CN112072126A - Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof - Google Patents

Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof Download PDF

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CN112072126A
CN112072126A CN202010899661.8A CN202010899661A CN112072126A CN 112072126 A CN112072126 A CN 112072126A CN 202010899661 A CN202010899661 A CN 202010899661A CN 112072126 A CN112072126 A CN 112072126A
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mxene
alc
lithium
air battery
hydrochloric acid
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宋慧宇
李芳�
郑广丽
杜丽
崔志明
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South China University of Technology SCUT
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses an Mxene flexible self-supporting lithium-air battery positive electrode material, an Mxene flexible composite film and a preparation method thereof. The method comprises the following steps: etching the MAX-phase ceramic material by hydrofluoric acid or a mixed solution of villiaumite and hydrochloric acid, ultrasonically stripping and vacuum filtering to obtain the Mxene flexible self-supporting lithium-air battery anode; and further carrying out intercalation treatment on the prepared Mxene flexible electrode to obtain the CNT-intercalated Mxene/CNT composite flexible electrode (Mxene flexible composite film). The flexible electrode prepared by the invention has a unique two-dimensional layered structure, large specific surface area, high electronic conductivity and high electrochemical stability, and can provide a channel for oxygen circulation and electrolyte transmission; the composite electrode after the CNT intercalation treatment effectively reduces the stacking of Mxene materials and provides enough storage space for discharge products. Has wide application prospect in lithium air batteries.

Description

Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof
Technical Field
The invention belongs to the technical field of battery electrode materials, and particularly relates to an Mxene flexible self-supporting lithium-air battery anode material, an Mxene flexible composite membrane and a preparation method thereof.
Background
With the increasing consumption of fossil energy, research on new clean energy is urgent. Electrochemical energy is a new energy source due to the advantages of high specific energy, long cycle life, high energy conversion efficiency, no pollution and the like. Wherein the lithium-air battery has an ultra-high theoretical specific energy density of 5210Wh kg-1(considering oxygen mass) or 11400Wh kg-1The lithium ion secondary battery is 5-10 times of the traditional lithium ion secondary battery (without considering oxygen), and is expected to replace gasoline to become a new generation of power energy. However, during discharge, lithium ions migrate from the anode to the cathode and react with oxygen in the cathode to produce the solid discharge product Li2O2. Insoluble Li2O2The lithium ion can be accumulated on the surface or in the pores of the positive electrode to block further transportation of oxygen and lithium ions, and meanwhile, the active reaction sites of the positive electrode are reduced, so that the overpotential is continuously increased, the side reaction is aggravated, and the service life of the battery is greatly reduced. The lithium-air battery cathode material is the primary factor influencing the performance of the battery, so that the design of an air cathode with large specific surface area and enough reactant diffusion channels is important.
In order to solve the problems, the anode material of the lithium-air battery mainly adopts a carbon material with large specific surface area, high conductivity and a porous structure at present. Chinese invention patent CN 104282918A discloses a method for preparing a modified carbon material lithium air anode, the surface of the carbon material contains hetero atoms or hetero atom groups to increase the anode-electrolyte-oxygen three-phase interface, which is beneficial to improving the discharge capacity; the Chinese invention patent CN 103367765A discloses a preparation method of a multilayer graphite lithium air anode, which utilizes inert gas to perform high-temperature expansion treatment on a graphite material to obtain multilayer graphite with the pore volume up to 98 percent, and solves the problem that the pores of the existing graphite material are poor in performanceLow volume and low specific discharge capacity. However, carbon materials tend to decompose above 3.5V during battery cycling and react with discharge products to form Li2CO3Causing capacity fade and cell polarization problems. Therefore, it is necessary to prepare a lithium-air battery positive electrode using a non-carbon material.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an Mxene flexible self-supporting lithium-air battery positive electrode material, an Mxene flexible composite film and a preparation method thereof.
In view of the above, the present invention is directed to the defects of the prior art, and the main object of the present invention is to provide a flexible self-supporting Mxene lithium-air battery positive electrode and a preparation method thereof. The flexible self-supporting electrode has a unique structure and a large specific surface area, can realize the rapid transportation of oxygen and electrolyte, does not need adhesives, and has good plasticity and flexibility.
