CN116190638A - Electrode material and electrode sheet of sodium ion battery, preparation method of electrode material and electrode sheet and battery - Google Patents

Electrode material and electrode sheet of sodium ion battery, preparation method of electrode material and electrode sheet and battery Download PDF

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CN116190638A
CN116190638A CN202310180618.XA CN202310180618A CN116190638A CN 116190638 A CN116190638 A CN 116190638A CN 202310180618 A CN202310180618 A CN 202310180618A CN 116190638 A CN116190638 A CN 116190638A
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ion battery
sodium ion
battery electrode
electrode material
vdw
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杨树斌
杜志国
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Beihang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a sodium ion battery electrode material, an electrode plate, a preparation method thereof and a battery, wherein the preparation steps of the sodium ion battery electrode material comprise: reacting the raw material with a chalcogenide hydride at a predetermined temperature to obtain the catalyst; the chalcogenide hydride includes: h 2 S、H 2 Se or H 2 One or more of Te; the raw material is selected from MAX phase material, MXene material or transition metal sulfur compound MY 2 At least one of (1), wherein the MY 2 M in (2) represents a transition metal element, Y represents one of sulfur, selenium or tellurium elementsA kind of module is assembled in the module and the module is assembled in the module.

Description

Electrode material and electrode sheet of sodium ion battery, preparation method of electrode material and electrode sheet and battery
The application is a divisional application, and the main application is an invention patent application of which the application date is 2022, 4, 18, the application number is 202210404234.7, and the invention name is a transition metal chalcogenide, a preparation method, application and an energy storage device thereof.
Technical Field
The invention belongs to the field of new materials and batteries, and particularly relates to a sodium ion battery electrode material, an electrode plate, a preparation method of the electrode plate and a battery.
Background
Two-dimensional nanocrystals such as graphene, hexagonal boron nitride (h-BN), and Transition Metal Chalcogenide (TMC) have attracted considerable attention because of their extremely high anisotropy. In particular, 2D TMC has various chemical functions, is composed of transition metals (m= V, nb, ta, mo, W, etc.) and chalcogenides (x=s, se, te), shows tunable electrical characteristics from semiconductors to semi-metals and metals, and has great prospects in the fields of electronics, optoelectronics, energy storage and conversion. Currently, the most widely studied 2D TMC nanocrystals are typically Van der Waals (vdW) layers, such as MoS 2 And WS (WS) 2 The layered counterparts can be easily prepared by mechanical, liquid phase and electrochemical stripping, based on a top-down method. During exfoliation, the bulk layered TMC compound, which has weak interlayer Van der Waals forces, can be cleaved by external forces (e.g., adhesion, shear, and ultrasonic) to form a monolayer and a small amount of 2D TMC nanocrystals. Compared to the van der waals TMC layer, 2D non-van der waals TMC is more difficult to prepare because these compounds exist in a three-dimensional bonding network without the interlayer van der waals forces, making them difficult to cut by a common delamination method, and greatly impeding their further development and widespread use.
Non-van der waals TMC may exist in various crystal structures such as cubic pyrite and NiAs type structures, which consist of metal atoms surrounded by six octahedral configuration sulfur atoms. These unique structural features have anisotropic in-plane and out-of-plane bonding, associated with tunable d-orbital electrons for specific transition metals, resulting in good non-van der Waals TMC nanocrystalsIs a function of the electrical properties of the battery. For example, non-Van der Waals vanadium sulfides, e.g. V 5 S 8 From VS 2 Layer composition at VS 6 Embedding V atoms in octahedral coordination, the embedded V atoms and other V atoms having localized and mobile 3d electrons, respectively, such that they have about 500S cm -1 Is a high conductivity metal property of the metal. More dramatically, by sequestering large amounts of non-van der Waals TMC to the 2D limit, fully exposed metals, abundant dangling bonds, and unsaturated coordination are occurring, which 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 remains a significant challenge due to their three-dimensional bonding structure.
Disclosure of Invention
The invention provides a novel electrode material with electrochemical activity, namely a transition metal chalcogenide, aiming at a sodium ion battery, and the preparation method of the electrode material comprises the following steps: reacting the raw material with a chalcogenide hydride at a predetermined temperature to obtain the catalyst; the chalcogenide hydride includes: h 2 S、H 2 Se or H 2 One or more of Te; the raw material is selected from MAX phase material, MXene material or transition metal sulfur compound MY 2 At least one of the MY 2 M in (2) represents a transition metal element; and Y represents one of sulfur, selenium or tellurium.
