A mechanically robust spiral fiber with ionic-electronic coupling for multimodal energy harvesting.

Wearable electronics are some of the most promising technologies with the potential to transform many aspects of human life such as smart healthcare and intelligent communication. The design of self-powered fabrics with the ability to efficiently harvest energy from the ambient environment would not only be beneficial for their integration with textiles, but would also reduce the environmental impact of wearable technologies by eliminating their need for disposable batteries. Herein, inspired by classical Archimedean spirals, we report a metastructured fiber fabricated by scrolling followed by cold drawing of a bilayer thin film of an MXene and a solid polymer electrolyte. The obtained composite fibers with a typical spiral metastructure (SMFs) exhibit high efficiency for dispersing external stress, resulting in simultaneously high specific mechanical strength and toughness. Furthermore, the alternating layers of the MXene and polymer electrolyte form a unique, tandem ionic-electronic coupling device, enabling SMFs to generate electricity from diverse environmental parameters, such as mechanical vibrations, moisture gradients, and temperature differences. This work presents a design rule for assembling planar architectures into robust fibrous metastructures, and introduces the concept of ionic-electronic coupling fibers for efficient multimodal energy harvesting, which have great potential in the field of self-powered wearable electronics.

Experimental and Theoretical Investigations of Out-of-Plane Ordered Nanolaminate Transition Metal Borides: M4CrSiB2 (M = Mo, W, Nb).

We report the synthesis of three out-of-plane chemically ordered quaternary transition metal borides (o-MAB phases) of the chemical formula M4CrSiB2 (M = Mo, W, Nb). The addition of these phases to the recently discovered o-MAB phase Ti4MoSiB2 shows that this is indeed a new family of chemically ordered atomic laminates. Furthermore, our results expand the attainable chemistry of the traditional M5SiB2 MAB phases to also include Cr. The crystal structure and chemical ordering of the produced materials were investigated using high-resolution scanning transmission electron microscopy and X-ray diffraction by applying Rietveld refinement. Additionally, calculations based on density functional theory were performed to investigate the Cr preference for occupying the minority 4c Wyckoff site, thereby inducing chemical order.

Recovery of oxidized two-dimensional MXenes through high frequency nanoscale electromechanical vibration.

MXenes hold immense potential given their superior electrical properties. The practical adoption of these promising materials is, however, severely constrained by their oxidative susceptibility, leading to significant performance deterioration and lifespan limitations. Attempts to preserve MXenes have been limited, and it has not been possible thus far to reverse the material's performance. In this work, we show that subjecting oxidized micron or nanometer thickness dry MXene films-even those constructed from nanometer-order solution-dispersed oxidized flakes-to just one minute of 10 MHz nanoscale electromechanical vibration leads to considerable removal of its surface oxide layer, whilst preserving its structure and characteristics. Importantly, electrochemical performance is recovered close to that of their original state: the pseudocapacitance, which decreased by almost 50% due to its oxidation, reverses to approximately 98% of its original value, with good capacitance retention ( ≈ 93%) following 10,000 charge-discharge cycles at 10 A g-1. These promising results allude to the exciting possibility for rejuvenating the material for reuse, therefore offering a more economical and sustainable route that improves its potential for practical translation.

On the Use of Ti3C2 T x MXene as a Negative Electrode Material for Lithium-Ion Batteries.

The pursuit of new and better battery materials has given rise to numerous studies of the possibilities to use two-dimensional negative electrode materials, such as MXenes, in lithium-ion batteries. Nevertheless, both the origin of the capacity and the reasons for significant variations in the capacity seen for different MXene electrodes still remain unclear, even for the most studied MXene: Ti3C2 T x . Herein, freestanding Ti3C2 T x MXene films, composed only of Ti3C2 T x MXene flakes, are studied as additive-free negative lithium-ion battery electrodes, employing lithium metal half-cells and a combination of chronopotentiometry, cyclic voltammetry, X-ray photoelectron spectroscopy, hard X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy experiments. The aim of this study is to identify the redox reactions responsible for the observed reversible and irreversible capacities of Ti3C2 T x -based lithium-ion batteries as well as the reasons for the significant capacity variation seen in the literature. The results demonstrate that the reversible capacity mainly stems from redox reactions involving the T x -Ti-C titanium species situated on the surfaces of the MXene flakes, whereas the Ti-C titanium present in the core of the flakes remains electro-inactive. While a relatively low reversible capacity is obtained for electrodes composed of pristine Ti3C2 T x MXene flakes, significantly higher capacities are seen after having exposed the flakes to water and air prior to the manufacturing of the electrodes. This is ascribed to a change in the titanium oxidation state at the surfaces of the MXene flakes, resulting in increased concentrations of Ti(II), Ti(III), and Ti(IV) in the T x -Ti-C surface species. The significant irreversible capacity seen in the first cycles is mainly attributed to the presence of residual water in the Ti3C2 T x electrodes. As the capacities of Ti3C2 T x MXene negative electrodes depend on the concentration of Ti(II), Ti(III), and Ti(IV) in the T x -Ti-C surface species and the water content, different capacities can be expected when using different manufacturing, pretreatment, and drying procedures.