The Mxene material is a novel transition metal carbide/nitride, has excellent electrochemical performance, is researched and applied to a super capacitor, a lithium ion battery and a lithium sulfur battery, but has no related application of a lithium air battery at present. The Mxene material has high specific surface area similar to graphene, high electronic conductivity and high charge-discharge electrochemical stability; the unique two-dimensional layered structure can provide a channel for the circulation of oxygen and electrolyte, and simultaneously provide reaction sites and storage spaces for reaction intermediates and products; and the film can be formed independently without depending on adhesives, has good flexibility and strong plasticity, and has great application potential in the aspect of lithium air battery anode materials. Therefore, the invention proposes to use Mxene materials for the preparation of lithium-air battery anodes.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of an Mxene flexible self-supporting lithium-air battery anode material, which comprises the following steps:
(1) soaking the MAX phase ceramic material in an acidic liquid for etching and washing to obtain a multilayer Mxene powder material;
(2) adding the multiple layers of Mxene powder materials in the step (1) into water, carrying out ultrasonic stripping treatment, centrifuging and taking supernate to obtain Mxene dispersion liquid (few-layer Mxene dispersion liquid);
(3) and (3) carrying out suction filtration on the Mxene dispersion liquid obtained in the step (2), taking filter residues, and drying to obtain the Mxene flexible self-supporting electrode.
Further, the MAX phase ceramic material in the step (1) is Ti2AlC、Ti2AlN、V2AlC、Nb2AlC、Ta2AlC、Cr2AlC、Ti3AlC2、Ti3SiC2、Ti3AlCN、Mo2Ga2C、Mo2Ti2AlC3、Mo2TiAlC2、Nb4AlC3At least one of; the acidic liquid is hydrofluoric acid or villaumite-hydrochloric acid mixed liquid; the mass percentage concentration of the hydrofluoric acid is 10% -50%; the villiaumite-hydrochloric acid mixed solution is a liquid obtained by uniformly mixing villiaumite and hydrochloric acid, the villiaumite is at least one of lithium fluoride, sodium fluoride and potassium fluoride, and the concentration of the hydrochloric acid is 11-12mol L-1(ii) a In the mixed solution of the villiaumite and the hydrochloric acid, the concentration of villiaumite in the mixed solution is 11-12mol L-1。
Preferably, the mass percentage concentration of the hydrofluoric acid is 40-50 wt%.
The multilayer Mxene powder material is MXT obtained by etchingxWherein T isxIs one or more of-OH functional group/-F functional group/-O functional group. The hydrofluoric acid etching is preferably as follows: slowly adding the MAX phase ceramic material into hydrofluoric acid, stirring at room temperature, repeatedly cleaning with deionized water, and vacuum-drying the precipitate to obtain powder. The stirring time is 10-12 h. The number of washing times is 5-6. Washing with deionized water until the pH is 6.0-7.0. The vacuum drying temperature is 20-25 ℃, and the vacuum drying time is 24-48 h.
The method for etching the fluoride salt and the hydrochloric acid comprises the following steps: dissolving lithium fluoride in concentrated hydrochloric acid, mixing and stirring, slowly adding MAX phase ceramic material, stirring in water bath, centrifuging to obtain precipitate, washing redundant lithium fluoride with dilute hydrochloric acid, repeatedly centrifuging and washing with deionized water, and finally vacuum drying the precipitate to obtain powder. The concentration of the concentrated hydrochloric acid is 11-12mol L-1. The water bathThe temperature is 35-40 ℃, and the time is 24-36 h. Washing with deionized water until the pH is 6.0-7.0. The vacuum drying temperature is 20-25 ℃, and the vacuum drying time is 24-48 h.
The MAX phase ceramic material is a ternary layered metal ceramic functional material and has a structure of Mn+1AXnM is a transition metal element (Mo, Ti, Nb), a is a group iiia or iva element (Al, Ga, Si, Ge, Sn), X is C or N, and N is different (N is 1,2,3), and can be divided into 211, 312, and 413 phases. Comprising Ti2AlC、Ti2AlN、V2AlC、Nb2AlC、Ta2AlC、Cr2AlC、Ti3AlC2、Ti3SiC2、Ti3AlCN、Mo2Ga2C、Mo2Ti2AlC3、Mo2TiAlC2、Nb4AlC3。
Further, the etching time in the step (1) is 24-36 h, and the etching temperature is 35-40 ℃.
Further, the time of the ultrasonic stripping treatment in the step (2) is 30-60 min; the mass-volume ratio of the multi-layer Mxene powder material to the water in the step (2) is 0.05-0.1: 1 g/mL; the rotating speed of the centrifugation in the step (2) is 3000-3500rpm, and the centrifugation time is 30-60 min.
