Patent Description:
The present invention is directed to compositions comprising free standing two dimensional crystalline solids, and methods of making the same.

Typically, two-dimensional, <NUM>-D, free-standing crystals exhibit properties that differ from those of their three-dimensional, <NUM>-D, counterparts. Currently, however, there are relatively few materials which can be described as <NUM>-D, atomically-scaled layered solids. Clearly the most studied freestanding <NUM>-D material is graphene, but other materials include hexagonal BN, certain transition metal oxides, hydroxides, and silicates, including clays, S<NUM>N, MoS<NUM> and WS<NUM> are also known. Currently, the number of non-oxide materials that have been exfoliated is limited to two fairly small groups, viz. hexagonal, van der Waals bonded structures (e.g. graphene and BN) and layered metal chalcogenides (e.g. MoS<NUM>, WS<NUM>, etc.).

Although graphene has attracted more attention than all other <NUM>-D materials together, its simple chemistry and the weak van der Waals bonding between layers in multi-layer structures limit its use. Given the properties of graphene for applications ranging from composite reinforcement to electronics, there is interest in other new materials which may also be described as <NUM>-D, atomically-scaled layered solids.

<CIT> describes a method of forming Mn+<NUM>AXn, wherein M is an early transition metal (such as Ti), A is a group III or IV element (such as Si) or mixtures thereof and X is C, N or mixture thereof.

<NPL> describe the self-extrusion of Ga filaments from bulk Cr<NUM>GaN.

<NPL>, describes the corrosion behavior of Ti<NUM>SiC<NUM>.

<NPL>, describes the topotactic transformation of Ti<NUM>SiC<NUM> into partially ordered cubic Ti(C<NUM>Si<NUM>).

<NPL> relates to Mn+1AXn phases as a class of solids.

This invention is directed to compositions comprising free standing and stacked assemblies of two dimensional crystalline solids, and methods of making the same.

The invention provides a composition as defined in claim <NUM>.

Still further embodiments provide polymer composites comprising an organic polymer and at least one composition described in the preceding paragraphs.

The invention also provides at least one stacked assembly as defined in claim <NUM>.

In some embodiments, the stacked assemblies described in the preceding paragraphs are capable of, or have atoms or ions, that are intercalated between at least some of the layers. In other embodiments, these atoms or ions are lithium. In still other embodiments, these structures are part of an energy storing device or a battery.

This invention also provides methods of preparing compositions as defined in claim <NUM>.

The following figures are presented as illustrative examples, and should not be considered to limit the scope of the invention in any way. Except where otherwise noted, the scales of the figures may be exaggerated for illustrative purposes.

The present invention may be understood more readily by reference to the following detailed description taken in connection with the accompanying Figures and Examples, which form a part of this disclosure. It is to be understood that this invention is not limited to the specific products, methods, conditions or parameters described and / or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of any claimed invention. Similarly, unless specifically otherwise stated, any description as to a possible mechanism or mode of action or reason for improvement is meant to be illustrative only, and the invention herein is not to be constrained by the correctness or incorrectness of any such suggested mechanism or mode of action or reason for improvement. Throughout this text, it is recognized that the descriptions refer both to compositions and to the articles and devices derived therefrom, as well as the methods of manufacture and use.

In the present disclosure the singular forms "a," "an," and "the" include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to "a material" is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.

When values are expressed as approximations by use of the antecedent "about," it will be understood that the particular value forms another embodiment. In general, use of the term "about" indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function, and the person skilled in the art will be able to interpret it as such. In some cases, the number of significant figures used for a particular value may be one non-limiting method of determining the extent of the word "about. " In other cases, the gradations used in a series of values may be used to determine the intended range available to the term "about" for each value. Where present, all ranges are inclusive and combinable. That is, reference to values stated in ranges includes each and every value within that range.

Various embodiments of this invention provide for crystalline compositions comprising at least one layer having first and second surfaces, each layer comprising a two-dimensional array of crystal cells; each crystal cell is an ordered array of atoms having an empirical formula of Mn+<NUM>Xn , such that each X is positioned within an octahedral array of M; wherein M is at least one Group IIIB, IVB, VB, or VIB metal; wherein each X is C or N (i.e., stoichiometrically X = CxNy, including where x + y = <NUM>); and n = <NUM>, <NUM>, or <NUM>. In some embodiments, these compositions comprise a plurality of layers. Other embodiments provide for stacked assemblies of such layers. Collectively, such compositions are referred to herein as "MXene," "MXene compositions," or "MXene materials. " Additionally, these terms "MXene," "MXene compositions," or "MXene materials" also refer to those compositions derived by the chemical exfoliation of MAX phase materials, whether these compositions are present as free-standing <NUM>-dimensional or stacked assemblies (as described further below). <FIG> provides a representation of the crystal cells of various Mn+<NUM>Xn (where n = <NUM>, <NUM>, or <NUM>) frameworks, presented however, in the context of corresponding MAX-phase materials (see also below). In various embodiments, each X is positioned within an octahedral array of M.

Analogous to other so-called two-dimensional, atomically-scaled layered solid materials, such as graphene or hexagonal BN, these MXene crystalline compositions are free-standing or be present in stacked compositions. As used herein, the term "free standing" refers to individual layers wherein the adjacent composite crystal layers are not bonded to one another by covalent bonds or connected by metal-lattice bonds, but may be joined by intervening hydrogen (or even weaker) bonding, such that each such layer can be physically manipulated. See e.g., <FIG> and <FIG>. However, this term does not preclude the deposition of these layers or stacked layers on substrates or within polymer compositions (see also below).

The term "crystalline compositions comprising at least one layer having first and second surfaces, each layer comprising a substantially two-dimensional array of crystal cells" refers to the unique character of these materials. For purposes of visualization, the two-dimensional array of crystal cells may be viewed as an array of cells extending in an x-y plane, with the z-axis defining the thickness of the composition, without any restrictions as to the absolute orientation of that plane or axes. According to the invention, the at least one layer having first and second surface contains but a single two-dimensional array of crystal cells, that is, the z-dimension is defined by the dimension of a single, i.e. one, crystal cell, such that the planar surfaces of said cell array defines the surface of the layer.

That is, as used herein, "a substantially two dimensional array of crystal cells" refers to an array which includes a lateral (in x-y dimension) array of crystals having a thickness of a single cell (e.g., corresponding to the M<NUM>X, M<NUM>X<NUM>, or M<NUM>X<NUM> cells as depicted in <FIG>), such that the top and bottom surfaces of the array are available for chemical modification.

It should also be appreciated that, analogous to graphene or hexagonal BN compositions, this description of a planar or two-dimensional array should not be interpreted to describe a necessarily flat structure; rather such compositions may also take the form of a curved or undulating plane, a scroll, or a cylinder or tube (e.g., analogous to the structure of a carbon or BN nanotube).

According to the invention, the compositions contain C or N atoms, or a mixture thereof, but in any case, these atoms are positioned within an octahedral or pseudo-octahedral array of M atoms, reminiscent of the positioning of the carbon or nitrogen atom within MAX-phase materials. While not necessarily being bound to the scientific accuracy of this statement, this arrangement appears to protect the C and/or N atoms from external chemical attack, while at the same time providing a degree of structural strength to the <NUM>-dimensional layers.

Given the difficulties in obtaining crystallographic evidence as to the crystallinity of materials having such few layers (e.g., less than about <NUM> cell layers), owing to the reduced level or lack of constructive interference of such few layers, these materials may be characterized by measuring the thickness of the individual layers (measured, for example, by Transmission Electron Micrography or atomic force microscopy). Depending on the particular empirical formula of the given material, the thickness of a given single cell layer will be on the order of about <NUM> to about <NUM> (preferably about <NUM>) for M<NUM>X compositions, about <NUM> to about <NUM> (preferably about <NUM>) for M<NUM>X<NUM> compositions, and about <NUM> to about <NUM> (preferably about <NUM>) for M<NUM>X<NUM> compositions. As described more fully below, one method of preparing these compositions is to react a precursor MAX phase material so as to remove the labile A-phase, and exfoliating the resulting structure. In these cases, it is so generally observed that the crystallinity of the resulting MXene framework, which existed in the original MAX phase structure, is sufficiently robust as to be retained during the preparation process, so that the thickness measurements by themselves can be used to characterize the materials, even in the absence of crystallographic analysis.