Out-Of-Plane Ordered Laminate Borides and Their 2D Ti-Based Derivative from Chemical Exfoliation.

Exploratory theoretical predictions in uncharted structural and compositional space are integral to materials discoveries. Inspired by M5 SiB2 (T2) phases, the finding of a family of laminated quaternary metal borides, M'4 M″SiB2 , with out-of-plane chemical order is reported here. 11 chemically ordered phases as well as 40 solid solutions, introducing four elements previously not observed in these borides are predicted. The predictions are experimentally verified for Ti4 MoSiB2 , establishing Ti as part of the T2 boride compositional space. Chemical exfoliation of Ti4 MoSiB2 and select removal of Si and MoB2 sub-layers is validated by derivation of a 2D material, TiOx Cly , of high yield and in the form of delaminated sheets. These sheets have an experimentally determined direct band gap of ≈4.1 eV, and display characteristics suitable for supercapacitor applications. The results take the concept of chemical exfoliation beyond currently available 2D materials, and expands the envelope of 3D and 2D candidates, and their applications.

Boridene: Two-dimensional Mo4/3B2-x with ordered metal vacancies obtained by chemical exfoliation.

Extensive research has been invested in two-dimensional (2D) materials, typically synthesized by exfoliation of van der Waals solids. One exception is MXenes, derived from the etching of constituent layers in transition metal carbides and nitrides. We report the experimental realization of boridene in the form of single-layer 2D molybdenum boride sheets with ordered metal vacancies, Mo4/3B2-xTz (where Tz is fluorine, oxygen, or hydroxide surface terminations), produced by selective etching of aluminum and yttrium or scandium atoms from 3D in-plane chemically ordered (Mo2/3Y1/3)2AlB2 and (Mo2/3Sc1/3)2AlB2 in aqueous hydrofluoric acid. The discovery of a 2D transition metal boride suggests a wealth of future 2D materials that can be obtained through the chemical exfoliation of laminated compounds.

Acoustomicrofluidic Synthesis of Pristine Ultrathin Ti3C2Tz MXene Nanosheets and Quantum Dots.

The conversion of layered transition metal carbides and/or nitrides (MXenes) into zero-dimensional structures with thicknesses and lateral dimensions of a few nanometers allows these recently discovered materials with exceptional electronic properties to exploit the additional benefits of quantum confinement, edge effects, and large surface area. Conventional methods for the conversion of MXene nanosheets and quantum dots, however, involve extreme conditions such as high temperatures and/or harsh chemicals that, among other disadvantages, lead to significant degradation of the material as a consequence of their oxidation. Herein, we show that the large surface acceleration-on the order of 10 million g's-produced by high-frequency (10 MHz) nanometer-order electromechanical vibrations on a chip-scale piezoelectric substrate is capable of efficiently nebulizing, and consequently dimensionally reducing, a suspension of multilayer Ti3C2Tz (MXene) into predominantly monolayer nanosheets and quantum dots while, importantly, preserving the material from any appreciable oxidation. As an example application, we show that the high-purity MXene quantum dots produced using this room-temperature chemical-free synthesis method exhibit superior performance as electrode materials for electrochemical sensing of hydrogen peroxide compared to the highly oxidized samples obtained through conventional hydrothermal synthesis. The ability to detect concentrations as low as 5 nM is a 10-fold improvement to the best reported performance of Ti3C2Tz MXene electrochemical sensors to date.

Flexible Free-Standing MoO3/Ti3C2T z MXene Composite Films with High Gravimetric and Volumetric Capacities.

