CN114944489A - Thin film layer with accordion MXene array and preparation method thereof, current collector, electrode and battery - Google Patents

Thin film layer with accordion MXene array and preparation method thereof, current collector, electrode and battery Download PDF

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CN114944489A
CN114944489A CN202210680388.9A CN202210680388A CN114944489A CN 114944489 A CN114944489 A CN 114944489A CN 202210680388 A CN202210680388 A CN 202210680388A CN 114944489 A CN114944489 A CN 114944489A
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mxene
accordion
array
film layer
metal
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CN114944489B (en
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杨树斌
曹振江
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M10/42—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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M2004/027—Negative 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a film layer with an accordion MXene array, a preparation method of the film layer, a current collector, an electrode and a battery. Wherein the film layer with the accordion MXene array contains accordion MXene materials which are arranged in an array shape. The invention provides a method for simply and effectively preparing ordered or vertically arranged structural matrixes, which is characterized in that accordion MXene materials have the characteristics of oriented arrangement and low curvature of MXene sheets and are spread on an interface layer under the action of the surface tension of a liquid-liquid two-phase mixed liquid interface, so that an ultrathin film layer with the oriented arrangement of the MXene sheets and an accordion MXene array structure is obtained. The accordion MXene array structure has simple preparation method and obvious effect when being applied to metal electrodes, provides a technical path for realizing application for practical application in high-power and high-capacity lithium metal batteries, and has obvious industrial practical value.

Description

Thin film layer with accordion MXene array and preparation method thereof, current collector, electrode and battery
Technical Field
The invention belongs to the technical field of new materials and batteries, and particularly relates to a thin film layer with an accordion MXene array, a preparation method of the thin film layer, a current collector, an electrode and a battery.
Background
Lithium metal negative electrode has the highest theoretical specific capacity (3860mAh g) -1 ) And the lowest electrochemical potential (-3.04V relative to the standard hydrogen electrode), is considered to be the most potential replacement for graphite negative electrodes (372mAh g) -1 ) The material of (1). In recent decades, to develop high performance Lithium Metal Batteries (LMBs), lithium metal negative electrodes have been used to mate with a variety of high capacity positive electrodes, including layered nickel rich positive electrodes, sulfur and oxygen, which typically have energy densities 2-6 times higher than Lithium Ion Batteries (LIBs). However, slow ion diffusion and high charge transfer resistance in lithium metal negative electrodes, especially under high-rate charge-discharge conditions, greatly exacerbate the growth and volume change of lithium dendrites, the lithium metal battery electrolyte is rapidly consumed, the coulombic efficiency is reduced, and the capacity is significantly attenuated.
In order to improve the diffusion and electron transfer capability of lithium ions in a lithium metal negative electrode and further improve the electrochemical performance of the lithium metal negative electrode, researchers have developed various methods, such as: constructing a three-dimensional matrix material, designing an artificial Solid Electrolyte Interface (SEI), a modified electrolyte and the like; among them, the three-dimensional matrix materials reported at present, including graphene aerogel, three-dimensional carbonaceous electrode, three-dimensional porous metal structure, etc., have been widely studied. The three-dimensional matrix material with the porous structure can adsorb a large amount of electrolyte, thereby increasing the local ion concentration in the electrolyte and reducing the ion concentration polarization under high current density. In addition, the three-dimensional structure can buffer the volume change of the electrode, and the whole volume change of the electrode is localized to improve the stability of the electrode, so that the electrochemical performance of the lithium metal negative electrode is improved.
However, these reported three-dimensional matrix materials are generally thick (over 100 μm) and structurally disordered random arrangements. According to diffusion coefficient equation D eff D × epsilon/τ (where, D eff Is the effective diffusion coefficient of the ion, and epsilon isPorosity, τ being the degree of curvature), the conductive path is determined by the ratio of porosity and degree of curvature. The random arrangement structure in the three-dimensional matrix material has high flexibility, so that the effective electron diffusion rate is low, the ion transmission is slow, and the electric field in the electrode and the lithium ion flux are not uniformly distributed. Furthermore, high tortuosity will lead to Li + The redox reaction of/Li only occurs at a limited cathode/electrolyte interface, resulting in very low rate performance: (<1mA cm -2 ). Sand' time-based lithium ion plating time model (t) Sand ＝πD eff (z c c 0 F) 2 /4(Jt a ) 2 ) And the thicker 3D negative electrode also has high flexibility, so that the growth of lithium dendrites is aggravated under the condition of high-rate charge and discharge, and the performance of the battery is remarkably reduced and potential safety hazards are caused. It can be seen that the degree of curvature plays a very important role in ion diffusion and charge transfer of the three-dimensional electrode.