These MXene materials (even individual or exfoliated layers) can also be characterized by measuring the X-ray diffraction (XRD) spectra of (optionally cold pressed) stacked layers (see, e.g., Example <NUM>, <FIG> and Example <NUM>, <FIG> below). That is, such stacking provides a sample of sufficient thickness (number of layers) to allow for sufficient constructive interference so as to provide for a measurable XRD pattern to be obtained. One distinguishing feature of XRD patterns thus generated is the presence of peaks at 2θ of ca. <NUM>-<NUM>° (i.e., between about <NUM>° and about <NUM>° when Cu Kα radiation is used), corresponding to the d-spacing (thickness) of the individual layers (including the surface coatings of each layer) and lower than the (<NUM>) peaks of the corresponding MAX phase materials. That this MXene peak occurs at lower 2θ values, reflecting higher d-spacings of the layers, than the corresponding (<NUM>) plane in a corresponding MAX phase material is consistent with the greater spacing of the crystal cells of the two materials in the former relative to the latter (e.g., referring to <FIG>, the individual layers of the Ti<NUM>C<NUM> in <FIG> are spaced further apart than the corresponding layers in <FIG>).

According to the invention, the terms "M" or "M atoms," "M elements," or "M metals" refers to one or more members of the Groups IIIB, IVB, VB, or VIB or (aka) Groups <NUM>-<NUM> of the periodic table, either alone or in combination, said members preferably including Sc, Y, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. In preferred embodiments, the transition metal is one or more of Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, and/or Mo. In other preferred embodiments, the transition metal is one or more of Ti, Zr, V, Cr, Nb, and/or Ta. In even more preferred embodiments, the transition metal is Ti, Ta, V, and/or Cr.

The empirical formula Mn+<NUM>Xn , wherein X is C, N, or a combination thereof, and n = <NUM>, <NUM>, or <NUM> gives rise to a number of possible composition. For example, and while not intending to be limited to this list, exemplary compositions when n = <NUM> includes those wherein the empirical formula is Sc<NUM>C, Sc<NUM>N, Ti<NUM>C, Ti<NUM>N, V<NUM>C, V<NUM>N, Cr<NUM>C, Cr<NUM>N, Zr<NUM>C, Zr<NUM>N, Nb<NUM>C, Nb<NUM>N, Hf<NUM>C, and Hf<NUM>N. Similarly, non-limiting exemplary compositions when n = <NUM> includes those wherein the empirical formula is Ti<NUM>C<NUM>, Ti<NUM>N<NUM>, V<NUM>C<NUM>, V<NUM>C<NUM>, Ta<NUM>C<NUM>, and Ta<NUM>N<NUM> and when n = <NUM> includes those wherein the empirical formula is Ti<NUM>C<NUM>, Ti<NUM>N<NUM>, V<NUM>C<NUM>, V<NUM>N<NUM>, Ta<NUM>C<NUM> and Ta<NUM>N<NUM>. Especially important embodiments include those where M comprises at least one Group IVB element, for example Ti, Zr, or Hf and those where M comprises at least one Group V elements, for example V, Nb, or Ta. More preferred independent embodiments include those where M is Ti or Ta, especially structures wherein the empirical formula is Ti<NUM>C, Ti<NUM>N, Ti<NUM>C<NUM>, Ti<NUM>N<NUM>, Ti<NUM>C<NUM>, or Ti<NUM>N<NUM>, or Ta<NUM>C<NUM>, Ta<NUM>N<NUM>, Ta<NUM>C<NUM> or Ta<NUM>N<NUM>, especially Ti<NUM>C or Ta<NUM>C<NUM>.

The range of compositions available can be seen as extending even further when one considers that each M-atom position within the overall Mn+<NUM>Xn matrix can be represented by more than one element. That is, one or more type of M-atom can occupy each M-positions within the respective matrices. In certain exemplary non-limiting examples, these can be (MAxMBy)<NUM>C or (MAxMBy)<NUM>N, (MAxMBy)<NUM>C<NUM> or (MAxMBy)<NUM>C<NUM>, or (MAxMBy)<NUM>C<NUM> or (MAxMBy)<NUM>C<NUM> , where MA and MB are independently members of the same group, and x + y = <NUM>. For example, in but one non-limiting example, such a composition can be (V<NUM>/<NUM>Cr<NUM>/<NUM>)<NUM>C<NUM>. In the same way, one or more type of X-atom can occupy each X-position within the matrices, for example solid solutions of the formulae Mn+<NUM>(CxNy)n, or (MAxMBy)n+<NUM>(CxNy)n.

In various embodiments, the composition's layer has first and second surfaces which are capable of being physically or chemically interrogated or modified. This feature distinguishes these compositions from sputtered matrices or so-called MAX phase compositions. While it may be possible to describe sputtered matrices or MAX phase compositions as containing two-dimensional arrays of crystal cells, in each case these are embedded within vertically integrated and practically bound to other layers within the respective matrices (e.g., in the case of sputtered matrices, to other neighboring sputtered layers or the substrate; in the case of MAX-phase compositions, to interleaved A-group element arrays), either by covalent, metallic, or lattice bonds, and which cannot be separately accessed. By contrast, in various embodiments of the present compositions, each layer has two available or accessible surfaces sandwiching each substantially two-dimensional array of crystal cells, each of which surfaces can be accessed for physical or chemical interrogation or modification.

The ability to functionalize the surfaces of the layers of the present invention provides a considerable synthetic and structural flexibility. Because of the arrangement of the M atoms within the Mn+<NUM>Xn framework, wherein each X is positioned within an octahedral array of M atoms, the "unfunctionalized" surface comprises largely M atoms. For example, in the absence of imperfections, a substantially planar array of crystal cells having an empirical formula Ti<NUM>C<NUM> will provide or present external surfaces comprising a planar array of Ti atoms (see, e.g., <FIG>). At the same time, owing to the chemical reactivity of Ti (or any of the M atoms), these surfaces will be coated with one or more organic or inorganic moieties, generally comprising heteroatoms or having heteroatom linking groups.

For example, in certain embodiments, at least one of the surfaces are coated with a coating comprising H, N, O, or S atoms, for example, a hydride, oxide, sub-oxide, nitride, sub-nitride, sulfide, or optionally a sub-sulfide. In preferred embodiments, the coating comprises a hydrated or anhydrous oxide, a sub-oxide, or some combination thereof. As used herein the terms "sub-oxide," "sub-nitride," or "sub-sulfide" is intended to connote a composition containing an amount reflecting a sub-stoichiometric or a mixed oxidation state of the M metal at the surface of oxide, nitride, or sulfide, respectively. For example, various forms of titania are known to exist as TiOx, where x can be less than <NUM>. Accordingly, the surfaces of the present invention may also contain oxides, nitrides, or sulfides in similar sub-stoichiometric or mixed oxidation state amounts.

In other embodiments, at least one surface is coated with a coating having a pendant moiety which is linked to the surface by an N, O, or S atom (e.g., an M-N, M-O, or M-S bond, respectively). Such surface coatings then may comprise at least one hydroxide, alkoxide, carboxylate, amine, amide, or thiol. These pendants may contain organic moieties, including saturated, unsaturated, and/or aromatic moieties. These organic moieties may optionally include heteroatoms, be linear or branched, and/or may contain one or more functional groups, for example amines and derivatives therefrom, (thio)carboxylic acids and derivatives therefrom, hydroxy or ether groups, and/or thiol groups. The moieties and/or optionally available functional groups may exist in their neutral or ionized state.

In other embodiments, the coating of at least one surface comprises at least one halide, for example F, Cl, Br, or I, preferably F. As used herein, the terms "halide" and, e.g., "fluoride" are intended to reflect the presence of metal-halogen or metal-fluorine bonds, respectively, without regard to the specific nominal charge on the halogen or fluorine.

The skilled artisan will be able to interchange the pendant groups by methods known in the art. Without the need for an exhaustive delineation of such methods, in one non-limiting example, a hydroxy or alkoxy surface may be prepared by providing an excess hydroxide or alkoxide so as to displace the halide from an initially presented M-halide surface or so as to hydrate or alkoxylate a metal oxide or sub-oxide surface. Similarly, an originally presented M-hydroxide surface may be converted to oxide or sub-oxide surface by application of heat or other dehydrating conditions. Nitrogen and sulfur surfaces may be analogously interconverted by methods known in the art for making such conversions. Similarly, hydrides may be prepared by exposing precursors to reducing conditions, either electrolytically or by contacting with reducing agents such as hydrides (e.g., NaBH<NUM>), hydrogen gas, or ammonia.

In certain embodiments, the compositions may be electrically conducting or semiconducting.

In certain embodiments, the compositions of the present invention comprises at least one individual layer having first and second surfaces, each layer comprising a substantially two-dimensional array of crystal cells having an empirical formula Ti<NUM>C<NUM> , with at least one surface coated with a coating comprising a hydroxide, an oxide, a sub-oxide, or a combination thereof. In other embodiments, the coating comprises fluorine or fluoride.

In other embodiments, the crystalline composition comprises at least one individual layer having first and second surfaces, each layer comprising a substantially two-dimensional array of crystal cells having an empirical formula Ta<NUM>C<NUM>, with at least one surface coated with a coating comprising a hydroxide, an oxide, a sub-oxide, or a combination thereof.

