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The MXene family of two-dimensional transition metal carbides and nitrides already includes ~50 members with distinct numbers of atomic layers, stoichiometric compositions and solid solutions, in-plane or out-of-plane ordering of atoms, and a variety of surface terminations. MXenes have shown properties that make them attractive for applications ranging from energy storage to electronics and medicine. Although this compositional variability allows fine-tuning of the MXene properties, it also creates challenges during the analysis of MXenes because of the presence of multiple light elements (for example, H, C, N, O, and F) in close proximity. Here, we show depth profiling of single particles of MXenes and their parent MAX phases with atomic resolution using ultralow-energy secondary-ion mass spectrometry. We directly detect oxygen in the carbon sublattice, thereby demonstrating the existence of oxycarbide MXenes. We also determine the composition of adjacent surface termination layers and show their interaction with each other. Analysis of the metal sublattice shows that Mo

Rechargeable aqueous Zn–MnO2 batteries have been considered as one of the promising alternative energy technologies due to their high abundance, environmental friendliness, and safety of both Zn–metal anodes and manganese oxide cathodes.

MXenes are a growing family of 2D transition-metal carbides and nitrides, which display excellent performance in myriad of applications. Theoretical calculations suggest that manipulation of the MXene surface termination (such as =O or -F) could strongly alter their functional properties; however, experimental control of the MXene surface termination is still in the developmental stage. Here, we demonstrate that annealing MXenes in an Ar + O

Identifying and understanding charge storage mechanisms is important for advancing energy storage, especially when new materials and electrolytes are explored. Well-separated peaks in cyclic voltammograms (CVs) are considered key indicators of diffusion-controlled electrochemical processes with distinct Faradic charge transfer. Herein, we report on an electrochemical system with separated CV peaks, accompanied by surface-controlled partial charge transfer, in 2D Ti3C2Tx MXene in water-in-salt electrolytes. The process involves the insertion/desertion of desolvation-free cations, leading to an abrupt change of the interlayer spacing between MXene sheets. This unusual behavior increases charge storage at positive potentials, thereby increasing the amount of energy stored. This also demonstrates new opportunities for the development of high-rate aqueous energy storage devices and electrochemical actuators using safe and inexpensive aqueous electrolytes.

One of the primary factors limiting further research and commercial use of the two-dimensional (2D) titanium carbide MXene Ti3C2, as well as MXenes in general, is the rate at which freshly made samples oxidize and degrade when stored as aqueous suspensions. Here, we show that including excess aluminum during synthesis of the Ti3AlC2 MAX phase precursor leads to Ti3AlC2 grains with improved crystallinity and carbon stoichiometry (termed Al-Ti3AlC2). MXene nanosheets (Al-Ti3C2) produced from this precursor are of higher quality, as evidenced by their increased resistance to oxidation and an increase in their electronic conductivity up to 20 000 S/cm. Aqueous suspensions of stoichiometric single- to few-layer Al-Ti3C2 flakes produced from the modified Al-Ti3AlC2 have a shelf life of over ten months, compared to 1 to 2 weeks for previously published Ti3C2, even when stored in ambient conditions. Freestanding films made from Al-Ti3C2 suspensions stored for ten months show minimal decreases in electrical conductivity and negligible oxidation. Furthermore, oxidation of the improved Al-Ti3C2 in air initiates at temperatures that are 100-150 °C higher than that of conventional Ti3C2. The observed improvements in both the shelf life and properties of Al-Ti3C2 will facilitate the widespread use of this material.

