Microelectrode study of pore size, ion size, and solvent effects on the charge/discharge behavior of microporous carbons for electrical double-layer capacitors

The capacitive behavior of TiC-derived carbon powders in two different electrolytes, NEt4BF4 in acetonitrile AN and NEt4BF4 in propylene carbonate PC, was studied using the cavity microelectrode CME technique. Comparisons of the cyclic voltammograms recorded at 10–1000 mV/s enabled correlation between adsorbed ion sizes and pore sizes, which is important for understanding the electrochemical capacitive behavior of carbon electrodes for electrical double-layer capacitor applications. The CME technique also allows a fast selection of carbon electrodes with matching pore sizes different sizes are needed for the negative and positive electrodes for the respective electrolyte system. Comparison of electrochemical capacitive behavior of the same salt, NEt4BF4, in different solvents, PC and AN, has shown that different pore sizes are required for different solvents, because only partial desolvation of ions occurs during the double-layer charging. Squeezing partially solvated ions into subnanometer pores, which are close to the desolvated ion size, may lead to distortion of the shape of cyclic voltammograms

Ring current effects: Factors affecting the NMR chemical shift of molecules adsorbed on porous carbons

Nuclear magnetic resonance (NMR) spectroscopy is increasingly being used to study the adsorption of molecules in porous carbons, a process which underpins applications ranging from electrochemical energy storage to water purification. Here we present density functional theory (DFT) calculations of the nucleus-independent chemical shift (NICS) near various sp2-hybridized carbon fragments to explore the structural factors that may affect the resonance frequencies observed for adsorbed species. The domain size of the delocalized electron system affects the calculated NICSs, with larger domains giving rise to larger chemical shieldings. In slit pores, overlap of the ring current effects from the pore walls is shown to increase the chemical shielding. Finally, curvature in the carbon sheets is shown to have a significant effect on the NICS. The trends observed are consistent with existing NMR results as well as new spectra presented for an electrolyte adsorbed on carbide-derived carbons prepared at different temperatures.A.C.F., J.M.G., and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (via the Supergen consortium; J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. CDC synthesis at Drexel University was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award #ER46473. V.P. acknowledges funding from the German Federal Ministry for Research and Education (BMBF) in support of the nanoEES3D project (Award 03EK3013) as part of the strategic funding initiative energy storage framework and thanks Prof. Eduard Arzt (INM) for his continuing support. Mohamed Shamma and Boris Dyatkin (Drexel University) are thanked for their support in the synthesis of CDC material. DFT calculations were performed using the Darwin Supercomputer of the University of Cambridge High Performance Computing Service, provided by Dell Inc. using Strategic Research Infrastructure Funding from the Higher Education Funding Council for England and funding from the Science and Technology Facilities Council.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/jp502387

Intercalation and delamination of layered carbides and carbonitrides

Intercalation and delamination of two-dimensional solids in many cases is a requisite step for exploiting their unique properties. Herein we report on the intercalation of two-dimensional Ti3C2, Ti3CN and TiNbC—so called MXenes. Intercalation of hydrazine, and its co-intercalation with N,N-dimethylformamide, resulted in increases of the c-lattice parameters of surface functionalized f-Ti3C2, from 19.5 to 25.48 and 26.8 Å, respectively. Urea is also intercalated into f-Ti3C2. Molecular dynamics simulations suggest that a hydrazine monolayer intercalates between f-Ti3C2 layers. Hydrazine is also intercalated into f-Ti3CN and f-TiNbC. When dimethyl sulphoxide is intercalated into f-Ti3C2, followed by sonication in water, the f-Ti3C2 is delaminated forming a stable colloidal solution that is in turn filtered to produce MXene ‘paper’. The latter shows excellent Li-ion capacity at extremely high charging rates

Convection Patterns in Liquid Oxide Films on ZrB 2 –SiC Composites Oxidized at a High Temperature

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/66000/1/j.1551-2916.2007.01784.x.pd

Molecular Dynamics Study of the Mechanical Properties of the Grapheme-like Titanium Carbide Ti2C

Molecular dynamics simulations have been performed to study the mechanical properties of two-dimensional titanium carbide under tensile deformation. Young modulus was calculated from the linear part of strain-stress curve. From the radial distribution function it is found that the structure of the simulated samples is preserved during the deformation process. Calculated values of the elastic constants are in good agreement with the DFT data

Molecular Dynamics Study of the Mechanical Properties of the Grapheme-like Titanium Carbide Ti2C

Molecular dynamics simulations have been performed to study the mechanical properties of two-dimensional titanium carbide under tensile deformation. Young modulus was calculated from the linear part of strain-stress curve. From the radial distribution function it is found that the structure of the simulated samples is preserved during the deformation process. Calculated values of the elastic constants are in good agreement with the DFT data

Electrical and Elastic Properties of Individual Single-Layer Nb₄C₃Tₓ MXene Flakes