In still other embodiments, the crystalline composition comprises at least one individual layer having first and second surfaces, each layer comprising a substantially two-dimensional array of crystal cells having an empirical formula (CrxVx)<NUM>C<NUM> (including where x = y = ½) with at least one surface coated with a coating comprising a hydroxide, an oxide, a sub-oxide, or a combination thereof.

As described above, certain additional embodiments provide MXene compositions which exhibit conductive or semi-conductive behavior, as well as those electronic devices (e.g., transistors, where the use of graphene and MoS<NUM> has been successfully demonstrated) which incorporate such compositions so as to take advantage of this property. Further, it is shown that variations in the nature of the surface coating effects that behavior, as shown by density functional theory (DFT) calculations (methods described in Example <NUM>, below) (<FIG>). For example, the calculated band structure of a single Ti<NUM>C<NUM> layer resembles a typical semi-metal with a finite density of states at the Fermi level. Indeed, the resistivity of the thin disk shown in <FIG> is estimated to about an order of magnitude higher than the same disc made with unreacted Ti<NUM>AlC powders, which translates to a resistivity of ≈ <NUM>µΩm. By contrast, when terminated with OH and F groups, the band structure has a semiconducting character with a clear separation between valence and conduction bands by <NUM> eV and <NUM> eV, respectively (<FIG>), thereby supporting the conclusion that it is possible to tune the electronic structure of exfoliated MAX layers - or MXene compositions - by varying the functional groups. Such further modifications of the functional groups themselves may provide additional flexibility in this regard.

Additional embodiments provide for the use or incorporation of MXene compositions into other materials, or the incorporation of other materials within them. For example, various embodiments provide polymer composites into which a MXene composition is incorporated. More particularly, further embodiments provide polymer composite compositions wherein the MXene compositions comprises between amounts in the range of about <NUM> wt% to about <NUM> wt%, relative to the combined weight of the polymer and MXene composition. Still other embodiments provide that the MXene composition is present in a range whose lower amount is about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM> wt% and the upper amount is about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, or about <NUM> wt%, relative to the combined weight of the polymer and the MXene composition comprising a polymer.

The polymer composite may be comprised of organic polymers, more specifically thermoset or thermoplastic polymers or polymer resins, elastomers, or mixtures thereof. Various embodiments include those wherein the polymer or polymer resin contains an aromatic or heteroaromatic moiety, for example, phenyl, biphenyl, pyridinyl, bipyridinyl, naphthyl, pyrimidinyl, including derivative amides or esters of terephthalic acid or naphthalic acid. Other embodiments provide that the polymer or polymer resin comprises polyester, polyamide, polyethylene, polypropylene, polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether etherketone (PEEK), polyamide, polyaryletherketone (PAEK), polyethersulfone (PES), polyethylenenimine (PEI), poly (p-phenylene sulfide) (PPS), polyvinyl chloride (PVC), fluorinated or perfluorinated polymer (such as a polytetrafluoroethylene (PTFE or TEFLON®), polyvinylidene difluoride (PVDF), a polyvinyl fluoride (PVF or TEDLAR®)) (TEFLON® and TEDLAR® are registered trademarks of the E. DuPont de Nemours Company, of Wilmington, Delaware).

It is believed that the planar nature of MXene layers may be well suited to organizing themselves in those anisotropic polymers, for example having planar moieties, e.g., aromatic moieties, especially when (but not only when) these planar organic moieties are directionally oriented to be parallel in a polymer composite composition. Such embodiments include the inclusion of MXene compositions into liquid crystal polymers. Moreover, the ability to produce MXene compositions having both hydrophobic and hydrophilic pendants provides for compatibility with a wide-ranging variety of polymer materials.

Additional embodiments of the present invention provide polymer composites, including those wherein the polymer composite is in a form having a planar configuration - for example, a film, sheet, or ribbon -- comprising a MXene layer or multilayer composition. Still further embodiments provide such polymer composites wherein the two-dimensional crystal layers of the MXene materials are aligned or substantially aligned with the plane of a polymer composite film, sheet, or ribbon, especially when the organic polymers are oriented in the plane of that film, sheet, or ribbon.

The large elastic moduli predicted by ab initio simulation, and the possibility of varying their surface chemistries (beyond those exemplified herein, which are terminated by hydroxyl and/or fluorine groups) render these nanosheets attractive as polymer composite fillers. For example, the elastic modulus of a single, exfoliated Ti<NUM>C<NUM>(OH)<NUM> layer, along the basal plane, is calculated to be around <NUM> GPa, which is within the typical range of transition metal carbides and significantly higher than most oxides and clays (see, e.g., <NPL>). And while the <NUM> GPa value is lower than that of graphene (e.g., as described in <NPL>), the ability to match the character of the MXene layered materials with that of the polymer matrix, as described above, is expected to ensure better bonding to and better dispersion in polymer matrices when these MXene layers are to be used as reinforcements in polymer composites. It is also important to note here that the functionalized Ti<NUM>C<NUM> sheets described herein were much more stable than graphene sheets under the <NUM> kV electron beam in the TEM.

Accordingly, still further embodiments provide that the MXene composition-filled composite polymers, especially when these polymer composites have a planar configuration, such as that of film, sheet, or ribbon, especially an oriented film, sheet, or ribbon, exhibit a flexural strength (bending rigidity) and/or stiffness than that of the corresponding film, sheet, or ribbon of the same polymer without the MXene composition. In some embodiments, this greater flexural strength and/or stiffness is independently at least <NUM>%, at least <NUM>%, or at least <NUM>% higher than the flexural strength or toughness than that exhibited by an otherwise equivalent, but unfilled material.

Thus far, the compositions of the invention have been described in terms of having individual layers having first and second surfaces, each layer comprising a two-dimensional array of crystal cells. However, the invention provides for stacked assemblies of at least two layers having first and second surfaces, each layer comprising a two-dimensional array of crystal cells, each crystal cell having the empirical formula of Mn+<NUM>Xn, such that each X is positioned within an octahedral array of M; wherein M is a Group IIIB, IVB, VB, or VIB metal; each X is C or N; and n = <NUM>, <NUM>, or <NUM>; and wherein the layers are characterized as having an average surface area and interlayer distance.

In various embodiments of these stacked assemblies, each layer may retain the characteristics as described above, but be held in place or edge-wise connected such that the assembly has up to about <NUM> layers of crystal layers. In various embodiments, these number of crystal layers in these assemblies may be described as having a range having a lower end of <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM> and an upper range of about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, and about <NUM>, with exemplary ranges of <NUM> to about <NUM>, <NUM> to about <NUM>, <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>.

In various embodiments, the composite layers characterized as having an average surface area. While the bounds of these areas are not necessarily limited to any particular values, in certain preferred embodiments, the average surface or planar area is defined by a range of areas, with individual embodiments having a lower range value of about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, , or about <NUM><NUM>, and having an upper range value of about <NUM>,<NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, or about <NUM><NUM>, with exemplary ranges of about <NUM><NUM> to about <NUM><NUM>, of about <NUM><NUM> to about <NUM><NUM>, of about <NUM><NUM> to about <NUM><NUM>, of about <NUM><NUM> to about <NUM><NUM>, <NUM><NUM> to about <NUM><NUM>, or about <NUM><NUM> to about <NUM><NUM>.

In other preferred embodiments, the average surface or planar area is defined by a range of areas, with individual embodiments having a lower range value of about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, or about <NUM><NUM> and having an upper range value of about <NUM>,<NUM><NUM> , about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, about <NUM><NUM>, or about <NUM><NUM>, with exemplary ranges of about <NUM><NUM> to about <NUM><NUM>, of about <NUM><NUM> to about <NUM><NUM>, of about <NUM><NUM> to about <NUM><NUM>, of about <NUM><NUM> to about <NUM><NUM>, <NUM><NUM> to about <NUM><NUM>, or about <NUM><NUM> to about <NUM><NUM>.

While the surface of these composite layer may be of any shape, it is convenient to describe such shapes as having a major and minor planar dimension (or x-axis and y-axis dimensions, using the envisioned x-y plane as described above). For example, if a quadrilateral or pseudo-quadrilateral shape, the major and minor dimension is the length and width dimensions. In preferred embodiments, the ratio of the lengths of the major and minor axes is in the range of about <NUM> to about <NUM> (<NUM>:<NUM>) to about <NUM> to about <NUM> (<NUM>:<NUM>), about <NUM> to about <NUM> (<NUM>:<NUM>) to about <NUM> to about <NUM> (<NUM>:<NUM>), more preferably about <NUM> to about <NUM> (<NUM>:<NUM>) to about <NUM> to about <NUM> (<NUM>:<NUM>), or about <NUM> to about <NUM> (<NUM>:<NUM>) to about <NUM> to about <NUM> (<NUM>:<NUM>).

