CN114944489B - Thin film layer with accordion MXene array, preparation method of thin film layer, current collector, electrode and battery - Google Patents

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

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CN114944489B
CN114944489B CN202210680388.9A CN202210680388A CN114944489B CN 114944489 B CN114944489 B CN 114944489B CN 202210680388 A CN202210680388 A CN 202210680388A CN 114944489 B CN114944489 B CN 114944489B
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accordion
mxene
array
film layer
metal
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CN114944489A (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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • 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 thereof, a current collector, an electrode and a battery. Wherein the film layer with the accordion MXene array contains accordion MXene materials, and the accordion MXene materials are arranged in an array. The invention provides a simple and effective method for preparing a matrix with an ordered or vertical arrangement structure, which utilizes the characteristics of the orientation arrangement and low curvature of an accordion MXene sheet layer of an accordion MXene material and the surface tension of a liquid-liquid two-phase mixed liquid interface to spread the accordion MXene material on the interface layer to obtain a thin film layer with an accordion MXene array structure, wherein the thin film layer is ultrathin and the MXene sheet layer is oriented and arranged. The accordion MXene array structure has the advantages that the preparation method is simple, the effect of being applied to the metal electrode is obvious, a technical path capable of realizing application is provided for practical application in the lithium metal battery with high power and high capacity, and the accordion MXene array structure has obvious industrial practical value.

Description

Thin film layer with accordion MXene array, preparation method of thin film layer, current collector, electrode and battery
Technical Field
The invention belongs to the technical field of new materials and batteries, and particularly relates to a film layer with an accordion MXene array, a preparation method thereof, a current collector, an electrode and a battery.
Background
The lithium metal anode has the highest theoretical specific capacity (3860 mAh g -1 ) And the lowest electrochemical potential (3.04V relative to a standard hydrogen electrode), is considered the most potential alternative to the graphite negative electrode (372 mAh g -1 ) Is a material of (3). For decades, to develop high performance Lithium Metal Batteries (LMBs), lithium metal cathodes have been used to mate with a variety of high capacity anodes, including layered nickel-rich anodes, sulfur, and oxygen, which typically have an energy density 2-6 times that of Lithium Ion Batteries (LIBs). However, slow ion diffusion and higher charge transfer resistance in lithium metal anodes, especially under high rate charge and discharge conditions, greatly exacerbate lithiumDendrite growth and volume change, rapid consumption of lithium metal battery electrolyte, reduced coulombic efficiency and significant capacity decay.
In order to improve the diffusion and electron transfer capabilities of lithium ions in lithium metal negative electrodes, and thus to improve the electrochemical performance of lithium metal negative electrodes, researchers have developed various methods, such as: constructing a three-dimensional matrix material, designing an artificial Solid Electrolyte Interface (SEI), modifying electrolyte and the like; among them, three-dimensional matrix materials, 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 therein and reducing the ion concentration polarization under high current density. In addition, the three-dimensional structure can buffer the volume change of the electrode, localize the whole volume change of the electrode to improve the stability of the electrode, thereby improving the electrochemical performance of the lithium metal anode.
However, these three-dimensional matrix materials have been reported to be generally thicker (over 100 μm) and to be randomly arranged in structural order. According to the diffusion coefficient equation D eff =d×ε/τ (where D eff For the effective diffusion coefficient of ions, ε is the porosity and τ is the tortuosity), the conductive path is determined by the ratio of the porosity to tortuosity. The random arrangement structure in the three-dimensional matrix material has high flexibility, so that the effective electron diffusivity is low, the ion transmission is slow, and the electric field and the lithium ion flux inside the electrode are unevenly distributed. In addition, high tortuosity will lead to Li + The redox reaction of Li occurs only at a limited negative electrode/electrolyte interface, resulting in extremely 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 ) The thicker 3D negative electrode has high curvature at the same time, and under the condition of high-rate charge and discharge, the growth of lithium dendrite can be aggravated, so that the battery performance is obviously reduced and potential safety hazards are caused. It can be seen that tortuosity plays a very important role in ion diffusion and charge transfer of three-dimensional electrodes.