As an increasing number of wireless devices are introduced to our daily lives, long-term environmentally stable conductive fabrics that can shield against electromagnetic radiation are increasingly desired. Herein, conventional cotton and linen fabrics were dip-coated in additive-free, aqueous Ti3C2Tx MXene dyes, which consist of only two-dimensional Ti3C2Tx flakes dispersed in water, to fabricate highly conductive fabrics for electromagnetic interference (EMI) shielding. Ti3C2Tx loading and electrical conductivity of the fabrics increased with the number of dip-coating cycles. After only 4 dip-coating cycles, EMI shielding effectiveness (SE) of Ti3C2Tx-coated (

Lightweight, ultrathin, and flexible electromagnetic interference (EMI) shielding materials are needed to protect electronic circuits and portable telecommunication devices and to eliminate cross-talk between devices and device components. Here, we show that a two-dimensional (2D) transition metal carbonitride, Ti3CNTx MXene, with a moderate electrical conductivity, provides a higher shielding effectiveness compared with more conductive Ti3C2Tx or metal foils of the same thickness. This exceptional shielding performance of Ti3CNTx was achieved by thermal annealing and is attributed to an anomalously high absorption of electromagnetic waves in its layered, metamaterial-like structure. These results provide guidance for designing advanced EMI shielding materials but also highlight the need for exploring fundamental mechanisms behind interaction of electromagnetic waves with 2D materials.

The specific cell capacitance, equivalent series resistance (ESR) and equivalent distributed resistance (EDR) of porous carbon-based supercapacitors linearly depend on the cationic molecular length of room-temperature ionic liquids.

Soft bioelectronic interfaces for mapping and modulating excitable networks at high resolution and at large scale can enable paradigm-shifting diagnostics, monitoring, and treatment strategies. Yet, current technologies largely rely on materials and fabrication schemes that are expensive, do not scale, and critically limit the maximum attainable resolution and coverage. Solution processing is a cost-effective manufacturing alternative, but biocompatible conductive inks matching the performance of conventional metals are lacking. Here, we introduce MXtrodes, a class of soft, high-resolution, large-scale bioelectronic interfaces enabled by Ti(3)C(2) MXene (a two-dimensional transition metal carbide nanomaterial) and scalable solution processing. We show that the electrochemical properties of MXtrodes exceed those of conventional materials, and do not require conductive gels when used in epidermal electronics. Furthermore, we validate MXtrodes in applications ranging from mapping large scale neuromuscular networks in humans to cortical neural recording and microstimulation in swine and rodent models. Finally, we demonstrate that MXtrodes are compatible with standard clinical neuroimaging modalities.

Two-dimensional transition metal carbides, nitrides and carbonitrides, popular by the name MXenes, are a promising class of materials as they exhibit intriguing optical, optoelectronic and electrochemical properties. Taking advantage of their metallic conductivity and hydrophilicity, titanium carbide MXenes (Ti3C2Tx and others) are used to fabricate solution processable transparent conducting electrodes (TCEs) for the design of three-electrode electrochromic cells. However, the tunable electrochromic behavior of various titanium-based MXene compositions across the entire visible spectrum has not yet been demonstrated. Here, we investigate the intrinsic electrochromic properties of titanium-based MXenes, Ti3C2Tx, Ti3CNTx, Ti2CTx, and Ti1.6Nb0.4CTx, where individual MXenes serve as a transparent conducting, electrochromic, and plasmonic material layer. Plasmonic extinction bands for Ti3C2Tx, Ti2CTx and Ti1.6Nb0.4CTx are centered at 800, 550 and 480 nm, which are electrochemically tunable to 630, 470 and 410 nm, respectively, whereas Ti3CNTx shows a reversible change in transmittance in the wide visible range. Additionally, the switching rates of MXene electrodes with no additional transparent conductor electrodes are estimated and correlated with the respective electrical figure of merit values. This study demonstrates that MXene-based electrochromic cells are tunable in the entire visible spectrum and suggests the potential of the MXene family of materials in optoelectronic, plasmonic, and photonic applications, such as tunable visible optical filters and modulators, to name a few.

