International audienceHerein we report on Li insertion into a new two-dimensional (2-D) layered Ti₂C-based material (MXene) with an oxidized surface, formed by etching Al from Ti₂AlC in HF at room temperature. Nitrogen sorption of treated powders showed desorption hysteresis consistent with the presence of slit-like pores. At 23 m² g-¹, the specific surface area was an order of magnitude higher than untreated Ti₂AlC. Cyclic voltammetry exhibited lithiation and delithiation peaks at 1.6 V and 2 V vs. Li+/Li, respectively. At C/25, the steady state capacity was 225 mAh g-¹; at 1C, it was 110 mAh g-¹ after 80 cycles; at 3C, it was 80 mAh g-¹ after 120 cycles; at 10C, it was 70 mAh g-¹ after 200 cycles. Since Ti₂C is a member of the MXene family - where M is an early transition metal and X is C and/or N - that to date includes Ti₃C₂, Ta₄C₃, TiNbC, and (V₀.₅,Cr₀.₅)₃C₂, our results suggest that MXenes are promising as anode materials for Li-ion batteries
Herein we show that heating 2D Ti3C2 in air results in TiO2 nanocrystals enmeshed in thin sheets of disordered graphitic carbon structures that can handle extremely high cycling rates when tested as anodes in lithium ion batteries. Oxidation of 2D Ti3C2 in either CO2 or pressurized water also resulted in TiO2-C hybrid structures. Similarly, other hybrids can be produced, as we show here for Nb2O5/C from 2D Nb2C.
MXenes are a recently discovered class of 2D materials with an excellent potential for energy storage applications. Because MXene surfaces are hydrophilic and attractive interaction forces between the layers are relatively weak, water molecules can spontaneously intercalate at ambient humidity and significantly influence the key properties of this 2D material. Using complementary X-ray and neutron scattering techniques, we demonstrate that intercalation with potassium cations significantly improves structural homogeneity and water stability in MXenes. In agreement with molecular dynamics simulations, intercalated potassium ions reduce the water self-diffusion coefficient by 2 orders of magnitude, suggesting greater stability of hydrated MXene against changing environmental conditions.
Electrochemical double layer capacitors (EDLCs), or supercapacitors, rely on electrosorption of ions by porous carbon electrodes and offer a higher power and a longer cyclic lifetime compared to batteries. Ionic liquid (IL) electrolytes can broaden the operating voltage window and increase the energy density of EDLCs. Herein, we present direct measurements of the ion dynamics of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide in an operating EDLC with electrodes composed of porous nanosized carbide-derived carbons (CDCs) and nonporous onion-like carbons (OLCs) with the use of in situ infrared spectroelectrochemistry. For CDC electrodes, IL ions (both cations and anions) were directly observed entering and exiting CDC nanopores during charging and discharging of the EDLC. Conversely, for OLC electrodes, IL ions were observed in close proximity to the OLC surface without any change in the bulk electrolyte concentration during charging and discharging of the EDLC. This provides experimental evidence that charge is stored on the surface of OLCs in OLC EDLCs without long-range ion transport through the bulk electrode. In addition, for CDC EDLCs with mixed electrolytes of IL and propylene carbonate (PC), the IL ions were observed entering and exiting CDC nanopores, while PC entrance into the nanopores was IL concentration dependent. This work provides direct experimental confirmation of EDLC charging mechanisms that previously were restricted to computational simulations and theories. The experimental measurements presented here also provide deep insights into the molecular level transport of IL ions in EDLC electrodes that will impact the design of the electrode materials' structure for electrical energy storage.
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