According to BruggThe eman relation, tortuosity (τ), relates to porosity (ε) and Bruggeman index (α): τ=ε α . In this case, at a tortuosity of 1, corresponding to the electrode with the fastest ion transport, it can be seen that the ideal electrode should be continuous and vertically aligned, with a three-dimensional matrix of ordered or vertically aligned structure critical to promote ion transport, reduce apparent resistance, greatly improve the rate capability and practicality of lithium metal anodes.
Disclosure of Invention
The invention aims at solving the technical problems that the growth and the volume change of lithium dendrite are greatly aggravated, the electrolyte of a lithium metal battery is rapidly consumed, the coulomb efficiency is reduced and the capacity is obviously attenuated when the lithium metal negative electrode has slow ion diffusion and higher charge transfer resistance, especially under the condition of high-rate charge and discharge.
In a first aspect, the present invention provides a film layer having an array of accordion MXene, the film layer comprising accordion MXene material, the accordion MXene material being arranged in an array.
In some embodiments, the chemical formula of the accordion MXene material described above is represented by 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 elements, T x Representing a surface functional group.
In some embodiments, M in the accordion MXene material described above is selected from one or more of the Ti, ta, nb, cr, V, mo elements.
In some embodiments, T as described above x comprising-F, -Cl, -Br, -I, -S, -O, -NH 4 At least one of them.
In some embodiments, the M in the accordion MXene material contains Nb element.
In some embodiments, X in the accordion MXene material described above is an element of C and/or N.
In some embodiments, the thickness of the film layer is between 1 μm and 100 μm.
The second aspect of the present invention provides a method for preparing the film layer, which includes the steps of: adding an accordion MXene material into a liquid-liquid two-phase system, so that the accordion MXene material is dispersed in an interface layer of the liquid-liquid two-phase system to form an accordion array film; transferring the accordion array film to the surface of a medium to obtain the thin film layer.
In some embodiments, more specific embodiments of the above preparation method comprise: the dispersion of the above-described accordion MXene material was added to a water-oil two-phase system.
In some embodiments, more specific embodiments of the above preparation method comprise: 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 film layer.
In some embodiments, the oil phase in the above water-oil two-phase system is selected from dichloromethane, chloroform, tetrachloromethane.
In some embodiments, the solvent in the dispersion of the above-described accordion MXene material is water.
In some embodiments, the dielectric layer is a metal foil.
In some embodiments, the metal foil comprises one or more of copper, nickel, and stainless steel.
A third aspect of the present invention provides a current collector comprising a conductive layer having a surface as described above with a thin film layer of an 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 comprises copper, nickel, or stainless steel.
A fourth aspect of the present invention provides an electrode comprising an electrochemically active metal 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 metals.
The fifth aspect of the present invention provides a method for preparing the electrode, comprising the steps of: and electroplating the metal on the current collector.
The sixth aspect of the present invention provides another method for preparing the electrode, including the steps of: the metal or the alloy of the metal is heated and melted and then compounded with the current collector.
A seventh aspect of the present invention provides a battery comprising the current collector described above; or, the above-mentioned electrode.
The beneficial technical effects of the invention are as follows:
1. the invention provides a simple and effective method for preparing ordered or vertical arrangement structural matrix, which utilizes the characteristics of the orientation arrangement and low curvature of an accordion MXene sheet layer of an accordion MXene material and the surface tension of a liquid-liquid two-phase mixed liquid interface to spread the accordion MXene material on an interface layer to obtain an ultrathin film layer with the orientation arrangement of the MXene sheet layer and an accordion MXene array structure;
2. when the membrane layer is used in a battery electrode, the membrane layer of the accordion MXene array is used as a matrix of metal lithium, and the membrane layer of the accordion MXene array has ultrathin array structure and low curvature, so that electrolyte can be quickly immersed, and quick diffusion of lithium ions is promoted; in the second aspect, the accordion MXene array structure can also provide a uniform electric field so as to lead lithium ions to be 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, so that a novel dendrite-free lithium metal battery is obtained, and the stability and safety of the battery are improved; in the fourth aspect, the accordion MXene array structure also has rich space, can provide buffer space for the volume change of lithium metal in the charge and discharge process, and improves the stability of the whole electrode. Through experimental tests, the accordion MXene array structure is applied to a battery cathode, and the electrochemical performance of the battery, including the cycle performance, the multiplying power performance and the coulombic efficiency, is effectively improved.