According to the Bruggeman relationship, tortuosity (τ) is related to porosity (ε) and Bruggeman index (α): tau ═ epsilon α . In this case, when the degree of curvature is 1, corresponding to the electrode having the fastest ion transport, it can be seen that the ideal electrode should be continuously and vertically arranged, and a three-dimensional matrix having an ordered or vertically arranged structure is crucial to promote ion transport, reduce apparent resistance, and greatly improve rate capability and practicality of a lithium metal negative electrode.
Disclosure of Invention
The invention aims to solve the technical problems that slow ion diffusion and high charge transfer resistance exist in a lithium metal negative electrode, particularly, the growth and volume change of lithium dendrite are greatly accelerated under the condition of high-rate charge and discharge, the electrolyte of a lithium metal battery is rapidly consumed, the coulombic efficiency is reduced, and the capacity is obviously attenuated.
The invention provides a film layer with an accordion MXene array, wherein the film layer contains accordion MXene materials which are arranged in an array shape.
In some embodiments, the chemical formula of the accordion MXene material is represented by M n+1 X n T x Which isIn the formula, M is one or more selected from transition metal elements, X is one or more selected from carbon, nitrogen and boron, and T is x Represents a surface functional group.
In some embodiments, M in the accordion MXene material is selected from one or more of Ti, Ta, Nb, Cr, V, and Mo elements.
In some embodiments, the above T x including-F, -Cl, -Br, -I, -S, -O, -NH 4 At least one of (1).
In some embodiments, M in the accordion MXene material contains Nb.
In some embodiments, X in the accordion MXene material is a C and/or N element.
In some embodiments, the thin film layer has a thickness of 1 μm to 100 μm.
The second aspect of the present invention provides a method for preparing the above thin film layer, comprising the steps of: adding the accordion MXene material into a liquid-liquid two-phase system to disperse the accordion MXene material in an interface layer of a liquid-liquid two phase to form an accordion array film; and transferring the accordion array film to the surface of a medium to obtain the thin film layer.
In some embodiments, a more specific embodiment of the above method of making, comprises: the dispersion of the accordion MXene material is added into a water-oil two-phase system.
In some embodiments, a more specific embodiment of the above method of making, comprises: and arranging a dielectric layer on the interface layer, and transferring the accordion array film to the surface of the dielectric layer by pulling the dielectric layer to obtain the thin film layer.
In some embodiments, the oil phase of the water-oil two-phase system is selected from dichloromethane, trichloromethane, tetrachloromethane.
In some embodiments, the solvent in the dispersion of accordion MXene material is water.
In some embodiments, the dielectric layer is a metal foil.
In some embodiments, the metal foil includes one or more of copper, nickel, and stainless steel.
The third aspect of the invention provides a current collector, which comprises a conductive layer, wherein the surface of the conductive layer is provided with the film layer with the accordion MXene array; or a thin film layer obtained by the above-mentioned production method.
In some embodiments, the conductive layer is a metal foil.
In some embodiments, the metal foil is made of copper, nickel, or stainless steel.
A fourth aspect of the invention provides an electrode comprising a metal having electrochemical activity and a current collector as described above;
in some embodiments, the electrochemically active metal is selected from at least one of lithium, sodium, zinc, calcium, and potassium.
The fifth aspect of the present invention provides a method for preparing the electrode, including the steps of: electroplating the metal onto the current collector.
A sixth aspect of the present invention provides another method for producing the above electrode, comprising the steps of: and heating and melting the metal or the metal alloy, and compounding the metal or the metal alloy with the current collector.
A seventh aspect of the invention provides a battery comprising the current collector described above; or, the above-mentioned electrode.
