Maria R. Lukatskaya

Flexible MXene/Carbon nanotube Composite Paper with High Volumetric Capacitance

Free-standing and flexible sandwich-like MXene/carbon nanotube (CNT) paper, composed of alternating MXene and CNT layers, is fabricated using a simple filtration method. These sandwich-like papers exhibit high volumetric capacitances, good rate performances, and excellent cycling stability when employed as electrodes in supercapacitors.

Transparent Conductive Two-Dimensional Titanium Carbide Epitaxial Thin Films

Since the discovery of graphene, the quest for two-dimensional (2D) materials has intensified greatly. Recently, a new family of 2D transition metal carbides and carbonitrides (MXenes) was discovered that is both conducting and hydrophilic, an uncommon combination. To date MXenes have been produced as powders, flakes, and colloidal solutions. Herein, we report on the fabrication of ∼1 × 1 cm2 Ti3C2 films by selective etching of Al, from sputter-deposited epitaxial Ti3AlC2 films, in aqueous HF or NH4HF2. Films that were about 19 nm thick, etched with NH4HF2, transmit ∼90% of the light in the visible-to-infrared range and exhibit metallic conductivity down to ∼100 K. Below 100 K, the films’ resistivity increases with decreasing temperature and they exhibit negative magnetoresistance—both observations consistent with a weak localization phenomenon characteristic of many 2D defective solids. This advance opens the door for the use of MXenes in electronic, photonic, and sensing applications.

Amine‐Assisted Delamination of Nb2C MXene for Li‐Ion Energy Storage Devices

2D Nb2CTx MXene flakes are produced using an amine-assisted delamination process. Upon mixing with carbon nanotubes and filtration, freestanding, flexible paper is produced. The latter exhibits high capacity and excellent stability when used as the electrode for Li-ion batteries and capacitors.

Development of a Green Supercapacitor Composed Entirely of Environmentally Friendly Materials

Owing to recent power- and energy-density advances, higher efficiencies, and almost unlimited lifetimes, electrical double-layer capacitors (EDLCs, also known as supercapacitors) are now used in a wide range of energy harvesting and storage systems, which include portable power and grid applications. Despite offering key performance advantages, many device components pose significant environmental hazards once disposed. They often contain fluorine, sulfur, and cyanide groups, which are harmful if discarded by using conventional landfill or incineration methods, and they are constructed by using multiple metallic parts, which contribute to a high ash content. We explore designs for a fully operational supercapacitor that incorporates materials completely safe to dispose of and easy to incinerate. The components, which include material alternatives for the current collector, electrolyte, separator, particle binder, and packaging, are all mutually compatible, and most of them exhibit better performance than commonly used materials. We selected a graphite foil as current collector, sodium acetate as electrolyte, an ester as porous membrane based on acetate cellulose, and polymers based on polyvinyl alcohol as environmentally benign solutions for device components. The presented materials all originate from simple and inexpensive source compounds, which decreases the environmental impact of their manufacture and renders them more viable for integration into commercial devices for large-scale stationary and transportation energy storage applications.

In situ environmental transmission electron microscopy study of oxidation of two-dimensional Ti3C2 and formation of carbon-supported TiO2

Two-dimensional Ti3C2, also known as “MXene”, was oxidized in air under two different oxidizing regimes in order to produce carbon-supported TiO2. In situ TEM analysis coupled with Raman spectroscopy revealed the formation of either anatase nanoparticles or planar rutile nanocrystals, which were controlled by the time, temperature and heating rate.

Room-Temperature Carbide-Derived Carbon Synthesis by Electrochemical Etching of MAX Phases**

Porous carbons are widely used in energy storage and gas separation applications, but their synthesis always involves high temperatures. Herein we electrochemically selectively extract, at ambient temperature, the metal atoms from the ternary layered carbides, Ti3 AlC2 , Ti2 AlC and Ti3 SiC2 (MAX phases). The result is a predominantly amorphous carbide-derived carbon, with a narrow distribution of micropores. The latter is produced by placing the carbides in HF, HCl or NaCl solutions and applying anodic potentials. The pores that form when Ti3 AlC2 is etched in dilute HF are around 0.5 nm in diameter. This approach forgoes energy-intensive thermal treatments and presents a novel method for developing carbons with finely tuned pores for a variety of applications, such as supercapacitor, battery electrodes or CO2 capture.

Separation and liquid chromatography using a single carbon nanotube

Use of a single template-grown carbon nanotube as a separation column to separate attoliter volumes of binary mixtures of fluorescent dyes has been demonstrated. The cylindrical nanotube walls are used as stationary phase and the surface area is increased by growing smaller multi-walled carbon nanotubes within the larger nanotube column. Liquid-liquid extraction is performed to separate selectively soluble solutes in a solvent, and chromatographic separation is demonstrated using thin, long nanotubes coated inside with iron oxide nanoparticles. The setup is also used to determine the diffusion coefficient of a solute at the sub-micrometer scale. This study opens avenues for analytical chemistry in attoliter volumes of fluids for various applications and cellular analysis at the single cell level.

Understanding the MXene Pseudocapacitance

MXenes have attracted great attention as next-generation capacitive energy-storage materials, but the mechanisms underlying their pseudocapacitive behavior are not well understood. Here we provide a theoretical description of the surface redox process of Ti3C2T x (T = O, OH), a prototypical MXene, in 1 M H2SO4 electrolyte, based on joint density functional theory with an implicit solvation model and the analysis of Gibbs free energy under a constant-electrode potential. From the dependence of the O/OH ratio (or the surface H coverage) and the surface charge on the applied potential, we obtain a clear picture of the capacitive energy-storage mechanism of Ti3C2T x that shows good agreement with previous experimental findings in terms of the integral capacitance and Ti valence change. We find a voltage-dependent redox/double-layer co-charging behavior: the capacitive mechanism is dominated by the redox process, but the electric double-layer charge works against the redox process. This new insight may be useful in improving the capacitance of MXenes.

Concentrated mixed cation acetate “water-in-salt” solutions as green and low-cost high voltage electrolytes for aqueous batteries

Electrolyte solutions are a key component of energy storage devices that significantly impact capacity, safety, and cost. Recent developments in “water-in-salt” (WIS) aqueous electrolyte research have enabled the demonstration of aqueous Li-ion batteries that operate with capacities and cyclabilities comparable with those of commercial non-aqueous Li-ion batteries. Critically, the use of aqueous electrolyte mitigates safety risks associated with non-aqueous electrolytes. However, the high cost and potential toxicity of imide-based WIS electrolytes limit their practical deployment. In this report, we disclose the efficacy of inexpensive, non-toxic mixed cation electrolyte systems for Li-ion batteries that otherwise provide the same benefits as current WIS electrolytes: extended electrochemical stability window and compatibility with traditional intercalation Li-ion battery electrode materials. We take advantage of the high solubility of potassium acetate to achieve the WIS condition in a eutectic mixture of lithium and potassium acetate with water-to-cation ratio as low as 1.3. Our work suggests an important direction for the practical realization of safe, low-cost, and high-performance aqueous Li-ion batteries.