2D carbides and nitrides (MXenes) are widely recognized for their exceptional promise for numerous applications. However, physical property measurements of their individual monolayers remain very limited despite their importance for revealing the intrinsic physical properties of MXenes. The first mechanical and electrical measurements of individual single‐layer flakes of Nb4C3Tx MXene, which are prepared via an improved synthetic method are reported. Characterization of field‐effect transistor devices based on individual single‐layer Nb4C3Tx flakes shows an electrical conductivity of 1024 ± 165 S cm−1, which is two orders of magnitude higher than the previously reported values for bulk Nb4C3Tx assemblies, and an electron mobility of 0.41 ± 0.27 cm2 V−1 s−1. Atomic force microscopy nanoindentation measurements of monolayer Nb4C3Tx membranes yield an effective Young's modulus of 386 ± 13 GPa, assuming a membrane thickness of 1.26 nm. This is the highest value reported for nanoindentation measurements of solution‐processable 2D materials, revealing the potential of Nb4C3Tx as a primary component for various mechanical applications. Finally, the agreement between the mechanical properties of 2D Nb4C3Tx MXene and cubic NbC suggests that the extensive experimental data on bulk carbides could be useful for identifying new MXenes with improved functional characteristics

Capacitance of two-dimensional titanium carbide (MXene) and MXene/carbon nanotube composites in organic electrolytes

Pseudocapacitive materials that store charges by fast redox reactions are promising candidates for designing high energy density electrochemical capacitors. MXenes - recently discovered two-dimensional carbides, have shown excellent capacitance in aqueous electrolytes, but in a narrow potential window, which limits both the energy and power density. Here, we investigated the electrochemical behavior of Ti3C2 MXene in 1M solution of 1-ethly-3-methylimidazolium bis- (trifluoromethylsulfonyl)-imide (EMITFSI) in acetonitrile and two other common organic electrolytes. This paper describes the use of clay, delaminated and composite Ti3C2 electrodes with carbon nanotubes in order to understand the effect of the electrode architecture and composition on the electrochemical performance. Capacitance values of 85 F g-1 and 245 F cm-3 were obtained at 2 mV s-1, with a high rate capability and good cyclability. In situ X-ray diffraction study reveals the intercalation of large EMI+ cations into MXene, which leads to increased capacitance, but may also be the rate limiting factor that determines the device performance

Performance improvement of MXene-based perovskite solar cells upon property transition from metallic to semiconductive by oxidation of Ti₃C₂Tₓ in air

The unique properties of MXenes that arise from terminating functional groups and oxidation of MXenes make them attractive for application in photovoltaic devices like perovskite solar cells (PSCs). Here, oxidation of Ti3C2Tx hydrocolloid was carried out to tune its properties desirable for an electron transport layer (ETL) in low-temperature processed PSCs. The calculations of the energy levels were carried out using the Vienna ab initio simulation package (VASP) code based on density functional theory (DFT). Oxidation of Ti_{3}C_{2}T_{x} can generate Ti–O bonds and effectively reduce the macroscopic defects of the film fabricated by spin-coating, while a transition from metallic material to semiconductor occurred after heavy oxidation. A better matching of energy levels between perovskite and ETL layer in the case of a hybrid of oxidized and pristine Ti_{3}C_{2}T_{x} renders a champion power conversion efficiency (PCE) of 18.29%. The improvement in PCE can be attributed to the increased electron mobility in the ETL, which promotes electron transport and reduces the electron–hole recombination. Hence, by presenting a simple method for high performance in PSCs by MXene-derived materials, this work demonstrates the great potential of these materials for applications in low-temperature processed PSCs and other photovoltaic technologies

Screen-printable microscale hybrid device based on MXene and layered double hydroxide electrodes for powering force sensors

Coplanar energy storage devices with interdigitated electrodes have attracted a significant amount of attention as micropower units for portable and flexible electronics, and self-powered systems. Herein, we propose a simple, cost-effective, and scalable two-step screen-printing process to fabricate flexible coplanar asymmetric microscale hybrid device (MHD) with a higher energy density compared to carbon-based microsupercapacitors. 2D titanium carbide MXene (Ti 3 C 2 T x ) with a large inlayer spacing is selected as negative electrode, and Co-Al layered double hydroxide (LDH) nanosheets are selected as positive electrode. The assembled coplanar, all-solid-state, asymmetric MHD possesses a higher energy density (8.84 μWh cm −2 ) compared to the MXene-based, coplanar, symmetric microsupercapacitors (3.38 μWh cm −2 ), and exhibit excellent flexibility and reliability, as well as cycling stability (92% retention of the initial capacitance after 10,000 cycles). Moreover, we integrate the coplanar asymmetric MHDs with the force sensing resistors as portable power source units to fabricate lightweight and inexpensive integrated force sensors, which can be used to detect applied pressure variation. The two-step screen-printing method can also be extended to other MXenes and various positive electrode materials for fabrication of coplanar asymmetric MHDs on flexible substrates. Therefore, we believe that the two-step screen-printing method opens up new avenues toward developing flexible coplanar asymmetric MHDs, thus promoting the application of MHDs based on MXenes for flexible integrated electronic devices