3. The accordion MXene array structure has the advantages that the preparation method is simple, the effect of being applied to the metal electrode is obvious, a technical path capable of realizing application is provided for the lithium metal battery with high power and high capacity, and the accordion MXene array structure has obvious industrial practical value.
Drawings
FIG. 1 is an SEM photograph of an accordion TiNbC-MXene (a) and a two-dimensional TiNbC-MXene according to an embodiment 1 of the present invention;
FIG. 2 is a schematic diagram (a) and a corresponding photograph (b) of a thin film layer having an accordion TiNbC-MXene array structure according to an embodiment 1 of the present invention;
FIG. 3 is a schematic diagram (a) of rapid spreading of an Accordion TiNbC-MXene dispersion in a water-oil two-phase interface layer in example 1 of the present invention, a top view (b) and a side view (c) of the prepared MXene thin film layer, and a contact angle photograph (d) of an electrolyte drop-wise onto the thin film layer;
FIG. 4 is a copper foil composite tape with a film layer of an accordion MXene array on the surface prepared in example 1 of the present invention;
FIG. 5 shows an array structure (a) of an accordion TiNbC-MXene and an accordion Ti in example 2 of the present invention 3 C 2 -contact angle test photographs of an MXene film layer of an MXene array structure (b) and a copper foil surface (c);
FIG. 6 shows an array of Accordion TiNbC-MXene at 1mAcm in example 4 of the present invention -2 Lower capacity of 0.1 to 5mAh cm -2 Voltage distribution of plated lithium (a); SEM images of the 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) The method comprises the steps of carrying out a first treatment on the surface of the Lithium growth photographs at different lithium plating times on an accordion TiNbC-MXene array were monitored in real time by a specific in situ optical microscope (f): 0min (g), 10min (h), 30min (i) and 60min (j), the plating current density was 2mA cm -2 ；
Fig. 7 SEM images of the comparative copper foil of example 4 of the present invention at different lithium plating capacities: 0.1mAh cm -2 (a)，1mAh cm -2 (b) And 5mAh cm -2 (c)；
FIG. 8 shows an array of Accordion TiNbC-MXene 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 for symmetrical cells (b) and coulombic efficiency contrast plot (c), and phasesVoltage distribution patterns (d-f) to be discharged;
FIG. 9 shows TiNbC-MXene-Li and Ti according to example 4 of the present invention 3 C 2 The MXene-Li and Cu-Li electrodes are between 1 and 20mA cm -2 The rate capability (a) of the TiNbC-MXene accordion array lithium electrode at different current densities of 5 (b) and 20 mAcm -2 (c) Cycle performance at high current densities.
FIG. 10 shows TiNbC-MXene-Li// LFP and Ti at 0.2C in example 5 of the present invention 3 C 2 Cycle performance (a) and rate performance (b) at 0.1C-4C for MXene-Li// LFP and Cu-Li// LFP full cells, and cycle performance (C) at 4C.
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 accordion MXene material in the application refers to an MXene material which is obtained by etching an A component in a MAX phase material and keeps the shape of the accordion, and the shape of the MXene material is different from that of a two-dimensional sheet (see figures 1a and b).
Example 1
The embodiment provides an MXene film layer with accordion-like array arrangement and a preparation method thereof, wherein an 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 material; more haveA method of making a body comprising: 2g of MAX phase (TiNbAlC) powder was added to 4g of lithium fluoride (LiF) and 40mL of 12mol mL -1 In a mixture of 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 the accordion TiNbC-MXene. FIG. 1a shows an SEM photograph of an accordion TiNbC-MXene, wherein the TiNbC-MXene is clearly seen to have a layered morphology similar to that of an accordion, the lamellar arrays are orderly arranged, and the lamellar spacing (gaps) is about 100nm, wherein the thickness of the MXene lamellar layer is about 1-3 nm, and the transverse dimension is several micrometers; FIG. 1b shows an SEM photograph of a typical two-dimensional TiNbC-MXene, and it can be seen that the two-dimensional sheets in the TiNbC-MXene with a two-dimensional morphology are arranged randomly, and the sheets are peeled off by assisting with ultrasound during etching of the A component by the MAX phase material.