Enhancing both the energy storage and power capabilities of electrochemical capacitors remains a challenge. Herein, Ti3C2T z MXene is mixed with MoO3 nanobelts in various mass ratios and the mixture is used to vacuum filter binder free, open, flexible, and free-standing films. The conductive Ti3C2T z flakes bridge the nanobelts, facilitating electron transfer; the randomly oriented, and interconnected, MoO3 nanobelts, in turn, prevent the restacking of the Ti3C2T z nanosheets. Benefitting from these advantages, a MoO3/Ti3C2T z film with a 8:2 mass ratio exhibits high gravimetric/volumetric capacities with good cyclability, namely, 837 C g-1 and 1836 C cm-3 at 1 A g-1 for an ≈ 10 µm thick film; and 767 C g-1 and 1664 C cm-3 at 1 A g-1 for ≈ 50 µm thick film. To further increase the energy density, hybrid capacitors are fabricated with MoO3/Ti3C2T z films as the negative electrodes and nitrogen-doped activated carbon as the positive electrodes. This device delivers maximum gravimetric/volumetric energy densities of 31.2 Wh kg-1 and 39.2 Wh L-1, respectively. The cycling stability of 94.2% retention ratio after 10 000 continuous charge/discharge cycles is also noteworthy. The high energy density achieved in this work can pave the way for practical applications of MXene-containing materials in energy storage devices.

Ultrafast, One-Step, Salt-Solution-Based Acoustic Synthesis of Ti3C2 MXene.

The current quest for two-dimensional transition metal carbides and nitrides (MXenes) has been to circumvent the slow, hazardous, and laborious multistep synthesis procedures associated with conventional chemical MAX phase exfoliation. Here, we demonstrate a one-step synthesis method with local Ti3AlC2 MAX to Ti3C2Tz MXene conversion on the order of milliseconds, facilitated by proton production through solution dissociation under megahertz frequency acoustic excitation. These protons combined with fluorine ions from LiF to selectively etch the MAX phase into MXene, whose delamination is aided by the acoustic forcing. These results have important implications for the future applicability of MXenes, which crucially depend on the development of more efficient synthesis procedures. For proof-of-concept, we show that flexible electrodes fabricated by this method exhibit comparable electrochemical performance to that previously reported.

Improved charge storage performance of a layered Mo1.33C MXene/MoS2/graphene nanocomposite.

The construction of nanocomposite electrodes based on 2D materials is an efficient route for property enrichment and for exploitation of constituent 2D materials. Herein, a flexible Mo1.33C i-MXene/MoS2/graphene (MOMG) composite electrode is constructed, utilizing an environment-friendly method for high-quality graphene and MoS2 synthesis. The presence of graphene and MoS2 between MXene sheets limits the commonly observed restacking, increases the interlayer spacing, and facilitates the ionic and electronic conduction. The as-prepared MOMG electrode delivers a volumetric capacitance of 1600 F cm-3 (450 F g-1) at the scan rate of 2 mV s-1 and retains 96% of the initial capacitance after 15 000 charge/discharge cycles (10 A g-1). The current work demonstrates that the construction of nanocomposite electrodes is a promising route towards property enhancement for energy storage applications.

Tailored synthesis approach of (Mo2/3Y1/3)2AlC i-MAX and its two-dimensional derivative Mo1.33CTz MXene: enhancing the yield, quality, and performance in supercapacitor applications.

A vacancy-ordered MXene, Mo1.33CTz, obtained from the selective etching of Al and Sc from the parent i-MAX phase (Mo2/3Sc1/3)2AlC has previously shown excellent properties for supercapacitor applications. Attempts to synthesize the same MXene from another precursor, (Mo2/3Y1/3)2AlC, have not been able to match its forerunner. Herein, we show that the use of an AlY2.3 alloy instead of elemental Al and Y for the synthesis of (Mo2/3Y1/3)2AlC i-MAX, results in a close to 70% increase in sample purity due to the suppression of the main secondary phase, Mo3Al2C. Furthermore, through a modified etching procedure, we obtain a Mo1.33CTz MXene of high structural quality and improve the yield by a factor of 6 compared to our previous efforts. Free-standing films show high volumetric (1308 F cm-3) and gravimetric (436 F g-1) capacitances and a high stability (98% retention) at the level of, or even beyond, those reported for the Mo1.33CTz MXene produced from the Sc-based i-MAX. These results are of importance for the realization of high quality MXenes through use of more abundant elements (Y vs. Sc), while also reducing waste (impurity) material and facilitating the synthesis of a high-performance material for applications.

Composition Tuning of Nanostructured Binary Copper Selenides through Rapid Chemical Synthesis and their Thermoelectric Property Evaluation.