MXenes have demonstrated high performance as negative electrodes in supercapacitors with aqueous electrolytes due to their high redox capacitance. However, oxidation limits their use under positive potential, requiring asymmetric devices with positive electrodes made of other materials which are usually less capacitive compared to MXenes and therefore limit the device performances. Here, we report the synthesis of two-dimensional molybdenum vanadium carbides (MoxV4 xC3), previously unexplored double transition metal MXenes, by selective etching of aluminum from MoxV4 xAlC3 MAX phase precursors. Unlike the ordered double transition metal MXenes reported previously, MoxV4 xC3 exhibits a Mo-V solid solution in the transition metal layers. We have synthesized and characterized four different compositions of MoxV4 xC3 with x ¼ 1, 1.5, 2, and 2.7. We showed that by changing the Mo : V ratio, the surface terminations (O : F ratio), and electrical and electrochemical properties of the resulting MXenes can be tuned. The Mo2.7V1.3C3 composition showed a remarkable volumetric capacitance (up to 860 F cm 3) and high electrical conductivity (830 S cm 1) at room temperature. Moreover, these solid solution MXenes have demonstrated the ability to operate in a wider range of positive potentials compared to other MXenes. Following this discovery, we coupled a Mo2.7V1.3C3 positive electrode with a well-studied Ti3C2 MXene negative electrode to create an all-MXene supercapacitor, as a proof of concept.

Two-dimensional (2D) transition metal carbides and nitrides known as MXenes have shown attractive functionalities such as high electronic conductivity, a wide range of optical properties, versatile transition metal and surface chemistry, and solution processability. Although extensively studied computationally, the magnetic properties of this large family of 2D materials await experimental exploration. 2D magnetic materials have recently attracted significant interest as model systems to understand low-dimensional magnetism and for potential spintronic applications. Here, we report on synthesis of Cr2TiC2Tx MXene and a detailed study of its magnetic as well as electronic properties. Using a combination of magnetometry, synchrotron X-ray linear dichroism, and field- and angular-dependent magnetoresistance measurements, we find clear evidence of a magnetic transition in Cr2TiC2Tx at approximately 30 K, which is not present in its bulk layered carbide counterpart (Cr2TiAlC2 MAX phase). This work presents the first experimental evidence of a magnetic transition in a MXene material and provides an exciting opportunity to explore magnetism in this large family of 2D materials.

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of Mn+1XnTx, in which two, three, or four atomic layers of a transition met...

MXenes are a prominent family of two-dimensional materials because of their metallic conductivity and abundant surface functionalities. Although MXenes have been extensively studied as bulk particles or free-standing films, thin and transparent films are needed for optical, optoelectronic, sensing, and other applications. In this study, we demonstrate a facile method to fabricate ultrathin (∼10 nm), Ti3C2Tx MXene films by an interfacial assembly technique. The self-assembling behavior of MXene flakes resulted in films with a high stacking order and strong plane-to-plane adherence, where optimal films of 10 nm thickness displayed a low sheet resistance of 310 Ω/□. By using surface tension, films were transferred onto various types of planar and curved substrates. Moreover, multiple films were consecutively transferred onto substrates from a single batch of solution, showing the efficient use of the material. When the films were utilized as gas sensing channels, a high signal-to-noise ratio, up to 320, was observed, where the gas response of films assembled from small MXene flakes was 10 times larger than that from large flakes. This work provides a facile and efficient method to allow MXenes to be further exploited for thin-film applications.

Ti3C2Tx MXene is an attractive two-dimensional (2D) material for a wide variety of applications; however, measured properties vary widely from study to study. A potential factor to the property dif...

MXenes, an emerging family of 2D transition metal carbides and nitrides, have shown promise in various applications, such as energy storage, electromagnetic interference shielding, conductive thin films, photonics, and photothermal therapy. Their metallic nature, wide range of optical absorption, and tunable surface chemistry are the key to their success in those applications. The physical properties of MXenes are known to be strongly dependent on their surface terminations. In this study, we investigated the electronic properties of Ti3C2Tx for different surface terminations, as achieved by different annealing temperatures, with the help of photoelectron spectroscopy, inverse photoelectron spectroscopy, and density functional theory calculations. We find that fluorine occupies solely the face-centered cubic adsorption site, whereas oxygen initially occupies at least two different adsorption sites, followed by a rearrangement after fluorine desorption at high annealing temperatures. The measured electroni...