The invention has the beneficial technical effects that:
1. the invention provides a method for simply and effectively preparing ordered or vertically arranged structural matrixes, which is characterized in that accordion MXene materials have the characteristics of oriented arrangement and low curvature of MXene sheets, and the accordion MXene materials are spread on an interface layer under the action of the surface tension of a liquid-liquid two-phase mixed liquid interface, so that an ultrathin film layer with the oriented arrangement of the MXene sheets and an accordion MXene array structure is obtained;
2. when the accordion MXene array is used in a battery electrode, a thin film layer of the accordion MXene array is used as a matrix of metal lithium, on the one hand, due to the ultra-thin array structure and the low curvature of an MXene sheet layer, an electrolyte can be quickly immersed, and the quick diffusion of lithium ions is promoted; in the second aspect, the accordion MXene array structure can also provide a uniform electric field, so that lithium ions are uniformly distributed; in the third aspect, the MXene material can also reduce the nucleation overpotential of lithium metal and inhibit the growth of lithium dendrites to obtain a novel lithium metal battery without dendrites, and the stability and the safety of the battery are improved; in a fourth aspect, the accordion MXene array structure provided by the invention has abundant space, can provide buffer space for volume change of lithium metal in a charging and discharging process, and improves the stability of the whole electrode. Through experimental tests, the accordion MXene array structure disclosed by the invention is applied to a battery cathode, and the electrochemical properties of the battery, including cycle performance, rate performance and coulombic efficiency, are effectively improved.
3. The accordion MXene array structure has simple preparation method and obvious effect when being applied to metal electrodes, provides a technical path for realizing application in high-power and high-capacity lithium metal batteries, and has obvious industrial practical value.
Drawings
FIG. 1 is an SEM photograph of accordion TiNbC-MXene (a) and two-dimensional TiNbC-MXene in example 1 of the present invention;
FIG. 2 is a schematic diagram (a) and a corresponding photograph (b) of a manufacturing process of a thin film layer having an accordion TiNbC-MXene array structure in example 1 of the present invention;
FIG. 3 is a schematic diagram of the rapid spreading of accordion TiNbC-MXene dispersion in a water-oil two-phase interface layer in example 1 of the present invention (a), the top view (b) and the side view (c) of the MXene thin film layer obtained by the preparation method, and the contact angle photograph (d) of dropping the electrolyte on the thin film layer;
fig. 4 is a copper foil composite tape with a film layer having an accordion MXene array on the surface prepared in example 1 of the present invention;
FIG. 5 shows the structure of the electrolyte in the accordion TiNbC-MXene array structure (a) and accordion Ti in example 2 of the present invention 3 C 2 Contact angle test photographs of the MXene film layer of the MXene array structure (b) and the copper foil surface (c);
FIG. 6 shows the accordion TiNbC-MXene array at 1mAcm in example 4 of the present invention -2 Lower capacity of 0.1To 5mAh cm -2 Voltage distribution (a) of plated lithium of (a); SEM images of accordion TiNbC-MXene array at different lithium plating capacities: 0mAh cm -2 (b)，0.1mAh cm -2 (c)，1mAh cm -2 (d) And 5mAh cm -2 (e) (ii) a Real-time monitoring of lithium growth photographs at different lithium plating times on accordion TiNbC-MXene arrays by specific in situ optical microscopy (f): 0min (g), 10min (h), 30min (i) and 60min (j), the plating current density is 2mA cm -2 ；
FIG. 7 SEM images of comparative example copper foils in inventive example 4 at different lithium plating capacities: 0.1mAh cm -2 (a)，1mAh cm -2 (b) And 5mAh cm -2 (c)；
FIG. 8 shows the accordion TiNbC-MXene array and accordion Ti in example 4 of the present invention 3 C 2 -nucleation overpotential test results for lithium plating on MXene arrays and Cu foils (a), Nyquist curve and coulombic efficiency contrast plot (c) for symmetric cells, and corresponding discharge voltage profiles (d-f);
FIG. 9 shows TiNbC-MXene-Li and Ti in example 4 of the present invention 3 C 2 -MXene-Li and Cu-Li electrodes at 1 to 20mA cm -2 The lithium electrode of the TiNbC-MXene accordion array has 5(b) and 20mA cm -2 (c) Cycling performance at high current density.
FIG. 10 shows TiNbC-MXene-Li// LFP, Ti under 0.2C in example 5 of the present invention 3 C 2 Cycle performance of MXene-Li// LFP and Cu-Li// LFP full cells (a) and rate performance at 0.1C-4C (b), and cycle performance at 4C (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 combination of steps, or that other methods or steps may be intervening between those steps specifically referred to. 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 from the market or prepared according to a conventional method well known to those skilled in the art.
