane's charge density, GO loading and interlayer spacing on salt retention was quantified by performing sensitivity analyses. For a high TDS produced water sample, the rGO membranes partially retained divalent cations (Ca:13%) and exhibited high dissolved oil rejection. The membranes were found to be suitable for the treatment of high TDS water with the goal of selectively removing organic impurities, and thus minimizing the impact of osmotic pressure effect. Performance of the membranes was also investigated for retention of water remediation related organic anions, using perfluoro octanoic (PFOA) acid as a model compound. rGO membranes exhibited a charge-dominated exclusion mechanism for retention (90%) of PFOA (1 ppm).

Enhanced Thermal Conductivity of High Internal Phase Emulsions with Ultra-Low Volume Fraction of Graphene Oxide.

Thermal conductivity enhancement in a multiphase fluid such as water-in-oil emulsion can substantially improve efficacies in a broad range of applications. However, nanoparticle additives that are often used to do so can catastrophically destabilize a delicate emulsion system, in our case, a high internal phase emulsion (HIPE), whereas large concentration of additives can adversely impact practical processing aspects. Therefore, means to enhance the thermal conductivity of emulsions with a minute concentration of additives (<1 wt %) is a major scientific challenge. We report the enhancement in thermal conductivity of HIPE, by consigning either lipophilic GO (fGO) in the oil phase or hydrophilic GO in the water phase in combination with a well-known emulsifier. The rheological properties of fGO-HIPE showed non-Newtonian viscoelastic behavior similar to that of the original emulsion but with lower elastic modulus and viscosity, indicating that GO incorporation has enhanced processability. The thermal conductivity enhancements can be predicted by thermal circuit models, and the HIPEs with fGO and GO demonstrated 21 and 13% enhancements over the parent emulsion with a minor 0.1 w/w addition, respectively. A possible role of ordered colloidal structures of GO and fGO underlining this prepercolation behavior is inferred from comprehensive imaging and thermal studies.

Synthesis and Stability of Water-in-Oil Emulsion Using Partially Reduced Graphene Oxide as a Tailored Surfactant.

Graphene oxide (GO) is widely known as an amphiphile having hydrophilic oxygen functionality and unoxidized graphitic patches as the hydrophobic domains. Exploiting this amphiphilicity, GO serves as a surfactant to stabilize oil-water interfaces. While there are numerous reports on GO as a surfactant, most of these reports concern oil-in-water (O/W) emulsions, and there are very few on the formation of water-in-oil (W/O) emulsions. We prepared W/O emulsions using partially reduced graphene oxide (prGO) as a surfactant. The partial reduction introduces a subtle hydrophilic-lipophilic balance (HLB), which favors the formation of the W/O emulsion. The morphological features and rheological characteristics of the W/O emulsion with 75:25 water-to-oil ratio were investigated and analyzed in detail. The W/O emulsion was found to have polydispersity with wide range of droplet sizes varying between 2 to 500 µm. Using confocal microscopy, the role of parameters such as extent of reduction, continuous phase volume fraction and the concentration of GO on the stability, microstructure and variation of droplet size distribution of the W/O emulsion were carefully monitored. With prGO concentration as large as 0.05% (w/w), highly concentrated emulsion will form, and are stable up to 20 days from formation; destabilization occurred from sedimentation and subsequent coalescence as the partially reduced GO was limited by its dispersion ability in the oil-phase studied here. Understanding the mechanisms behind the transient stability will enable the development of novel emulsion compositions containing GO as a multifunctional additive.

Synthesis of graphene oxide membranes and their behavior in water and isopropanol.

Graphene oxide (GO) membrane has been synthesized on commercial polysulfone ultrafiltration membranes (Pore size: 17 nm) using the drop casting method followed by baking at 90 C for 24 h. Baking resulted in the reduction of GO and removal of bulk water intercalated in the GO sheets. Deposited GO film showed high stability under shear stress variation. This work shows that water adsorption on the GO membrane determines its permeation performance. Despite the higher viscosity of isopropyl alcohol (IPA), its permeability was 7 times higher than water through the baked ("dry") GO membranes, which were never contacted with water. However, IPA permeability of GO membranes dropped to 44% (of deionized water) when contacted with water ("hydrated" or "wet" GO membranes). Extensive size exclusion (rejection) studies with various dye and dendrimer molecules showed pore size reduced from 3.3 nm in the "dry" state to 1.3 nm in the "wet" state of GO membranes. FT-IR characterization of GO membrane suggested adsorption of water on the nanochannels of the active layer. Also, significant decay in flux was observed for water (82% of its initial flux) as compared to IPA (38% of its initial flux) for initially dry GO membranes.

Shear Assisted Electrochemical Exfoliation of Graphite to Graphene.