MXenes, a relatively new class of two-dimensional (2D) transition-metal carbides, carbonitrides, and nitrides, exhibit unique properties such as high electronic conductivity, a wide range of optical characteristics, hydrophilicity, and mechanical stability. Because of the high electronic conductivity, MXenes have shown promise in many applications, such as energy storage, electromagnetic interference shielding, antennas, and transparent coatings. 2D titanium carbide (Ti3C2Tx, where Tx represents surface terminations), the first discovered and most studied MXene, has the highest electronic conductivity exceeding 10 000 S cm–1. There have been several efforts to alter the conductivity of MXenes, such as manipulation of the transition-metal layer and control of surface terminations. However, the impact of the C and N site composition on electronic transport has not been explored. In this study, the effects of synthesis methods on optoelectronic properties of 2D titanium carbonitride, Ti3CNTx, were systematic...

One of the primary factors limiting further research and commercial use of the two-dimensional (2D) titanium carbide MXene Ti

Soft bioelectronic interfaces for mapping and modulating excitable networks at high resolution and at large scale can enable paradigm-shifting diagnostics, monitoring, and treatment strategies. Yet, current technologies largely rely on materials and fabrication schemes that are expensive, do not scale, and critically limit the maximum attainable resolution and coverage. Solution processing is a cost-effective manufacturing alternative, but biocompatible conductive inks matching the performance of conventional metals are lacking. Here, we introduce MXtrodes, a novel class of soft, high-resolution, large-scale bioelectronic interfaces enabled by Ti3C2 MXene and scalable solution processing. We show that the electrochemical properties of MXtrodes exceed those of conventional materials, and do not require conductive gels when used in epidermal electronics. Furthermore, we validate MXtrodes in a number of applications ranging from mapping large scale neuromuscular networks in humans to delivering cortical microstimulation in small animal models. Finally, we demonstrate that MXtrodes are compatible with standard clinical neuroimaging modalities.

Alloying is a long-established strategy to tailor properties of metals for specific applications, thus retaining or enhancing the principal elemental characteristics while offering additional functionality from the added elements. We propose a similar approach to the control of properties of two-dimensional transition metal carbides known as MXenes. MXenes (Mn+1Xn) have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites presents promising routes for tailoring the chemical, optical, electronic, or mechanical properties of MXenes. Herein, we systematically investigated three interrelated binary solid-solution MXene systems based on Ti, Nb, and/or V at the M-site in a M2XTx structure (Ti2-yNbyCTx, Ti2-yVyCTx, and V2-yNbyCTx, where Tx stands for surface terminations) showing the evolution of electronic and optical properties as a function of composition. All three MXene systems show unlimited solubility and random distribution of metal elements in the metal sublattice. Optically, the MXene systems are tailorable in a nonlinear fashion, with absorption peaks from ultraviolet to near-infrared wavelength. The macroscopic electrical conductivity of solid solution MXenes can be controllably varied over 3 orders of magnitude at room temperature and 6 orders of magnitude from 10 to 300 K. This work greatly increases the number of nonstoichiometric MXenes reported to date and opens avenues for controlling physical properties of different MXenes with a limitless number of compositions possible through M-site solid solutions.

Two-dimensional (2D) transition metal carbides and nitrides known as MXenes have shown attractive functionalities such as high electronic conductivity, a wide range of optical properties, versatile transition metal and surface chemistry, and solution processability. Although extensively studied computationally, the magnetic properties of this large family of 2D materials await experimental exploration. 2D magnetic materials have recently attracted significant interest as model systems to understand low-dimensional magnetism and for potential spintronic applications. Here, we report on synthesis of Cr

One of the primary factors limiting further research and the commercial use of the two-dimensional (2D) MXene titanium carbide (Ti3C2), as well as MXenes in general, is the rate at which freshly made samples oxidize and degrade when stored as aqueous suspensions. Here, we show that including excess aluminum during synthesis of the Ti3AlC2 MAX phase precursor leads to the creation of Ti3AlC2 grains with improved stoichiometry and crystallinity. Ti3C2 nanosheets produced from the improved Ti3AlC2 are of higher quality, as evidenced by their increased resistance to oxidation and an increase in their electrical conductivity to 20,000 S/cm. Our results indicate that defects created during the synthesis of Ti3C2 (and by inference, other MXenes) lead to the previously observed instability. We show that by eliminating those defects results in Ti3C2 that is highly stable in aqueous solutions and in air. Aqueous suspensions of single- to few-layer Ti3C2 flakes produced from the modified Ti3AlC2 have a shelf life of over ten months, compared to one to two weeks for Ti3C2 produced from conventional Ti3AlC2, even when stored in ambient conditions. Freestanding films made from Ti3C2 suspensions stored for ten months show minimal decreases in electrical conductivity and negligible oxidation. Oxidation of the improved Ti3C2 in air initiates at temperatures that are 100-150°C higher than conventional Ti3C2. The observed improvements in both the shelf life and properties of Ti3C2 will facilitate the widespread use of this material.

