CN114976035B - MXene film with corrugation shape, preparation method thereof, metal composite material, application and battery - Google Patents

MXene film with corrugation shape, preparation method thereof, metal composite material, application and battery Download PDF

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CN114976035B
CN114976035B CN202210641308.9A CN202210641308A CN114976035B CN 114976035 B CN114976035 B CN 114976035B CN 202210641308 A CN202210641308 A CN 202210641308A CN 114976035 B CN114976035 B CN 114976035B
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mxene
metal
lithium
film
mxene film
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CN114976035A (en
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杨树斌
顾佳男
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/38—Moulds, cores or other substrates
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/78—Shapes other than plane or cylindrical, e.g. helical
    • 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 corrugated MXene film, a preparation method thereof, a metal composite material, an application and a battery, wherein the MXene film contains a MXene material and has a periodic corrugated shape; the preparation method of the MXene film comprises the following steps: the dispersion containing the MXene material is obtained after molding by a template with a periodic ripple appearance; the MXene film corrugation is compounded with the metal lithium with electrochemical activity, so that on one hand, the effect similar to that of forming uniform lithium ions and electric fields in an array structure and inducing uniform deposition of the metal lithium can be achieved; on the other hand, the appearance of the corrugation has a smooth interface, and the tip effect caused by a sharp interface of a composite component in the array structure is avoided; in yet another aspect, the MXene component contained in the MXene film can also act as a nucleating agent to further reduce the nucleation overpotential of the metallic lithium, promote the controlled deposition of the metal, and thus provide a metallic battery having excellent long cycle performance and high safety performance.

Description

MXene film with corrugation shape, preparation method thereof, metal composite material, application and battery
Technical Field
The invention belongs to the technical field of new materials and batteries, and particularly relates to a corrugated MXene film, a preparation method thereof, a metal composite material, application and a battery.
Background
Lithium (Li) metal has the highest specific capacity (3860 mAh/g) and the lowest electrochemical potential (-3.04V), and is considered to be the most potential negative electrode material of lithium-based secondary batteries, but as a negative electrode material, lithium metal is unevenly deposited at interface positions to form dendrites during repeated charge and discharge, and as lithium dendrites grow uncontrollably, a separator is likely to be pierced to form a battery short circuit, which causes a safety problem, preventing further application of lithium metal as a negative electrode material in batteries.
In order to solve the technical problem of lithium dendrite growth, researchers have tried various technical approaches, mainly including: (1) Preparing a three-dimensional (3D) matrix with stable performance and good conductivity, and compositing the three-dimensional (3D) matrix with metal lithium to obtain a metal lithium composite material, wherein the metal lithium composite material promotes uniform plating layers of the metal lithium in the charge and discharge process, such as rGO film-Li, carbon nanotube foam-Li, 3D Cu foam-Li, 3D Ni network-Li and the like, but the material generally has low coulombic efficiency and low volume capacity due to a large number of porous structures; (2) Improved SEI films, e.g. graphene films, alloy layers, moS in SEI films 2 Layers, mxnes or polymers, etc.; (3) Additives such as LiF, polysulfide, or fluoroethylene carbonate (FEC) are added to the electrolyte to grow a stable and uniform SEI film in situ.
The applicant has previously conducted a series of studies on this technical problem, including: compounding metal lithium with an MXene material (CN 202010002855.3), and taking the MXene material as a nucleating agent to induce the growth of the metal lithium, so that the generation of sharp lithium dendrites is avoided; alternatively, lithium metal is combined with copper metal to form a lithium metal composite material (Advanced Materials,2019,31 (29): 1901310.1-1901310.6.; CN 201910206942.8) of a vertical array structure to form a skeleton of the vertical array structure, and it has been found that the combination of a metal skeleton having an array structure in lithium metal can form a uniform electric field to inhibit the induction of uniform deposition of lithium metal, but in such a vertical array structure, the tip needle effect is highly amplified due to the presence of a very small radius of curvature (sharp edge of the metal skeleton), resulting in an upper surface of the electrode being prone to lithium deposition. Therefore, how to further improve this vertical array structure is a technical problem that we further need to solve.