The preparation method of the MXene film layer arranged in the accordion-shaped array in the embodiment comprises the following steps: dispersing the Accordion TiNbC-MXene into a water-oil two-phase system, spreading the Accordion TiNbC-MXene on the interface under the surface tension of the interface layer of the water-oil two-phase system to form a TiNbC-MXene Accordion array film, and transferring the Accordion array film to the surface of a medium to obtain the MXene film layer arranged in an Accordion-shaped array.
More specific implementation, as shown in fig. 2a and b, includes:
1. preparing 1.2mg ml of the prepared Accordion TiNbC-MXene and deionized water -1 Is a dispersion of (a);
2. dropwise adding the dispersion liquid into a water-dichloromethane two-phase mixed liquid, and quickly sinking the accordion TiNbC-MXene under the action of gravity until the interface layer of the water-dichloromethane is quickly spread to form a TiNbC-MXene accordion array film; FIG. 3a shows a schematic diagram of rapid spreading of an Accordion TiNbC-MXene dispersion at a water-oil two-phase interface layer, the surface tension existing at the water-oil interface layer is a key driving force for the assembly process of the liquid-liquid interface, and by experiment we observe that the Accordion TiNbC-MXene rapidly spreads to the whole interface layer once contacting the water-dichloromethane interface layer, so as to reduce the Gibbs free energy (Gγ) of the water-oil interface layer;
3. placing a copper strip on the water-dichloromethane two-phase interface, slowly pulling along one direction, spreading the TiNbC-MXene accordion array film on the copper strip, and drying to obtain the copper foil composite strip with the MXene film layers distributed in an accordion array manner on the copper strip. FIG. 3b shows a top-down SEM photograph of a composite tape, showing a uniform distribution of an array of Accordion TiNbC-MXene on the surface of the composite tape, with many vertically oriented nanoscale gaps, and a thickness of the array of about 15 μm seen from side view (3 c). Fig. 4 a-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 exhibits excellent stability under the effect of folding or twisting.
When an electrolyte was dropped on the surface of the MXene layer on the surface of the resulting copper foil composite tape, it was found that the contact angle between the electrolyte and the surface of the MXene layer was almost zero (fig. 3 d), because of the accordion MXene array structure of the MXene film layer, the electrolyte was able to directly and rapidly infiltrate into the bottom of the base (copper tape). The composite strip is used as a current collector of the lithium battery electrode, and is beneficial to uniform distribution of lithium ions in the electrode.
The copper strip may also be replaced with a thin film material (corresponding to a dielectric layer) made of other materials in this embodiment, including but not limited to a metal material, and the current collector in the electrode is typically a metal material such as copper strip/foil, nickel strip/foil, stainless steel strip/foil, nickel plated copper strip/foil, and the like due to the excellent conductive properties of the metal material. The MXene film layer with the accordion array structure is arranged on the surface of the metal strips or the metal foils, so that the novel surface-modified current collector is obtained, and the current collector can be applied to lithium metal batteries.
Other liquid phase types can be selected for the liquid-liquid two-phase system, and the water-oil two-phase system is preferred from the viewpoint of convenience and easiness in implementation because the MXene material has hydrophilicity; other types of liquids may also be selected for the oil phase, such as: organic solvents such as chloroform and tetrachloromethane are within the technical concept of the invention as long as 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 of the invention can be further controlled by adjusting the particle size of the 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
The present embodiment provides another film layer with an array of accordion MXene of Ti 3 C 2 MXene was prepared similarly to TiNbC-MXene in example 1, except that the MAX phase material was Ti 3 AlC 2 。
The preparation method of the MXene film layer of the present example is similar to that of example 1. FIGS. 5 a-c show the electrolyte in an array structure (a) of an accordion TiNbC-MXene, an accordion Ti 3 C 2 The contact angle test photograph of the MXene film layer of the MXene array structure (b) and the copper foil surface (c) shows that the contact angle on the MXene film layer is obviously smaller than that of the copper foil, which is related to the MXene array structure, and the surface of the TiNbC-MXene array structure shows the minimum contact angle (-0 DEG) which is lower than that of Ti 3 C 2 An MXene array structure (-22 °), which may be related to a linbc-MXene that is easier to etch, with a more perfect accordion array structure.
Example 3
The present embodiment provides another MXene film layer with an accordion-like array arrangement, the accordion MXene material being Ti 2 C-MXene was prepared similarly to TiNbC-MXene in example 1, except that the MAX phase material was Ti 2 AlC. The process for the preparation of the MXene film layer was similar to that of example 1.