The accordion MXene material in the application refers to MXene material which is obtained by etching the component A in the MAX phase material and keeps the accordion shape, and the shape is different from that of MXene material of a two-dimensional sheet (see fig. 1a and b).
Example 1
The embodiment provides an MXene thin film layer with accordion-shaped array arrangement and a preparation method thereof, wherein the accordion MXene material adopts TiNbC-MXene, and the preparation method of the accordion TiNbC-MXene comprises the following steps: etching Al in the MAX phase material TiNbAlC to obtain the product; more specifically, the preparation method comprises the following steps: 2g of MAX phase (TiNbAlC) powder was added to 4g of lithium fluoride (LiF) and 40mL of 12mol mL -1 Hydrochloric acid (HCl). Subsequently, the mixture was heated to 50 ℃ for 48 hours, then filtered and washed several times until the pH reached about 7, and the filtered product was freeze-dried to give accordion TiNbC-MXene. FIG. 1a shows an SEM photograph of TiNbC-MXene of an accordion, which clearly shows that TiNbC-MXene is in a layered morphology similar to that of an accordion, the lamellar array is orderly arranged, the lamellar spacing (gap) is about 100nm, wherein the thickness of MXene lamellar is about 1-3 nm, and the transverse dimension is several microns; FIG. 1b shows an SEM photograph of a typical two-dimensional TiNbC-MXene, and it can be seen that two-dimensional lamellae in the two-dimensional TiNbC-MXene are randomly arranged, and the lamellae are peeled off and peeled off by ultrasound in the process of etching the A component by the MAX phase material.
The preparation method of the MXene thin film layer arranged in the accordion-shaped array in the embodiment comprises the following steps: the method comprises the steps of dispersing accordion TiNbC-MXene into a water-oil two-phase system, spreading the accordion TiNbC-MXene on an interface to form a TiNbC-MXene accordion array film under the action of surface tension of an interface layer of a water-oil two phase, and transferring the accordion array film to the surface of a medium to obtain the MXene film layer arranged in an accordion-shaped array.
A more specific implementation, as shown in fig. 2a and b, includes:
1. the prepared accordion TiNbC-MXene and deionized water are prepared into 1.2mg ml -1 The dispersion of (1);
2. dropwise adding the dispersion into a water-dichloromethane two-phase mixed solution, and quickly sinking the accordion TiNbC-MXene under the action of gravity until the accordion TiNbC-MXene quickly spreads on an interface layer of water-dichloromethane to form a TiNbC-MXene accordion array film; fig. 3a shows a schematic diagram of the rapid spreading of accordion TiNbC-MXene dispersion in a water-oil two-phase interface layer, the surface tension existing at the water-oil interface is a key driving force in the assembly process of the liquid-liquid interface, and we observe through experiments that accordion TiNbC-MXene spreads to the whole interface rapidly once contacting the water-dichloromethane interface, so as to reduce gibbs free energy (G γ) of the water-oil interface;
3. and placing a copper belt on the water-dichloromethane two-phase interface, slowly pulling along one direction, spreading the TiNbC-MXene accordion array film on the copper belt, and drying to obtain the copper foil composite belt with the MXene thin film layer arranged in an accordion-shaped array on the copper belt. FIG. 3b shows a top-down SEM of the composite tape, where a uniform distribution of the accordion TiNbC-MXene array is seen on the surface of the composite tape, where there are many nanoscale gaps in the vertical direction, and the thickness of the array is about 15 μm as seen from the side view (3 c). Fig. 4a to c show photographs of the prepared copper foil composite tape, and it can be seen that the MXene film layer has good contact with the metal copper foil and still shows excellent stability under the folding or twisting action.
The electrolyte is dripped on the surface of the MXene layer on the surface of the obtained copper foil composite belt, and the contact angle between the electrolyte and the surface of the MXene layer is almost zero (fig. 3d), because the MXene thin film layer has an accordion MXene array structure, the electrolyte can directly and quickly permeate into the bottom of the matrix (copper belt). The composite tape is used as a current collector of a lithium battery electrode, and is beneficial to the uniform distribution of lithium ions in the electrode.