In some embodiments, the sodium ion battery electrode material has an expanded body morphology of two-dimensional sheet stacks.
In some embodiments, the sodium ion battery electrode material has a two-dimensional lamellar morphology.
In some embodiments, the thickness of the two-dimensional sheet is between 2nm and 10 nm.
In some embodiments, the two-dimensional sheet has metal M vacancies.
In some embodiments, the two-dimensional sheet has a monoclinic crystal structure, or, a hexagonal crystal structure.
In some embodiments, the sodium ion battery electrode material described aboveThe chemical formula is represented by M a Y 2a 2 And a is more than or equal to 3 and less than or equal to 5, wherein M represents one or more of transition metal elements.
In some embodiments, the above M is selected from one or more of the elements vanadium, titanium, chromium, molybdenum, tungsten, or niobium.
In some embodiments, the predetermined temperature in the above-described preparation method is between 600 ℃ and 800 ℃.
In some embodiments, the predetermined temperature is preferably 700 ℃.
The invention also provides a sodium ion battery positive plate, which comprises the sodium ion battery positive plate material; and a conductive agent and a current collector.
In some embodiments, the conductive agent comprises ketjen black;
in some embodiments, the current collector is a metallic titanium foil.
The invention also provides a preparation method of the positive plate of the sodium ion battery, which comprises the following steps: mixing the sodium ion battery anode material and the conductive agent to prepare slurry; the slurry is coated on the current collector and dried to obtain the final product.
The invention also provides a sodium ion battery, which comprises the sodium ion battery electrode material or the sodium ion battery electrode plate.
The invention provides a new technical path for preparing 2D non-Van der Waals transition metal sulfide, and obtains a transition metal chalcogenide material with a novel structure, which has two-dimensional ultrathin characteristics, highly exposed surface, high conductivity and unique vacancy structure. In particular, the 2D non-van der Waals transition metal chalcogenide compound provides a novel electrode material for the development of novel energy storage devices of non-lithium ions aiming at ions with larger ionic radius such as zinc ions, sodium ions, aluminum ions and the like.
Drawings
FIG. 1 shows a heat-treated product of example 1 of the present inventionIn the journey by MAX-V 2 Conversion of GeC to 2DNon-vdWV 3 S 4 A process schematic of (a); the obtained 2D Non-vdWV 3 S 4 XRD pattern (b) and XPS measurement spectrum (c);
FIG. 2 is a schematic diagram of a 2D Non-vdW V in example 1 of the present invention 3 S 4 SEM images of (a);
FIG. 3 is a schematic diagram of a 2D Non-vdW V in example 1 of the present invention 3 S 4 Morphology characterization of (c) 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) of (a); 2D Non-vdW V 3 S 4 AFM image (e) and corresponding thickness analysis (f);
FIG. 4 shows the precursor MAX-V in example 1 of the present invention 2 SEM image of GeC;
FIG. 5 is a schematic diagram of a 2D Non-vdW V in example 1 of the present invention 3 S 4 The structure and electrical characteristics of (a) include: 2D Non-vdW V 3 S 4 SEM images (a) of (a) showing ultra-thin transparent nanoplatelets; 2D Non-vdWV 3 S 4 Corresponding FFT patterns of HRTEM images and (inset) showing regular atomic arrangements of hexagonal crystal forms and single crystal features (b); 2D Non-vdW V 3 S 4 Wherein a plurality of V voids are circled; monoclinic V in top view 3 S 4 Wherein V vacancies are highlighted in a dashed circle (d); 2D Non-vdW V 3 S 4 A raman spectrum (e) showing typical peaks of V-S bond vibrational modes; 2D Non-vdW V 3 S 4 And MXene V 2 CT x The current-voltage curve (f) of (2) reveals V 3 S 4 Metal features of nanocrystals;
FIG. 6 is a 2D Non-vdW V in example 1 of the present invention 3 S 4 High resolution V2 p XPS spectrum (a) and high resolution S2 p XPS spectrum (b) of the nanocrystals, indicating the presence of V-S bonds as well as V-O bonds therein;
