CN114920292A - Transition metal chalcogenide compound, preparation method and application thereof, and energy storage device - Google Patents
Transition metal chalcogenide compound, preparation method and application thereof, and energy storage device Download PDFInfo
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Abstract
The invention discloses a transition metal chalcogenide compound, a preparation method, application and an energy storage device thereof, wherein the chemical formula of the transition metal chalcogenide compound is represented as M a Y 2a‑2 (ii) a The method comprises the following steps: reacting the raw material with a sulfur hydride at a certain temperature to obtain the product; the raw material is selected from MAX phase material, MXene material or transition metal chalcogenide compound MY 2 At least one of; wherein, the M represents a transition metal element; y represents one of sulfur, selenium or tellurium, and a is more than or equal to 3 and less than or equal to 5. The invention provides a new technical path for preparing 2D non-van der Waals transition metal sulfide and obtains a transition metal chalcogenide compound with a novel structureThe invention also provides the application of the material as ion storage based on the structural characteristics, wherein the material has two-dimensional ultrathin characteristics, a highly exposed surface, high conductivity and a unique vacancy structure, and can be used as an electrode material of a battery or a super capacitor.
Description
Technical Field
The invention belongs to the field of new materials and batteries, and particularly relates to a transition metal chalcogenide compound, a preparation method and application thereof and an energy storage device.
Background
Two-dimensional nanocrystals such as graphene, hexagonal boron nitride (h-BN), and transition metal chalcogenide compounds (TMC) have attracted much attention because of their extremely high anisotropy. In particular, 2D TMC has a variety of chemical functions, is composed of transition metals (M ═ V, Nb, Ta, Mo, W, etc.) and chalcogens (X ═ S, Se, Te), shows tunable electrical characteristics from semiconductors to semimetals and metals, and has great prospects in the fields of electronics, optoelectronics, energy storage and conversion. Currently, the most extensively studied 2D TMC nanocrystals are typically van der waals (vdW) layers, such as MoS 2 And WS 2 The layered counterparts can be easily prepared on a top-down basis by mechanical, liquid-phase and electrochemical stripping. During the peeling process, the bulk layered TMC compound with weak van der waals force between layers can be cut by external forces (such as adhesion, shear force and ultrasonic wave) to form a monolayer and a small amount of 2D TMC nanocrystals. Compared to van der waals TMC layers, 2D non-van der waals TMC is more difficult to prepare because these compounds are present in three-dimensional bonding networks without the presence of inter-layer van der waals forces, making them difficult to cut by common peeling methods and greatly hindering their further development and widespread use.
Non-van der waals TMC can exist in various crystal structures, such as cubic pyrite and NiAs type structures, which are composed of metal atoms surrounded by six sulfur atoms in an octahedral configuration. These unique structural features have anisotropic in-plane and out-of-plane bonding, associated with tunable d-orbital electrons of specific transition metals, resulting in good electrical properties for non-van der waals TMC nanocrystals. For example, non-van der Waals vanadium sulfides, such as V 5 S 8 From VS 2 Layer composition at VS 6 The V atoms are inserted in octahedral coordination, the inserted V atoms and the other V atoms having localized and mobile 3d electrons, respectively, so that they have about 500S cm -1 High conductivity metal properties. More remarkably, by isolating large amounts of non-van der Waals TMC to the 2D limit, it is sufficientExposed metals, rich dangling bonds and unsaturated coordination are emerging, a feature that is not present in 2D van der waals TMC, which can provide many electrochemically active sites. Unfortunately, to date, the preparation of two-dimensional non-van der waals TMC nanocrystals has remained a significant challenge due to their three-dimensional bonding structure.
Disclosure of Invention
The present invention is directed to the technical problem that a 2D non-van der Waals transition metal chalcogenide compound is difficult to prepare, and a first aspect of the present invention provides a method for preparing a transition metal chalcogenide compound, wherein the chemical formula of the transition metal chalcogenide compound is represented as M a Y 2a-2 (ii) a The method comprises the following steps: reacting the raw material with a sulfur hydride at a certain temperature to obtain the product; the raw material is selected from MAX phase material, MXene material or transition metal chalcogenide compound MY 2 At least one of; wherein M in the chemical formula represents a transition metal element; y represents one of sulfur, selenium or tellurium, and a is more than or equal to 3 and less than or equal to 5.
In some embodiments, the MAX phase material in the feedstock has a chemical formula of M 2 AX, wherein M represents a transition metal element, A represents at least one of aluminum, gallium, indium, lead, silicon, germanium and tin elements, and X represents carbon and/or nitrogen elements.
In some embodiments, the chemical formula of the MXene material in the feedstock is represented as M 2 XT x Wherein M represents a transition metal element, X represents a carbon and/or nitrogen element, T x Represents a functional group.
In some embodiments, the transition metal chalcogenide compound has the formula M 3 Y 4 Or M 5 Y 8 。
In some embodiments, M in the above formula is selected from one or more of vanadium, titanium, chromium, molybdenum, tungsten, or niobium.