Furthermore, the filter membrane used in the suction filtration in the step (3) has the pore size of 0.1-0.45 μm. The suction filtration was carried out using a microfiltration membrane or Celgard 3501 septum.
Preferably, the drying of step (3) is vacuum drying; the vacuum drying temperature is 60-80 deg.C, and the vacuum drying time is 6-12 h.
The invention provides a Mxene flexible self-supporting lithium-air battery positive electrode material prepared by the preparation method.
The invention provides a preparation method of an Mxene flexible composite membrane, which comprises the following steps:
(1) soaking the MAX phase ceramic material in an acidic liquid for etching and washing to obtain a multilayer Mxene powder material;
(2) adding the multiple layers of Mxene powder materials in the step (1) into water, carrying out ultrasonic stripping treatment, centrifuging and taking supernate to obtain Mxene dispersion liquid;
(3) and (3) adding multi-wall Carbon Nanotubes (CNTs) into water, performing ultrasonic dispersion uniformly to obtain a multi-wall carbon nanotube dispersion liquid (CNT solution), then dropwise adding the multi-wall carbon nanotube dispersion liquid (CNT solution) into the Mxene dispersion liquid obtained in the step (2), stirring, performing dropwise suction filtration, taking filter residues, and drying to obtain the Mxene flexible composite membrane (the CNT intercalation Mxene/CNT composite flexible self-supporting electrode).
Further, the MAX phase ceramic material in the step (1) is Ti2AlC、Ti2AlN、V2AlC、Nb2AlC、Ta2AlC、Cr2AlC、Ti3AlC2、Ti3SiC2、Ti3AlCN、Mo2Ga2C、Mo2Ti2AlC3、Mo2TiAlC2、Nb4AlC3At least one of; the acidic liquid in the step (1) is hydrofluoric acid or a villaumite-hydrochloric acid mixed solution; the mass percentage concentration of the hydrofluoric acid is 10% -50%; the villiaumite-hydrochloric acid mixed solution is a liquid obtained by uniformly mixing villiaumite and hydrochloric acid, the villiaumite is at least one of lithium fluoride, sodium fluoride and potassium fluoride, and the concentration of the hydrochloric acid is 11-12mol L-1(ii) a In the villaumite-hydrochloric acid mixed solution, the villaumite concentration is 11-12mol L-1(ii) a The etching time in the step (1) is 24-36 h, and the etching temperature is 35-40 ℃.
Further, the time of the ultrasonic stripping treatment in the step (2) is 30-60 min; the mass-volume ratio of the multi-layer Mxene powder material to the water in the step (2) is 0.05-0.1: 1 g/mL; the rotation speed of the centrifugation in the step (2) is 3000-3500rpm, and the centrifugation time is 30-60 min; the mass fraction of the multi-walled Carbon Nanotube (CNT) dispersion liquid in the step (3) is 9-10%; the multi-walled carbon nano-tube accounts for 1 to 10 percent of the composite film by mass; the aperture size of the filter membrane used in the step (3) is 0.1-0.45 μm. The suction filtration adopts a microporous filter membrane active Celgard 3501 diaphragm.
Preferably, the time of the ultrasound in the step (3) is 30-60 min.
Preferably, the stirring time of the step (3) is 5-10 min.
Preferably, the drying in the step (3) is vacuum drying, the temperature of the vacuum drying is 60-80 ℃, and the time of the vacuum drying is 6-12 h.
The invention provides a Mxene flexible composite membrane prepared by the preparation method.
The Mxene flexible self-supporting electrode material developed by the invention can be applied to energy storage and conversion devices of lithium air batteries, lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, aluminum ion batteries, lithium sulfur batteries and super capacitors. When the electrolyte is applied to the lithium-air battery, gas is easy to transmit, the storage space of a discharge product is large, the electrolyte is convenient to transport, and the conductivity is good.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the Mxene flexible self-supporting lithium-air battery anode material has larger specific surface area and richer surface reaction sites, and is beneficial to gas transmission, liquid circulation and storage of reaction products; the conductive and heat-conducting properties are good, the mechanical stability is high, and the oxidation resistance is excellent;
(2) the Mxene flexible self-supporting lithium air battery anode material prepared by the invention has good flexibility, strong plasticity, certain shape recovery capability, no need of adding a conductive agent or an adhesive, and self-supporting characteristic;
(3) the preparation method is simple to operate, and the prepared flexible electrode is good in electrochemical performance.