Additionally, in various embodiments, the interlayer distances (i.e., the distances between the composite crystal layers) in these stacked assemblies is in the range of about <NUM> to about <NUM>, preferably in the range of about <NUM> to about <NUM>. When prepared by the methods described below (i.e., removing the labile A-phase elements from MAX phase materials, see below), these interlayer distances may be consistent with the atomic radii of the removed elements. For example, the atomic diameter of Al is about <NUM> and that of Sn about <NUM>.

Certain embodiments of the present invention provide stacked assemblies which are capable of intercalating atoms and/or ions between at least some of the layers of two-dimensional crystal layers. For example, these atoms and/or ions can be metal or metalloid atoms or ions, including alkali, alkaline earth, and transition metals. In some embodiments, these are alkali metal atoms and/or ions (e.g., Li, Na, K, and/or Cs); and most preferably lithium. In some embodiments, these atoms and/or ions are able to move into and out of the stacked assemblies.

These multilayer structures or assemblies may be used for the same types of applications described above for the MXene layer compositions.

Additionally, the ability to intercalate lithium atoms and/or ions, together with the electrical properties of the MXene layers described above, provides the opportunities that these stacked assemblies may be used as energy storing devices (e.g., anodes) comprising these intercalated stacked composition, or the energy storage devices themselves, for example, batteries, comprising these elements.

Density functional theory (DFT) calculations at <NUM> and in Li-rich environments show that the formation of Ti<NUM>C<NUM>Li<NUM> as a result of the intercalation of Li into the space vacated by the Al atoms (<FIG>) assuming reaction <MAT> has an enthalpy change of <NUM> eV. One possible reason for the positive value maybe the fact that Li has an atomic radius of <NUM> pm, whereas that of Al is <NUM> pm. The structure shown in <FIG> would provide a capacity of <NUM> mAhg-<NUM>, which is comparable to the <NUM> mAhg-<NUM> of graphite for (LiC<NUM>).

Accordingly, various embodiments of the present invention include Li-ion batteries (<FIG>) and pseudo-capacitor electrodes, wherein the MXene layers or assemblies replace layered transition metal oxides, which show useful red-ox properties and Li-intercalation, but which have lower electrical conductivities than described herein for the MXene materials.

The ability of MXene to intercalate ions, including lithium ions, so as to allow these materials to act as Li-ion batteries and/or pseudo-capacitor electrodes, is shown in Example <NUM>, below.

In addition to the compositions of the MXene materials, various embodiments provide for the preparation of such materials. Certain embodiments provide methods of preparing compositions comprising: (a) removing substantially all of the A atoms from a MAX-phase composition having an empirical formula of Mn+<NUM>AXn; wherein M is an early transition metal or a mixture thereof, wherein A is a so-called A-group element (typically described, see below, as including Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, and Pb); wherein X is C or N, or a combination thereof; and wherein n = <NUM>, <NUM>, or <NUM> so as to provide a free standing composition comprising a framework of a substantially two-dimensional composite crystal layer having first and second surfaces.

MAX phase compositions are generally recognized as comprising layered, hexagonal carbides and nitrides have the general formula: Mn+<NUM>AXn, (MAX) where n = <NUM> to <NUM>, in which M is typically described as an early transition metal (comprising a Group IIIB, IVB, VB, or VIB metal), A is described as an A-group (mostly IIIA and IVA, or groups <NUM> and <NUM>) element and X is either carbon and/or nitrogen. See, e.g., <NPL>); <NPL>). While Ti<NUM>AlC<NUM> is among the most widely studied of these materials, more than <NUM> MAX phases are currently known to exist and are useful in the present invention. While not intending to be limiting, representative examples of MAX phase materials useful in the present invention include: (<NUM>) Ti<NUM>CdC, Sc<NUM>InC, Ti<NUM>AlC, Ti<NUM>GaC, Ti<NUM>InC, Ti<NUM>TlC, V<NUM>AlC, V<NUM>GaC, Cr<NUM>GaC, Ti<NUM>AlN, Ti<NUM>GaN, Ti<NUM>InN, V<NUM>GaN, Cr<NUM>GaN, Ti<NUM>GeC, Ti<NUM>SnC, Ti<NUM>PbC, V<NUM>GeC, Cr<NUM>AlC, Cr<NUM>GeC, V<NUM>PC, V<NUM>AsC, Ti<NUM>SC, Zr<NUM>InC, Zr<NUM>TlC, Nb<NUM>AlC, Nb<NUM>GaC, Nb<NUM>InC, Mo<NUM>GaC, Zr<NUM>InN, Zr<NUM>TlN, Zr<NUM>SnC, Zr<NUM>PbC, Nb<NUM>SnC, Nb<NUM>PC, Nb<NUM>AsC, Zr<NUM>SC, Nb<NUM>SC, Hf<NUM>InC, Hf<NUM>TlC, Ta<NUM>AlC, Ta<NUM>GaC, Hf<NUM>SnC, Hf<NUM>PbC, Hf<NUM>SnN, Hf<NUM>SC; (<NUM>) Ti<NUM>AlC<NUM>, V<NUM>AlC<NUM>, Ti<NUM>SiC<NUM>, Ti<NUM>GeC<NUM>, Ti<NUM>SnC<NUM>, Ta<NUM>AlC<NUM>, and (<NUM>) Ti<NUM>AlN<NUM>, V<NUM>AlC<NUM>, Ti<NUM>GaC<NUM>, Ti<NUM>SiC<NUM>, Ti<NUM>GeC<NUM>, Nb<NUM>AlC<NUM>, and Ta<NUM>AlC<NUM>. Solid solutions of these materials can also be used as described herein (e.g., see Example <NUM>).

MAX phase materials are themselves known to exist as laminated structures with anisotropic properties. These materials are layered hexagonal (space group P6<NUM>/mmc), with two formula units per unit cell (<FIG>). Near close-packed M-layers are interleaved with pure A-group element layers, with the X-atoms filling the octahedral sites between the former.

Within the MAX phase structure, the Mn+<NUM>Xn layers are chemically quite stable, possibly owing to the strength of the M-X bond. By comparison, the A-group atoms are the most reactive species, reflective of their relatively weak binding. For example, heating Ti<NUM>SiC<NUM> in a C-rich atmosphere or heating in molten cryolite or molten aluminum is known to result in the loss of Si and the formation of TiCx. In the case of cryolite, the vacancies that form lead to the formation of a partially ordered cubic TiC<NUM> phase. In both cases, the high temperatures lead to a structural transformation from a hexagonal to a cubic lattice and a partial loss of layering. In some cases, such as Ti<NUM>InC, simply heating in vacuum at ≈ <NUM>, results in loss of the A-group element and TiCx formation. Removing of both the M and A elements from MAX structure by high temperature chlorination results in a porous carbon known as carbide derived carbon with useful and unique properties.

By contrast, the present methods surprisingly provide for the preparation of compositions comprising layers or stacked assemblies of at least one layer having first and second surfaces, each layer comprising a substantially two-dimensional array of crystal cells, each crystal cell deriving from the Mn+<NUM>Xn layers of MAX phase compositions. These compositions are free-standing or can be organized into stacked assemblies of coated crystal layers.

As used herein, the term "removing substantially all of the A atoms from a MAX-phase composition" connotes embodiments wherein at least <NUM> atomic % of the A atoms are removed from a finally recovered sample, relative to the original MAX phase composition. In other more preferred independent embodiments, more than about <NUM> atomic %, more than about <NUM> atomic %, more than about <NUM> atomic %, more than about <NUM> atomic %, more than about <NUM> atomic %, more than about <NUM> atomic %, and more than about <NUM> atomic % of the A atoms are removed from a finally recovered sample, relative to the original MAX phase composition.

Certain embodiments provide a process for removing these A atoms comprising treatment with an acid, preferably a strong acid capable of reacting with the A atoms. Such acids may be organic or inorganic acids, and may be applied in the gas or liquid phase, provided the resulting A-atom product can be removed from the lattice. In this regard, strong acids which include fluorine atoms appear to be especially preferred. Aqueous hydrofluoric acid is among those acids which appear especially useful. However, the skilled artisan will appreciate that any reactant known to react preferentially with the A atoms of a given MAX phase composition, relative to the Mn+<NUM>Xn may also be useful, for example selective chelants. Uses of such reactants are considered within the scope of this invention.