In some embodiments, the above preparation method wherein the chalcogenide hydride is selected from H 2 S、H 2 Se or H 2 And Te.
In some embodiments, the temperature of the reaction in the above preparation method is between 600 ℃ and 1200 ℃.
In some embodiments, the above preparation method further comprises the steps of: and a stripping step, namely ultrasonically stripping the transition metal chalcogenide compound obtained by the reaction to obtain the transition metal chalcogenide compound with the two-dimensional lamellar morphology.
In a second aspect, the present invention provides a transition metal chalcogenide compound having a chemical formula M a Y 2a-2 Wherein, the M represents a transition metal element; y represents one of sulfur, selenium or tellurium, and a is more than or equal to 3 and less than or equal to 5; the transition metal chalcogenide compound has the appearance of an expansion body stacked by two-dimensional sheets; or the transition metal chalcogenide compound has the morphology of a two-dimensional sheet layer.
In some embodiments, the two-dimensional sheet of the transition metal chalcogenide compound has a monoclinic crystal structure, or a hexagonal crystal structure.
In some embodiments, the thickness of the two-dimensional sheet of transition metal chalcogenide compound is between 2nm and 10 nm.
In some embodiments, the two-dimensional sheet of transition metal chalcogenide compounds described above presents metal M vacancies.
In some embodiments, the transition metal chalcogenide compound has the formula M 3 Y 4 Or M 5 Y 8 。
The third aspect of the present invention provides a transition metal chalcogenide compound obtained by the method for producing a transition metal chalcogenide compound described above, or an application of the transition metal chalcogenide compound described above to an electrode material for a battery, a capacitor, or a supercapacitor.
In some embodiments, the battery in the above-described application is a lithium ion battery, a zinc ion battery, a sodium ion battery, a lithium ion battery, or an aluminum ion battery.
The fourth aspect of the present invention provides an energy storage device, including a battery, a capacitor or a super capacitor, wherein the electrode material of the energy storage device contains the transition metal chalcogenide compound obtained by the above method for preparing a transition metal chalcogenide compound, or the above transition metal chalcogenide compound.
The invention provides a new technical path for preparing 2D non-van der Waals transition metal sulfides, and obtains a transition metal chalcogenide compound material with a novel structure, which has two-dimensional ultrathin characteristics, a highly exposed surface, high conductivity and a unique vacancy structure. In particular, the 2D non-Van der Waals transition metal sulfur-based compound provided by the invention provides a novel electrode material for the development of a novel non-lithium ion energy storage device aiming at ions with larger ionic radius such as zinc ions, sodium ions, aluminum ions and the like.
Drawings
FIG. 1 shows the heat treatment process performed by MAX-V in example 1 of the present invention 2 Conversion of GeC into 2D Non-vdW V 3 S 4 A process schematic of (a); the obtained 2D Non-vdW V 3 S 4 An XRD spectrum (b) and an XPS measurement spectrum (c);
FIG. 2 shows 2D Non-vdW V in example 1 of the present invention 3 S 4 SEM picture of (1);
FIG. 3 shows 2D Non-vdW V in example 1 of the present invention 3 S 4 Comprising: 2D Non-vdW V 3 S 4 A cross-sectional TEM image (a) and a TEM image (b); 2D Non-vdW V 3 S 4 Cross-sectional HRTEM images (c-d); 2D Non-vdW V 3 S 4 AFM images (e) and corresponding thickness analysis (f);
FIG. 4 shows the precursors MAX-V in example 1 of the present invention 2 SEM images of GeC;
FIG. 5 shows 2D Non-vdW V in example 1 of the present invention 3 S 4 Including: 2D Non-vdW V 3 S 4 SEM image (a) of (a), showing ultrathin transparent nanosheets; 2D Non-vdW V 3 S 4 HRTEM images of (a) and corresponding FFT patterns of (an inset) show regular atomic arrangement of hexagonal crystal type and single crystal characteristics (b); 2D Non-vdW V 3 S 4 HRTEM image (c) of (a), wherein a number of V vacancies are circled; monoclinic V in plan view 3 S 4 An atomic model of (1), whereinV vacancies are highlighted with dashed circles (d); 2D Non-vdW V 3 S 4 (ii) a raman spectrum (e) showing typical peaks of the V-S bond vibrational mode; 2D Non-vdW V 3 S 4 And MXene V 2 CT x Current-voltage curve (f) of (d), revealing V 3 S 4 Metallic features of the nanocrystals;
FIG. 6 shows 2D Non-vdW V in example 1 of the present invention 3 S 4 High resolution V2 p XPS spectra (a) and high resolution S2 p XPS spectra (b) of the nanocrystals, indicating the presence of V-S bonds and V-O bonds therein;
FIG. 7 shows 2D Non-vdW V in example 1 of the present invention 3 S 4 X-ray absorption near-edge structure (XANES) spectra (a) and V of nanocrystal VK edge 3 S 4 、V 2 O 5 And a fourier transform of the EXAFS spectrum of the V foil (b);