FIG. 7 is a 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 edges 3 S 4 、V 2 O 5 And fourier transform of the EXAFS spectrum of the V foil (b);
FIG. 8 shows a 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 Converted Non-vdW V 3 S 4 SEM image (b) of (a) does not show a pronounced lamellar morphology;
FIG. 9 is a 2D Non-vdW V in example 4 of the present invention 3 S 4 Electrochemical performance of zinc storage in aqueous electrolytes, 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 Cyclic performance (b) and rate performance (c); non-vdW V 3 S 4 7000 at 5000mA g -1 Lower cycle performance (d);
FIG. 10 shows a precursor V in example 4 of the present invention 2 GeC at 50mA g -1 Cyclic performance at current density of (2);
FIG. 11 is a graph showing the 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 discharge charging process 3 S 4 2D contour plot (a) of in situ XRD measurement of nanocrystals, 50mA g -1 Lower a corresponding discharge charge curve (b); by means of 2D Non-vdW V 3 S 4 V vacancies on basal plane store Zn 2+ Schematic diagram (c) of (a); post-discharge 2D Non-vdW V 3 S 4 HRTEM images (d) of nanocrystals, showing good crystallinity; 2DNon-vdW V in discharge state 3 S 4 Elemental mapping images of V (e), S (f) and Zn (g) species of nanocrystals;
FIG. 12 is an EIS spectrum of electrochemical impedance of a zinc-ion cell in example 4 of the present invention;
FIG. 13 shows the assembly of embodiment 4 of the present inventionThe battery adopts the circulation performance in 0.05M potassium hydrogen phthalate electrolyte, the voltage range is 0.3 to 1.6V, and the current density is 50mA g -1 ；
FIG. 14 is a 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 CV curves (a) and logarithmic relationship of anode and cathode peak currents and scan rates (b) showing mixed pseudocapacitance behavior during discharge-charge cycles;
FIG. 15 is a 2D Non-vdW V in example 5 of the present invention 3 S 4 Electrochemical performance of sodium storage, comprising: 2D Non-vdW V 3 S 4 At 50mA g -1 A constant current discharge-charge curve at current density (a); 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 The rate capability (c) of the nanocrystals; non-vdW V 3 S 4 700 at 2A g -1 Cycle performance at current density (d);
FIG. 16 is a 2D Non-vdWTi in example 6 of the present invention 5 S 8 Precursor Ti of Ti 2 XRD pattern of SnC;
FIG. 17 is a 2D Non-vdWTi in example 6 of the present invention 5 S 8 SEM image (a), TEM image (b), HRTEM image (c) and FFT image (d);
FIG. 18 is a 2D Non-vdWTi in example 6 of the present invention 5 S 8 STEM diagram (a), element distribution diagram of Ti (b) and S (c).
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods 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, carrying out high-temperature heat treatment under the atmosphere of chalcogenide hydride, and finding that the chalcogenide hydride can etch the A component in the heat treatment process; on the other hand chalcogen element can replace X element to form MS 2 The method comprises the steps of carrying out a first treatment on the surface of the In yet another aspect, the MS 2 Van der Waals interstitial vanadium atoms of the layer self-intercalate to form M 1+x S 2 A layer, finally forming 2D non-Van der Waals M 3 S 4 Or M 5 S 8 A nanocrystal. The 2D non-van der Waals transition metal chalcogenide has a unique two-dimensional layer stacked expansion body structure, and can be obtained into an ultrathin sheet of the 2D non-van der Waals transition metal chalcogenide through simple treatment (such as ultrasonic).
In the invention, the MAX phase material is replaced by the MXene material, namely, after the A component in the MAX phase material is etched in advance, the product MXene material reacts with chalcogenide hydride at a certain temperature, and the 2D non-van der Waals transition metal chalcogenide sheet can be obtained.
The present invention also found that the substitution of the feedstock with van der Waals transition metal chalcogenide MY 2 Reacting with chalcogenide hydride at a certain temperature, and transition metal chalcogenide MY 2 Can be converted to produce non-van der Waals transition metal chalcogenide.