Disclosure of Invention
In order to solve the tip effect generated after the framework of the vertical array structure is compounded with the metal lithium, the first aspect of the invention provides the MXene film with the corrugated shape, wherein the MXene film contains the MXene material and has the periodic corrugated shape.
In some embodiments, the MXene film has a sinusoidal wave-like morphology.
In some embodiments, the ripple size of the MXene film satisfies the relationship: 2r/w is between 0.5 and 1.0, and h/w is between 1.0 and 2.3, wherein r is the radius of curvature, w is the wave width, and h is the wave height.
In some embodiments, the thickness of the MXene film is between 1 μm and 500 μm.
In some embodiments, the chemical formula of the MXene material described above is represented by M n+1 X n T x Wherein M is selected from one or more of transition metal elements, X is selected from one or more of carbon, nitrogen or boron elements, T x Represents a functional group, and comprises one or more of-F, -Cl, br, I, -O, -S and OH, wherein n is more than or equal to 1 and less than or equal to 4.
The second aspect of the present invention provides a method for preparing the MXene film described above, comprising: the dispersion containing the MXene material is obtained after molding through a template with a periodic ripple morphology.
In some embodiments, the surface of the template has a sinusoidal wave-like topography.
In some embodiments, the ripple size of the template satisfies the relationship: 2r/w is between 0.5 and 1.0, and h/w is between 1.0 and 2.3, wherein r is the radius of curvature, w is the wave width, and h is the wave height.
In some embodiments, the template is obtained by sequentially winding or stacking at least two films with different widths at intervals.
In some embodiments, the thickness of the film is between 1 μm and 500 μm.
In some embodiments, the template is a shaft having a corrugated surface.
In some embodiments, a binder and/or a conductive agent is also included in the dispersion.
In some embodiments, the binder comprises: one or more of polyvinylidene fluoride, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol or sodium carboxymethyl cellulose; the above-mentioned conductive agent includes: one or more of graphene, carbon nanotubes and carbon black.
In some embodiments, the dispersion is in a liquid state, wherein the solvent is selected from one or more of water, N-methylpyrrolidone, N-dimethylformamide, ethanol, isopropanol, acetone, toluene, or N-hexane.
In some embodiments, the dispersion is in a liquid state, wherein the concentration of the MXene material is between 0.1mg ml -1 To 10mg ml -1 。
The third aspect of the invention provides a metal composite material, which is obtained by compounding metal and the MXene film with the ripple morphology; or the MXene film is obtained by compounding metal and the MXene film obtained by the preparation method.
In some embodiments, the metal comprises: at least one of metallic lithium, metallic sodium, metallic zinc, metallic aluminum and metallic magnesium.
In a fourth aspect, the present invention provides the use of a metal composite as described above as a battery electrode.
The fifth aspect of the present invention provides a method for preparing the metal composite material, comprising the steps of: is obtained by electroplating metal on the MXene film; or, the metal or the alloy of the metal is melted and then coated on the MXene film, and the alloy is obtained after cooling.
A sixth aspect of the present invention provides a battery comprising the above metal composite; or the metal composite material obtained by the preparation method.
The invention adopts the technical conception that a hard template is utilized to prepare an MXene film with a corrugated section, the MXene film is used as a composite component to be compounded with metal lithium to obtain a metal lithium composite electrode, and in the metal lithium electrode, the shape of the MXene film corrugation can be similar to that of an array structure to form uniform lithium ions and electric fields on one hand, and the effect of uniform deposition of the metal lithium is induced; on the other hand, the appearance of the corrugation has a smooth interface, and the tip effect caused by a sharp interface of a composite component in the array structure is avoided; on the other hand, the MXene component contained in the MXene film can also play a role of a nucleating agent, so that the nucleation overpotential of the metal lithium is further reduced, the controllable deposition of the metal lithium is promoted, and the metal lithium battery with excellent long-cycle performance and high safety performance is further obtained; in addition, the corrugated MXene film also has structural elasticity, so that the metal lithium composite electrode provided by the invention has flexibility or bendability, and a new technical approach is provided for the research and development design of flexible metal lithium batteries.