FIG. 8 shows the vdW VS at a high temperature of 600 ℃ in example 2 of the present invention 2 And Non-vdW V 3 S 4 Shows significantly different diffraction peaks and indicates vdW VS 2 Will be converted into Non-vdW V after heat treatment 3 S 4 Transformed Non-vdW V 3 S 4 Does not exhibit a distinct lamellar morphology;
FIG. 9 shows 2D Non-vdW V in example 4 of the present invention 3 S 4 Electrochemical properties of zinc storage in an aqueous electrolyte comprising: 50mA g obtained from cycles 1, 2 and 5 -1 A lower constant current discharge-charge curve (a) showing a high reversible capacity during discharge-charge; Non-vdW V 3 S 4 -600、 Non-vdW V 3 S 4 700 and Non-vdW V 3 S 4 800 at 50mA g -1 The cycle performance (b) and rate performance (c) of (a); Non-vdW V 3 S 4 7000 at 5000mA g -1 (ii) cycle performance (d);
FIG. 10 shows a precursor V in example 4 of the present invention 2 GeC at 50mA g -1 Current density of (a);
FIG. 11 shows 2D Non-vdW V in the zinc storage discharge-charge cycle in example 4 of the present invention 3 S 4 Material characterization of nanocrystals, comprising: 2D Non-vdW V in discharging and charging process 3 S 4 2D contour plot (a) of in situ XRD measurements of nanocrystals, and 50mA g -1 The corresponding discharging and charging curve (b) is obtained; using 2D Non-vdW V 3 S 4 V-vacancy storing Zn on basal plane 2 + Schematic diagram (c); 2D Non-vdW V after discharge 3 S 4 HRTEM image (d) of nanocrystals, showing good crystallinity; 2D Non-vdW V in discharge state 3 S 4 Elemental mapping images of v (e), s (f), and zn (g) species of the nanocrystals;
FIG. 12 is an EIS spectrum of the electrochemical impedance of the zinc ion battery in example 4 of the present invention;
FIG. 13 shows the cycle performance of the assembled battery in example 4 of the present invention using 0.05M potassium hydrogen phthalate electrolyte, with a voltage range of 0.3 to 1.6V and a current density of 50mA g -1 ；
FIG. 14 shows 2D Non-vdW V in example 4 of the present invention 3 S 4 At a scan rate of 0.01 to 50mV s -1 And a log plot of anode and cathode peak currents and scan rates (b), showing the mixed pseudocapacitance behavior during discharge-charge cycles;
FIG. 15 shows 2D Non-vdW V in example 5 of the present invention 3 S 4 Electrochemical properties of sodium storage, including: 2D Non-vdW V 3 S 4 At 50mA g -1 A constant current discharge-charge curve (a) at current density; Non-vdW V 3 S 4 -600、Non-vdW V 3 S 4 -700、Non-vdW V 3 S 4 800 and V 2 GeC at 50mA g -1 Cycling performance at current density (b); Non-vdW V 3 S 4 Rate capability of the nanocrystal (c); Non-vdW V 3 S 4 700 at 2A g -1 Cycling performance at current density (d);
FIG. 16 shows 2D Non-vdW Ti in example 6 of the present invention 5 S 8 And its precursor Ti 2 An XRD spectrum of SnC;
FIG. 17 shows 2D Non-vdW Ti in example 6 of the present invention 5 S 8 SEM picture (a), TEM picture (b), HRTEM picture (c) and FFT map (d);
FIG. 18 shows 2D Non-vdW Ti in example 6 of the present invention 5 S 8 STEM map (a), element distribution maps of Ti (b), and S (c).
Detailed Description
The technical solution of the present invention will be described below by way of specific examples. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after the combined steps, or that other methods or steps may be intervening between those explicitly mentioned. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased in the market or prepared according to a conventional method well known to those skilled in the art.
The technical scheme of the invention comprises the following steps: taking MAX phase material as a precursor, and carrying out high-temperature heat treatment in the atmosphere of chalcogenide, wherein the chalcogenide can etch the A component in the MAX phase material on one hand in the heat treatment process; on the other hand, chalcogen elements can replace X elements to form MS 2 (ii) a In yet another aspect, MS 2 Self-intercalated formation of M by Van der Waals interstitial vanadium atoms 1+x S 2 Layer, finally 2D non van der Waals M is formed 3 S 4 Or M 5 S 8 A nanocrystal. The 2D non-van der Waals transition metal sulfur compound has a unique expansion body structure with two-dimensional layer accumulation, and a 2D non-van der Waals transition metal sulfur compound ultrathin sheet layer can be obtained through simple treatment (such as ultrasonic treatment).
In the invention, the MAX phase material is replaced by MXene material, namely, the component A in the MAX phase material is etched in advance, and the product MXene material reacts with chalcogenide at a certain temperature to obtain the 2D non-van der Waals transition metal chalcogenide compound sheet layer.
The present invention also found that the raw material was replaced with a Van der Waals transition metal chalcogenide compound MY 2 Reacting with chalcogenide at a certain temperature to obtain transition metal chalcogenide MY 2 Can be converted to produce non-van der Waals transition metal sulfur compounds.