The extraction of the A group layers may be done at room, or even moderate, temperature, for example in the range of about <NUM> to about <NUM>, preferably in temperature ranges wherein the lower temperature is about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM> , about <NUM>, or about <NUM> , and wherein the upper temperature is about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM>. Exemplary examples of ranges include temperatures in the range of about <NUM> to about <NUM>, about <NUM> to about <NUM>, or about <NUM> to about <NUM>. The extractions may be conducted using liquid or gas phase extraction methods. Gas phase reactions are generally to be done at the higher temperatures.

In further embodiments, the chemically treated materials are subjected to sonication, either using ultrasonic or mega sonic energy sources. This sonication may be applied during or after the chemical treatment.

One embodiment of the chemical exfoliation process for one representative material is diagrammatically illustrated in <FIG>, and described further below. In this example, the treatment of Ti<NUM>AlC<NUM> powders for <NUM> in aqueous HF resulted in the formation of exfoliated <NUM>-D Ti<NUM>C<NUM> layers. The term "exfoliated" refers to a process of delaminating the individual (or multiple individual layers) from the stacked assemblies (see, e.g., the second step illustrated in <FIG>). The exposed Ti surfaces appear to be terminated by OH and/or F (see Examples below). While not intending to be bound by the correctness of any single theory or mechanism, based on the experimental information provided below, it appears that the following simplified reactions occur when Ti<NUM>AlC<NUM> is immersed in aqueous HF:.

Ti<NUM>AlC<NUM> + 3HF = AlF<NUM> + <NUM>/<NUM><NUM> + Ti<NUM>C<NUM>     (<NUM>).

Ti<NUM>C<NUM> + <NUM><NUM>O = Ti<NUM>C<NUM>(OH)<NUM> + H<NUM>     (<NUM>).

Ti<NUM>C<NUM> + 2HF = Ti<NUM>C<NUM>F<NUM> + H<NUM>     (<NUM>).

Reaction (<NUM>) appears to be a necessary step, at least to the extent that it provides for the extraction of AlF<NUM> in some form (e.g., perhaps some soluble derivative, such as H<NUM>AlF<NUM>), followed or accompanied by reaction (<NUM>) and/or (<NUM>). Evidence consistent with the aforementioned reactions and that they result in the exfoliation of <NUM>-D Ti<NUM>C<NUM> layers, with OH and/or F surface groups is presented below. Reactions (<NUM>) and (<NUM>) are simplified in that they assume the terminations are OH or F, respectively, when in fact they may be a combination of both.

Non-limiting examples of MXene compositions prepared by chemical exfoliation are illustrated in <FIG>.

In other embodiments, the exfoliation can be accomplished electrochemically. In various embodiments, MAX phase materials are selectively exfoliated to form the corresponding MXene by the application of potentiostatic or galvanostatic polarization. See Example <NUM>, below.

It should also be recognized that, in addition to those embodiments described for the compositions provided above, other embodiments provide for compositions provided by the methods of preparation described herein. For example, those composition obtained from subjecting a MAX phase material to a chemical exfoliation process, said exfoliation process comprising treatment with aqueous HF and sonication, wherein a substantial portion of the A atoms are removed should also be considered.

Powder of Ti<NUM>AlC<NUM> was prepared by ball-milling Ti<NUM>AlC (> <NUM> wt. % <NUM>-ONE-<NUM>, Voorhees, NJ) and TiC (<NUM>% Johnson Matthey Electronic, NY) powders in a <NUM>:<NUM> molar ratio for <NUM> using zirconia balls. The mixture was heated to <NUM> for <NUM> under argon, Ar. The resulting loosely held compact was crushed in a mortar and pestle. Roughly <NUM> of powders are then immersed in ≈ <NUM> of a <NUM> % concentrated hydrofluoric acid, HF, (Fisher Scientific, Fair Lawn, NJ) solution at room temperature for <NUM>. The resulting suspension was then washed several times using de-ionized water and centrifuged to separate the powders. In some cases, to align the flakes and produce free-standing discs, the treated powders were cold pressed at a load corresponding to a stress of about <NUM> GPa in a steel die.

X-ray diffraction (XRD) patterns were obtained with a powder diffractometer (Siemens D500, Germany) using Cu Kα radiation, and a step scan of <NUM>° and <NUM> per step. Si powder was added to some samples as an internal standard. A scanning electron microscope, (SEM, Zeiss Supra 50VP, Germany) was used to obtain high magnification images of the treated powders. Transmission electron microscopes, TEMs, (JEOL JEM-2100F and JEM <NUM>, Japan; FEI, Tecnai G2 TF20UT FEG, Netherlands) operating at <NUM> kV were used to characterize the exfoliated powders. Chemical analysis in the TEM was carried out using an ultra-thin window X-ray energy dispersive spectrometer, EDAX (EDAX, Mahwah, NJ). The TEM samples were prepared by deposition of the flakes - from an isopropanol suspension - on a lacey-<NUM> mesh carbon-coated copper grid. Raman spectroscopy of the cold pressed samples was carried out on a microspectrometer (inVia, Renishaw plc, Gloucestershire, UK) using an Ar ion laser (<NUM>) and a grating with <NUM> lines/mm. This corresponds to a spectral resolution of <NUM>-<NUM> and a spot size of <NUM> in the focal plane. X-ray photoelectron spectroscopy, XPS, (PHI <NUM>, ULVAC-PHI, Inc. , Japan) was used to analyze the surfaces of samples before and after exfoliation.

Theoretical calculations were performed by density functional theory (DFT) using the plane-wave pseudo-potential approach, with ultrasoft pseudopotentials and Perdew Burke Ernzerhof (PBE) exchange - Wu-Cohen (WC) correlation functional, as implemented in the CASTEP code in Material Studio software (Version <NUM>). A 8x8x1 Monkhorst-Pack grid and planewave basis set cutoff of <NUM> eV were used for the calculations. Exfoliation was modeled by first removing Al atoms from the Ti<NUM>AlC<NUM> lattice. Exposed Ti atoms located on the bottom and top of the remaining Ti<NUM>C<NUM> layers were saturated by OH (<FIG>) or F groups followed by full geometry optimization until all components of the residual forces became less than <NUM> eV/Å. Equilibrium structures for exfoliated layers were determined by separating single Ti<NUM>C<NUM> layers by a <NUM> thick vacuum space in a periodic supercell followed by the aforementioned full geometry optimization. Band structures of the optimized materials were calculated using a k point separation of <NUM>. 015Å-<NUM>. The elastic properties of the <NUM>-D structures were calculated by subjecting the optimized structure to various strains and calculating the resulting second derivatives of the energy density.

XRD spectra of the initial Ti<NUM>AlC-TiC mixture after heating to <NUM> for <NUM> resulted in peaks that corresponded mainly to Ti<NUM>AlC<NUM> (bottom curve in <FIG>). When the Ti<NUM>AlC<NUM> powders were placed into the HF solution, bubbles, believed to be H<NUM>, were observed suggesting a chemical reaction. Ultrasonication of the reaction products in methanol for <NUM> resulted in significant weakening of the peaks and the appearance of an amorphous broad band around <NUM>° (top spectrum in <FIG>). In other words, exfoliation leads to a loss of diffraction signal in the out-of-plane direction, and the non-planar shape of the nanosheets results in broadening of peaks corresponding to in-plane diffraction. When the same powders were cold pressed at <NUM> GPa, into free-standing, <NUM> thick and <NUM> diameter discs (<FIG>), their XRD showed that most of the non-basal plane peaks of Ti<NUM>AlC<NUM> - most notably the most intense peak at ≈ <NUM>° - disappear (curve labeled "HF etched" in <FIG>). On the other hand, the (<NUM>) peaks, such as the (<NUM>), (<NUM>) and (<NUM>), broadened, lost intensity, and shifted to lower angles compared to their location before treatment. Using the Scherrer formula, as described in B. Cullity, Elements of X-ray diffraction, Addison-Wesley <NUM>, the average particle dimension in the [<NUM>] direction after treatment is estimated to be <NUM><NUM>±<NUM>, which corresponds to roughly ten Ti<NUM>C<NUM>(OH)<NUM> layers. To identify the peaks we simulated XRD patterns of hydroxylated, viz. Ti<NUM>C<NUM>(OH)<NUM>, (curve labeled "Ti<NUM>C<NUM>(OH)<NUM>" in <FIG>) and fluorinated, Ti<NUM>C<NUM>F<NUM>, structures (curved labeled as such in <FIG>). Clearly, both were in good agreement with the XRD patterns of the pressed sample (curve labeled "HF etched" in <FIG>), the agreement was better with the former. The disappearance of the most intense diffraction peak of Ti<NUM>AlC<NUM> at <NUM>° and the good agreement between the simulated XRD spectra for Ti<NUM>C<NUM>(OH)<NUM> and the experimental results provides strong evidence of the formation of the latter. The presence of OH groups after treatment was confirmed by FTIR.