In this embodiment, the copper strip may be replaced by a thin film material (corresponding to the dielectric layer) made of other materials, including but not limited to a metal material, and since the metal material has excellent conductivity, the current collector in the electrode is usually a metal material, such as a copper strip/foil, a nickel strip/foil, a stainless steel strip/foil, a nickel-plated copper strip/foil, and the like. The MXene film layer with the accordion array structure is arranged on the surface of the metal strip or the metal foil, so that the novel surface modified current collector is obtained, and the current collector can be applied to lithium metal batteries without limitation.
The liquid-liquid two-phase system can also select other liquid phase types, and as MXene materials have hydrophilicity, a water-oil two-phase system is preferred from the aspects of convenience and easy implementation; the oil phase can also be selected from other types of liquid, such as: organic solvents such as trichloromethane and tetrachloromethane are used, but the technical idea of the invention is that the array arrangement of the accordion MXene material is realized through a liquid-liquid two-phase or multi-phase interface.
The thickness of the accordion MXene array can be further controlled by regulating the particle sizes of different MXene materials, and in some embodiments, the thickness of the accordion MXene array can be adjusted between 1 μm and 100 μm.
Example 2
This example provides another thin film layer with accordion MXene array, where the material of the accordion MXene is Ti 3 C 2 -MXene prepared in a similar manner to TiNbC-MXene of example 1 except that the starting MAX phase material was Ti 3 AlC 2 。
The MXene film layer of this example was prepared in a similar manner to example 1. FIGS. 5 a-c show the electrolyte solution in the structure of accordion TiNbC-MXene array (a) and accordion Ti 3 C 2 Contact angle test photographs of the MXene thin film layer of the MXene array structure (b) and the copper foil surface (c) show that the contact angle on the MXene thin film layer is obviously smaller than that on the copper foil, which is related to the MXene array structure, while the surface of the TiNbC-MXene array structure shows the smallest contact angle (0 degrees) which is lower than that of Ti 3 C 2 -MXene array structure (-22 °),this may be related to the TiNbC-MXene being easier to etch with a more perfect accordion array structure.
Example 3
This embodiment provides another MXene thin film layer with accordion-like array arrangement, where the material of the accordion-like MXene is Ti 2 C-MXene, prepared in a similar manner to TiNbC-MXene in example 1, except that the MAX phase material was Ti 2 And (4) AlC. The MXene film layer was prepared similarly to example 1.
Similarly, in other embodiments, the accordion MXene material may also be Ti 3 CNT x 、Ti 4 N 3 T x 、TiNbC、TiNbCN、Ta 4 C 3 T x And the like.
Example 4
The embodiment provides a lithium metal negative electrode and a preparation method thereof, wherein the preparation method comprises the following steps: the surface of the MXene film layer of the accordion-shaped array is plated with lithium metal. In this example, the lithium metal plated on the composite copper tape obtained in example 1 was selected.
The more specific implementation method comprises the following steps: the composite copper strip in the embodiment 1 is cut into a circular sheet and assembled into a CR2032 type button symmetrical battery, wherein the electrolyte is 1M LiPF 6 Solutions in EC, EMC, DEC (v: v: v ═ 1:1:1) and 1% VC. At 1.0mAcm -2 The specific deposition capacity of a symmetric cell with an accordion TiNbC-MXene array was tested at constant current density to study the growth of lithium metal on the TiNbC-MXene accordion array.
FIG. 6a shows the lithium plating capacity of 0.1 to 5mAh cm -2 The evolution process of the lithium coating on the accordion TiNbC-MXene array in the process is characterized by SEM test (figure 6 b-e), and it can be seen that at the initial nucleation stage, the lithium coating is 0.1mAh cm -2 At low plating levels of (a), lithium metal nucleates uniformly on the MXene nanosheets of the accordion TiNbC-MXene array, due to uniform electric field and ion concentration distribution (fig. 6 c); in contrast, a large number of heterogeneous nucleation sites for lithium were observed on the copper foil (fig. 7 a). With platingThe lithium capacity is increased to 1mAh cm -2 Lithium metal further grows in the interstices between the accordion TiNbC-MXene array (fig. 6 d). At this time, a large number of lithium dendrites were found on the copper foil (FIG. 7b), but not in the accordion Ti 3 C 2 A small amount of lithium dendrites was also observed on the-MXene coated copper foil. Further increase the capacity of the lithium plating to 5mAh cm -2 It can be seen that the lithium plating fills and covers the array, presenting a dendrite-free and smooth surface, consisting of a dense and uniformly distributed lithium, with many grain boundaries (fig. 6 e). Under the same conditions, the surface of the copper foil is randomly plated with a large number of lithium dendrites, and a non-uniform surface with a loose porous structure is presented (fig. 7 c). When the lithium plating is completely stripped, the accordion TiNbC-MXene array structure keeps complete array morphology without collapse.