It should be noted that, the chalcogen element in the present invention includes sulfur (S), selenium (Se) and tellurium (Te), the above examples have been described by taking sulfur element in chalcogen element as an example, and since Se and Te elements have similar chemical and physical properties to those of S element, 2D non-van der waals transition metal chalcogenide compound (e.g., V) can be obtained by adjusting experimental conditions 3 Se 4 、V 3 Te 4 、Ti 5 Se 8 、Ti 5 Te 8 Etc.) nanocrystals.
Example 1
To better illustrate the technical features of the present invention, this example provides a two-dimensional non-van der Waals vanadium-based sulfur-based compound V 3 S 4 And the preparation method comprises the following steps:
1) preparation of MAX phase material: vanadium powder (V, 99.9%, 100-200 mesh, Allatin reagent), germanium powder (Ge, 99.999%, 100 mesh, alpha-Enthai), graphite (C, 99.9%, 10 mesh, alpha-Enthai) were sealed in an agate container with agate balls and ground at 600rpm for 20 h. The molar ratio of V/Ge/C was 2:1.05: 1. The powder mixture was then transferred to a tube furnace and heated at 3 ℃ for a period of min -1 At a heating rate of 1400 ℃. The mixture was held at this temperature for 4 hours to give a MAX phase material, labelled MAX-V 2 GeC；
2) Preparation of 2D non-Van der Waals V 3 S 4 And (3) nanocrystal: at 10 deg.C for min under Ar flow -1 Heating rate of (3) heating the V prepared in step 1 2 GeC (300mg) and then H was passed in at different temperatures (600, 700 and 800 ℃ C.) 2 S/Ar(10vol.％H 2 S) the mixture. Maintaining the temperature for 2 hours to obtain the product 2D non-van der Waals V 3 S 4 A nanocrystal of thenUltrasonic treatment in IPA solvent to obtain product labeled non-vdW V 3 S 4 X (X represents the reaction temperature).
FIG. 1a shows a MAX phase material (MAX-V) 2 GeC) into 2D non-Van der Waals vanadium-based sulfur-based compound (V) 3 S 4 ) In a process diagram of (1), MAX-V at high temperature (600 to 800 ℃ C.) 2 Germanium layer in GeC reacts with hydrogen sulfide to form germanium sulfide (GeS) at temperature higher than 600 deg.C, and the GeS intermediate is in gas state at the temperature range, and can be easily removed from the reaction system to obtain high-purity V 3 S 4 . At the same time, through VS 2 Self-intercalated V-atoms of Van der Waals interstitial vanadium of the layer 1+x S 2 Layer, eventually gradually forming 2D non-van der Waals V 3 S 4 And (3) a layer.
FIG. 1b shows the resulting non-Van der Waals V 3 S 4 XRD pattern of (A), it can be seen that non-van der Waals V 3 S 4 In (002), (101), (011), (110),
And (204) a series of strong peaks at 15.3 °, 17.0 °, 28.0 °, 31.0 °, 34.6 °, 44.5 ° and 45.1 °, MAX-V, respectively, were detected 2 The main peak of GeC at 41.1 ° is not visible; it can also be seen that non-van der Waals V 3 S 4 Is free of any other impurities, indicating that in our synthesis process, MAX-V 2 Complete conversion of GeC occurred. X-ray photoelectron spectroscopy (XPS) measurement spectroscopy (fig. 1c and inset) further showed that the resulting product showed S and V species, free of any germanium element, indicating that the germanium layer was separated from V in our conversion reaction 2 GeC was completely removed.
2D non-Van der Waals TMC-V Using Scanning Electron Microscopy (SEM) 3 S 4 The morphology and microstructure of (a) were characterized, as shown in fig. 2, the prepared sample had an expanded accordion-like layered structure, similar to the reported morphology of accordion MXenes; 2D non-Van der Waals TMC-V Using Transmission Electron Microscopy (TEM) 3 S 4 Are characterized, as shown in FIG. 3a andb shows that the prepared sample has a highly expanded structure similar to that of MXenes in an accordion shape and a precursor V 2 The morphology of the GeC block (as shown in FIG. 4) has significantly different morphological characteristics, and after simple ultrasound, the 2D non-Van der Waals TMC-V of the high-expansion structure 3 S 4 Can be peeled off to obtain a two-dimensional sheet of ultrathin layers. To further evaluate the thickness of the resulting 2D layer, ultrathin slice experimental images were performed, with cross-sectional HRTEM images as shown in fig. 3c and D, with many thin nanosheets between 2.0 to 4.0nm thick. Atomic Force Microscope (AFM) images (fig. 3e) further revealed the presence of ultrathin nanoplates with an average thickness of 3.2nm (fig. 3f), in full agreement with cross-sectional HRTEM observations (fig. 3d and e). Of course, in some embodiments, the ultrathin nanoplatelets of the present invention can have a thickness between 2nm and 10 nm.