Drawings
FIG. 1 shows Ti used in example 12AlC phase ceramic material and multilayer Ti prepared from same2CTxXRD pattern of the powder material.
FIG. 2 is a multilayer Ti prepared in example 12CTxSEM image of the powder material.
FIG. 3 shows Ti prepared in example 12CTxPositive electrode lithium-air battery charge-discharge curve.
FIG. 4 is a multilayer Ti prepared in example 32CTxSEM image of the powder material.
FIG. 5 shows Ti prepared in example 32CTxPositive electrode lithium-air battery charge-discharge curve.
Detailed description of the preferred embodiments.
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of an Mxene flexible self-supporting lithium-air battery anode material specifically comprises the following steps:
(1) preparation of multilayer Mxene powder material: 6g of lithium fluoride were dissolved in 60mL of 12mol L-1And mixing and stirring the mixed solution in the concentrated hydrochloric acid solution for 10min to obtain the mixed etching solution. 2g of Ti2Slowly adding AlC into the mixed etching solution, stirring for 24h in a water bath at 40 ℃, centrifuging to obtain a precipitate, and adding 1mol L of AlC-1And washing the precipitate for multiple times by using the dilute hydrochloric acid solution to remove redundant lithium fluoride, then repeatedly carrying out centrifugal washing for 3 times by using deionized water, and carrying out vacuum drying on the obtained precipitate for 48 hours at the temperature of 25 ℃ to obtain the multi-layer Mxene powder material. The multi-layer Mxene powder material is Ti2CTxWherein T isxIs one or more of-OH functional group/-F functional group/-O functional group. Ti2AlC ceramic material and multilayer Ti2CTxThe XRD pattern of the powder is shown in FIG. 1.
Prepared multilayer Ti2CTxThe SEM image of the powder material is shown in fig. 2 as having a good layered structure with a severe stacking of the lamellae and a thickness of about 7-8 μm. The adsorbed functional groups (OH, F, O) are on Ti2CTxThe surfaces are randomly distributed, and the interaction exists between layers.
(2) Preparation of few-layer Mxene dispersion: taking 1g of the multilayer Mxene powder material obtained in the step (1), adding 10mL of deionized water, carrying out ultrasonic treatment on the multilayer Mxene material for 30min under 100W of ultrasonic power, and simultaneously introducing Ar2And (6) protecting. Centrifuging at 3000rpm for 30min, collecting supernatantA few layers of Mxene dispersion were obtained.
The prepared few-layer Mxene material keeps a good two-dimensional layered structure, the layered structure is opened, the peeling between layers is realized, and the materials are changed into few-layer materials from multi-layer materials. The interlayer distance is obviously increased, the specific surface area is increased, the transportation of oxygen and the transfer of electrolyte are facilitated, and meanwhile, enough space is provided for the deposition of discharge products.
(3) And (3) carrying out vacuum filtration on the small-layer Mxene layering liquid obtained in the step (2) by adopting Celgard 3501 membranes to form the Mxene flexible film.
(4) And (4) drying the flexible film obtained in the step (3) at 60 ℃ in vacuum for 6 hours to obtain the Mxene flexible self-supporting electrode.
The prepared Mxene flexible self-supporting electrode has good flexibility, has certain recovery capability after being bent by tweezers, does not damage the whole structure in the deformation process, and has good plasticity.
(5) The prepared Mxene flexible self-supporting electrode is assembled into an air battery to test the electrochemical performance of the air battery: using a round piece with the diameter of 8mm at the cut part of the Mxene flexible film as an air electrode, using a metal lithium piece as a negative electrode, using Celgard 2500 as a diaphragm, and using 1.0mol L of the round piece-1The lithium air battery is assembled by using LiTFSI (lithium bis (trifluoromethane sulfonyl) imide) TEGDME (tetraethylene glycol dimethyl ether) as electrolyte in a glove box, standing for 5 hours in high-purity oxygen, and testing the charge-discharge performance, wherein a testing instrument is Xinwei CT-3008W-5V-S4. The charge and discharge curves of the prepared Mxene flexible self-supporting electrode as an air cathode of a lithium air battery are shown in fig. 3. As can be seen from FIG. 3, the constant current charge and discharge test results show that the charge and discharge capacity is 100mAg-1Under the current density, the first discharge specific capacity of the lithium-air battery is 317.3mAh g-1(calculated as the total flexible electrode mass).