Similarly, in other embodiments, the accordion MXene material may alternatively be Ti 3 CNT x 、Ti 4 N 3 T x 、TiNbC、TiNbCN、Ta 4 C 3 T x Etc.
Example 4
The embodiment provides a lithium metal anode and a preparation method thereof, wherein the preparation method comprises the following steps: and (3) electroplating lithium metal on the surface of the MXene film layer of the accordion-shaped array. In this example, the composite copper strip obtained in example 1 was selected for the plating of metallic lithium.
More specific implementation method steps comprise: the composite copper tape of example 1 was cut into disks and assembled into CR2032 type button cell with electrolyte of 1M LiPF 6 Solutions in EC, EMC, DEC (v: v=1:1:1) and 1% vc. At 1.0mAcm -2 The specific deposition capacity of a symmetric cell with an array of concertina TiNbC-MXene was tested to investigate the growth of metallic lithium on the TiNbC-MXene accordion array.
FIG. 6a shows that the lithium plating capacity is 0.1 to 5mAh cm -2 Characterization of the evolution of the lithium coating on the Accordion TiNbC-MXene array during this process by SEM testing (FIGS. 6 b-e), it can be seen that during the initial nucleation stage, at 0.1mAh cm -2 At low plating levels of (c) lithium metal uniformly nucleates and grows on the MXene nanoplatelets of the accordion linbc-MXene array due to uniform electric field and ion concentration profile (fig. 6 c); in contrast, a large number of heterogeneous nucleation sites for lithium were observed on the copper foil (fig. 7 a). As the lithium plating capacity increases to 1mAh cm -2 Lithium metal further grows in the interstices between the array of accordion TiNbC-MXene (fig. 6 d). At this time, a large amount of lithium dendrites were found on the copper foil (FIG. 7 b), without being accordion-plated with Ti 3 C 2 Small amounts of lithium dendrites were also observed on the MXene covered copper foil. Further increasing the capacity of the lithium plating layer 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 dense and uniformly distributed lithium, with many grain boundaries (fig. 6 e). Under the same conditions, the surface of the copper foil was randomly plated with a large number of lithium dendrites, exhibiting a non-uniform surface of a loose porous structure (fig. 7 c). When the lithium plating is completely stripped, the accordion TiNbC-MXene array structure keeps the complete array form and does not collapse.
Using a specially designed transparent quartz cell (FIG. 6 f), at 2mA cm -2 Chronopotentiometry at constant plating current density and-2.0V cutoff potential byThe in situ optical microscope further monitored the lithium growth process on the Accordion TiNbC-MXene array in real time (FIGS. 6 g-j). In the initial stage, the accordion TiNbC-MXene array was framed white in the photomicrograph, exhibiting an accordion structure with uniform array spacing (fig. 6 g). After 10 minutes of electroplating, it can be seen that the lithium plating grew in bright color into the interstices of the accordion TiNbC-MXene, the rim of the accordion being white (fig. 6 h). When electroplated for 30 minutes, a bright and uniformly distributed electroplated lithium was observed within the accordion TiNbC-MXene array, with no apparent protrusions on the surface (marked by purple shape, fig. 6 i). Notably, even at 2mA cm -2 For 60 minutes, the accordion TiNbC-MXene array remained flat without any lithium dendrites (fig. 6 j). Even at high rates, no dendrite phenomenon after lithium plating can be attributed to low tortuosity of the array and nanogaps in the array, which facilitates superosmotic electrolytes and uniform electric fields, facilitating rapid lithium ion/charge transport at high current densities.
To gain insight into the nucleation behavior of lithium metal on an accordion MXene array, the nucleation overpotential (μn) was calculated using the difference between the tip voltage (μt) and the mass transfer control overpotential, and as a result, the output μn (9.9 mV) of the accordion TiNbC-MXene array was much lower than that of the accordion Ti, as shown in FIG. 8a 3 C 2 An MXene array (16.1 mV) and copper foil (28.3 mV), which indicates a significant reduction in the lithium plating barrier on the linbc-MXene accordion array due to fast ion dynamics, low charge transfer resistance and uniformly distributed high lithium ion conductor LiF, ensuring fast transfer of electrons and lithium ions into the low bending accordion linbc-MXene array (fig. 8 b).