The exfoliation characteristics of graphite as a function of applied anodic potential (1-10 V) in combination with shear field (400-74 400 s(-1)) have been studied in a custom-designed microfluidic reactor. Systematic investigation by atomic force microscopy (AFM) indicates that at higher potentials thicker and more fragmented graphene sheets are obtained, while at potentials as low as 1 V, pronounced exfoliation is triggered by the influence of shear. The shear-assisted electrochemical exfoliation process yields large (∼10 µm) graphene flakes with a high proportion of single, bilayer, and trilayer graphene and small ID/IG ratio (0.21-0.32) with only a small contribution from carbon-oxygen species as demonstrated by X-ray photoelectron spectroscopy measurements. This method comprises intercalation of sulfate ions followed by exfoliation using shear induced by a flowing electrolyte. Our findings on the crucial role of hydrodynamics in accentuating the exfoliation efficiency suggest a safer, greener, and more automated method for production of high quality graphene from graphite.

Flux accentuation and improved rejection in graphene-based filtration membranes produced by capillary-force-assisted self-assembly.

Separation and flux performance were compared in graphene-based membranes that differed only in the method of deposition of reduced graphene oxide platelets. Membranes with higher degree of order were produced by evaporation-induced capillary-force self-assembly, which showed higher steric rejection properties while simultaneously accentuating water permeance compared to membranes produced by the traditional vacuum filtration technique. These studies attempt to establish structure-property correlations in graphene-based membranes.

The inside-out supercapacitor: induced charge storage in reduced graphene oxide.

Iontronic circuits are built using components which are analogous to those used in electronic circuits, however they involve the movement of ions in an electrolyte rather than electrons in a metal or semiconductor. Developments in these circuits' performance have led to applications in biological sensing, interfacing and drug delivery. While transistors, diodes and elementary logic circuits have been demonstrated for ionic circuits if more complex circuits are to be realized, the precident set by electrical circuits suggests that a component which is analogous to an electrical capacitor is required. Herein, an ionic supercapacitor is reported, our experiments show that charge may be stored in a conductive porous reduced graphene oxide film that is contacted by two isolated aqueous solutions and that this concept extends to an arbitrary polarizable sample. Parametric studies indicate that the conductivity and porosity of this film play important roles in the resultant device's performance. This ionic capacitor has a specific capacitance of 8.6 F cm-3 at 1 mV s-1 and demonstrates the ability to filter and smooth signals in an electrolyte at a variety of low frequencies. The device has the same interfaces as a supercapacitor but their arrangement is changed, hence the name inside-out supercapacitor.

New Class of High-Energy, High-Power Capacitive Devices Enabled by Stabilized Lithium Metal Anodes.

Lithium-ion capacitors (LIC) combine the energy storage mechanisms of lithium-ion batteries and electric double layer capacitors (EDLC) and are supposed to promise the best of both worlds: high energy and power density combined with a long life. However, the lack of lithium cation sources in the carbon cathode demands the cumbersome step of prelithiation of the graphite anode, mainly by using sacrificial lithium metal, hindering the mass adoption of LICs. Here, in a conceptually new class of devices termed lithium metal capacitors (LMC), we replace the graphite anode with a lithium metal anode stabilized by a complex yet stable solid-electrolyte interface (SEI). Via a specialized formation process, the well-explored synergetic reaction between the LiNO3 additive and controlled amounts of polysulfides in an ether-based electrolyte stabilizes the SEI on the lithium metal electrode. Optimized devices at the coin cell level deliver 55 mAh g-1 at a fast 30C discharge rate and maintain 95% capacity after 8000 cycles. At the pouch-cell level, energy densities of 13 Wh kg-1 are readily achieved, indicating the transferability of the technology to practical scales. The LMC, a new class of capacitive device, eliminates the prelithiation process of the conventional LIC, allowing practical production at scale and offering exciting avenues for exploring versatile cathode chemistries on account of using a lithium metal anode.

Localized deoxygenation and direct patterning of graphene oxide films by focused ion beams.

Exposure to controlled doses (~4.65 × 10(-3) to 2.79 × 10(-2) nC/µm(2) ion fluence) of Ga ions via a focused ion beam (FIB) deoxygenates graphene oxide (GO) and increases the electrical conductivity in 100 × 100 µm(2) patches by several orders of magnitude compared to that in unexposed GO. Raman spectra and the carbon/oxygen ratio in exposed areas are indicative of chemically reduced graphene oxide (rGO). This novel FIB-induced conversion technique is harnessed for the direct imprinting of complex micrometer-scale shapes and sub-20-nm lines of rGO in insulating films and flakes of GO establishing the capability of generating features varying in size from approximately tens of nanometers to approximately hundreds of micrometers in a maskless, efficient manner.

Photochemically engineered ultra-stable 1T MoS2 by flow synthesis.