Example 2
A preparation method of an Mxene flexible self-supporting lithium-air battery anode material specifically comprises the following steps:
(1) preparation of multilayer Mxene powder material: slowly adding 1g of MAX phase ceramic material into 10mL of hydrofluoric acid solution, stirring at room temperature for 24h with the concentration of hydrofluoric acid being 40%, centrifuging to obtain precipitate, and then using deionized waterThe water washing was repeated 5 times, and the resulting precipitate was vacuum dried at 25 ℃ for 48h to give a multilayered Mxene powder material. The multi-layer Mxene powder material is Ti2CTxWherein T isxIs one or more of-OH functional group/-F functional group/-O functional group.
The multilayer Mxene powder material prepared had a good layered structure with severe stacking of the layers. The adsorbed functional groups (OH, F, O) are on Ti2CTxThe surfaces are randomly distributed, and the interaction exists between layers.
(2) Preparation of few-layer Mxene dispersion: taking the multilayer Mxene powder (multilayer Ti) obtained in the step (1)2CTxPowder material) 1g, adding 10mL of deionized water, carrying out ultrasonic treatment on the multilayer Mxene material for 30min under 100W ultrasonic power, and simultaneously introducing Ar2And (6) protecting. Then, the mixture was centrifuged at 3000rpm for 30 min. The supernatant was collected to obtain a small layer of Mxene dispersion.
The prepared few-layer Mxene material keeps a good two-dimensional layered structure, the layered structure is opened, the peeling between layers is realized, and the materials are changed into few-layer materials from multi-layer materials. The interlayer distance is obviously increased, the specific surface area is increased, the transportation of oxygen and the transfer of electrolyte are facilitated, and meanwhile, enough space is provided for the deposition of discharge products.
(3) And (3) carrying out vacuum filtration on the small-layer Mxene layering liquid obtained in the step (2) by adopting Celgard 3501 membranes to form the Mxene flexible film.
(4) And (4) drying the flexible film obtained in the step (3) at 60 ℃ in vacuum for 6 hours to obtain the Mxene flexible self-supporting electrode.
The prepared Mxene flexible self-supporting electrode has good flexibility, has certain recovery capability after being bent by tweezers, does not damage the whole structure in the deformation process, and has good plasticity.
Example 3
A preparation method of an Mxene flexible self-supporting lithium-air battery anode material specifically comprises the following steps:
1g of lithium fluoride was added to 10mL of 12mol L-1To the hydrochloric acid solution, 1g of Ti was slowly added with stirring2AlC。After the addition was complete, the mixture was stirred in a water bath at 35 ℃ for 24h to give multiple layers of Mxene (multiple layers of Ti)2CTxPowdered material) dispersion, washed 4-5 times with deionized water until pH is around 6. Then, this was subjected to ultrasonic treatment for 1 hour, and centrifuged at 3500rpm for 1 hour to remove the bottom precipitate, thereby obtaining a Mxene dispersion with less exfoliation. And (3) performing vacuum filtration by using Celgard 3501 membrane to form a Mxene flexible film, and then performing vacuum drying for 6h at 80 ℃ to obtain the Mxene flexible self-supporting electrode.
As shown in FIG. 4, a multilayer Ti was prepared2CTxThe powder material has a good laminar structure with a severe stacking of the sheets, the thickness of the sheets being about 7-8 μm. The adsorbed functional groups (OH, F, O) are on Ti2CTxThe surfaces are randomly distributed, and the interaction exists between layers.
The prepared Mxene flexible self-supporting electrode has good flexibility and mechanical strength, can be bent to a certain degree, has no damage to the whole structure in the deformation process, and has good plasticity.
The prepared Mxene flexible self-supporting electrode is assembled into an air battery to test the electrochemical performance of the air battery: a round piece with the diameter of 8mm at the cut part of the Mxene flexible film is used as an air electrode, a metal lithium piece is used as a negative electrode, Celgard 2500 is used as a diaphragm, 1.0mol of L-1LiTFSI (lithium bis (trifluoromethane sulfonyl) imide) TEGDME (tetraethylene glycol dimethyl ether) is used as electrolyte, a lithium air battery is assembled in a glove box, the lithium air battery is kept stand in high-purity oxygen for 5 hours, the charge and discharge performance is tested, and a test instrument is Xinwei CT-3008W-5V-S4.
The charge and discharge curves of the prepared Mxene flexible self-supporting electrode as an air cathode of a lithium air battery are shown in fig. 5. As can be seen from FIG. 5, the constant current charge-discharge test result shows that the first discharge specific capacity of the lithium-air battery is 109mAh g-1 (calculated according to the mass of the active material) under the current of 0.01 mA.