Drawings
FIG. 1 is a schematic view of the process (a) for preparing a corrugated MXene film according to example 1 of the present invention; SEM photographs (b and c) and optical photographs (inset in c) of the surface and interface of the corrugated MXene film in example 2; cyclic resistance response test results (d) for corrugated and flat MXene films;
FIG. 2 shows plating capacities of 0.5, 4.0 and 8.0mAh cm in example 3 of the present invention -2 SEM photographs of the lower lithium metal composite electrode (a, b, c); COMSOL Multiphysics finite element multiple physical field simulation (d); in-situ optical microscope pictures of the corrugated MXene film (e) and the copper foil (f) in the electroplating process;
FIG. 3 is a simulated groove pattern (a) of COMSOL Multiphysics of the present invention; simulation results of lithium deposition behavior at different 2r/w values (b); as the 2r/w value increases, the lithium deposition degree (dd Li ) A graph (c) of the relationship with 2r/w values; a sinusoidal model (d);
FIG. 4 shows the lithium deposition degree (dd) Li ) Fitting relation graph (a) with 2r/w value;lithium deposition degree (dd Li ) A graph (b) of fit to h/w values;
FIG. 5 shows the contact angle test result (a) of the electrolyte in example 3 of the present invention; a nucleation curve (b) for deposition of metallic lithium on corrugated MXene film, planar MXene film and copper foil; cycling performance curves (c) for different symmetrical cells; testing the rate performance of the corrugated MXene-Li symmetrical battery;
FIG. 6 is photographs of the pouch versus battery of example 4 of the present invention (a and b); electroplating and stripping curves (c) at different angles for a symmetric battery containing a metallic lithium composite electrode of the invention; plating and stripping curves (d) at different angles for symmetrical cells containing a comparative electrode; constant current cycling performance (e) of symmetric batteries containing the metallic lithium composite electrode of the invention at different electroplating depths;
FIG. 7 is a graph showing the cycling performance (a) at 0.2C and the number of charge and discharge cycles (inset in a) for different full cells in example 5 of the present invention; rate capability (b) of different full cells; cycling performance at 6.4C in different full cells (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.
Example 1
The invention provides a preparation method of a corrugated MXene film, which comprises the following steps: the MXene-containing dispersion was coated and shaped on a template having a corrugated surface to give a MXene film. In this example, an embodiment is given in which a MXene-containing dispersion is coated and dried on a template having a corrugated surface, and then formed, wherein the template having a corrugated surface is formed by alternately winding film materials of different widths to form a roll, and the surface of the roll presents a periodic array of corrugated surfaces; then, the MXene-containing dispersion was applied to the corrugated surface, and after drying, a corrugated MXene film was obtained, and a schematic illustration of the production process was shown in FIG. 1 a. A circular winding pattern is shown in fig. 1a, but the invention is not limited to the winding method shown in the schematic diagram; in other embodiments, the films or sheets may also be stacked and arranged to provide a corrugated surface as well. The corrugated template of the present invention may also be obtained by other methods, such as a template having a particular corrugated surface by fine machining, and the present invention is not limited to the source of the template. The method for preparing the corrugated template through winding or laminating the film materials with different widths can simply obtain the corrugations with different curved surface sizes through the thickness and width regulation of the film materials, and is particularly simple and convenient for general finish machining of micron-sized corrugated surfaces which are difficult to manufacture, and has economical and practical applicability.
In a more specific embodiment of this example, the film is a metal copper foil or sheet, and the thickness of the film is optionally between 1 μm and 500 μm, preferably between 10 μm and 100 μm.
Because the MXene material itself is hydrophilic, water is non-toxic and harmless as a solvent, and is easily dried, it is preferable that the solvent in the dispersion containing the MXene material is an aqueous solution, and of course, other common solvents such as one or more of water, N-methylpyrrolidone, N-dimethylformamide, ethanol, isopropanol, acetone, toluene, or N-hexane may be selected. In some preferred embodiments, to adjust the viscosity or increase the strength of the film, some functional ingredients such as binders, e.g., one or more of polyvinylidene fluoride, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, or sodium carboxymethyl cellulose, or other composite components such as conductive agents, including one or more of graphene, carbon nanotubes, carbon black, may also be added to the dispersion.
