Interparticle interactions and rheological signatures of Ti3C2Tz MXene dispersions.

HYPOTHESIS: We hypothesize that dispersed Ti3C2Tz MXene particle interactions are reflected in the bulk viscoelastic properties of the dispersions and can be analyzed using classical colloidal theory for anisotropic particles. The relevant kinetic theory for Brownian anisotropic particles is given by the Doi and Edwards (D-E) Model, and the Maxwell Model is used to fit the relaxation times as a function of frequency. Such behavior is relevant to a variety of MXene processing techniques, particularly printing and coating. EXPERIMENTS: Small oscillatory shear tests were performed for dilute Ti3C2Tz MXene aqueous dispersions as a function of their concentration and temperature. Scanning electron microscopy (SEM), X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), ζ potential measurements, Dynamic Light Scattering (DLS) were used to characterize the Ti3C2Tz MXene nanoparticles. FINDINGS: Ti3C2Tz dispersions show gel-like and viscous-like behavior at low and high temperatures, respectively. Experimental relaxation times fitted to the Maxwell model are found to be close to the theoretical values. However, at high temperatures, relaxation time values differ due to the inter-particle interactions, even in the dilute concentration regime. For Ti3C2Tz dispersions, aggregation, and clustering can have dramatic consequences for dispersion rheology, including gelation, as the sample transitions from liquid-like to solid-like behavior.

Water-dispersible Ti3C2Tz MXene nanosheets by molten salt etching.

Molten-salt etching of Ti3AlC2 MAX phase offers a promising route to produce 2D Ti3C2Tz (MXene) nanosheets without hazardous HF. However, molten-salt etching results in MXene clays that are not water dispersible, thus preventing further processing. This occurs because molten-salt etching results in a lack of -OH terminal groups rendering the MXene clay hydrophobic. Here, we demonstrate a method that produces water-dispersible Ti3C2Tz nanosheets using molten salt (SnF2) to etch. In molten salt etching, SnF2 diffuses between the layers to form AlF3 and Sn as byproducts, separating the layers. The stable, aqueous Ti3C2Tz dispersion yields a ζ potential of -31.7 mV, because of -OH terminal groups introduced by KOH washing. X-ray diffraction and electron microscopy confirm the formation of Ti3C2Tz etched clay with substantial d-spacing as compared with clay etched with HF. This work is the first to use molten salt etching to successfully prepare colloidally stable aqueous dispersions of Ti3C2Tz nanosheets.

Electronic and Optical Property Control of Polycation/MXene Layer-by-Layer Assemblies with Chemically Diverse MXenes.

MXenes, 2D nanomaterials derived from ceramic MAX phases, have drawn considerable interest in a wide variety of fields including energy storage, catalysis, and sensing. There are many possible MXene compositions due to the chemical and structural diversity of parent MAX phases, which can bear different possible metal atoms "M", number of layers, and carbon or nitrogen "X" constituents. Despite the potential variety in MXene types, the bulk of MXene research focuses upon the first MXene discovered, Ti3C2T. With the recent discovery of polymer/MXene multilayer assemblies as thin films and coatings, there is a need to broaden the accessible types of multilayers by including MXenes other than Ti3C2Tz; however, it is not clear how altering the MXene type influences the resulting multilayer growth and properties. Here, we report on the first use of MXenes other than Ti3C2Tz, specifically Ti2CTz and Nb2CTz, for the layer-by-layer (LbL) assembly of polycation/MXene multilayers. By comparing these MXenes, we evaluate both how changing M (Ti vs Nb) and "n" (Ti3C2Tzvs Ti2CTz) affect the growth and properties of the resulting multilayer. Specifically, the aqueous LbL assembly of each MXene with poly(diallyldimethylammonium) into films and coatings is examined. Further, we compare the oxidative stability, optoelectronic properties (refractive index, absorption coefficient, optical conductivity, and direct and indirect optical band gaps), and the radio frequency heating response of each multilayer. We observe that MXene multilayers with higher "n" are more electrically conductive and oxidatively stable. We also demonstrate that Nb2CTz containing films have lower optical band gaps and refractive indices at the cost of lower electrical conductivities as compared to their Ti2CTz counterparts. Our work demonstrates that the properties of MXene/polycation multilayers are highly dependent on the choice of constituent MXene and that the MXene type can be altered to suit specific applications.

Layer-by-Layer Assembly of Reduced Graphene Oxide and MXene Nanosheets for Wire-Shaped Flexible Supercapacitors.