Example 4
A preparation method of an Mxene flexible composite film specifically comprises the following steps:
taking 19mL of the small-layer Mxene dispersion liquid in the embodiment 1, adding deionized water, and carrying out ultrasonic treatment for 15 min; weighing 50mg of multi-walled carbon nanotube dispersion liquid, adding deionized water, and carrying out ultrasound for 30 min. And sequentially carrying out suction filtration on the low-layer Mxene dispersion liquid, the CNT dispersion liquid and the low-layer Mxene dispersion liquid in a vacuum suction filtration mode to form a low-layer Mxene/CNT/low-layer Mxene sandwich structure film, and carrying out vacuum drying on the film for 6 hours at the temperature of 60 ℃ to obtain the sandwich composite flexible electrode. The mass ratio of the Mxene to the CNT of the composite flexible electrode few layer is 19: 1.
example 5
A preparation method of an Mxene flexible composite film specifically comprises the following steps:
taking 18mL of the small-layer Mxene dispersion liquid in the embodiment 1, adding deionized water, and carrying out ultrasonic treatment for 30 min; weighing 100mg of multi-walled carbon nanotube dispersion liquid, adding deionized water, and performing ultrasonic treatment for 60 min. And sequentially carrying out suction filtration on the low-layer Mxene dispersion liquid, the CNT dispersion liquid and the low-layer Mxene dispersion liquid in a vacuum suction filtration mode to form a low-layer Mxene/CNT/low-layer Mxene sandwich structure film, and carrying out vacuum drying on the film for 12 hours at the temperature of 60 ℃ to obtain the sandwich composite flexible electrode. The mass ratio of the Mxene to the CNT of the composite flexible electrode few layer is 9: 1.
example 6
A preparation method of an Mxene flexible composite film specifically comprises the following steps:
taking 17mL of the small-layer Mxene dispersion liquid in the embodiment 1, adding deionized water, and carrying out ultrasonic treatment for 30 min; weighing 150mg of multi-walled carbon nanotube dispersion liquid, adding deionized water, and performing ultrasonic treatment for 60 min. And sequentially carrying out suction filtration on the low-layer Mxene dispersion liquid, the CNT dispersion liquid and the low-layer Mxene dispersion liquid in a vacuum suction filtration mode to form a low-layer Mxene/CNT/low-layer Mxene sandwich structure film, and carrying out vacuum drying on the film for 12 hours at the temperature of 60 ℃ to obtain the sandwich composite flexible electrode. The mass ratio of the Mxene to the CNT of the composite flexible electrode few layer is 5.7: 1.
example 7
A preparation method of an Mxene flexible composite film specifically comprises the following steps:
taking 19mL of Mxene dispersion liquid of the embodiment 3, adding deionized water and carrying out ultrasonic treatment for 15 min; weighing 50mg of multi-walled carbon nanotube dispersion liquid, adding deionized water, and carrying out ultrasound for 30 min. Then, the CNT dispersion was dropwise added to the Mxene solution, and stirred for 5min to obtain a mixed solution. The mixed solution was filtered dropwise with Celgard 3501 septum to obtain Mxene/CNT composite flexible membrane (wherein the mass of CNT is 5% of the total mass of the membrane). And drying the composite film for 6h at 80 ℃ under a vacuum condition to obtain the Mxene/CNT composite flexible electrode material.
The prepared Mxene/CNT composite flexible electrode has good flexibility, strong mechanical property and strong plasticity. Due to the insertion of the carbon nano tube, a large number of layered structures of the Mxene are opened, the specific surface area is increased, and gas transmission and ion diffusion are facilitated.
Example 8
A preparation method of an Mxene flexible composite film specifically comprises the following steps:
taking 18mL of Mxene dispersion liquid of the embodiment 3, adding deionized water and carrying out ultrasonic treatment for 30 min; weighing 100mg of multi-walled carbon nanotube dispersion liquid, adding deionized water, and performing ultrasonic treatment for 60 min. Then, the CNT dispersion was dropwise added to the Mxene solution, and stirred for 10min to obtain a mixed solution. The mixed solution was filtered dropwise with Celgard 3501 septum to obtain Mxene/CNT composite flexible membrane (wherein the mass of CNT is 10% of the total mass of the membrane). And drying the composite film for 12h at 80 ℃ under a vacuum condition to obtain the Mxene/CNT composite flexible electrode material.