The Coulombic Efficiency (CE) of half cells was studied based on the good dendrite-free lithium plating behavior achieved by rapid ion diffusion and charge transfer in the accordion TiNbC-MXene array (fig. 8 c). All cells cycled between 0 and 1.0V with a lithium plating capacity of 1mAh cm -2 The current density is 1mAh cm -2 . In the first three cycles, the average CE of the Accordion TiNbC-MXene array was 98.2%, and then stabilized around 99.8% in the subsequent cycles (890 cycles), with the Accordion Ti 3 C 2 MXene array (230 cycles) and copperCompared with the foil (170 cycles), the lithium metal utilization rate is highest, and the cycle life is increased by 300-400%. The corresponding voltage distribution for lithium plating/stripping on the TiNbC-MXene accordion MXene array is shown in FIG. 8 d. The Accordion TiNbC-MXene array showed a small overpotential of 18mV even after 800 cycles (FIGS. 8 d-f) compared to copper foil (48 mV overpotential).
Furthermore, the symmetrical cells were further assembled to evaluate the cycling stability of the Accordion TiNbC-MXene array, the corresponding electrodes in the symmetrical cells were prepared by plating the Accordion MXene array with a capacity of 6mAh cm -2 Is marked as TiNbC-MXene-Li) and corresponding accordion Ti 3 C 2 The MXene array lithium metal electrode and copper foil lithium metal electrode are labeled (Ti 3 C 2 MXene-Li and Cu-Li). The test shows that: the symmetric battery with TiNbC-MXene-Li realizes excellent cycle stability within 1100h, has low overpotential of 16mV, and is superior to Ti 3 C 2 MXene-Li (26 mV) and Cu-Li (46 mV). Conversely, ti is 3 C 2 The symmetrical cells of MXene-Li and Cu-Li failed suddenly after an over-potential ramp up process and at approximately 700 hours and 600 hours, respectively. Symmetric cells with TiNbC-MXene-Li show excellent deep stripping/electroplating behavior at 1mA cm -2 At a current density of up to 20mAh cm -2 Is stable for more than 800 hours at a high area capacity.
At 1 to 20mA cm -2 The rate capability of TiNbC-MXene-Li was further studied at the current density of (C). As shown in FIG. 9a, when the current density is gradually increased to 5mA cm -2 When the overpotential of TiNbC-MXene-Li is kept at 35mV, which is superior to Ti 3 C 2 MXene-Li (46 mV) and Cu-Li (78 mV). Even at extremely high current densities of 10mA cm -2 Even up to 20mA cm -2 In the case of TiNbC-MXene-Li, a stable overpotential of 102mV can still be provided without short-circuiting. However, ti is 3 C 2 The overpotential of the MXene-Li (202 mV) and Cu-Li electrodes (560 mV) increases significantly (FIG. 9 a). We have further studied the cycling stability of TiNbC-MXene-Li electrodes at high rates. At 5mA cm -2 When the TiNbC-MXene-Li symmetrical battery is used, the battery can stably run for 28000 minutes. Even at 20mA cm -2 The TiNbC-MXene-Li also maintained a stable overpotential (103 mV) with long-term cycling stability (2500 cycles) with only a slight increase in overpotential (115 mV) paving the way for practical lithium metal cathodes in high power lithium metal batteries (fig. 9 b-c). These excellent rate capability of TiNbC-MXene-Li symmetrical cells are attributed to the fast transport paths of ions and electrons in the low-bending arrays, and the lithium-philic halogen functional groups (-F) of TiNbC-MXene nanoplatelets, by which dendrite-free lithium-plated layers can be effectively tuned and buffered against volume changes of lithium metal.
Example 5
The present embodiment provides a lithium metal full cell, wherein LiFePO is used 4 (LFP) as a positive electrode material, a full cell (negative electrode, positive electrode capacity ratio=2.0); the lithium metal negative electrode was an array of accordion TiNbC-MXene and an accordion Ti as in example 4 above 3 C 2 Plating capacity of 6mAh cm on the-MXene array -2 Is marked as TiNbC-MXene-Li// LFP, ti 3 C 2 MXene-Li// LFP, comparative example is a full cell assembled of copper foil lithium-plated electrodes, labeled Cu-Li// LFP. Constant current charge/discharge measurements were performed in the voltage range of 2.0 and 4.0V, with Li/Li + In contrast, at 0.2 to 4C (1c=172 mA g -1 ) Is performed at different current densities.