In the present invention, the chalcogen elements include sulfur (S), selenium (Se) and tellurium (Te), and the above examples are described by taking the sulfur element in the chalcogen element as an example, and since Se and Te elements are in the same group as the S element and have similar chemical and physical properties, 2D non-Van der Waals transition metal chalcogenide (such as V can be obtained by adjusting the 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 characteristics of the invention, the embodiment provides a two-dimensional non-Van der Waals vanadium-based sulfur compound V 3 S 4 And a preparation method thereof, comprising the steps of:
1) Preparing MAX phase material: vanadium powder (V, 99.9%, 100-200 mesh, alar Ding Shiji), germanium powder (Ge, 99.999%,100 mesh, alpha elsa), graphite (C, 99.9%,10 mesh, alpha elsa) were sealed in an agate container with agate balls and milled at 600rpm for 20h. 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 minute -1 Is heated at 1400 ℃. Maintaining the mixture at this temperature for 4 hours to obtain a MAX phase material, designated MAX-V 2 GeC；
2) Preparation of 2D non-Van der Waals V 3 S 4 Nanocrystalline: at Ar flow rate at 10deg.C for min -1 Heating V prepared in step 1 at a heating rate of 2 GeC (300 mg) and then H is introduced when different temperatures (600, 700 and 800 ℃ C.) are reached 2 S/Ar(10vol.％H 2 S) mixture. Maintaining the temperature for 2 hours to obtain the 2D non-Van der Waals V product 3 S 4 Nanocrystalline, then ultrasonic processing in IPA solvent, the obtained product is marked as non-vdW V 3 S 4 X (X represents the reaction temperature).
FIG. 1a shows a phase consisting of MAX phase material (MAX-V 2 GeC) to 2D non-Van der Waals vanadinyl thio Compound (V) 3 S 4 ) Is shown in (a) MAX-V at high temperature (600 to 800 ℃) 2 The germanium layer in GeC is reacted with hydrogen sulfide to form germanium sulfide (GeS) at a temperature higher than 600deg.C, and the GeS intermediate is in gaseous state at the temperature range, so that it can be easily removed from the reaction system to obtain high purity V 3 S 4 . At the same time by VS 2 V is formed by self-intercalation of vanadium atoms in Van der Waals gaps of layers 1+x S 2 A layer, eventually forming 2D non-Van der Waals V 3 S 4 A layer.
FIG. 1b shows the resulting non-Van der Waals V 3 S 4 As can be seen from the XRD pattern of (C), non-Van der Waals V 3 S 4 At (002), (101), (011), (110),
Figure BDA0004102252510000071
And (204) a series of strong peaks at 15.3 °, 17.0 °, 28.0 °, 31.0 °, 34.6 °, 44.5 ° and 45.1 °, respectively, were detected, whereas MAX-V 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 MAX-V in our synthesis 2 GeC undergoes complete conversion. X-ray photoelectron Spectrometry (XPS) measurement spectra (FIG. 1c and inset) further show that the resulting product shows S and V species, without any germanium element, indicating that in our conversion reaction the germanium layer is formed from V 2 And completely removing GeC.
2D non-Van der Waals TMC-V Using Scanning Electron Microscopy (SEM) 3 S 4 The morphology and microstructure of the prepared samples were characterized as shown in fig. 2, and the prepared samples had an expanded accordion layered structure, similar to the reported morphology of accordion mxnes; 2D non-Van der Waals TMC-V Using Transmission Electron Microscopy (TEM) 3 S 4 Characterized by morphology and microstructure of the sample prepared, as shown in FIGS. 3a and b, has a highly expanded structure, resembling an accordion-like MXenes, with precursor V 2 The morphology of GeC block (shown in figure 4) has significantly different morphology characteristics, and after simple ultrasound, the 2D non-Van der Waals TMC-V of the highly expanded structure 3 S 4 Can be peeled off to obtain an ultra-thin two-dimensional sheet. To further evaluate the thickness of the resulting 2D layer, a microtome experimental plot was performed, cross-sectional HRTEM images as shown in fig. 3c and D, with many thin nanoplatelets between 2.0 and 4.0nm thick. Atomic Force Microscope (AFM) images (fig. 3 e) further revealed the presence of ultra-thin nanoplatelets with an average thickness of 3.2nm (fig. 3 f), in complete agreement with cross-sectional HRTEM observations (fig. 3d and e). Of course, in some embodiments, the ultra-thin nanoplatelets of the present invention may have a thickness between 2nm and 10 nm.