The prepared Mxene/CNT composite flexible electrode keeps a good two-dimensional shape structure, a large number of CNTs are uniformly distributed among Mxene layers, and the interlayer spacing is further increased. The increased interlayer spacing is beneficial to the rapid transportation and diffusion of electrolyte ions in the charge and discharge process, and the charge and discharge capacity of the lithium-air battery is further improved.
Example 9
A preparation method of an Mxene flexible composite film specifically comprises the following steps:
taking 17mL of the Mxene dispersion liquid of the embodiment 3, adding deionized water and carrying out ultrasonic treatment for 30 min; weighing 150mg of multi-walled carbon nanotube dispersion liquid, adding deionized water, and performing ultrasonic treatment for 60 min. Then, the CNT dispersion was dropwise added to the Mxene solution, and stirred for 10min to obtain a mixed solution. The mixed solution was filtered dropwise with Celgard 3501 septum to obtain Mxene/CNT composite flexible membrane (wherein the mass of CNT is 15% of the total mass of the membrane). And drying the composite film for 12h at 80 ℃ under a vacuum condition to obtain the Mxene/CNT composite flexible electrode material.
The prepared Mxene/CNT composite flexible electrode has unchanged layered structure after CNT intercalation treatment, large specific surface area and benefit for gas transmission. The self-supporting performance is good, the combination of a conductive agent and an adhesive is not needed, and the operation steps are simplified.
Example 10
A preparation method of an oxygen-doped Mxene flexible composite film specifically comprises the following steps:
the mixed solution of Mxene/CNT obtained in example 7 was dried under vacuum at 60 ℃ for 12 hours to obtain Mxene/CNT mixed powder. 2g of Mxene/CNT mixed powder was taken, and 10% H was added2O2And heating and stirring the solution in a water bath at 60 ℃ for 20min, repeatedly washing the solution with deionized water, and performing suction filtration by using a Celgard 3501 diaphragm to obtain the oxygen-doped Mxene/CNT composite flexible membrane.
Example 11
10mL of the Mxene dispersion of example 1 was added with deionized water and stirred for 30 min. 1mL of 5mg mL was added dropwise to the Mxene dispersion-1Ru3+Stirring the solution and the mixed solution for 30min, and then dropwise adding and filtering by using a Celgard 3501 diaphragm while stirring to obtain Ru3+@ Mxene flexible self-supporting films. To Ru3+0.01mol L of @ Mxene flexible self-supporting film is dripped on-1NaBH4And soaking the solution (in ice water bath for 10min), performing suction filtration after no bubbles are generated, and repeatedly cleaning with deionized water to obtain the nano ruthenium modified Mxene flexible self-supporting electrode.
Example 12
10mL of the Mxene dispersion of example 1 was added with deionized water and stirred for 30 min. 1mL of 5mg mL was added dropwise to the Mxene dispersion-1Ru3+Stirring the solution and the mixed solution for 30min, then dropwise adding and filtering by using a Celgard 3501 diaphragm while stirring, and removing the solvent by freeze drying to obtain Ru3+@ Mxene flexible film. Ru is mixed3+And (3) reducing the @ Mxene flexible membrane for 4h at 200 ℃ in hydrogen to obtain the nano ruthenium modified Mxene flexible self-supporting electrode.
Example 13
10mL of the Mxene/CNT mixed dispersion of example 8 was taken, and deionized water was added thereto and stirred for 30 min. 1mL of 5mg mL was added dropwise to the Mxene/CNT mixed dispersion-1Ru3+The solution, mixed solution, was stirred for 30min, then Celgar was usedd 3501 diaphragm dropwise adding and filtering under stirring to obtain Ru3+@ Mxene/CNT hybrid flexible film. To Ru3+0.01mol L of @ Mxene/CNT composite flexible membrane is dripped on-1NaBH4And soaking the solution (in ice water bath for 10min), performing suction filtration after no bubbles are generated, and repeatedly cleaning with deionized water to obtain the nano ruthenium modified Mxene/CNT composite flexible self-supporting electrode.
Example 14
10mL of the Mxene/CNT mixed dispersion of example 8 was taken, and deionized water was added thereto and stirred for 30 min. 1mL of 5mg mL was added dropwise to the Mxene/CNT mixed dispersion-1Ru3+Stirring the solution and the mixed solution for 30min, then dropwise adding and filtering by using a Celgard 3501 diaphragm while stirring, and removing the solvent by freeze drying to obtain Ru3+@ Mxene/CNT composite flexible film. Ru is mixed3+And (3) reducing the @ Mxene/CNT composite flexible membrane for 4h at 200 ℃ in hydrogen to obtain the Mxene/CNT composite flexible self-supporting electrode modified by nano ruthenium.