Further DFT geometry optimization of the hydroxylated (<FIG>) and fluorinated structure resulted in <NUM>% and <NUM>% expansion of the original Ti<NUM>AlC<NUM> lattice, respectively, as observed. If Al were simply removed, and not replaced by functional groups, the DFT optimization caused the structure to contract by <NUM> %, which is not observed. The increase of the c-lattice parameters upon reaction (<FIG>) is thus strong evidence for the validity of reactions <NUM>, <NUM>.

Raman spectra of Ti<NUM>AlC<NUM>, before and after HF treatment, are shown in <FIG>. Peaks II, III, and IV vanished after treatment, while peaks VI and VII, merged, broadened and downshifted. Such downshifting has been observed in Raman spectra of very thin layers of inorganic layered compounds, and is characteristic of such materials. See, e.g., <NPL>. The line broadening, and the spectral shifts in the Raman spectra are consistent with exfoliation and are in agreement with the broadened XRD profiles. In analogy with Ti<NUM>SiC<NUM> (see <NPL>) peaks I to III in <FIG> can be assigned to Al-Ti vibrations, while peaks V and VI involve only Ti-C vibrations. The fact that only the latter two exist after etching confirms both the mode assignments, but more importantly the loss of Al from the structure. Note that peaks V and VI are combined, broadened and downshifted after reaction.

The Ti 2p XPS spectra, before and after treatment, are shown in <FIG>. The C <NUM> and Ti 2p peaks before treatment match previous work on Ti<NUM>AlC<NUM>. See, e.g., <NPL>. The presence of Ti-C and Ti-O bonds was evident from both spectra, indicating the formation of Ti<NUM>C<NUM>(OH)<NUM> after treatment. The Al and F peaks (not shown) were also observed and their concentrations were calculated to be around <NUM> at. % and <NUM> at. %, respectively. Aluminum fluoride (AlF<NUM>) - a reaction product, see below - can probably account for most of the F signal seen in the spectra. The O <NUM> main signal (not shown at -<NUM>-<NUM>) suggest the presence of OH group. See, e.g., <NPL>.

A SEM image of a ≈ <NUM><NUM> Ti<NUM>AlC<NUM> particle (<FIG>) shows how the basal planes fan out and spread apart as a result of the HF treatment. EDAX of the particles showed them to be comprised of Ti, C, O and F, with little, or no, Al. This implies that the Al layers were replaced by oxygen (i.e. OH) and/or F. Note that the exfoliated particles maintained the pseudo-ductility of Ti<NUM>AlC<NUM> and could be easily cold press into freestanding disks (<FIG>). This property can prove crucial in some potential applications, such as anodes for Li-ion batteries, as described above.

TEM analysis of exfoliated sheets (<FIG>) shows them to be quite thin and transparent to electrons since the carbon grid is clearly seen below them. This fact strongly suggests a very thin foil, especially considering the high atomic number of Ti. The corresponding selected area diffraction, SAD (inset in <FIG>) shows the hexagonal symmetry of the basal planes. EDAX of the same flake showed the presence of Ti, C, O, and F. <FIG> show cross-sections of exfoliated single- and double-layer MXene sheets. <FIG>show high-resolution TEM micrographs and a simulated structure of two adjacent OH-terminated Ti<NUM>C<NUM> sheets, respectively. The experimentally observed interplanar distances and angles are found to be in good agreement with the calculated structure. <FIG>show stacked multilayer MXene sheets. The exfoliated layers can apparently also be rolled into conical shapes (<FIG>); some are bent to radii of < <NUM> (<FIG>). Note that if Al atoms had been replaced by C atoms, the concomitant formation of strong Ti-C bonds - as when, for example, Ti<NUM>SiC<NUM> reacts with cryolite at <NUM>- exfoliation would not have been possible. It follows that the reaction must have resulted in a solid in which the Ti-Al bonds are replaced by much weaker hydrogen or van der Waals bonds. This comment notwithstanding, the EDAX results consistently show the presence of F in the reaction products implying that, as noted above, the terminations are most likely a mixture of F and OH. The presence of up to <NUM> at. % F has also been confirmed using XPS. In the latter case, however, some of it could originate from AlF<NUM> residue in the sample.

Lastly, it is instructive to point out the similarities between MXene and graphene such as,.

Also, as cross-sectional TEM (<FIG>) shows, some nanosheets were bent to radii < <NUM> without fracture, which is evidence for strong and flexible Ti<NUM>C<NUM> layers. Similar scrolls were produced by sonication of graphene. See, e.g., <NPL>; <NPL>. It is possible that the sonication used for exfoliation caused some nanosheets to roll into scrolls, as schematically shown in <FIG>.

Ta<NUM>AlC<NUM> powder (ca. <NUM>) was immersed in approximately <NUM> of a <NUM> % concentrated hydrofluoric acid, HF, (Fisher Scientific, Fair Lawn, NJ) solution at room temperature for <NUM>. The resulting suspension was then washed several times using deionized water and centrifuged to separate the powders.

XRD analysis of the resulting material showed sharp peaks corresponding only to TaC, known to be an impurity in the starting material (i.e., in addition to peaks attributable to TaC, the XRD spectrum contained only broad peaks centered around <NUM> values of ca. <NUM>° and <NUM>-<NUM>°). However, the XRD spectrum of a sample obtained by cold pressing the resulting material, showed strong, albeit broadened peaks at about <NUM> = <NUM>° and <NUM>° (apparently shifted from <NUM> - <NUM> in XRD of Ta<NUM>AlC<NUM>), smaller peaks at about <NUM> = <NUM>° (apparently shifted from <NUM> - <NUM>° in XRD of Ta<NUM>AlC<NUM>), <NUM>°, and <NUM>°, and broad, albeit low intensity peaks centered at about <NUM> = <NUM>-<NUM>° and <NUM>°, none of which appear to correspond to TaC, but which are interpreted as being consistent with simulated spectra of Ta<NUM>C<NUM>(OH)<NUM>. Compared with the XRD spectra of the original XRD spectrum of Ta<NUM>AlC<NUM> (and its an accompanying pattern simulated by CrystalMaker®), the XRD pattern of the cold-pressed material also showed no evidence of otherwise distinguishing peaks at <NUM> - <NUM>°, <NUM>°.

An illustrative XRD spectrum for an exfoliated, characterized to be Ta<NUM>C<NUM>(OH)x(F)y, are shown in <FIG>.

Ti<NUM>AlC powder (Kanthal Corp. , Sweden) was immersed in approximately <NUM> of a <NUM> % concentrated hydrofluoric acid, HF, (Fisher Scientific, Fair Lawn, NJ) solution at room temperature for <NUM>. The resulting suspension was then washed several times using deionized water and centrifuged to separate the powders. SEM micrographs and XRD spectra of the resulting materials are shown in <FIG>.

The TiNbAlC powders were made by mixing elemental titanium, Ti (Alfa Aesar, Ward Hill, USA, <NUM> wt % purity; <NUM> mesh), niobium, Nb (Atlantic Equipment Engineers, Bergenfield, USA, <NUM> wt % purity; <NUM> mesh), and the same Al and C used above, in the molar ratio of <NUM>:<NUM>:<NUM>:<NUM>, respectively, in a ball mill for <NUM>. The powders were then heated at the rate of <NUM> / min in a tube furnace to <NUM> for <NUM> under flowing Ar. After cooling to room temperature, powders were processed as described above (see Table <NUM>). SEM micrographs and XRD spectra of the resulting materials are shown in <FIG>.

The XRD patterns for TiNbAlC, before and after HF treatment (<FIG>), show that the intensity of the TiNbAlC peaks decreased significantly after HF treatment (considering that <NUM> wt% Si was used as an internal reference) and a new broad peak at ≈<NUM>° <NUM> appeared after cold pressing. Here again a shoulder at a larger d spacing compared to the main peak is observed. The latter is most likely due to some exfoliated (Ti<NUM>,Nb<NUM>)<NUM>AlC<NUM> that was present as a second phase in the starting powder. SEM micrographs (<FIG>) clearly show exfoliated TiNbAlC particles. TEM micrographs, after sonication (not shown), show thin sheets composed of Ti, Nb, C, O, and F in an atomic ratio that EDX shows to be <NUM>:<NUM>:<NUM>:<NUM>:<NUM>, respectively. HRTEM of a TiNbC layer (not shown) and its corresponding SAED again show hexagonal symmetry. At <NUM>, the perpendicular separation of the (<NUM>) lattice planes results in an a lattice constant of <NUM>. EELS for TiNbAlC after HF treatment and confirms the presence of Ti, Nb, C, F (not shown), and O, but no Al.