MXenes, a class of two-dimensional (2D) transition metal carbides and nitrides, have a wide range of potential applications due to their unique electronic, optical, plasmonic, and other properties. Herein, we explore the use of the Ti3C2 MXene in organic–inorganic lead halide perovskite solar cells (PSCs). SnO2–Ti3C2 MXene nanocomposites with different contents of Ti3C2 (0, 0.5, 1.0, 2.0, and 2.5 wt‰) were used as electron transport layers (ETLs) in low-temperature processed planar-structured PSCs. Mixing SnO2 with 1.0 wt‰ Ti3C2 effectively increases the power conversion efficiency (PCE) from 17.23% to 18.34%, whereas the device prepared with pristine Ti3C2 as the ETL achieves a PCE of 5.28%. Photoluminescence and electrochemical impedance spectroscopy results reveal that metallic Ti3C2 MXene nanosheets provide superior charge transfer paths, enhancing electron extraction, electron mobility, and decreasing the electron transfer resistance at the ETL/perovskite interface, and thus leading to higher photocurrents. This work proposes a new field of application for MXenes and a promising method to increase the efficiency of solar cells.

We report on the high temperature thin film growth of BaTiO3 on Ti3C2Tx MXene flakes using van der Waals epitaxy on a degradable template layer. MXene was deposited on amorphous and crystalline substrates by spray- and dip-coating techniques, while the growth of BaTiO3 at 700 °C was accomplished using pulsed laser deposition in an oxygen rich environment. We demonstrate that the MXene flakes act as a temporary seed layer, which promotes highly oriented BaTiO3 growth along the (111) direction independent of the underlying substrate. The lattice parameters of the BaTiO3 films are close to the bulk value suggesting that the BaTiO3 films remains unstrained, as expected for van der Waals epitaxy. The initial size of the MXene flakes has an impact on the orientation of the BaTiO3 films with larger flake sizes promoting a higher fraction of the polycrystalline film to grow along the (111) direction. The deposited BaTiO3 film adopts the same morphology as the original flakes and piezoresponse force microscopy shows a robust ferroelectric behavior for individual grains. Transmission electron microscopy results indicate that the Ti3C2Tx MXene fully decomposes during the BaTiO3 deposition and the surplus Ti atoms are readily incorporated into the BaTiO3 film. Electrical measurements show a similar dielectric constant as a BaTiO3 film grown without the MXene seed layer. The demonstrated process has the potential to overcome the longstanding issue of integrating highly oriented complex oxide thin films directly on any desired substrate.

Lightweight, ultrathin, and flexible electromagnetic interference (EMI) shielding materials are needed to protect electronic circuits and portable telecommunication devices and to eliminate cross-talk between devices and device components. Here, we show that a two-dimensional (2D) transition metal carbonitride, Ti