Reduced energy consumption and environmentally friendly, abundant constituents are gaining more attention for the synthesis of energy materials. A rapid, highly scalable, and process-temperature-sensitive solution synthesis route is demonstrated for the fabrication of thermoelectric Cu2-xSe. The process relies on readily available precursors and microwave-assisted thermolysis, which is sensitive to reaction conditions; yielding Cu1.8Se at 200 °C and Cu2Se at 250 °C within 6-8 min reaction time. Transmission electron microscopy (TEM) revealed crystalline nature of as-made particles with irregular truncated morphology, which exhibit a high phase purity as identified by X-ray powder diffraction (XRPD) analysis. Temperature-dependent transport properties were characterized via electrical conductivity, Seebeck coefficient, and thermal diffusivity measurements. Subsequent to spark plasma sintering, pure Cu1.8Se exhibited highly compacted and oriented grains that were similar in size in comparison to Cu2Se, which led to its high electrical and low thermal conductivity, reaching a very high power-factor (24 µW/K-2cm-1). Density-of-states (DOS) calculations confirm the observed trends in electronic properties of the material, where Cu-deficient phase exhibits metallic character. The TE figure of merit (ZT) was estimated for the materials, demonstrating an unprecedentedly high ZT at 875 K of 2.1 for Cu1.8Se sample, followed by 1.9 for Cu2Se. Synthetic and processing methods presented in this work enable large-scale production of TE materials and components for niche applications.

Synthesis of (V2/3Sc1/3)2AlC i-MAX phase and V2-xC MXene scrolls.

We report the synthesis and characterization of a new laminated i-MAX phase, (V2/3Sc1/3)2AlC, with in-plane chemical ordering between the M-elements. We also present evidence for the solid solution (V2-xScx)2AlC, where x ≤ 0.05. Chemical etching of the Al and Sc results in a two-dimensional (2D) MXene counterpart: V2-xC from the latter phase. Furthermore, etching with HF yields single-sheet MXene of flat morphology, while LiF + HCl gives MXene scrolls. We also show a 4× reduction in etching time for (V2-xScx)2AlC compared to V2AlC, suggesting that traces of Sc changes the phase stability, and make the material more susceptible to etching. The results show a path for improved control of MXene synthesis and morphology, which may be applicable also for other MAX/MXene systems.

A Tungsten-Based Nanolaminated Ternary Carbide: (W,Ti)4C4- x.

Nanolamellar transition metal carbides are gaining increasing interests because of the recent developments of their two-dimensional (2D) derivatives and promising performance for a variety of applications from energy storage, catalysis to transparent conductive coatings, and medicine. To develop more novel 2D materials, new nanolaminated structures are needed. Here we report on a tungsten-based nanolaminated ternary phase, (W,Ti)4C4- x, synthesized by an Al-catalyzed reaction of W, Ti, and C powders at 1600 °C for 4 h, under flowing argon. X-ray and neutron diffraction, along with Z-contrast scanning transmission electron microscopy, were used to determine the atomic structure, ordering, and occupancies. This phase has a layered hexagonal structure ( P63 /mmc) with lattice parameters, a = 3.00880(7) Å, and c = 19.5633(6) Å and a nominal chemistry of (W,Ti)4C4- x (actual chemistry, W2.1(1)Ti1.6(1)C2.6(1)). The structure is comprised of layers of pure W that are also twin planes with two adjacent atomic layers of mixed W and Ti, on either side. The use of Al as a catalyst for synthesizing otherwise difficult to make phases, could in turn lead to the discovery of a large family of nonstoichiometric ternary transition metal carbides, synthesized at relatively low temperatures and shorter times.

Electronic and optical characterization of 2D Ti2C and Nb2C (MXene) thin films.

Two-dimensional (2D) transition metal carbides and/or nitrides (MXenes) are a new class of 2D materials, with extensive opportunities for property tailoring due to the numerous possibilities for varying chemistries and surface terminations. Here, Ti2AlC and Nb2AlC MAX phase epitaxial thin films were deposited on sapphire substrates by physical vapor deposition. The films were then etched in LiF/HCl solutions, yielding Li-intercalated, 2D Ti2CT z and Nb2CT z films, whose terminations, transport and optical properties were characterized. The former exhibits metallic conductivity, with weak localization below 50 K. In contrast, the Nb-based film exhibits an increase in resistivity with decreasing temperature from RT down to 40 K consistent with variable range hopping transport. The optical properties of both films were determined from spectroscopic ellipsometry in the 0.75 to 3.50 eV range. The results for Ti2CT z films confirm the metallic behavior. In contrast, no evidence of metallic behavior is observed for the Nb2CT z film. The present work therefore demonstrates that one fruitful approach to alter the electronic and optical properties of MXenes is to change the nature of the transition metal.

2D Transition Metal Carbides (MXenes) for Carbon Capture.