The 2D non-Van der Waals V prepared can be further studied by Scanning Electron Microscope (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 lattice fringes is 0.29nm, which is the same as the monoclinic V 3 S 4 (200) The interplanar spacing between the facets (fig. 5 d) correlates. These 2D V 3 S 4 Good crystallinity of nanocrystals can also be demonstrated by hexagonal diffraction spots (inset in fig. 5 b) in a Fast Fourier Transform (FFT) pattern. In the above-described HRTEM analysis,
Figure BDA0004102252510000081
and->
Figure BDA0004102252510000082
Calculated distance and +.>
Figure BDA0004102252510000083
The surface-to-surface spacing of the surfaces is well matched. More notably, a large number of V vacancies are observed in the HRTEM image (fig. 5 c), which should be the result of V atom migration during self-intercalation at high temperature. This can be accomplished by non-van der Waals TMC-V in Electron Dispersive Spectroscopy (EDS) analysis 3 S 4 The relatively low V/S atomic ratio in the plane of 0.7:1 is further demonstrated.
To determine the 2D non-Van der Waals V produced 3 S 4 The chemical structure of the nanocrystals was raman measured. As shown in FIG. 5e, there are four major peaks at 276.2, 401.1, 682.5 and 984.5cm -1 And corresponds to the rocking and stretching vibration modes of the V-S bond. The presence of V-S bonds can be further demonstrated by high resolution XPS spectra (fig. 6a and b) and V K side-expanded X-ray absorption fine structure spectra (EXAFS, fig. 7a and b). As can be seen in FIG. 5f, the 2D non-Van der Waals TMC-V of the invention 3 S 4 Nanocrystals showed a linear current-voltage relationship with a low resistance of 3.2kΩ ≡ -1 MXene V only 2 CT x (16.6kΩ□ -1 ) One fifth) far below the metal 1T TMD, demonstrating 2D non-Van der Waals V 3 S 4 The high conductivity of the nanocrystals.
Example 2
This example provides another method for preparing two-dimensional non-Van der Waals vanadium-based chalcogenide, which consists of VS 2 Conversion to V 3 S 4 The specific implementation steps of the implementation mode include:
1) Hydrothermal synthesis of VS 2 : with NH 4 VO 3 And TAA is used as a precursor, and two-dimensional Van der Waals VS is synthesized by a simple hydrothermal method 2 (vdWVS 2 ) The method comprises the steps of carrying out a first treatment on the surface of the For more specific embodiments, please see nature2020,577, 647;
2) Heat treatment to vdWVS 2 To non-van der waals V 3 S 4 Nanocrystalline (Non-vdW V) 3 S 4 ) Is converted into: at H 2 S/Ar(10vol％H 2 S) preparing by thermal annealing at 600 ℃ for 1h under the flow rate to obtain two-dimensional Non-vdW V 3 S 4 。
FIG. 8a shows vdWVS 2 And Non-vdW V 3 S 4 As can be seen from the XRD pattern of (C), non-vdW V after heat treatment 3 S 4 Characteristic peaks of (2) and vdWVS 2 With significant differences, demonstrating vdWVS 2 Heat treatment in an atmosphere containing hydrogen sulfide can promote vdWVS 2 To Non-vdW V 3 S 4 And (3) transformation. But the Non-vdW V prepared in the comparative example 3 S 4 It is apparent that the 2D TMC prepared using MAX phase material as precursor has significantly different structural morphology features, as shown in fig. 8b, without the characteristics of layered expansion body and two-dimensional morphology.
Example 3
The embodiment provides another preparation method of two-dimensional non-van der Waals vanadium-based sulfur compound, which is obtained by taking an MXenes material containing V element as a precursor and performing high-temperature conversion reaction in the atmosphere of chalcogenide.
To produce 2D non-Van der Waals V 3 S 4 The specific implementation steps of the nanocrystalline comprise: MXnes Material V 2 CT x Powder placingPlacing in a high temperature reaction furnace at Ar flow rate of 10deg.C for min -1 Heating at different temperature (600-1200 ℃) and introducing H 2 S/Ar(10vol.％H 2 S) mixture. Maintaining the temperature for 2 hours to obtain the 2D non-Van der Waals V product 3 S 4 And (3) nanocrystalline.