The prepared 2D non-van der Waals V may be further investigated by Scanning Electron Microscopy (SEM) and High Resolution TEM (HRTEM) measurements 3 S 4 The crystal structure of the layer. As shown in fig. 5a and b, atoms are regularly arranged in a hexagonal system in an ultra-thin layer, showing high crystallinity. The measurement of FIG. 5c clearly shows that the spacing between the lattice fringes is 0.29nm, which is related to the monoclinic V 3 S 4 (200) Interplanar spacing between faces (FIG. 5d) is relevant. These 2D V 3 S 4 Good crystallinity of the nanocrystals can also be demonstrated by hexagonal diffraction spots in a Fast Fourier Transform (FFT) pattern (inset in fig. 5 b). In the above-mentioned HRTEM analysis,
and
calculated spacing of points and
the inter-planar distances of the faces are well matched. More notably, a large number of V vacancies were observed in the HRTEM image (fig. 5c), which should be the result of the migration of the V atoms from the intercalation process at high temperatures. This may be by electronsNon-van der Waals TMC-V in Dispersion Spectroscopy (EDS) analysis 3 S 4 The relatively low V/S atomic ratio of 0.7:1 in the plane is further demonstrated.
To determine the 2D non-Van der Waals V prepared 3 S 4 Chemical structure of the nanocrystals, raman measurements were performed. As shown in FIG. 5e, there are four major peaks at 276.2, 401.1, 682.5, and 984.5cm -1 Here, the rocking and stretching vibration modes corresponding to the V-S bond. The presence of the V-S bond can be further demonstrated by high resolution XPS spectra (FIGS. 6a and b) and V K side-extended X-ray absorption fine structure spectra (EXAFS, FIGS. 7a and b). As can be seen in FIG. 5f, the 2D non-van der Waals TMC-V of the present invention 3 S 4 The nanocrystals showed a linear current-voltage relationship with a low resistance of 3.2k Ω □ -1 MXene V alone 2 CT x (16.6kΩ□ -1 ) One fifth of that) is much lower than the metal 1T TMD, demonstrating 2D non-van der waals V 3 S 4 High conductivity of the nanocrystals.
Example 2
This example provides another two-dimensional non-van der Waals vanadium-based sulfur-based compound, from VS 2 Is converted into V 3 S 4 The specific implementation steps of the method comprise:
1) hydrothermal synthesis of VS 2 : by NH 4 VO 3 And TAA as a precursor, and synthesizing two-dimensional Van der Waals VS by a simple hydrothermal method 2 (vdW VS 2 ) (ii) a For more specific embodiments, see Nature 2020,577,647;
2) heat treatment to vdW VS 2 To non-van der Waals V 3 S 4 Nanocrystal (Non-vdW V) 3 S 4 ) The transformation of (2): at H 2 S/Ar(10vol％H 2 S) flow, and performing thermal annealing at the high temperature of 600 ℃ for 1h to obtain two-dimensional Non-vdW V 3 S 4 。
FIG. 8a shows vdW VS 2 And Non-vdW V 3 S 4 The XRD pattern of (A) shows that Non-vdW V is treated by heat 3 S 4 Characteristic peak of and vdW VS 2 With significant differences, illustrating vdW VS 2 Under an atmosphere containing hydrogen sulfideCan promote vdW VS 2 To Non-vdW V 3 S 4 And (4) transformation. But Non-vdW V prepared in comparative example 3 S 4 Obviously, the characteristics of a layered expansion body and a two-dimensional morphology are not available, as shown in fig. 8b, it can be seen that 2D TMC prepared by using a MAX-phase material as a precursor has significantly different structural morphology characteristics.
Example 3
This example provides another two-dimensional non-van der waals vanadium-based chalcogenide compound, which is obtained by performing a high-temperature transformation reaction in a chalcogen hydride atmosphere using an MXenes material containing V as a precursor.
To prepare 2D non-van der Waals V 3 S 4 The specific implementation steps of the nanocrystal are as follows: mixing MXenes material V 2 CT x Placing the powder in a high temperature reaction furnace at Ar flow rate for 10 min -1 Heating at a heating rate of (1), introducing H at different temperatures (600-1200 ℃), and 2 S/Ar(10vol.％H 2 s) the mixture. Maintaining the temperature for 2 hours to obtain the product 2D non-van der Waals V 3 S 4 And (4) nanocrystals.
Wherein MXenes material V 2 CT x By MAX phase material V 2 The Al in the Al is etched by the AlC, and different etching agents can be selected, such as hydrofluoric acid solution, mixed solution of halogen metal salt and acid solution or molten metal salt and the like; more specifically, in the present embodiment, V is 2 And placing the AlC in HF acid solution, and etching for 24 hours at 80 ℃.
Example 4
From the above examples, it can be seen that the 2D non-van der waals vanadium-based sulfur-based compound prepared by the present invention has two-dimensional ultra-thin characteristics, a highly exposed surface, high conductivity, and a unique vacancy structure, which we believe can be used for ion storage (such as lithium ions, sodium ions, zinc ions, aluminum ions, etc.), as a battery electrode material or an electrode material of a supercapacitor.
