Production of Quasi-2D Platelets of Nonlayered Iron Pyrite (FeS2) by Liquid-Phase Exfoliation for High Performance Battery Electrodes.

Over the past 15 years, two-dimensional (2D) materials have been studied and exploited for many applications. In many cases, 2D materials are formed by the exfoliation of layered crystals such as transition-metal disulfides. However, it has recently become clear that it is possible to exfoliate nonlayered materials so long as they have a nonisotropic bonding arrangement. Here, we report the synthesis of 2D-platelets from the earth-abundant, nonlayered metal sulfide, iron pyrite (FeS2), using liquid-phase exfoliation. The resultant 2D platelets exhibit the same crystal structure as bulk pyrite but are surface passivated with a density of 14 × 1018 groups/m2. They form stable suspensions in common solvents and can be size-selected and liquid processed. Although the platelets have relatively low aspect ratios (∼5), this is in line with the anisotropic cleavage energy of bulk FeS2. We observe size-dependent changes to optical properties leading to spectroscopic metrics that can be used to estimate the dimensions of platelets. These platelets can be used to produce lithium ion battery anodes with capacities approaching 1000 mAh/g.

Equipartition of Energy Defines the Size-Thickness Relationship in Liquid-Exfoliated Nanosheets.

Liquid phase exfoliation is a commonly used method to produce 2D nanosheets from a range of layered crystals. However, such nanosheets display broad size and thickness distributions and correlations between area and thickness, issues that limit nanosheet application potential. To understand the factors controlling the exfoliation process, we have liquid-exfoliated 11 different layered materials, size-selecting each into fractions before using AFM to measure the nanosheet length, width, and thickness distributions for each fraction. The resultant data show a clear power-law scaling of nanosheet area with thickness for each material. We have developed a simple nonequilibrium thermodynamics-based model predicting that the power-law prefactor is proportional to both the ratios of in-plane-tearing/out-of-plane-peeling energies and in-plane/out-of-plane moduli. By comparing the experimental data with the modulus ratio calculated from first-principles, we find close agreement between experiment and theory. This supports our hypothesis that energy equipartition holds between nanosheet tearing and peeling during sonication-assisted exfoliation.

Negative Gauge Factor Piezoresistive Composites Based on Polymers Filled with MoS2 Nanosheets.

Nanocomposite strain sensors, particularly those consisting of polymer-graphene composites, are increasingly common and are of great interest in the area of wearable sensors. In such sensors, application of strain yields an increase in resistance due to the effect of deformation on interparticle junctions. Typically, widening of interparticle separation is thought to increase the junction resistance by reducing the probability of tunnelling between conducting particles. However, an alternative approach would be to use piezoresistive fillers, where an applied strain modifies the intrinsic filler resistance and so the overall composite resistance. Such an approach would broaden sensing capabilities, as using negative piezoresistive fillers could yield strain-induced resistance reductions rather than the usual resistance increases. Here, we introduce nanocomposites based on polyethylene oxide (PEO) filled with MoS2 nanosheets. Doping of the MoS2 by the PEO yields nanocomposites which are conductive enough to act as sensors, while efficient stress transfer leads to nanosheet deformation in response to an external strain. The intrinsic negative piezoresistance of the MoS2 leads to a reduction of the composite resistance on the application of small tensile strains. However, at higher strain the resistance grows due to increases in junction resistance. MoS2-PEO composite gauge factors are approximately -25 but fall to -12 for WS2-PEO composites and roughly -2 for PEO filled with MoSe2 or WSe2. We develop a simple model, which describes all these observations. Finally, we show that these composites can be used as dynamic strain sensors.

Solvent exfoliation stabilizes TiS2 nanosheets against oxidation, facilitating lithium storage applications.

Titanium disulfide is a promising material for a range of applications, including lithium-ion battery (LIB) anodes. However, its application potential has been severely hindered by the tendency of exfoliated TiS2 to rapidly oxidize under ambient conditions. Herein, we confirm that, although layered TiS2 powder can be exfoliated by sonication in aqueous surfactant solutions, the resultant nanosheets oxidise almost completely within hours. However, we find that upon performing the exfoliation in the solvent cyclohexyl-pyrrolidone (CHP), the oxidation is almost completely suppressed. TiS2 nanosheets dispersed in CHP and stored at 4 °C in an open atmosphere for 90 days remained up to 95% intact. In addition, CHP-exfoliated nanosheets did not show any evidence of oxidation for at least 30 days after being transformed into dry films even when stored under ambient conditions. This stability, probably a result of a residual CHP coating, allows TiS2 nanosheets to be deployed in applications. To demonstrate this, we prepared lithium ion battery anodes from nano : nano composites of TiS2 nanosheets mixed with carbon nanotubes. These anodes displayed reversible capacities (920 mA h g-1) close to the theoretical value and showed good rate performance and cycling capability.

Liquid phase exfoliation of MoO2 nanosheets for lithium ion battery applications.

Molybdenum dioxide (MoO2) is a layered material which shows promise for a number of applications in the electrochemical energy storage arena. Mostly studied as a bulk layered material, MoO2 has not previously been exfoliated in large quantities. Here we demonstrate the liquid phase exfoliation of MoO2 in the solvent isopropanol, yielding reasonable amounts of good quality nanosheets. However, we found that, when dispersed in isopropanol under ambient conditions, MoO2 nanosheets are gradually oxidized to higher oxides such as MoO3 over a period of days. Conversely, if the nanosheets are processed into dried films immediately after exfoliation, and before oxidation has had a chance to progress, the nanosheets are relatively stable under ambient conditions, remaining unoxidised unless the films are heated. We also found that MoO2 nanosheets can be size selected by controlled centrifugation and show size-dependent optical properties. This allows us to propose spectroscopic metrics which allow concentration- and size-estimation from extinction spectra. Finally, we found that liquid-exfoliated MoO2 nanosheets could be used to produce lithium ion battery anodes with capacities of up to 1140 mA h g-1.

Non-resonant light scattering in dispersions of 2D nanosheets.

Extinction spectra of nanomaterial suspensions can be dominated by light scattering, hampering quantitative spectral analysis. No simple models exist for the wavelength-dependence of the scattering coefficients in suspensions of arbitrary-sized, high-aspect-ratio nanoparticles. Here, suspensions of BN, talc, GaS, Ni(OH)2, Mg(OH)2 and Cu(OH)2 nanosheets are used to explore non-resonant scattering in wide-bandgap 2D nanomaterials. Using an integrating sphere, scattering coefficient (σ) spectra were measured for a number of size-selected fractions for each nanosheet type. Generally, σ scales as a power-law with wavelength in the non-resonant regime: σ(λ)∝[λ/〈L〉]-m, where 〈L〉 is the mean nanosheet length. For all materials, the scattering exponent, m, forms a master-curve, transitioning from m = 4 to m = 2, as the characteristic nanosheet area increases, indicating a transition from Rayleigh to van der Hulst scattering. In addition, once material density and refractive index are factored out, the proportionality constant relating σ to [λ/〈L〉]-m, also forms a master-curve when plotted versus 〈L〉.