The concentration of the MXene material in the dispersion may be adjusted according to the actual process, and in some embodiments the MXene material in the dispersion is between 0.1mg ml -1 To 10mg ml -1 。
Of course, the MXene-containing dispersion of the present invention is not limited to a liquid dispersion, and may be a gel-state MXene-containing dispersion, which may be molded by being applied to a mold plate.
In other embodiments, it is also possible that the metallic or polymeric composite material containing the MXene material is rolled from a reel having a corrugated surface.
Example 2
This example provides a method for preparing a particular corrugated MXene film using the method of example 1, wherein the dispersion comprises MXene (Ti 3 C 2 T x And graphene oxide (GO, manufactured by Hummers method) and deionized water, wherein the mass ratio MXene: GO is 8:2, and the mass concentration of the solid content in the dispersion liquid is adjusted to be 5mg mL -1 . The dispersion is coated on the corrugated surface of the metallic copper, and the MXene film can be easily removed from the corrugated surface after drying because the copper foil has hydrophobicity, so that the MXene film with the corrugation is obtained. The same method was used to coat the dispersion on a planar copper foil to give a comparative planar MXene film.
FIGS. 1b and c show SEM photographs of the corrugated MXene film, and it can be seen that the surface of the MXene film exhibits an ordered corrugated structure having a wavelength of about 7 μm and a thickness of about 10 μm, and the MXene film has excellent flexibility (inset in FIG. 1 c). FIG. 1d is a cyclic resistance response test result, and it can be seen that the MXene film having the corrugated structure has a more regular resistance response than the MXene film having the planar structure. This further shows that the corrugated MXene film has a more regular structure.
Example 3
The embodiment provides a metal lithium composite material and application thereof in a metal lithium battery electrode, wherein the metal lithium composite material comprises metal lithium and a corrugated MXene film, and in the embodiment, the metal lithium composite electrode is obtained by a method for electroplating lithium on the MXene film, and the specific implementation steps comprise:
corrugated MXene film and metallic lithium (counter electrode) were assembled into a battery device with an electrolyte of 1M lithium bis (trifluoromethane) sulfonimide (LiTFSI) organic solution+1.0% LiNO 3 The solvent was dioxane/dimethoxyethane (DOL/DME) (1:1 vol) using 4mA cm -2 Is subjected to lithium plating.
The electroplating process of lithium metal on corrugated MXene film was observed by in situ optical microscopy, and FIGS. 2a, b and c show electroplating capacities of 0.5, 4.0 and 8.0mAh cm, respectively -2 SEM photograph of the underlying metallic lithium composite electrode, when the plating capacity was 0.5mAh cm -2 (FIG. 2 a), metallic lithium grows mainly in the voids of the corrugations of the MXene film, and as the plating capacity increases (FIGS. 2b and c), metallic lithium grows gradually in the corrugated gaps of the MXene film, and the metallic lithium composite electrode changes gradually to be dense, and no lithium dendrites are observed in the process. The finite element multi-physical field simulation was performed using COMSOL Multiphysics, and as shown in fig. 2d, the concentration gradient of lithium ions was significantly reduced with the increase of metallic lithium plating, which can be attributed to the uniform electric field generated by the unique ripple result, ensuring uniform deposition of lithium ions. The in-situ optical microscope photograph during the electroplating process can also be used for seeing the electroplated lithium on the corrugated MXene film, and the capacity is up to 1.28mAh cm -2 The whole composite electrode surface was smooth, no lithium dendrites appeared (fig. 2 e); in contrast, during continuous lithium plating of the metal copper foil surface, lithium dendrites that clearly grow uncontrollably appear (fig. 2 f).