Use a specially designed transparent quartz cell (FIG. 6f) at 2mA cm -2 Chronopotentiometry at constant plating current density and-2.0V cut-off potential, lithium growth process on accordion TiNbC-MXene array was further monitored in real time by in situ optical microscopy (FIGS. 6 g-j). In the initial stage, the accordion TiNbC-MXene array was framed white in the photo, assuming an accordion structure with uniform array pitch (fig. 6 g). After 10 minutes of electroplating, the lithium plating was seen to grow in bright color into the interstices of the accordion TiNbC-MXene, with the accordion frame being white (fig. 6 h). When electroplated for 30 minutes, bright and evenly distributed electroplated lithium was observed in the accordion TiNbC-MXene array with no apparent protrusions on the surface (marked by purple shapes, FIG. 6 i). It is worth noting that even at 2mA cm -2 The accordion TiNbC-MXene array still maintained a flat surface without any lithium dendrites for 60 minutes of electroplating at current density (fig. 6 j). Even at high rates, the absence of dendrites after lithium plating can be attributed to the low tortuosity of the array and the nanogaps in the array, which facilitates the super-permeation of electrolyte and uniform electric field, facilitating rapid lithium ion/charge transport at high current densities.
To gain insight into the nucleation behavior of lithium metal on accordion MXene arrays, the difference between the tip voltage (. mu.t) and the mass transfer control overpotential was used to calculate the nucleation overpotential (. mu.n), and the result is shown in FIG. 8a, which is a graph of the hand windThe output mu n (9.9mV) of the TiNbC-MXene array is far lower than that of Ti of the accordion 3 C 2 -MXene array (16.1mV) and copper foil (28.3mV), which indicates a significant reduction of the lithium coating barrier on TiNbC-MXene accordion array due to fast ion kinetics, low charge transfer resistance and uniformly distributed high lithium ion conductor LiF, ensuring fast transfer of electrons and lithium ions into the low-curvature accordion TiNbC-MXene array (fig. 8 b).
The Coulombic Efficiency (CE) of the half-cell was studied based on the good dendrite-free lithium plating behavior achieved by fast ion diffusion and charge transfer in the accordion TiNbC-MXene array (fig. 8 c). All cells were cycled between 0 to 1.0V with a lithium plating capacity of 1mAh cm -2 Current density of 1mAh cm -2 . The mean CE of the accordion TiNbC-MXene array was 98.2% in the first three cycles, then stabilized at around 99.8% in the subsequent cycles (890 cycles) versus accordion Ti 3 C 2 Compared with a copper foil (170 cycles), the MXene array (230 cycles) has the highest utilization rate of lithium metal, and the cycle life is increased by 300-400%. The corresponding voltage distribution for lithium plating/stripping on TiNbC-MXene accordion MXene array is shown in FIG. 8 d. Compared to copper foil (overpotential of 48 mV), the accordion TiNbC-MXene array showed a small overpotential of 18mV even after 800 cycles (FIGS. 8 d-f).
In addition, symmetric cells were further assembled to evaluate the cycling stability of accordion TiNbC-MXene arrays, with corresponding electrodes in the symmetric cells by plating a capacity of 6mAh cm on the accordion MXene array -2 Lithium metal electrode assembly (labeled TiNbC-MXene-Li), corresponding accordion Ti 3 C 2 -MXene array lithium metal electrode and copper foil lithium metal electrode label (Ti) 3 C 2 -MXene-Li and Cu-Li). The test shows that: the symmetrical battery with TiNbC-MXene-Li realizes excellent cycle stability within 1100h, and the low overpotential is 16mV, which is superior to Ti 3 C 2 MXene-Li (26mV) and Cu-Li (46 mV). In contrast, Ti 3 C 2 Symmetric cells of-MXene-Li and Cu-Li underwent a gradual overpotential increase and suddenly failed in approximately 700 hours and 600 hours, respectively. Symmetric cell with TiNbC-MXene-Li exhibits excellent deep stripping/platingBehavior at 1mA cm -2 At a current density of up to 20mAh cm -2 Is stable for over 800 hours at high area capacity.