Wherein the MXnes material V 2 CT x By MAX phase material V 2 AlC etching Al to obtain different etchants, such as hydrofluoric acid solution, mixed solution of halogen metal salt and acid solution or molten metal salt, etc.; in the present embodiment, more specifically, V 2 AlC is put in HF acid solution and etched for 24 hours at 80 ℃.
Example 4
From the above examples, it can be seen that the 2D non-van der waals vanadium-based chalcogenide compound prepared according to the present invention has two-dimensional ultra-thin characteristics, highly exposed surfaces, high conductivity, and unique vacancy structures, which we consider to be useful for ion storage (such as lithium ion, sodium ion, zinc ion, aluminum ion, etc.), as an electrode material of a battery or an electrode material of a supercapacitor.
In this example we provide a mode of application of the 2D non-van der waals vanadium-based sulfur-based compound of the invention for zinc ions with larger ionic radius in aqueous electrolyte, namely, a zinc ion battery, wherein the 2D non-van der waals vanadium-based sulfur-based compound of the invention is used as electrode material to prepare working electrode, then zinc foil is used as counter electrode, glass fiber is used as separator, and electrolyte is 3mol L in deionized water -1 Zinc trifluoromethane sulfonate (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 80wt.%2D V 3 S 4 Mixing 10wt.% ketjen black and 10wt.% PVDF in NMP, uniformly coating on Ti foil, and vacuum drying at 120 ℃ for 12 h; constant current discharge/charge tests were performed on blue electric systems (CT 2001A) with voltages in the range of 0.3-1.6V (vs. Zn/Zn 2+ )。
As shown in FIGS. 9a and b, the temperature of 700℃is from V 2 GeC converted 2D non-Van der Waals V 3 S 4 (Non-vdW V 3 S 4 -700) at 50mA g -1 Can realize 341mAh g under the current density of (3) -1 Is far higher than V 2 GeC precursor (18 mAh g) -1 See FIG. 10), 2D TMC-V produced at other temperatures 3 S 4 (200～300mAh g -1 ) And transition metal chalcogenides that have been reported to date. More importantly, 2DNon-vdW V 3 S 4 700 at 50 to 10000mA g -1 Exhibits high rate performance at different current densities (fig. 9 c). Even at 10000mA g -1 At a high current density of 2DNon-vdW V 3 S 4 The reversible capacity of-700 remains at 162mAh g -1 This is due to the enrichment of zinc ions in vacancy 2D V 3 S 4 Fast diffusion in nanocrystals. In addition, at 5000mA g -1 After 1200 cycles, 152mA g -1 The stable capacity of (a) was maintained at 71% capacity retention (FIG. 9 d), indicating 22DNon-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 charging mechanism in the nanocrystal is further subjected to in-situ XRD and TEM measurement in the constant current discharge charging process. In the two-dimensional contour plot of the in situ XRD pattern (FIG. 11 a), 2D Non-vdW V 3 S 4 (002), (101), (011), (110),
Figure BDA0004102252510000101
Figure BDA0004102252510000102
(204) Characteristic peaks at 15.3 °, 17.0 °, 28.0 °, 31.0 °, 34.6 °, 44.5 °, 45.1 ° in face remain unchanged during discharge and charge (fig. 11 b). This indicates that 2D Non-vdW V 3 S 4 Nanocrystalline in Zn 2+ The intercalation and delamination have good structural stability, and are in good agreement with the results of ex-situ XRD measurements. This is attributable to the large number of V vacancies in the highly exposed surfaces and basal planes, which not only facilitate access to the electrolyte, but also facilitate Zn during discharge-charge 2+ Is shown (fig. 11 c). This can be further verified by the reduced semi-circular diameter in the Electrochemical Impedance Spectroscopy (EIS) spectrum (fig. 12). Thus, the cycle is repeated, 2D Non-vdW V 3 S 4 The nanocrystals still maintained their original structure and good crystallinity as shown in the HRTEM image (fig. 11 d). 2D Non-vdW V in discharge state 3 S 4 Elemental mapping images of the layers (fig. 11 e-g) showed uniform distribution of V, S and Zn species. />