To understand the effect of ripple size on metallic lithium plating behavior, we designed a fluted model (as shown in FIG. 3 a) in which the process of depositing metal into the fluted model was simulated using COMSOL Multiphysics, where w is the flute bottom width and h is the flute depthR is the radius of curvature of the groove, as can be seen from figures 3b and c, the lithium deposition (dd Li ) As the 2r/w value increases, the lithium deposition degree reaches the maximum under the condition of 2 r/w=1. FIG. 4a shows that dd is obtained Li And a linear relationship of 2 r/w; FIG. 4b fits to obtain dd Li And h/w, by which the design of the corrugated template can be aided to obtain the optimal corrugated size. It can be seen that a larger radius of curvature r favors the deposition of metallic lithium, with an optimal amount of lithium deposition when r=0.5 w, h=w, which curve resembles a sine wave curve, and therefore it is preferred that the corrugated template have sinusoidal shaped corrugations (as shown in fig. 3d, where r is the radius of curvature, w is the wave width, and h is the wave height).
To further explore nucleation behavior on metallic lithium corrugated MXene films, contact angle tests were performed, as shown in fig. 5a, where the contact angle (θ) of the electrolyte on corrugated MXene films was close to zero, significantly lower than the contact angles on planar MXene films (25 °) and copper foil (43.7 °). Demonstrating the better lyophilicity of corrugated MXene films, the overpotential test results are given in fig. 5b, which shows that corrugated MXene films have an overpotential value of 13.5mV, significantly lower than planar MXene films (35.1 mV) and copper foil (26.1 mV), which can homogenize the electric field and reduce the local current density due to the corrugated structure. In addition, corrugated MXene films also exhibit relatively low charge transfer overpotential (2.7 mV), below the planar MXene film (5.0 mV) and copper foil (8.1 mV), meaning that the corrugated structure facilitates rapid transfer of lithium ions and electrons.
The obtained metal lithium composite electrode was first assembled with 2032 type button symmetric battery to evaluate the electrochemical performance of the electrode, as shown in FIG. 5c, the metal lithium composite electrode (Sine-wave analogous MXene-Li) of the present invention was fabricated at 1.0mA cm -2 Is 1.0mAh cm -2 The lower part of the alloy shows stable cycle performance, and the cycle life is longer than 1280 hours, and is obviously better than that of a planar MXene film composite electrode (Flat MXene-Li,1100 hours) and a copper foil plating lithium electrode (Cn-Li, 800 hours). Notably, even after 1280 hours, the metal of the present inventionThe mass transfer control overpotential of the lithium composite electrode is still below 20mV. FIG. 5d shows the rate capability of the lithium metal composite electrode of the present invention at different current densities, as can be seen, at up to 16.0mA cm -2 Still has good rate capability and low mass transfer control overpotential (-100 mV).
Example 4
This example provides a soft pack symmetric battery containing the metallic lithium composite electrode of the present invention to demonstrate the flexible nature of the electrode of the present invention. The metallic lithium composite electrode obtained in example 3 above was assembled according to a conventional method to obtain a soft-pack symmetrical battery (as shown in fig. 6a and b). The soft-packed battery containing the metal lithium composite electrode of the present invention can still be normally plated-peeled off under 0-45 DEG bending (FIG. 6 c); the cell failed at 15 ° bend in comparison to the electrode of the planar MXene film (fig. 6 d). The MXene film has the structural elasticity generated by the corrugated structure, can also endow the metal lithium composite electrode with the characteristic of flexibility when being used as a carrier of metal lithium, and can be used for energy storage devices in some special fields, such as batteries on wearable equipment. Fig. 6e also shows the plating-stripping curves of the soft-pack symmetrical battery at different plating capacities, showing high capacity and excellent stability.