At 1 to 20mA cm -2 Under the current density of (D), the rate capability of TiNbC-MXene-Li is further studied. As shown in FIG. 9a, as the current density was gradually increased to 5mA cm -2 When the overpotential of TiNbC-MXene-Li is kept at 35mV, which is better than that of Ti 3 C 2 MXene-Li (46mV) and Cu-Li (78 mV). Even at very high current densities of 10mA cm -2 Even up to 20mA cm -2 In this case, TiNbC-MXene-Li still provides a stable overpotential of 102mV without short circuit. However, Ti 3 C 2 The overpotential of the-MXene-Li (202mV) and Cu-Li electrodes (560mV) increased significantly (FIG. 9 a). We also further investigated the cycling stability of TiNbC-MXene-Li electrodes at high rate. At 5mA cm -2 And the TiNbC-MXene-Li symmetrical battery can stably run for 28000 minutes. Even at 20mA cm -2 The TiNbC-MXene-Li can also keep a stable overpotential (103mV) and has long-term cycling stability (2500 cycles), and the overpotential is only slightly increased (115mV), thereby paving a way for practical lithium metal negative electrodes in high-power lithium metal batteries (FIGS. 9 b-c). The excellent rate performance of the TiNbC-MXene-Li symmetrical battery is attributed to the rapid transmission path of ions and electrons in a low-bending array, and the lithium-philic halogen functional group (-F) of the TiNbC-MXene nanosheet can effectively adjust to obtain a lithium-plated layer without dendrites and buffer the volume change of lithium metal through the low-bending accordion TiNbC-MXene array.
Example 5
This embodiment provides a lithium metal full cell, wherein LiFePO is used 4 (LFP) assembling the whole battery as a positive electrode material (the capacity ratio of the negative electrode to the positive electrode is 2.0); the lithium metal cathode was the accordion TiNbC-MXene array and accordion Ti in example 4 above 3 C 2 Plating capacity on-MXene array of 6mAh cm -2 The assembled full cell is marked as TiNbC-MXene-Li// LFP, Ti 3 C 2 -MXene-Li// LFP, comparative example is full cell assembled by copper foil lithium-plated electrode, marked Cu-Li// LFP. Constant current charge/discharge measurements were made over a voltage range of 2.0 and 4.0V, with Li/Li + In contrast, at 0.2 to 4C (1C ═ 172mA g -1 ) At different current densities.
The test result is shown in FIG. 10, the TiNbC-MXene-Li// LFP full cell stably runs for 280 cycles at 0.2C, and the capacity retention rate reaches 92%. In contrast, after 50 cycles, the capacity of the Cu-Li// LFP full cell began to decrease significantly (fig. 10 a). In addition, TiNbC-MXene-Li// LFP full cell also had high rate performance (FIG. 10 b). When the discharge rate is increased to 4C, the discharge capacity of the TiNbC-MXene-Li// LFP full cell is still maintained at 130mAh g -1 Is far higher than Cu-Li// LFP (97mAh g) -1 ) And Ti 3 C 2 -MXene-Li//LFP(114mAh g -1 ) Discharge capacity of the full cell. Furthermore, the TiNbC-MXene-Li// LFP full cell also showed excellent durability, the coulombic efficiency was 99% after 1000 cycles, and the capacity retention rate reached 86% even at a high rate of 4C (FIG. 10C). This long-cycle stability at full cell high rate further confirms that the accordion MXene array structure has fast ion and charge transfer kinetics in metal cells.
Example 6
The lithium metal battery of the present invention may also implement the composition of the accordion MXene array structure and the lithium metal by using other preparation methods, and this embodiment provides another lithium metal negative electrode and its preparation method, where the preparation method includes: the thin film layer of the accordion-shaped MXene array is contacted with molten lithium metal or an alloy thereof, so that the molten lithium metal or the alloy thereof is infiltrated among the accordion-shaped MXene array structures, and the lithium metal electrode containing the accordion-shaped MXene array is obtained after cooling.
The specific implementation method comprises the following steps:
1. heating lithium metal or lithium metal alloy to 400-800 ℃, and melting into liquid;
2. and coating the liquid molten lithium or lithium alloy on the copper foil with the accordion MXene array film layer on the surface, and cooling and solidifying to obtain the lithium metal electrode.