To verify the 2D Non-vdW V of the present invention 3 S 4 As a source of electrochemical properties of electrode materials, this comparative example assembled a button cell in a similar manner to example 3, except that the electrolyte was replaced with a Zn-free electrolyte 2+ 0.05M potassium hydrogen phthalate buffer solution (ph=4). 2D Non-vdW V during charging and discharging 3 S 4 The capacity of the nanocrystals was negligible, 6mAh g -1 (FIG. 13), this demonstrates 2D Non-vdW V 3 S 4 Is derived entirely from Zn 2+ Instead of proton intercalation. In addition, 2D Non-vdW V 3 S 4 The mixed pseudocapacitive behavior of nanocrystals can be measured at 0.1 to 50mV s by Cyclic Voltammograms (CV) of 0.3 to 1.6V -1 Is demonstrated at the scan rate of (a) (fig. 14 a). The fit of the b values (according to the relationship: i=avb) shows that the b values of the anode and cathode peaks are 0.88 and 0.85, respectively (fig. 14 b), corresponding to the zinc stored mixed pseudocapacitance behavior, which can be attributed to the 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 chalcogenide compound prepared according to the present invention for sodium ion storage, more specifically, 2D Non-vdW V 3 S 4 As a working electrode made of a sodium ion battery electrode material, a metal sodium is used as a counter electrode, a polypropylene porous diaphragm and an electrolyte is 1M NaPF 6 Assembling to obtain a button sodium ion battery to test electrochemical performance; the working electrode was prepared by combining 80wt.%2D V 3 S 4 10wt.% ketjen black and 10wt.% PVDF were mixed in NMP, uniformly coated on Cu foil, and vacuum at 120 DEG CDrying for 12h to obtain; constant current discharge/charge tests were performed on blue-electric systems (CT 2001A) with voltages in the range of 0.05-3.0V (vs. Na/Na + )。
As shown in FIGS. 15a and b, the temperature of 700℃is from V 2 GeC converted 2D non-Van der Waals V 3 S 4 (Non-vdW V 3 S 4 -700) at 50mA g -1 Can achieve 500mAh g at current density -1 Is far higher than V 2 GeC precursor (20 mAh g) -1 ) 2D TMC-V produced at other temperatures 3 S 4 (230～350mAh g -1 )。2DNon-vdW V 3 S 4 700 at 50 to 5000mA g -1 Exhibits high rate performance at different current densities (fig. 15 c). Even at 2A g -1 At a high current density of 2DNon-vdW V 3 S 4 The reversible capacity of 700 is still kept at 360mAh g -1 (FIG. 15 d), which is also attributable to sodium ion enriched in vacancies 2D V 3 S 4 Fast diffusion in nanocrystals. Further indicates that 2DNon-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 Ti 5 S 8 And a preparation method thereof, comprising the steps of:
1) Preparing MAX phase material: titanium powder (Ti, 99.99%,300 mesh, alar Ding Shiji), tin powder (Sn, 99.95%,100 mesh, alar Ding Shiji), graphite (C, 99.9%,10 mesh, alpha elsha) were sealed in an agate container with agate balls and ball milled at 600rpm for 20 hours. 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 minute -1 Is heated at 1300 ℃. Maintaining the mixture at this temperature for 2 hours to obtain a MAX phase material, designated MAX-Ti 2 SnC；
2) Preparation of 2D non-Van der Waals Ti 5 S 8 Nanocrystalline: at Ar flow rate at 10deg.C for min -1 Heating the Ti prepared in step 1 at a heating rate 2 SnC (300 mg) and then H is introduced when different temperatures (800, 900 and 1000 ℃ C.) are reached 2 S/Ar(10vol.％H 2 S) mixture. Maintaining the temperature for 2 hours to obtain the product 2D non-Van der Waals Ti 5 S 8 Nanocrystalline, then ultrasonic processing is carried out in IPA solvent, and the obtained product is marked as non-vdWTi 5 S 8 X (X represents the reaction temperature). MAX-Ti at high temperature (800 to 1200 ℃ C.) 2 The tin layer in SnC reacts with hydrogen sulfide to form tin sulfide (SnS) at a temperature higher than 700 ℃, and the SnS intermediate is in a gaseous state in the temperature range, so that the tin sulfide can be easily removed from the reaction system to obtain high-purity Ti 5 S 8 . At the same time by TiS 2 Formation of Ti by self-intercalation of vanadium atoms in Van der Waals gaps of layer 1+x S 2 A layer, finally, 2D non-Van der Waals Ti is gradually formed 5 S 8 A layer.
