RESUMEN
The presence of strong anharmonic effects in surface functionalized MXenes greatly challenges the use of harmonic lattice dynamics calculations to predict their phonon spectra and lattice thermal conductivity at finite temperatures. Herein, we demonstrate the workflow for training and validating machine learning potentials in terms of moment tensor potential (MTP) for MXenes including Mo2TiC2, Mo2TiC2O2, Mo2TiC2F2 and Janus-Mo2TiC2OF monolayers. Then, the MTPs of MXenes are successfully combined with the harmonic lattice dynamics calculations to obtain the temperature renormalized phonon spectra, three-phonon scattering rates, phonon relaxation times and lattice thermal conductivity at finite temperatures. Furthermore, combining MTPs with classic molecular dynamics simulations at finite temperatures directly enables the calculation of phonon quasi-particle spectral energy density with a full inclusion of all anharmonic effects in MXenes. Our current results indicate that anharmonic effects are found to be relatively weak in Mo2TiC2 and Mo2TiC2O2 monolayers, whereas the phonon quasi-particle spectral energy densities largely resemble those of harmonic or renormalized lattice dynamics calculations. Significant broadening of spectral energy density at finite temperature is predicted for Mo2TiC2F2 and Janus-Mo2TiC2OF monolayers, implying strong anharmonic effects in those MXenes. Our work paves a new way for fast and reliable calculation of the phonon scattering process and lattice thermal conductivity of MXenes within MTPs trained from first-principles molecular dynamics simulations in the future.
RESUMEN
Utilizing the latest SCAN-rVV10 density functional, we thoroughly assess the electrochemical properties of 35 Mo-based ordered double transition metal MXenes, including clean Mo2MC2 (M = Sc, Ti, V, Zr, Nb, Hf, Ta) and surface functionalized structures Mo2MC2T2 (T = H, O, F and OH), for the potential use as anode materials in lithium ion batteries (LIBs). The first principles molecular dynamics simulations in combination with the calculations of the site adsorption preferences for Li atoms on all investigated MXenes reveal that both Li-saturated adsorption structures and theoretical capacities of Mo-based MXenes are fundamentally influenced by the surface terminations. We find that the adsorption of Li atoms on either -OH or -F functionalized MXenes is chemically unstable. In particular, the F-groups prefer to form a separate fluoride layer with Li atoms, detaching from the Mo2MC2 substrates. The Li atoms could form a stable single adsorption layer on the -H, -O and intrinsic MXenes surface, exhibiting theoretical capacities in the range from 121 mA h g-1 to 195 mA h g-1. Besides -F and -OH terminations, the remaining Mo-based MXenes also possess superior flat open circuit voltage (OCV) profiles with the most reversible storage capacity below 1.0 V during the charging/discharging cycles. We further predict the low barrier heights of Li-ion diffusion, at a range of 0.03-0.06 eV for most Mo-based MXenes except -O and -H terminations, exceeding that of graphene or Ti3C2. Furthermore, combining the Vineyard transition state theory (TST) with the phonon spectra obtained from density functional perturbation theory (DFPT), the mean planar diffusion coefficient is calculated to be 2 × 10-8 m2 s-1 at 300 K for intrinsic Mo2MC2 monolayers. Although the overall specific capacity is fundamentally restricted with the relatively heavy molecular mass of MXenes, we conclude that Mo-based structures, especially the intrinsic Mo2MC2 (M = Sc, Ti, V) monolayers, might be promising anode materials from the aspect of fast charging/discharging application for LIBs.
RESUMEN
Using SCAN-rVV10+U, we show Cr2TiC2 and Cr2TiC2T2 (T = -F and -OH) MXenes are moderate band gap semiconductors mostly in the antiferromagnetic state. All investigated MXene structures show large Seebeck coefficients (>400 µV/K), especially Cr2TiC2 (>800 µV/K) and Cr2TiC2F2 (>700 µV/K). The hole relaxation time of p-type Cr2TiC2(OH)2 is found to be â¼8 ps, ensuring its superior electron transport properties in comparison to other investigated MXenes. It is also discovered that the surface functionalization could decrease the phonon thermal conduction and that Cr2TiC2(OH)2 has the smallest lattice thermal conductivity (â¼6.5 W/m·K) and the largest electron thermal conduction (>50 W/m·K with n = 1019 cm-3). We predict the ZT value of p-type Cr2TiC2(OH)2 can reach 3.0 at 600 K with the maximum thermoelectric conversion efficiency of 20%. Overall, the thermoelectric property of Cr-based ordered double transition metal MXenes is far superior to that of any known two-dimensional structures in the MXene family.
RESUMEN
The doping effect of graphene nanoplatelets (GNPs) on electrical insulation properties of polyethylene (PE) was studied by combining experimental and theoretical methods. The electric conduction properties and trap characteristics were tested for pure PE and PE/GNPs composites by using a direct measurement method and a thermal stimulated current (TSC) method. It was found that doping smaller GNPs is more beneficial to decrease the conductivity of PE/GNPs. The PE/GNPs composite with smaller size GNPs mainly introduces deep energy traps, while with increasing GNPs size, besides deep energy traps, shallow energy traps are also introduced. These results were also confirmed by density functional theory (DFT) and the non-equilibrium Green's function (NEGF) method calculations. Therefore, doping small size GNPs is favorable for trapping charge carriers and enhancing insulation ability, which is suggested as an effective strategy in exploring powerful insulation materials.