(V<NUM>/<NUM>Cr<NUM>/<NUM>)<NUM>AlC<NUM> powder was made by ball milling powders of <NUM>. 2Al+2C (molar ratios) for <NUM> hours, then heating the mixture under Ar to <NUM>, soaking at this temperature for <NUM> hours, and cooling to room temperature, after which a powder was obtained from the sintered mass using diamond coated milling bit. The powders were then exfoliated by stirring them in <NUM>% aqueous HF at room temperature for <NUM> hr (<NUM> gm powder in <NUM> acid). SEM micrographs and XRD spectra of the resulting materials are shown in <FIG>.

Ti<NUM>Al(CN) powder was prepared was made by ball milling Ti:AlN:C = <NUM>:<NUM>:<NUM> (molar ratios) for <NUM> hours, then heating the mixture at <NUM>/min to <NUM>, holding <NUM> hours, then cooling, all under Argon (C and Ti powders were purchased from Alfa Aesar, Ward Hill, MA). AlN powder was purchased from Sigma-Aldrich. The resulting material was crushed using mortar and pestle. The resulting powder was immersed and stirred in <NUM> % concentrated hydrofluoric acid, HF, (Fisher Scientific, Fair Lawn, NJ) solution at room temperature for <NUM>. The resulting suspension was then washed several times using deionized water and centrifuged to separate the powders. SEM micrographs and XRD spectra of the resulting materials are shown in <FIG>.

Starting with Ti<NUM>AlC<NUM> powders as a representative material, a series of experiments were conducted to determine the effects of various process parameters on the chemical exfoliation of MAX phase materials to form the corresponding MXene compositions. In evaluating the effect of temperature on exfoliation, Ti<NUM>AlC<NUM> powders were stirred in <NUM>% aqueous HF for <NUM> hours at different temperatures (e.g., <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>). The effect of processing time was studied by stirring Ti<NUM>AlC<NUM> powders with <NUM>% aqueous HF for <NUM> hours at room temperature over the time range of <NUM> to <NUM> hours. In testing the effect of initial particle size, Ti<NUM>AlC<NUM> powders were crushed in ball milling machine and separated with sieves first, then exfoliated by stirring with <NUM>% aqueous HF at room temperature for <NUM> hours. <FIG>, <FIG>, <FIG>, and <FIG> illustrate the effect of HF temperature, time of treatment, and initial particle size, respectively. The specific conditions employed, where different than those described above, are provided in each figure.

Ti<NUM>SnC was made by ball milling 2Ti+Sn+C (molar ratios) for <NUM> hr, then heating the mixture at a ramp rate of <NUM>/minute to <NUM>, holding for <NUM> hours and cooling to room temperature, all under Ar atmosphere. The resulting material was crushed using mortar and pestle to form a powder (Ti, Sn, and C powders were purchased from Alfa Aesar, Ward Hill, MA). Exfoliation of Ti<NUM>SnC was demonstrated by selectively electrochemically removing Sn upon application of a repeated sequence composed of a short cathodic polarization (either potentiostatic or galvanostatic) followed by a long anodic polarization (either potentiostatic or galvanostatic) to an electrochemical system (see <FIG> for a representative set of conditions; SWPP = square wave potential polarization; SWCP = square wave current polarization. Δmtot refers to the loss in sample weight as a result of the electrochemical treatment). In this system, a hot pressed sample of Ti<NUM>SnC was used as the anode, and Pt was used as the reference and working electrode. The electrolyte was either aqueous <NUM> or <NUM> HCl, and high purity Ar gas was constantly purged through the working solution to maintain an inert atmosphere.

The rapid electrochemical corrosion of the anode material resulted in the formation of a finely dispersed powder which was collected at the bottom of the reaction vessel, washed with deionized water, and dried. The dried powder was subjected to a series of tests, the results of which are shown in <FIG>. <FIG> shows the dramatic difference in Raman spectra between the product (curves a and b) and the starting material (curves c-e), consistent with the changes seen in other similar transformations (compare, for example, the curves in <FIG>). Similarly, changes in the XRD spectra (<FIG>) are indicative of the absence of starting material. Finally, EDX spectra shown in <FIG>(A-C) show that the powder is devoid of appreciable Sn, confirming its elimination (Note: the presence of O in these EDX spectra is consistent with a surface coating of the MXene comprising oxide or hydroxide. The presence of Si in the spectra is attributed to the substrate used in the measurement.

The electrochemical behavior of MXene compositions (exfoliated MX phase compositions) was compared to the corresponding MAX phase material in lithium ion battery tests. [The electrolyte used was a mixture of ethylene carbonate and dimethyl carbonate (EC/DMC) with lithium hexafluorophosphate (LiPF<NUM>). After cell assembly inside a glove box, both Galvanostatic (GV) and Cyclic Voltammetry (CV) tests were used to study the electrochemical behavior of MAX phases in Li batteries. These electrochemical tests were carried out using a BioLogic VMP-<NUM> potentiostat/galvanostat. ] Electrodes were prepared using MAX phase and MXene compositions in a number of electrode configurations, including (a) cold pressed electrode with neither binder nor carbon black; (b) film of powder on copper foil with binder and without carbon black; (c) film f powder on copper foil with binder and carbon black; and (d) film of carbon black alone with a polyvinylidene-difluoride, PVDF, binder. CV and GV techniques were used to characterize the electrochemical nature of the resulting electrodes / cells. <FIG>(A/B) shows the results where the performance of electrodes prepared using carbon black (CB) and binder, comparing the additional presence of Ti<NUM>AlC<NUM> and exfoliated Ti<NUM>AlC<NUM>; i.e., MXene Ti<NUM>C<NUM>(OH)x(F)y. As shown in <FIG>, the capacity of the MXene containing compositions showed significantly higher capacity an order of magnitude higher) than a comparable electrode made from the corresponding MAX phase material. It is known that lithium capacity in MAX phase materials is extremely low, owing to the lack of space between the layers into which ions may migrate. The significant increase in capacity with the electrodes containing the MXene composition results are consistent with the migration / intercalation of lithium within the stacked layers of MXene.

Testing comparable to that described in Example <NUM> with Ti<NUM>C<NUM> (derived from Ti<NUM>AlC<NUM>) was also done with Ti<NUM>C derived from Ti<NUM>AlC. As described below, testing demonstrated the insertion of Li into a new two-dimensional (<NUM>-D) layered Ti<NUM>C-based material (MXene) with an oxidized surface, formed by etching Al from Ti<NUM>AlC in HF at room temperature. Nitrogen sorption of treated powders showed desorption hysteresis consistent with the presence of slit-like pores. At <NUM><NUM>·g-<NUM>, the specific surface area was an order of magnitude higher than untreated Ti<NUM>AlC. Cyclic voltammetry exhibited lithiation and delithiation peaks at <NUM> V and <NUM> V vs. Li+/Li, respectively. At C/<NUM>, the steady state capacity was <NUM> mAh·g-<NUM>; at 1C, it was <NUM> mAh·g-<NUM> after <NUM> cycles; at 3C, it was <NUM> mAh·g-<NUM> after <NUM> cycles; at 10C, it was <NUM> mAh·g-<NUM> after <NUM> cycles.

Pre-reacted, -<NUM> mesh, Ti<NUM>AlC powders were commercially obtained (<NUM>-ONE-<NUM>, Voorhees, NJ, > <NUM> wt. The exfoliation process was carried by immersing the Ti<NUM>AlC powder in diluted (<NUM>%) hydrofluoric acid, HF, (Fisher Scientific, Fair Lawn, NJ) for <NUM> at room temperature, as described above. The materials were characterized by SEM (Zeiss Supra 50VP, Germany), EDS (Oxford Inca X-Sight, Oxfordshire, UK), and gas sorption analysis (Quantachrome Autosorb-<NUM> with N<NUM> adsorbate) as described above (i.e., samples were outgassed under vacuum at <NUM> for <NUM>. Nitrogen sorption analysis at <NUM> was used for calculating the specific surface area (SSA) using the Brunauer- Emmet-Teller (BET) equation).

X-ray diffraction, XRD, of the reacted powders indicated that the Al was selectively etched from the structure. EDS confirmed that the Al layers were replaced by O and F. SEM images of Ti<NUM>AlC particles after HF treatment (<FIG> resemble images of exfoliated graphite and clearly show HF-induced delamination that are typical of MXenes.

The N<NUM> sorption isotherm of the treated powders (<FIG> has a hysteresis loop with indications of the presence of mesopores and a shape typical for slit pores. The SSA calculated using the BET equation, for the HF treated Ti<NUM>AlC was <NUM><NUM>·g-<NUM>. This value is about an order of magnitude times higher than the as-received Ti<NUM>AlC powders measured at ≈<NUM><NUM>·g-<NUM>.