As the demand for wearable electronic devices increases, interest in small, light, and deformable energy storage devices follows suit. Among these devices, wire-shaped supercapacitors (WSCs) are considered key components of wearable technology due to their geometric similarity to woven fiber. One potential method for creating WSC devices is the layer-by-layer (LbL) assembly technique, which is a "bottom-up" method for electrode fabrication. WSCs require conformal and adhesive coatings of the functional material to the wire-shaped substrate, which is difficult to obtain with other processing techniques such as vacuum filtration or spray-coating. However, the LbL assembly technique produces conformal and robust coatings that can be deposited onto a variety of substrates and shapes, including wires. In this study, we report WSCs made using the LbL assembly of alternating layers of positively charged reduced graphene oxide functionalized with poly(diallyldimethylammonium chloride) and negatively charged Ti3C2Tx MXene nanosheets conformally deposited on activated carbon yarns. In this construct, the added LbL film enhances capacitance, energy density, and power density by 240, 227, and 109%, respectively, relative to the uncoated activated carbon yarn, yielding high specific and volumetric capacitances (237 F g-1, 2193 F cm-3). In addition, the WSC possesses good mechanical stability, retaining 90% of its initial capacity after 200 bending cycles. This study demonstrates that LbL coatings on carbon yarns are promising as linear energy storage devices for fibrous electronics.

Flocculation of MXenes and Their Use as 2D Particle Surfactants for Capsule Formation.

MXenes, transition metal carbides or nitrides, have gained great attention in recent years due to their high electrical conductivity and catalytic activity, hydrophilicity, and diverse surface chemistry. However, high hydrophilicity and negative ζ potential of the MXene nanosheets limit their processability and interfacial assembly. Previous examples for modifying the dispersibility and wettability of MXenes have focused on the use of organic ligands, such as alkyl amines, or covalent modification with triethoxysilanes. Here, we report a simple method to access MXene-stabilized oil-in-water emulsions by using common inorganic salts (e.g., NaCl) to flocculate the nanosheets and demonstrate the use of these Pickering emulsions to prepare capsules with shells of MXene and polymer. Ti3C2Tz nanosheets are used as the representative MXene. The salt-flocculated MXene nanosheets produce emulsions that are stable for days, as determined by optical microscopy imaging. The incorporation of a diisocyanate in the discontinuous oil phase and diamine in the continuous water phase led to interfacial polymerization and the formation of capsules. The capsules were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), confirming the presence of both polymer and nanosheets. The addition of ethanol to the capsules led to the removal of the toluene core and retention of the shell structure. The ability to assemble MXene nanosheets at fluid-fluid interfaces without the use of ligands or cosurfactants expands the accessible material constructs relevant for biomedical engineering, water purification, energy storage, electromagnetic electronics, catalysis, and so on.

Minimizing two-dimensional Ti3C2Tx MXene nanosheet loading in carbon-free silicon anodes.

Silicon anodes are promising for high energy batteries because of their excellent theoretical gravimetric capacity (3579 mA h g-1). However, silicon's large volume expansion and poor conductivity hinder its practical application; thus, binders and conductive additives are added, effectively diluting the active silicon material. To address this issue, reports of 2D MXene nanosheets have emerged as additives for silicon anodes, but many of these reports use high MXene compositions of 22-66 wt%, still presenting the issue of diluting the active silicon material. Herein, this report examines the question of what minimal amount of MXene nanosheets is required to act as an effective additive while maximizing total silicon anode capacity. A minimal amount of only 4 wt% MXenes (with 16 wt% sodium alginate and no carbon added) yielded silicon anodes with a capacity of 900 mA h gSi-1 or 720 mA h gtotal-1 at the 200th cycle at 0.5 C-rate. Further, this approach yielded the highest specific energy on a total electrode mass basis (3100 W h kgtotal-1) as comapared to other silicon-MXene constructs (∼115-2000 Wh kgtotal-1) at a corresponding specific power. The stable electrode performance even with a minimal MXene content is attributed to several factors: (1) highly uniform silicon electrodes due to the dispersibility of MXenes in water, (2) the high MXene aspect ratio that enables improved electrical connections, and (3) hydrogen bonding among MXenes, sodium alginate, and silicon particles. All together, a much higher silicon loading (80 wt%) is attained with a lower MXene loading, which then maximizes the capacity of the entire electrode.