In this example, we provide a way of applying the 2D non-van der Waals vanadium-based sulfur-based compound of the present invention to zinc ions with larger ionic radius in an aqueous electrolyte, i.e., provide a method of using the compound in an aqueous electrolyteThe zinc ion battery is characterized in that the 2D non-van der Waals vanadium-based sulfur compound is used as an electrode material to prepare a working electrode, then a zinc foil is used as a counter electrode, glass fiber is used as a diaphragm, and electrolyte is 3mol L in deionized water -1 Zinc trifluoromethanesulfonate (Zn (CF) 3 SO 3 ) 2 ) Assembling to obtain a button zinc ion battery for testing electrochemical performance; wherein the working electrode is prepared by mixing 80 wt.% of 2D V 3 S 4 10 wt.% ketjen black and 10 wt.% PVDF in NMP, uniformly coated on Ti foil, and vacuum dried at 120 ℃ for 12 h; constant current discharge/charge tests were carried out on a blue-ray system (CT2001A) at a voltage in the range of 0.3-1.6V (vs. Zn/Zn) 2+ )。
As shown in FIGS. 9a and b, from V at 700 deg.C 2 2D non-van der Waals V converted from GeC 3 S 4 (Non- vdW V 3 S 4 700) at 50mA g -1 Can realize 341mAh g under the current density -1 Is much higher than V 2 GeC precursor (18mAh g) -1 Please see fig. 10), 2D TMC-V produced at other temperatures 3 S 4 (200～300mAh g -1 ) And the transition metal chalcogenides that have been reported so far. More importantly, 2D Non-vdW V 3 S 4 700 at 50 to 10000mA g -1 Shows high rate performance at different current densities (fig. 9 c). Even at 10000mA g -1 At high current density of (2D Non-vdW V) 3 S 4 The reversible capacity of-700 was still maintained at 162mAh g -1 This is due to the vacancy-enriched 2D V of the zinc ion 3 S 4 Rapid diffusion in nanocrystals. In addition, at 5000mA g -1 After 1200 cycles of the next run, 152mA g -1 The stable capacity of (2) was maintained at a capacity retention rate of 71% (FIG. 9D), indicating that 22D Non-vdW V 3 S 4 Is a promising ion storage electrode material.
To clarify Zn 2+ In 2D Non-vdW V 3 S 4 The discharge charge mechanism in the nano-crystal is further subjected to in-situ XRD and TEM measurement in the constant current discharge charge process. Two-dimensional contour plot of in situ XRD pattern (FIG. 1)1a) Medium, 2D Non-vdW V 3 S 4 (002), (101), (011) and (110),
(204) The characteristic peaks of the faces at 15.3 °, 17.0 °, 28.0 °, 31.0 °, 34.6 °, 44.5 °, 45.1 ° remain unchanged during discharge and charge (fig. 11 b). This indicates that 2D Non-vdW V 3 S 4 Nanocrystals in Zn 2+ The intercalated and delaminated materials have good structural stability and are in good agreement with non-in-situ XRD measurement results. This can be attributed to the large number of V vacancies in the highly exposed surfaces and basal planes, which not only facilitates access to the electrolyte, but also contributes to Zn during discharge-charge 2+ Fast transfer (fig. 11 c). This can be further verified by the reduced semicircular diameter in the Electrochemical Impedance Spectroscopy (EIS) spectrum (fig. 12). Thus, repeating the cycle, 2D Non-vdW V 3 S 4 The nanocrystals still retained their original structure and good crystallinity as shown in HRTEM images (fig. 11 d). 2D Non-vdW V in discharge state 3 S 4 The elemental mapping images of the layers (fig. 11 e-g) show V, S and a uniform distribution of Zn species.
To verify the 2D Non-vdW V of the present invention 3 S 4 As a source of electrochemical properties for the electrode material, this comparative example assembled a button cell in a similar manner as example 3, except that the electrolyte was replaced with a Zn-free electrolyte 2+ 0.05M potassium hydrogen phthalate buffer (pH 4). 2D Non-vdW V upon charging and discharging 3 S 4 The capacity of the nanocrystal is negligible, 6mAh g -1 (FIG. 13), this confirms 2D Non-vdW V 3 S 4 The electrochemical behavior of (A) is entirely due to Zn 2+ Rather than proton intercalation. Furthermore, 2D Non-vdW V 3 S 4 The mixed pseudocapacitance behavior of nanocrystals can be measured at 0.1 to 50mV s by a Cyclic Voltammogram (CV) of 0.3 to 1.6V -1 Is measured at the scanning rate (fig. 14 a). The fitting result of the b value (according to the relationship: i ═ a ν b) shows the b values of the anode peak and the cathode peak0.88 and 0.85, respectively (FIG. 14b), corresponding to the mixed pseudo-capacitive behavior of zinc storage, which can be attributed to 2D Non-vdW V 3 S 4 There is a highly exposed surface.