In a specific embodiment, the steps include: after heating lithium metal to 400 ℃ for melting, coating the surface of the thin film layer of the accordion TiNbC-MXene array prepared in the embodiment 1 of the invention to obtain the lithium metal electrode.
It should be noted that MXene material is a two-dimensional material, and is represented by the chemical formula 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 is x Represents a functional group including-F, -Cl, Br, I, -O, -S, -OH, -NH 4 One or more of (a); n is more than or equal to 1 and less than or equal to 4. Other types of accordion MXene materials are selected for compounding with metal and the metal composite material is used for an electrode of a battery under the teaching of the invention, and the technical idea of the invention also belongs to the technical idea of the invention.
In the invention, compared with the application of the unionized MXene material in a lithium metal electrode, the bivariate MXene material containing the Nb element shows lower nucleation overpotential of the lithium metal, and more excellent cycle performance and rate performance, which is attributed to the fact that the bivariate MXene containing the Nb is easier to prepare and obtain the MXene material with uniform particle size distribution and obvious accordion structure; on the other hand, the doping of the Nb element can change the electron distribution of the MXene sheet layer, so that the migration of electrons in the electrode is obviously enhanced, and the electric field distribution is homogenized. Therefore, the accordion MXene material containing the Nb element is more preferable in the present invention.
It should be noted that, since metals with electrochemical activity, including metals Na, Zn, K, Ca, and Mg, have the same problems as lithium metal when used in the negative electrode material of metal battery (including metal dendrite growth, etc.), the thin film layer of the accordion MXene array of the present invention can also be used to be compounded with these metals to obtain a composite metal electrode, and applied in the corresponding metal battery system.
The foregoing descriptions of specific exemplary embodiments of the present invention have been 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 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 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. A film layer with an accordion MXene array is characterized in that accordion MXene materials are contained in the film layer and arranged in an array shape.
2. The film layer of claim 1, wherein the formula of the accordion MXene material is M n+ 1 X n T x Wherein M is one or more of transition metal elements, X is one or more of carbon, nitrogen and boron, and T is x Represents a surface functional group;
preferably, the M is selected from one or more of Ti, Ta, Nb, Cr, V and Mo elements;
preferably, said T x including-F, -Cl, -Br, -I, -S, -O, -NH 4 At least one of (1).
3. The film layer of claim 2, wherein M comprises Nb;
and/or X is C and/or N element.
And/or the thickness of the thin film layer is between 1 μm and 100 μm.
4. A method of making a film layer according to any of claims 1 to 3, comprising the steps of:
adding the accordion MXene material into a liquid-liquid two-phase system, and dispersing the accordion MXene material in an interface layer of a liquid-liquid two phase to form an accordion array film;
and transferring the accordion array film to the surface of a medium to obtain the film layer.
5. The method of claim 4, wherein a more specific embodiment of the method comprises:
adding the dispersion liquid of the accordion MXene material into a water-oil two-phase system;
and/or arranging a dielectric layer on the interface layer, and transferring the accordion array film to the surface of the dielectric layer by pulling the dielectric layer to obtain the film layer.
6. The method according to claim 5, wherein the oil phase of the water-oil two-phase system is selected from the group consisting of dichloromethane, trichloromethane, tetrachloromethane;
and/or the solvent in the dispersion liquid of the accordion MXene material is water;
and/or the dielectric layer is a metal foil; preferably, the material of the metal foil comprises one or more of copper, nickel and stainless steel.
7. A current collector comprising an electrically conductive layer, a surface of the electrically conductive layer comprising the thin film layer of any one of claims 1 to 3; or, a film layer obtained by the production method according to any one of claims 4 to 6;
preferably, the conductive layer is a metal foil; more preferably, the metal foil is made of copper, nickel or stainless steel.
8. An electrode comprising an electrochemically active metal, and a current collector according to claim 7;
preferably, the metal is selected from at least one of lithium, sodium, zinc, calcium and potassium.
9. A method of preparing the electrode of claim 8, comprising the steps of:
electroplating the metal onto the current collector;
and/or heating and melting the metal or the metal alloy, and compounding the metal or the metal alloy with the current collector.
10. A battery comprising the current collector of claim 7;
or, an electrode according to claim 8.
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