Global warming caused by burning of fossil fuels is indisputably one of mankind's greatest challenges in the 21st century. To reduce the ever-increasing CO2 emissions released into the atmosphere, dry solid adsorbents with large surface-to-volume ratio such as carbonaceous materials, zeolites, and metal-organic frameworks have emerged as promising material candidates for capturing CO2 . However, challenges remain because of limited CO2 /N2 selectivity and long-term stability. The effective adsorption of CO2 gas (≈12 mol kg-1 ) on individual sheets of 2D transition metal carbides (referred to as MXenes) is reported here. It is shown that exposure to N2 gas results in no adsorption, consistent with first-principles calculations. The adsorption efficiency combined with the CO2 /N2 selectivity, together with a chemical and thermal stability, identifies the archetype Ti3 C2 MXene as a new material for carbon capture (CC) applications.

On the Structural Stability of MXene and the Role of Transition Metal Adatoms.

In the present communication, the atomic structure and coordination of surface adsorbed species on Nb2C MXene is investigated over time. In particular, the influence of the Nb adatoms on the structural stability and oxidation behavior of the MXene is addressed. This investigation is based on the plane-view geometry observations of single Nb2C MXene sheets by a combination of atomic-resolution scanning transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS) and STEM image simulations.

Tailoring Structure, Composition, and Energy Storage Properties of MXenes from Selective Etching of In-Plane, Chemically Ordered MAX Phases.

The exploration of 2D solids is one of our time's generators of materials discoveries. A recent addition to the 2D world is MXenes that possses a rich chemistry due to the large parent family of MAX phases. Recently, a new type of atomic laminated phases (coined i-MAX) is reported, in which two different transition metal atoms are ordered in the basal planes. Herein, these i-MAX phases are used in a new route for tailoriong the MXene structure and composition. By employing different etching protocols to the parent i-MAX phase (Mo2/3 Y1/3 )2 AlC, the resulting MXene can be either: i) (Mo2/3 Y1/3 )2 C with in-plane elemental order through selective removal of Al atoms or ii) Mo1.33 C with ordered vacancies through selective removal of both Al and Y atoms. When (Mo2/3 Y1/3 )2 C (ideal stoichiometry) is used as an electrode in a supercapacitor-with KOH electrolyte-a volumetric capacitance exceeding 1500 F cm-3 is obtained, which is 40% higher than that of its Mo1.33 C counterpart. With H2 SO4 , the trend is reversed, with the latter exhibiting the higher capacitance (≈1200 F cm-3 ). This additional ability for structural tailoring will indubitably prove to be a powerful tool in property-tailoring of 2D materials, as exemplified here for supercapacitors.

W-Based Atomic Laminates and Their 2D Derivative W1.33 C MXene with Vacancy Ordering.

Structural design on the atomic level can provide novel chemistries of hybrid MAX phases and their MXenes. Herein, density functional theory is used to predict phase stability of quaternary i-MAX phases with in-plane chemical order and a general chemistry (W2/3 M21/3 )2 AC, where M2 = Sc, Y (W), and A = Al, Si, Ga, Ge, In, and Sn. Of over 18 compositions probed, only two-with a monoclinic C2/c structure-are predicted to be stable: (W2/3 Sc1/3 )2 AlC and (W2/3 Y1/3 )2 AlC and indeed found to exist. Selectively etching the Al and Sc/Y atoms from these 3D laminates results in W1.33 C-based MXene sheets with ordered metal divacancies. Using electrochemical experiments, this MXene is shown to be a new, promising catalyst for the hydrogen evolution reaction. The addition of yet one more element, W, to the stable of M elements known to form MAX phases, and the synthesis of a pure W-based MXene establishes that the etching of i-MAX phases is a fruitful path for creating new MXene chemistries that has hitherto been not possible, a fact that perforce increases the potential of tuning MXene properties for myriad applications.

Sodium hydroxide and vacuum annealing modifications of the surface terminations of a Ti3C2 (MXene) epitaxial thin film.

We investigate, and quantify, changes in structure and surface terminations of epitaxial thin films of titanium carbide (Ti3C2) MXene, when treated by sodium hydroxide solution followed by vacuum annealing at 550 °C. Using X-ray photoelectron spectroscopy and scanning transmission electron microscopy, we show that NaOH treatment produce an increase in the c-lattice parameter together with an increase in the O terminations and a decrease in the F terminations. There is also an increase in the percentage of the binding energy of Ti-species in Ti 2p XPS region, which suggests an increase in the overall oxidation state of Ti. After subsequent annealing, the c-lattice parameter is slightly reduced, the overall oxidation state of Ti is decreased, and the F surface terminations are further diminished, leaving a surface with predominantly O as the surface terminating species. It is important to note that NaOH treatment facilitates removal of F at lower annealing temperatures than previously reported, which in turn is important for the range of attainable properties.