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of M

Two-dimensional transition metal carbides, carbonitrides, and nitrides, called MXenes, exhibit high metallic conductivity, ion intercalation capability, and reversible redox activity, prompting their applications in energy storage and conversion, electromagnetic interference (EMI) shielding, and electronics, among many other fields. It has been shown that replacement of ∼50% of carbon atoms in the most popular MXene family member, titanium carbide (Ti3C2Tx), by nitrogen atoms, forming titanium carbonitride (Ti3CNTx), leads to drastically different properties. Such properties include very high negative charge in solution and extreme EMI shielding effectiveness, exceeding all known materials, even metals at comparable thicknesses. Here, by using ultraviolet photoemission spectroscopy (UPS), the electronic structures of Ti3CNTx and Ti3C2Tx are systematically investigated and compared as a function of charge carrier density. We observe that, in contrast to Ti3C2Tx, the Ti 3p core-level of Ti3CNTx exhibits a counterintuitive shift to a lower binding energy of up to ∼250 meV upon increasing the electron density, which is a spectroscopic signature of negative electronic compressibility (NEC). These experimentally measured chemical potential shifts are well captured by the density functional theory (DFT) calculation. The DFT results also further suggest that the hybridization of titanium–nitrogen bonding in Ti3CNTx helps to promote the available states of Ti atoms for receiving more electrons above the fermi level and leads to the observed NEC. Our findings explain the differences in electronic properties between the two very important and widely studied MXenes and also suggest a new strategy to apply the NEC effect of Ti3CNTx in energy and charge storage applications.

MXenes are an emerging family of highly-conductive 2D materials which have demonstrated state-of-the-art performance in electromagnetic interference shielding, chemical sensing, and energy storage. To further improve performance, there is a need to increase MXenes’ electronic conductivity. Tailoring the MXene surface chemistry could achieve this goal, as density functional theory predicts that surface terminations strongly influence MXenes' Fermi level density of states and thereby MXenes’ electronic conductivity. Here, we directly correlate MXene surface de-functionalization with increased electronic conductivity through in situ vacuum annealing, electrical biasing, and spectroscopic analysis within the transmission electron microscope. Furthermore, we show that intercalation can induce transitions between metallic and semiconductor-like transport (transitions from a positive to negative temperature-dependence of resistance) through inter-flake effects. These findings lay the groundwork for intercalation- and termination-engineered MXenes, which promise improved electronic conductivity and could lead to the realization of semiconducting, magnetic, and topologically insulating MXenes., Two-dimensional transition metal carbides and nitrides (MXenes) have emerged as highly conductive and stable materials, of promise for electronic applications. Here, the authors use in situ electric biasing and transmission electron microscopy to investigate the effect of surface termination and intercalation on electronic properties.

Introduction of new nanomaterials with conductivity, salt adsorption capacity (SAC) and rate (SAR) exceeding that of carbon electrodes may greatly improve capacitive deionization of water. However, those materials show a different electrochemical behavior, which must be studied and optimized for practical use. Here, effects of operating conditions on desalination performance of pre-conditioned Ti3C2Tx-MXene-based electrodes in a symmetric membrane capacitive deionization (MCDI) system were investigated. Specifically, influences of discharge potential, half-cycle length (HCL), and flow rate were systematically studied. Results showed different degrees of performance dependence on operating conditions. For instance, lower discharge potentials increased SAC and SAR by 152%. However, longer HCL increased SAC by 32% while decreasing SAR by 54%. Finally, faster flow rates decreased both SAC and SAR by 20%. Desalination performances of symmetric pre-conditioned MXene and activated carbon cloth (ACC) electrodes were gravimetrically and volumetrically compared in MCDI system. Pre-conditioned MXene electrodes gravimetrically performed 30% lower than ACC due to their notably higher density. Yet, pre-conditioned MXene electrodes volumetrically outperformed ACC by 162%. Results suggest that although MXenes offer high electrochemical activity and hydrophilicity, making them promising candidates for CDI applications, the strong dependence of desalination performance of MXenes on operating conditions requires in-depth understanding and warrants further research.

We report on the high temperature thin film growth of BaTiO3 on Ti3C2Tx MXene flakes using van der Waals epitaxy on a degradable template layer. MXene was deposited on amorphous and crystalline substrates by spray- and dip-coating techniques, while the growth of BaTiO3 at 700 °C was accomplished using pulsed laser deposition in an oxygen rich environment. We demonstrate that the MXene flakes act as a temporary seed layer, which promotes highly oriented BaTiO3 growth along the (111) direction independent of the underlying substrate. The lattice parameters of the BaTiO3 films are close to the bulk value suggesting that the BaTiO3 films remains unstrained, as expected for van der Waals epitaxy. The initial size of the MXene flakes has an impact on the orientation of the BaTiO3 films with larger flake sizes promoting a higher fraction of the polycrystalline film to grow along the (111) direction. The deposited BaTiO3 film adopts the same morphology as the original flakes and piezoresponse force microscopy shows a robust ferroelectric behavior for individual grains. Transmission electron microscopy results indicate that the Ti3C2Tx MXene fully decomposes during the BaTiO3 deposition and the surplus Ti atoms are readily incorporated into the BaTiO3 film. Electrical measurements show a similar dielectric constant as a BaTiO3 film grown without the MXene seed layer. The demonstrated process has the potential to overcome the longstanding issue of integrating highly oriented complex oxide thin films directly on any desired substrate.