The electrochemical behavior of exfoliated Ti<NUM>AlC in Li batteries was investigated using coin cells (CR <NUM>) prepared as follows. The working electrodes were made with <NUM> wt% Ti<NUM>C (as described above) and <NUM> wt. % Super P carbon black mixed with <NUM> wt. % Poly(vinylidene fluoride) dissolved in <NUM>-Methyl-<NUM>-pyrrolidinone. The mixture was then spread onto a copper foil and dried at ca. <NUM> for <NUM>, under a mechanical vacuum. CR <NUM> coin-type cells were assembled using MXene as the positive electrode and Li metal foil as the negative electrode, separated by a sheet of borosilicate glass fiber (Whatman GF/A) separator saturated with <NUM> LiPF<NUM> solution in a <NUM>:<NUM> weight mixture of ethylene carbonate and diethyl carbonate (EC:DEC) as the electrolyte. The cells were assembled inside an Ar-filled glove box with H<NUM>O and O<NUM> contents < <NUM> ppm, to avoid any moisture contamination.

The cells were subjected to cyclic voltammetry and galvanostatic charge-discharge cycling using a potentiostat (VMP4, Biologic, S. Electrochemical characterization was typically performed between <NUM> V and <NUM> V vs. Li+/Li.

Typical cyclic voltammetry curves, at a rate of <NUM> mV·s-<NUM>, for the exfoliated Ti<NUM>C are shown in <FIG>. A broad, irreversible peak was observed around <NUM> V, during the first lithiation cycle (reduction); it was absent in subsequent cycles. This irreversible peak was assigned to the formation of a solid electrolyte interphase (SEI) and to an irreversible reaction with the electrode material. In all subsequent cycles, broad reversible peaks were observed at <NUM> V and <NUM> V vs. Li+/Li during lithiation and de-lithiation, respectively. Because these peak potentials are similar to those reported for TiO<NUM> and lithiated titania, these peaks were tentatively assigned to the following redox reaction:.

Ti<NUM>COx + yLi+ + ye- ↔ LiyTi<NUM>COx     (<NUM>).

The rationale for this assignment is that drying at <NUM>, prior to assembling the coin cells, rids MXene of water or any OH species and leads to an oxygen terminated surface. In other words, the assumption is made that the Ti<NUM>COx surface is similar to that of titania. Like in the case of the titanates, even if the potentials vs. Li are relatively high, it is an advantage from a safety stand point. Ex situ XRD results (not shown) after lithiation produced no new peaks, but a downshift of the MXene peaks was observed, with an increase of the c parameter by <NUM>% which indicates intercalation of Li between the MXene layers, and not a conversion reaction.

<FIG> shows the galvanostatic charge/discharge curves at a rate of C/<NUM> (<NUM> Li+ per formulae exchanged in <NUM>). The capacity loss in the first cycle can again be attributed to a SEI layer formation at potentials below <NUM>. 9V vs. Li+/Li, as well as to the irreversible reduction of electrochemically active surface groups such as fluorine or possibly hydroxyls. The specific capacity stabilized after five cycles at ≈ <NUM> mAh·g-<NUM>. This value corresponds to y ≈ <NUM> in reaction <NUM>.

At <NUM> mAh·g-<NUM>, the capacity of the treated powders is about <NUM> times higher than that of the as-received Ti<NUM>AlC (ca. <NUM> mAh·g-<NUM> at C/<NUM>) powders. This increase in capacity is traceable to the higher surface area, more open structure and weaker bonds between the MX layers after HF treatment. In addition to the morphological changes, the Li insertion sites are also now different (i.e. the site binding energies) which could also explain the differences in capacity.

The specific capacities vs. cycle number at different cycling rates (C/<NUM>, C/<NUM>, 1C, 3C, and 10C) calculated from galvanostatic curves are shown in <FIG>. The highest capacity was obtained at a rate of C/<NUM>. The specific capacity values stabilize after <NUM> cycles, for all scan rates. At a C/<NUM> rate, the capacity is <NUM> mAh·g-<NUM>, which corresponds to y ≈ <NUM>. At rates of <NUM> C and <NUM> C, the capacities, after <NUM> cycles, were, respectively, <NUM> mAh·g-<NUM> and <NUM> mAh·g-<NUM>. Even at rates of 10C, a stable capacity of <NUM> mAh·g-<NUM> was obtained for more than <NUM> cycles. These results clearly demonstrate that it is possible to stably electrochemically intercalate Li+ ions in the interlayer spaces between exfoliated Ti<NUM>C sheets, and achieve stability.

The exfoliated Ti<NUM>C, produced by HF treatment of Ti<NUM>AlC powders, showed reversible capacity about <NUM> times higher than pristine Ti<NUM>AlC, due to its open structure, weaker interlaminar forces, and higher SSA. Electrochemical measurements showed intercalation and deintercalation of Li+ ions at <NUM> V and <NUM> V vs. Li+/Li, respectively. The exfoliated Ti<NUM>C material exhibited a stable capacity of <NUM> mAh·g-<NUM> at a C/<NUM> rate, corresponding to about one Li per Ti<NUM>COx formula unit. A stable cycling capacity of <NUM> mAh·g-<NUM> was observed after <NUM> cycles at a 3C rate, and <NUM> mAh·g-<NUM> was observed after <NUM> cycles at a 10C rate.

Similar experiments with Ti<NUM>CN, TiNbC, and Ta<NUM>C<NUM> have also shown that these materials can also be intercalated with Li and used in lithium ion batteries.

To measure the sheet resistances and the contact angle, MXene discs (<NUM> in diameter, <NUM> thick) were cold-pressed from the reacted powders. The latter were placed in a die and cold-pressed to a load corresponding to a stress of <NUM> GPa. The surface or sheet resistances of cold-pressed, free-standing MXene discs were measured using a four-probe technique (Cascade Probe Station CPS-<NUM>-<NUM> with <NUM>-point probe head Alessi C4S-<NUM>, Cascade Microtech, Inc. , Beaverton, USA).

Contact angle measurements of deionized water were also performed at room temperature using the sessile drop technique. Ten microliter water drops were placed on the surfaces of cold-pressed MXene discs. The contact angles were measured from photographs taken with a CCD camera yielding an accuracy of approximately ±<NUM>°.

The densities of the cold-pressed discs of the various MXene compositions (Table <NUM>) varied between <NUM>/cm3 for Ti2C to <NUM>/cm3 for Ta4C3. If one assumes the c lattice parameters listed in Table <NUM> and OH terminated surfaces of MXene sheets, then it is possible to calculate the theoretical densities. The last row in Table <NUM> lists the measured densities of the pressed discs. The numbers in parentheses list the % of theoretical densities that range from <NUM> to ≈<NUM>%.

The sheet resistivity and resistivities of the various MXene discs are also shown in Table <NUM>. The resistivity values are higher than the MAX phases before treatment (<<NUM>Ω / □) presumably because of the replacement of the A layers with OH and/or F. When it is assumed that surface groups are similar in all of the exfoliated MAX phases, the difference in the resistivity between the different phases can be partially explained by the different number of atomic layers (<NUM>, <NUM>, and <NUM> for M<NUM>X, M<NUM>X<NUM>, and M<NUM>X<NUM> phases, respectively). It is important to note that the resistivity values reported in TABLE <NUM> should be significantly higher than single MXene sheets because of the method by which the resistivity was measured. For example, the resistivity of bulk sintered Ti<NUM>AlC<NUM> is <NUM>µΩm. <NUM> When Ti<NUM>AlC<NUM> powders were cold-pressed at <NUM> GP, their resistivity increased to <NUM>µΩ-m, a, roughly, <NUM> time increase.

Contact angle measurement results for water droplets on the cold-pressed discs of exfoliated phases are also listed in TABLE <NUM>. These values are lower than those of the corresponding MAX phases -- that were also measured in this work on cold-pressed samples, which were around <NUM>°. The reduction in contact angle can be explained by the presence of OH surface groups after the HF treatment. In contradistinction, graphene can be transformed from superhydrophopic to superhydrophilic by altering the surface groups. The hydrophilicity of the MXenes would be an advantage when using aqueous electrolytes in energy storage devices or dispersing in water and alcohols for further processing.

Claim 1:
A composition comprising at least one free-standing layer having first and second surfaces, each layer comprising:
a two-dimensional array of crystal cells having a thickness of a single crystal cell, wherein the top and bottom surfaces of the array are available for chemical modification,
each crystal cell having an empirical formula of Mn+<NUM> Xn,
such that each X is positioned within an octahedral array of M,
wherein M is at least one Group IIIB, IVB, VB, or VIB metal,
wherein each X is C and/or N,
and n = <NUM>, <NUM>, or <NUM>;
wherein at least one of the surfaces of each layer has bound thereto alkoxide, carboxylate, halide, hydroxide, hydride, oxide, sub-oxide, nitride, subnitride, sulfide, thiol, or a combination thereof.