The test results are shown in FIG. 10, and the TiNbC-MXene-Li// LFP full cell stably runs for 280 cycles at 0.2C, and the capacity retention rate is as high as 92%. In contrast, after 50 cycles, the capacity of the cu—li// LFP full cell began to decrease significantly (fig. 10 a). In addition, the TiNbC-MXene-Li// LFP full cell also has 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 kept at 130mAh g -1 Far higher than Cu-Li// LFP (97 mAh g) -1 ) And Ti is 3 C 2 -MXene-Li//LFP(114mAh g -1 ) Discharge capacity of the full cell. Furthermore, the TiNbC-MXene-Li// LFP full cell also exhibited excellent durability, with a coulombic efficiency of 99% after 1000 cycles, even at a high rate of 4CThe volume retention still reached 86% (fig. 10 c). The long cycle stability of this full cell at high rates further demonstrates the rapid ion and charge transfer kinetics of the accordion MXene array structure in metal cells.
Example 6
The lithium metal battery of the invention can also realize the compounding of the accordion MXene array structure and lithium metal by other preparation methods, and the embodiment provides another lithium metal anode and a preparation method thereof, wherein the preparation method comprises the following steps: the thin film layer of the accordion-like MXene array of the invention is contacted with molten lithium metal or alloy thereof, so that the molten lithium metal or alloy thereof is permeated between the structures of the accordion-like MXene array, and the lithium metal electrode containing the accordion-like MXene array is obtained after cooling.
The specific implementation steps comprise:
1. heating lithium metal or lithium metal alloy to 400-800 ℃ and melting into liquid state;
2. and coating 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: and (3) heating lithium metal to 400 ℃ for melting, and then coating the surface of the 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, since the MXene material is a two-dimensional material, the chemical formula is represented as 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; t (T) x Represents a functional group of the polymer, comprising-F, -Cl, br, I, -O, -S, -OH, -NH 4 One or more of the following; n is more than or equal to 1 and less than or equal to 4. Other types of accordion MXene materials are selected for the composition with the metal and the metal composite is used for the electrode of the battery in the light of the present invention, which are also within the technical idea of the present invention.
In the invention, compared with the application of a single-element accordion MXene material in a lithium metal electrode, the binary accordion MXene material containing Nb element has the advantages that the nucleation overpotential of the lithium metal is lower, the cycle performance and the multiplying power performance are better, and on one hand, the binary accordion MXene containing Nb can be more easily prepared into the MXene material with uniform particle size distribution and obvious accordion structure; on the other hand, the Nb element doping can change the electron distribution of the MXene lamellar, so that the migration of electrons in the electrode is obviously enhanced, and the electric field distribution is homogenized. Therefore, an accordion MXene material containing Nb element is more preferable in the present invention.
It should be further noted that, since the electrochemically active metals including the metal Na, zn, K, ca, mg are used as the anode material of the metal battery, the same problems as those of lithium metal (including metal dendrite growth, etc.) exist, and therefore, the film layer of the accordion MXene array of the present invention can be used for compositing with these metals to obtain a composite metal electrode, and be applied to the corresponding metal battery system.
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 (18)

1. A method of preparing a film layer having an array of accordion mxenes, comprising the steps of:
adding an accordion MXene material into a liquid-liquid two-phase system, so that the accordion MXene material is dispersed in an interface layer of the liquid-liquid two-phase system to form an accordion array film;
and transferring the accordion array film to the surface of a medium to obtain the film layer.
2. As claimed inThe preparation method of 1, wherein the chemical formula of the accordion MXene material is represented by 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 elements, and T represents a surface functional group.
3. The method of claim 2, wherein M is selected from one or more of the elements Ti, ta, nb, cr, V, mo.
4. The method of claim 2, wherein, the T comprises-F, -Cl, -Br, -I, -S, -O, -NH 4 At least one of them.
5. The method of claim 2, wherein M comprises Nb element.
6. The method of claim 2, wherein X is C and/or N.
7. The method of claim 2, wherein the thin film layer has a thickness of 1 μm to 100 μm.
8. The preparation method according to any one of claims 1 to 7, characterized in that it comprises, in a more specific embodiment:
adding the dispersion of the accordion MXene material to 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.