A novel synthesis method for stable conversion of 2H to 1T MoS2 is developed by photoirradiation of ammonium intercalated 2H-MoS2. The synthesized 1T phase in the final product showed excellent long-term stability, and orders of magnitude improvement in electrical conductivity. The denser active sites in the synthesized material contributed to an enhanced HER activity. The methodology can be translated to a continuous flow process paving the way for the large-scale production of 1T MoS2.

Nanoscale hydrodynamics: enhanced flow in carbon nanotubes.

Nanoscale structures that could mimic the selective transport and extraordinarily fast flow possible in biological cellular channels would have a wide range of potential applications. Here we show that liquid flow through a membrane composed of an array of aligned carbon nanotubes is four to five orders of magnitude faster than would be predicted from conventional fluid-flow theory. This high fluid velocity results from an almost frictionless interface at the carbon-nanotube wall.

A saccharide-based binder for efficient polysulfide regulations in Li-S batteries.

The viability of lithium-sulfur batteries as an energy storage technology depends on unlocking long-term cycle stability. Most instability stems from the release and transport of polysulfides from the cathode, which causes mossy growth on the lithium anode, leading to continuous consumption of electrolyte. Therefore, development of a durable cathode with minimal polysulfide escape is critical. Here, we present a saccharide-based binder system that has a capacity for the regulation of polysulfides due to its reducing properties. Furthermore, the binder promotes the formation of viscoelastic filaments during casting which endows the sulfur cathode with a desirable web-like microstructure. Taken together this leads to 97% sulfur utilisation with a cycle life of 1000 cycles (9 months) and capacity retention (around 700 mAh g-1 after 1000 cycles). A pouch cell prototype with a specific energy of up to 206 Wh kg-1 is produced, demonstrating the promising potential for practical applications.

A High Throughput and Unbiased Machine Learning Approach for Classification of Graphene Dispersions.

Significant research to define and standardize terminologies for describing stacks of atomic layers in bulk graphene materials has been undertaken. Most methods to measure the stacking characteristics are time consuming and are not suited for obtaining information by directly imaging dispersions. Conventional optical microscopy has difficulty in identifying the size and thickness of a few layers of graphene stacks due to their low photon absorption capacity. Utilizing a contrast based on anisotropic refractive index in 2D materials, it is shown that localized thickness-specific information can be captured in birefringence images of graphene dispersions. Coupling pixel-by-pixel information from brightfield and birefringence images and using unsupervised statistical learning algorithms, three unique data clusters representing flakes (unexfoliated), nanoplatelets (partially exfoliated), and 2D sheets (well-exfoliated) species in various laboratory-based and commercial dispersions of graphene and graphene oxide are identified. The high-throughput, multitasking capability of the approach to classify stacking at sub-nanometer to micrometer scale and measure the size, thickness, and concentration of exfoliated-species in generic dispersions of graphene/graphene oxide are demonstrated. The method, at its current stage, requires less than half an hour to quantitatively assess one sample of graphene/graphene oxide dispersion.

Efficient Permeance Recovery of Organically Fouled Graphene Oxide Membranes.

The emergence of facile approaches for the large-scale production of graphene oxide (GO) membranes necessitates a clearer understanding of their potential to foul and, more importantly, strategies for efficient recovery of membrane performance following fouling. Here, we systematically investigated the feasibility of water, ethanol, and hypochlorite as cleaning agents to remove organic foulants over a GO membrane. Among them, 100 ppm hypochlorite solution showed a remarkable ability to remove bovine serum albumin (BSA) and could recover the membrane flux up to 98% after five cycles of BSA filtration and cleaning. The potential of hypochlorite was also demonstrated for permeance recovery during molecular filtration of tannic acid and methyl blue. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray diffraction (XRD) analyses were used to study the oxidative effects of hypochlorite on the GO membrane, and it was determined that exposure to higher concentrations of hypochlorite (>1000 ppm) degrades the structure of GO membrane and deteriorates the membrane performance after three cycles of cleaning. The studies demonstrate that the use of a modest concentration of hypochlorite is effective in restoring permeance of this class of high flux nanofiltration membranes.

Expansion-tolerant architectures for stable cycling of ultrahigh-loading sulfur cathodes in lithium-sulfur batteries.

Lithium-sulfur batteries can displace lithium-ion by delivering higher specific energy. Presently, however, the superior energy performance fades rapidly when the sulfur electrode is loaded to the required levels-5 to 10 mg cm-2- due to substantial volume change of lithiation/delithiation and the resultant stresses. Inspired by the classical approaches in particle agglomeration theories, we found an approach that places minimum amounts of a high-modulus binder between neighboring particles, leaving increased space for material expansion and ion diffusion. These expansion-tolerant electrodes with loadings up to 15 mg cm-2 yield high gravimetric (>1200 mA·hour g-1) and areal (19 mA·hour cm-2) capacities. The cells are stable for more than 200 cycles, unprecedented in such thick cathodes, with Coulombic efficiency above 99%.