Two-dimensional heterostructures, such as Fe2O3/MXene nanoparticles, can be attractive anode materials for lithium-ion batteries (LIBs) due to the synergy between high lithium-storage capacity of Fe2O3 and stable cyclability and high conductivity provided by MXene. Here, we improved the storage performance of Ti3C2T x (MXene)/Fe2O3 nanocomposite by confining Fe2O3 nanoparticles into Ti3C2T x nanosheets with different mixing ratios using a facile and scalable dry ball-milling process. Composites of Ti3C2T x-25 wt % Fe2O3 and Ti3C2T x-50 wt % Fe2O3 synthesized by ball-milling resulted in uniform distribution of Fe2O3 nanoparticles on Ti3C2T x nanosheets with minimum oxidation of MXene as compared to composites prepared by hydrothermal or wet sonication. Moreover, the composites demonstrated minimum restacking of the nanosheets and higher specific surface area. Among all studied composites, the Ti3C2T x-50 wt % Fe2O3 showed the highest reversible specific capacity of ∼270 mAh g-1 at 1C (∼203 mAh g-1 based on the composite) and rate performance of 100 mAh g-1 at 10C. This can open the door for synthesizing stable and high-performance MXene/transition metal oxide composites with significantly enhanced electrochemical performance for LIB applications.

MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti4N3 and Ti2N are the only nitride MXenes reported so far. Here by ammoniation of Mo2CTx and V2CTx MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures of the resulting Mo2N and V2N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo2N retains the MXene structure and V2C transforms to a mixed layered structure of trigonal V2N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo2N and V2N are three and one order of magnitude larger than those of the Mo2CTx and V2CTx precursors, respectively. This study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis.

Author(s): Yang, Y; Hantanasirisakul, K; Frey, NC; Anasori, B; Green, RJ; Rogge, PC; Waluyo, I; Hunt, A; Shafer, P; Arenholz, E; Shenoy, VB; Gogotsi, Y; May, SJ | Abstract: MXenes are a rapidly-expanding family of 2D transition metal carbides and nitrides that have attracted attention due to their excellent performance in applications ranging from energy storage to electromagnetic interference shielding. Numerous other electronic and magnetic properties have been computationally predicted, but not yet realized due to the experimental difficulty in obtaining uniform surface terminations (Tx), necessitating new design approaches for MXenes that are independent of surface terminations. In this study, we distinguished the contributions of surface and sub-surface Ti atoms to the electronic structure of four Ti-containing MXenes (Ti2CTx, Ti3C2Tx, Cr2TiC2Tx, and Mo2TiC2Tx) using soft x-ray absorption spectroscopy. For MXenes with no Ti atoms on the surface transition metal layers, such as Mo2TiC2Tx and Cr2TiC2Tx, our results show minimal changes in the spectral features between the parent MAX phase and its MXene. In contrast, for MXenes with surface Ti atoms, here Ti3C2Tx and Ti2CTx, the Ti L-edge spectra are significantly modified compared to their parent MAX phase compounds. First principles calculations provide similar trends in the partial density of states derived from surface and sub-surface Ti atoms, corroborating the spectroscopic measurements. These results reveal that electronic states derived from sub-surface M-site layers are largely unperturbed by the surface terminations, indicating a relatively short length scale over which the Tx terminations alter the nominal electron count associated with Ti atoms and suggesting that desired band features should be hosted by sub-surface M-sites that are electronically more robust than their surface M-site counterparts.