Example 5
This example provides an embodiment of the 2D Non-Van der Waals vanadium-based sulfur-based compounds prepared according to the present invention for sodium ion storage, more specifically, 2D Non-vdW V 3 S 4 The working electrode is made of sodium ion battery electrode material, metal sodium is used as a counter electrode, a polypropylene porous diaphragm is used, and the electrolyte is 1M NaPF 6 Assembling the organic solution to obtain the button sodium-ion battery to test the electrochemical performance; the working electrode was prepared by mixing 80 wt.% 2D V 3 S 4 10 wt.% ketjen black and 10 wt.% PVDF in NMP, uniformly coated on Cu foil, and vacuum dried at 120 ℃ for 12 h; constant current discharge/charge tests were carried out on a blue system (CT2001A) at a voltage in the range of 0.05-3.0V (vs. Na/Na) + )。
As shown in FIGS. 15a and b, from V at 700 deg.C 2 2D non-van der Waals V converted from GeC 3 S 4 (Non- vdW V 3 S 4 700) at 50mA g -1 Can realize 500mAh g under the current density -1 Is much higher than V 2 GeC precursor (20mAh g) -1 ) 2D TMC-V produced at other temperatures 3 S 4 (230～350 mAh g -1 )。2D Non-vdW V 3 S 4 700 at 50 to 5000mA g -1 Shows high rate performance at different current densities (fig. 15 c). Even at 2A g -1 At high current density of (2D Non-vdW V) 3 S 4 The reversible capacity of-700 is still maintained at 360mAh g -1 (FIG. 15d), which is also attributable to sodium ion vacancy-enriched 2D V 3 S 4 Rapid diffusion in nanocrystals. Further indicates 2D Non-vdW V 3 S 4 Is a promising ion storage electrode material.
Example 6
This example provides a two-dimensional non-van der Waals titanium-based chalcogenide compound Ti 5 S 8 And itThe preparation method comprises the following steps:
1) preparation of MAX phase material: titanium powder (Ti, 99.99%, 300 mesh, avadin reagent), tin powder (Sn, 99.95%, 100 mesh, avadin reagent), graphite (C, 99.9%, 10 mesh, alpha aesar) were sealed in an agate container with agate balls and ball milled at 600rpm for 20 h. The molar ratio of Ti/Sn/C was 2:1.5: 1. The powder mixture was then transferred to a tube furnace and heated at 3 ℃ for a period of min -1 At a heating rate of 1300 ℃. The mixture was held at this temperature for 2 hours to give a MAX phase material, labelled MAX-Ti 2 SnC；
2) Preparation of 2D non-Van der Waals Ti 5 S 8 Nano-crystalline: at 10 deg.C for min under Ar flow -1 Heating rate of (3) heating the Ti obtained in the step 1 2 SnC (300mg) and then H when different temperatures (800, 900 and 1000 ℃ C.) were reached 2 S/Ar(10vol.％H 2 S) the mixture. Maintaining the temperature for 2 hours to obtain the product 2D non-van der Waals Ti 5 S 8 Carrying out ultrasonic treatment on the nano-crystal in IPA solvent to obtain a product labeled non-vdW Ti 5 S 8 X (X represents the reaction temperature). At high temperature (800 to 1200 ℃), MAX-Ti 2 The tin layer in SnC reacts with hydrogen sulfide to form tin sulfide (SnS) at the temperature higher than 700 deg.c, and the SnS intermediate is gaseous in the temperature range and can be easily eliminated from the reaction system to obtain high purity Ti 5 S 8 . At the same time, by TiS 2 Self-intercalated vanadium atom of van der Waals gap of layer to form Ti 1+x S 2 Layer, eventually, 2D non-van der Waals Ti is gradually formed 5 S 8 And (3) a layer.
FIG. 16 shows the resulting non-van der Waals Ti 5 S 8 XRD pattern of (A), it can be seen that non-van der Waals Ti 5 S 8 Diffraction peaks corresponding to the (002), (101), (102), (103), (104), (006), (105), (110), (112), (106), (202) and (008) crystal planes appear at 15.5 °, 31.1 °, 34.0 °, 38.4 °, 43.9 °, 47.6 °, 50.3 °, 53.5 °, 56.0 °, 57.4 °, 64.9 ° and 65.1 °, while MAX-Ti 2 The main diffraction peak of SnC disappeared; it can also be seen that non-van der Waals Ti 5 S 8 Does not contain any other impurities in the XRD diffraction pattern of (A), indicating that MAX-Ti is present in our synthesis process 2 The complete transition of SnC occurs.