FIG. 16 shows the resulting non-Van der Waals Ti 5 S 8 As can be seen from the XRD pattern of non-Van der Waals Ti 5 S 8 Diffraction peaks corresponding to (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 °, whereas 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 XRD diffraction patterns, indicating that MAX-Ti is in our synthesis 2 The SnC undergoes a complete transition.
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) are characterized, as shown in FIG. 17a, the prepared sample has a highly expanded structure, similar to an accordion-like MXnes, which is significantly different from the bulk morphology characteristics of the MAX phase, 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 give an ultra-thin two-dimensional sheet (fig. 17 b). In a High Resolution TEM (HRTEM) image (fig. 17 c), atoms are regularly arranged in a hexagonal system in an ultrathin layer, showing high crystallinity, with a interplanar spacing of 0.28nm for the (100) crystal planes. Fast fourier transform (FF)T) hexagonal diffraction spots in the pattern (FIG. 17 d) to further demonstrate the preparation of a film with good Ti 5 S 8 A monocrystalline structure. The elemental scanning analysis results of TEM (FIG. 18) show the presence of uniformly present Ti and S elements, indicating that Ti is converted 2 SnC is used for preparing a non-van der Waals two-dimensional material Ti 5 S 8 。
In summary, the invention provides a new technical path for preparing 2D non-van der Waals transition metal sulfide, and obtains a transition metal chalcogenide material with a novel structure, which has two-dimensional ultrathin characteristics, highly exposed surface, high conductivity and unique vacancy structure. In particular, the 2D non-van der Waals transition metal chalcogenide compound provides a novel electrode material for the development of novel energy storage devices of non-lithium ions aiming at ions with larger ionic radius such as zinc ions, sodium ions, aluminum ions and the like.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for 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 the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. The sodium ion battery electrode material is characterized by comprising the following preparation steps of: reacting the raw material with a chalcogenide hydride at a predetermined temperature to obtain the catalyst; the chalcogenide hydride includes: h 2 S、H 2 Se or H 2 One or more of Te; the raw material is selected from MAX phase material, MXene material or transition metal sulfur compound MY 2 At least one of (a), whereinThe MY 2 M in (2) represents a transition metal element, and Y represents one of sulfur, selenium or tellurium elements.
2. The sodium ion battery electrode material of claim 1, wherein the transition metal chalcogenide has a two-dimensional lamellar stacked expander morphology;
or, the transition metal chalcogenide has a morphology of two-dimensional lamellae.
3. The sodium ion battery electrode material of claim 2, wherein the two-dimensional sheet has a thickness of between 2nm and 10 nm;
and/or, the two-dimensional sheet has metal M vacancies.
4. The sodium ion battery electrode material of claim 2, wherein the two-dimensional sheet has a monoclinic crystal structure, or a hexagonal crystal structure.
5. The sodium ion battery electrode material of claim 1, wherein the sodium ion battery electrode material has a chemical formula represented by M a Y 2a2 A is more than or equal to 3 and less than or equal to 5, and M represents one or more of transition metal elements; preferably, M is selected from one or more of vanadium, titanium, chromium, molybdenum, tungsten or niobium elements.
6. The sodium ion battery electrode material of any one of claims 1 to 5, wherein the predetermined temperature is between 600 ℃ and 800 ℃; preferably 700 ℃.
7. A sodium ion battery electrode sheet, comprising: a sodium ion battery positive electrode material as defined in any one of claims 1 to 6; and a conductive agent and a current collector.
8. The sodium ion battery electrode sheet of claim 7, wherein the conductive agent comprises ketjen black;
and/or the current collector is a metal copper foil.
9. A method for preparing the sodium ion battery electrode sheet according to claim 7 or 8, comprising the steps of:
mixing the sodium ion battery anode material and the conductive agent to prepare slurry;
and coating the slurry on the current collector and drying to obtain the current collector.
10. A sodium ion battery comprising:
a sodium ion battery electrode material as defined in any one of claims 1 to 6;
or, the sodium ion battery electrode sheet as defined in claim 7 or 8;
or, the sodium ion battery electrode plate obtained by the preparation method of claim 9.
CN202310180618.XA 2022-04-18 2022-04-18 Electrode material and electrode sheet of sodium ion battery, preparation method of electrode material and electrode sheet and battery Pending CN116190638A (en)

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