Example 5
The embodiment provides a full cell containing the metal lithium composite electrode, wherein the positive electrode material in the full cell is lithium iron phosphate (LiFePO) 4 ) LiFePO is prepared 4 Mixing PVDF and conductive carbon black according to the ratio of 7:2:1, adding NMP to prepare slurry, coating the slurry on aluminum foil, drying the slurry to obtain a positive plate, assembling the positive plate with the metal lithium composite electrode obtained in the example 3 and electrolyte according to a conventional method to obtain a button 2032 type full cell (marked as Sine-wave analogous MXene Li// LFP), and testing electrochemical performance. The metal lithium composite negative electrode is replaced by a planar MXene film Li-plated electrode and a copper foil Li-plated electrode respectively by the same method, so that a comparison full battery is obtained, and the comparison full battery is marked as Flat MXene-Li// LFP and Cu-Li// LFP respectively.
FIG. 7a is a magnification at 0.2CThe full battery of the invention still shows 157mAh g after 160 cycles according to the charge-discharge curve -1 Is higher than the capacity of the comparative full cell Flat MXene-Li// LFP (145 mAh g -1 ) And Cu-Li// LFP (77 mAh g) -1 ). When the current density was increased to 6.4C (FIGS. 7b and C), the cell of the present invention still exhibited the best capacity (-100 mAh g) over 420 cycles -1 ) Is significantly better than the comparison full cell Flat MXene-Li// LFP (53 mAh g -1 ) And Cu-Li// LFP (12 mAh g) -1 ). The excellent electrochemical performance of the full battery of the invention benefits from the unique corrugated structure of the metal composite lithium anode, can eliminate the tip effect in the carrier in the array structure, and simultaneously effectively homogenize the distribution of lithium ions and batteries, wherein the MXene component can also act as a speech nucleating agent, and the metal lithium has low nucleation overpotential, so that the metal lithium is uniformly and controllably deposited.
Of course, in other embodiments, the positive electrode material in the full cell of the present invention may be replaced with other types of materials, such as lithium cobaltate, lithium manganese iron phosphate, ternary materials, lithium manganate, and the like.
Because the MXene material has excellent conductivity, the MXene film can also be used as a current collecting carrier, and the anode material or the cathode material is loaded on the MXene film with the corrugated shape, so that the novel flexible battery is assembled, that is, the MXene film is not limited to be used on a metal lithium battery, can be used as the current collecting carrier of the flexible battery, and provides a new technical approach and material for the research and development of the flexible battery.
Example 6
The present embodiment provides another method for preparing a metal composite material, taking lithium metal as an example, and the steps include melting lithium metal into a liquid state, coating the liquid state on the surface of the MXene film, and cooling to obtain the metal composite electrode.
More specifically, the implementation method comprises the following steps: in an argon (purity is more than 99.999%) environment, adding 400mg of metal lithium blocks into a stainless steel pot, heating to 200 ℃ and melting the metal lithium blocks into a liquid state; and then coating liquid metal lithium on the surface of the MXene film, and obtaining the metal composite electrode after natural cooling. Since the MXene material itself has a lithium-philicity, liquid metallic lithium can be easily spread on the surface of the film.
In another embodiment, other metal components may also be added to the molten metal lithium mass to form a metal lithium alloy that acts to regulate the surface tension of the molten liquid metal. One specific embodiment is: in an argon (purity is more than 99.999%) environment, adding 400mg of metal lithium blocks into a stainless steel pot, heating to 200 ℃, melting the metal lithium blocks into a liquid state, maintaining the heating temperature, adding 40mg of metal magnesium sheets into the liquid metal lithium, stirring and mixing, melting the metal magnesium sheets to form a liquid lithium magnesium alloy, coating the liquid lithium magnesium alloy on the surface of the MXene film, and naturally cooling to obtain the metal composite material.
According to the technical teaching of the invention, the corrugated MXene film can be also applied to compounding other types of metals, such as metal sodium (Na), zinc (Zn), aluminum (Al), magnesium (Mg) and the like, so as to obtain metal composite materials, and the metal composite materials are used for electrodes of corresponding metal batteries, so that novel metal sodium batteries, metal zinc batteries, metal aluminum batteries, metal magnesium batteries and the like are obtained.
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 (16)

1. The preparation method of the MXene film is characterized by comprising the following steps: and forming the dispersion containing the MXene material through a template with a periodic ripple morphology to obtain the MXene film, wherein the MXene film has the periodic ripple morphology.