9. The method of claim 8, wherein the oil phase in the water-oil two-phase system is selected from the group consisting of methylene chloride, chloroform, and tetrachloromethane;
and/or the solvent in the dispersion of the accordion MXene material is water;
and/or, the dielectric layer is a metal foil.
10. The method of claim 9, wherein the metal foil comprises one or more of copper, nickel, and stainless steel.
11. A film layer prepared by the preparation method of any one of claims 1 to 10.
12. A current collector comprising a conductive layer having a surface comprising the thin film layer of claim 11.
13. The current collector of claim 12, wherein the conductive layer is a metal foil.
14. The current collector of claim 13, wherein the metal foil comprises copper, nickel, stainless steel.
15. An electrode comprising an electrochemically active metal and a current collector according to any one of claims 12 to 14.
16. The electrode of claim 15, wherein the metal is selected from at least one of the metals lithium, sodium, zinc, calcium, potassium.
17. A method of preparing an electrode according to claim 15 or 16, comprising the steps of:
electroplating the metal onto the current collector;
and/or, after heating and melting the metal or the alloy of the metal, the metal or the alloy of the metal is compounded with the current collector.
18. A battery comprising a current collector according to any one of claims 12 to 14; or an electrode as claimed in claim 15 or 16.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112563330A (en) * 2020-12-06 2021-03-26 南开大学 Vertical monomolecular field effect transistor integrated device based on two-dimensional material nano-pores and preparation method
EP3957601A1 (en) * 2020-08-19 2022-02-23 Technische Universität Dresden Method for the synthesis of mxenes, mxene nanosheets and their use

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3613094B1 (en) * 2017-04-20 2023-11-01 Auburn University Electrochemical systems comprising mxenes and max phase compositions and methods of using the same
KR102100849B1 (en) * 2018-02-26 2020-04-21 한국과학기술연구원 Anode for lithium metal battery comprising Nb2C thin film, preparation method thereof and lithium metal battery comprising the same
EP3614463A1 (en) * 2018-08-20 2020-02-26 BGT Materials Limited Electrode structure of electrochemical energy storage device and manufacturing method thereof
WO2021113509A1 (en) * 2019-12-03 2021-06-10 Drexel University Dispersion and stabilization of mxene materials and mxene materials for energy storage applications
CN110890549B (en) * 2019-12-06 2023-03-24 武汉大学 Array type positive current collector for liquid metal battery
WO2021131643A1 (en) * 2019-12-25 2021-07-01 株式会社村田製作所 Electroconductive composite structure and method for producing same
CN111293317A (en) * 2020-02-29 2020-06-16 天津国安盟固利新材料科技股份有限公司 Multifunctional composite negative plate for chargeable and dischargeable solid battery, preparation method and secondary battery
CN112047341B (en) * 2020-08-31 2022-03-04 山东大学 Nb-shaped alloy2C MXene material and preparation method and application thereof
CN112490442B (en) * 2020-11-25 2021-12-17 燕山大学 Lithium ion battery cathode material and preparation method and application thereof
CN112599729B (en) * 2020-11-27 2021-12-28 重庆标能瑞源储能技术研究院有限公司 Lithium ion battery with high cycle performance
CN112811906A (en) * 2021-01-08 2021-05-18 北京航空航天大学 Medium-entropy MAX phase material, medium-entropy two-dimensional material and preparation method thereof
CN113937295B (en) * 2021-10-15 2023-04-18 山东大学 Self-assembled MXene/chitosan composite membrane and preparation method and application thereof
CN114551811A (en) * 2022-02-22 2022-05-27 北京航空航天大学 Preparation method of vertical MXene array pole piece, vertical MXene array pole piece and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3957601A1 (en) * 2020-08-19 2022-02-23 Technische Universität Dresden Method for the synthesis of mxenes, mxene nanosheets and their use
CN112563330A (en) * 2020-12-06 2021-03-26 南开大学 Vertical monomolecular field effect transistor integrated device based on two-dimensional material nano-pores and preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
基于阵列电极的新型混合电容器;刘文燚;栗林坡;桂秋月;邓伯华;李园园;物理化学学报;36(2);全文 *

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