2D non-Van der Waals TMC-Ti Using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) 5 S 8 The morphology and microstructure of (a) was characterized, as shown in fig. 17a, the prepared sample had a highly expanded structure, similar to accordion-like MXenes, with significantly different morphology characteristics than the MAX phase bulk, and after simple ultrasound, the 2D non-van der waals TMC-Ti of the highly expanded structure 5 S 8 Can be peeled off to obtain a two-dimensional sheet of ultrathin layers (fig. 17 b). In the high resolution tem (hrtem) image (fig. 17c), the atoms are regularly arranged in a hexagonal system in the ultrathin layer, showing high crystallinity, with a face-to-face spacing of 0.28nm for the (100) facets. Hexagonal diffraction spots in Fast Fourier Transform (FFT) patterns (FIG. 17d) to further demonstrate that the prepared has good Ti 5 S 8 A single crystal structure. The element plane scan analysis result of TEM (FIG. 18) shows that Ti and S elements exist uniformly, indicating that Ti is transformed 2 SnC prepares non-van der Waals two-dimensional material Ti 5 S 8 。
In conclusion, the invention provides a new technical path for preparing 2D non-van der Waals transition metal sulfides, obtains a transition metal chalcogenide compound material with a novel structure, has two-dimensional ultrathin characteristics, a highly exposed surface, high conductivity and a unique vacancy structure, and also provides the application of the transition metal chalcogenide compound material as an ion storage based on the structural characteristics, and can be used as an electrode material of a battery or a super capacitor. In particular, the 2D non-van der Waals transition metal chalcogenide compound provided by the invention provides a novel electrode material for developing a novel non-lithium ion energy storage device aiming at ions with larger ionic radius such as (zinc ions, sodium ions, aluminum ions and the like).
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (11)
1. A method for preparing a transition metal chalcogenide compound, characterized in that the chemical formula of the transition metal chalcogenide compound is M a Y 2a-2 (ii) a The method comprises the following steps: reacting the raw material with a sulfur hydride at a certain temperature to obtain the product; the raw material is selected from MAX phase material, MXene material or transition metal chalcogenide compound MY 2 At least one of; wherein, the M represents a transition metal element; y represents one of sulfur, selenium or tellurium, and a is more than or equal to 3 and less than or equal to 5.
2. The method of claim 1, wherein the MAX phase material has a chemical formula of M 2 AX, wherein M represents a transition metal element, A represents at least one of aluminum, gallium, indium, lead, silicon, germanium and tin elements, and X represents carbon and/or nitrogen elements;
or the chemical formula of the MXene material is represented as M 2 XT x Wherein M represents a transition metal element, X represents a carbon and/or nitrogen element, T x Represents a functional group.
3. The method according to claim 1 or 2, wherein the transition metal chalcogenide compound has a chemical formula of M 3 Y 4 Or M 5 Y 8 ；
And/or M is selected from one or more of vanadium, titanium, chromium, molybdenum, tungsten or niobium.
4. The production method according to claim 1 or 2, wherein the sulfur-based hydride is selected from H 2 S、H 2 Se or H 2 At least one of Te;
and/or the temperature of the reaction is between 600 ℃ and 1200 ℃;
and/or, the preparation method further comprises the steps of: and a stripping step, namely ultrasonically stripping the transition metal chalcogenide compound obtained by the reaction to obtain the transition metal chalcogenide compound with the two-dimensional sheet morphology.
5. A transition metal chalcogenide compound characterized by having a chemical formula represented by M a Y 2a-2 Wherein, the M represents a transition metal element; y represents one of sulfur, selenium or tellurium, and a is more than or equal to 3 and less than or equal to 5; the transition metal chalcogenide compound has the appearance of an expansion body stacked by two-dimensional sheets; or the transition metal chalcogenide compound has the morphology of a two-dimensional sheet layer.
6. The transition metal chalcogenide compound according to claim 5, wherein the two-dimensional sheet layer has a monoclinic crystal structure, or a hexagonal crystal structure;
and/or the thickness of the two-dimensional lamella is between 2nm and 10 nm;
and/or the two-dimensional sheet layer has metal M vacant sites.
7. A transition metal chalcogenide compound characterized in that the chemical formula of the transition metal chalcogenide compound is M a Y 2a-2 (ii) a The M represents a transition metal element; y represents one of sulfur, selenium or tellurium, and a is more than or equal to 3 and less than or equal to 5; the transition metal chalcogenide compound has an expansion body shape of two-dimensional lamellar stacking.
8. The transition metal chalcogenide compound according to claim 7, wherein the transition metal chalcogenide compound has a chemical formula of M 3 Y 4 Or M 5 Y 8 ；
And/or M is selected from one or more of vanadium, titanium, chromium, molybdenum, tungsten or niobium elements;
and/or the two-dimensional lamellae have a monoclinic crystal structure, or a hexagonal crystal structure;
and/or the thickness of the two-dimensional lamella is between 2nm and 10 nm;
and/or the two-dimensional sheet layer has metal M vacancies.
9. Use of a transition metal chalcogenide compound obtained by the process of preparation according to any one of claims 1 to 4 or of a transition metal chalcogenide compound according to any one of claims 5 to 8 for an electrode material of a battery, a capacitor or a supercapacitor.
10. Use according to claim 13, wherein the battery is a lithium ion battery, a zinc ion battery, a sodium ion battery, a lithium ion battery or an aluminium ion battery.
11. An energy storage device, which comprises a battery, a capacitor or a super capacitor, wherein the electrode material of the energy storage device contains the transition metal chalcogenide compound obtained by the preparation method according to any one of claims 1 to 4, or the transition metal chalcogenide compound according to any one of claims 5 to 8.
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