2. The method of claim 1, wherein the MXene film has a thickness of 1 μm to 500 μm.
3. The method of manufacturing of claim 1, wherein the MXene film has a sinusoidal wave like morphology.
4. The method of claim 1, wherein the MXene film has a ripple size satisfying the relationship: 2r/wBetween 0.5 and 1.0,h/wbetween 1.0 and 2.3, wherein,rin the form of a radius of curvature,win order to be a wave width,his wave height.
5. The method of claim 1, wherein the MXene material has a chemical formula of M n+1 X n T x Wherein M is selected from one or more of transition metal elements, X is selected from one or more of carbon, nitrogen or boron elements, T x Represents a functional group, including one or more of-F, -Cl, br, I, -O, -S and-OH, and is 1-1n≤4。
6. The method of manufacturing according to claim 1, wherein the surface of the template has a sinusoidal wave-like topography;
and/or, the ripple size of the template satisfies the relation: 2r/wBetween 0.5 and 1.0,h/wbetween 1.0 and 2.3, wherein,rin the form of a radius of curvature,win order to be a wave width,his wave height.
7. The method of claim 1, wherein the template is obtained by sequentially winding or stacking at least two films having different widths at intervals.
8. The method of claim 7, wherein the film has a thickness of 1 μm to 500 μm.
9. The method of claim 7, wherein the template is a shaft having a corrugated topography on a surface.
10. The method of claim 1, wherein the dispersion further comprises a binder and/or a conductive agent;
and/or the dispersion is in a liquid state, wherein the solvent is selected from one or more of water, N-methylpyrrolidone, N-dimethylformamide, ethanol, isopropanol, acetone, toluene or N-hexane;
and/or the dispersion is in a liquid state, wherein the concentration of the MXene material is between 0.1mg ml -1 To 10mg ml -1 。
11. The method of manufacturing of claim 10, wherein the binder comprises: one or more of polyvinylidene fluoride, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol or sodium carboxymethyl cellulose: the conductive agent includes: one or more of graphene, carbon nanotubes and carbon black.
12. A metal composite material, characterized in that the metal composite material is obtained by compounding a metal with an MXene film obtained by the production method according to any one of claims 1 to 11.
13. The metal composite of claim 12, wherein the metal comprises: at least one of metallic lithium, metallic sodium, metallic zinc, metallic aluminum and metallic magnesium.
14. Use of the metal composite according to claim 12 or 13 as a battery electrode.
15. A method of producing the metal composite material according to claim 12 or 13, wherein the metal composite material is obtained by electroplating a metal on the MXene film;
or, the metal or the alloy of the metal is melted and then coated on the MXene film, and the alloy is obtained after cooling.
16. A battery comprising the metal composite material according to claim 12 or 13; or, a metal composite material according to the production method of claim 15.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108568926A (en) * 2017-11-21 2018-09-25 中国科学院金属研究所 A method of efficiently preparing highly directional, high-densit two-dimensional material film
WO2019126031A1 (en) * 2017-12-22 2019-06-27 Drexel University Crumpled mesoporous mxene powders synthesized by acid-, base-, or salt-induced crumpling
KR20200121674A (en) * 2019-04-16 2020-10-26 한국과학기술원 Method of mxene thin film and mxene thin film manufactured therefrom

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9755241B2 (en) * 2015-04-08 2017-09-05 Nanotek Instruments, Inc. Alkali metal secondary battery containing a dendrite-intercepting layer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108568926A (en) * 2017-11-21 2018-09-25 中国科学院金属研究所 A method of efficiently preparing highly directional, high-densit two-dimensional material film
WO2019126031A1 (en) * 2017-12-22 2019-06-27 Drexel University Crumpled mesoporous mxene powders synthesized by acid-, base-, or salt-induced crumpling
KR20200121674A (en) * 2019-04-16 2020-10-26 한국과학기술원 Method of mxene thin film and mxene thin film manufactured therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
All-pseudocapacitive asymmetric MXene-carbon-conducting polymer supercapacitors;Ke Li et al.;《Nano Energy》;第75卷;第1-8页 *

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