Example 15
10mL of the Mxene dispersion of example 1 was added with deionized water and stirred for 30 min. 1mL of 5mg mL was added dropwise to the Mxene dispersion-1Ru3+Stirring the solution and the mixed solution for 30min, and then dropwise adding and filtering by using a Celgard 3501 diaphragm while stirring to obtain Ru3+@ Mxene flexible film. To Ru3+0.001mol L of @ Mxene flexible membrane-1And filtering the NaOH solution, repeatedly washing the NaOH solution by using deionized water, and drying to obtain the nanometer ruthenium dioxide modified Mxene flexible self-supporting electrode. A
Example 16
10mL of the Mxene/CNT mixed dispersion of example 8 was taken, and deionized water was added thereto and stirred for 30 min. 1mL of 5mg mL was added dropwise to the Mxene/CNT mixed dispersion-1Ru3+Stirring the solution and the mixed solution for 30min, and then dropwise adding and filtering by using a Celgard 3501 diaphragm while stirring to obtain Ru3+@ Mxene/CNT hybrid flexible film. To Ru3+0.001mol L of @ Mxene/CNT composite flexible membrane-1And filtering the NaOH solution, repeatedly washing with deionized water, and drying to obtain the Mxene/CNT composite flexible self-supporting electrode modified by the nano ruthenium dioxide.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of an Mxene flexible self-supporting lithium-air battery positive electrode material is characterized by comprising the following steps:
(1) soaking the MAX phase ceramic material in an acidic liquid for etching and washing to obtain a multilayer Mxene powder material;
(2) adding the multiple layers of Mxene powder materials in the step (1) into water, carrying out ultrasonic stripping treatment, centrifuging and taking supernate to obtain Mxene dispersion liquid;
(3) and (3) carrying out suction filtration on the Mxene dispersion liquid obtained in the step (2), taking filter residues, and drying to obtain the Mxene flexible self-supporting electrode.
2. The method for preparing the Mxene flexible self-supporting lithium-air battery anode material according to claim 1, characterized in that, the MAX phase ceramic material in the step (1) is Ti2AlC、Ti2AlN、V2AlC、Nb2AlC、Ta2AlC、Cr2AlC、Ti3AlC2、Ti3SiC2、Ti3AlCN、Mo2Ga2C、Mo2Ti2AlC3、Mo2TiAlC2、Nb4AlC3At least one of; the acidic liquid is hydrofluoric acid or villaumite-hydrochloric acid mixed liquid; the mass percentage concentration of the hydrofluoric acid is 40% -50%; the villiaumite-hydrochloric acid mixed solution is a liquid obtained by uniformly mixing villiaumite and hydrochloric acid, the villiaumite is at least one of lithium fluoride, sodium fluoride and potassium fluoride, and the concentration of the hydrochloric acid is 11-12mol L-1(ii) a In the mixed solution of the villiaumite and the hydrochloric acid, the concentration of villiaumite in the mixed solution is 11-12mol L-1。
3. The method for preparing the Mxene flexible self-supporting lithium air battery anode material according to claim 1, characterized in that the etching time of the step (1) is 24h-36h, and the etching temperature is 35 ℃ -40 ℃.
4. The method for preparing the Mxene flexible self-supporting lithium-air battery cathode material according to claim 1, characterized in that, the ultrasonic stripping treatment time of the step (2) is 30-60 min; the mass-volume ratio of the multi-layer Mxene powder material to the water in the step (2) is 0.05-0.1: 1 g/mL; the rotating speed of the centrifugation in the step (2) is 3000-3500rpm, and the centrifugation time is 30-60 min.
5. The method for preparing the Mxene flexible self-supporting lithium air battery anode material according to the claim 1, characterized in that the pore size of the filter membrane used in the suction filtration of the step (3) is 0.1 μm-0.45 μm.
6. An Mxene flexible self-supporting lithium-air battery positive electrode material prepared by the preparation method of any one of claims 1 to 5.
7. A preparation method of an Mxene flexible composite film is characterized by comprising the following steps:
(1) soaking the MAX phase ceramic material in an acidic liquid for etching and washing to obtain a multilayer Mxene powder material;
(2) adding the multiple layers of Mxene powder materials in the step (1) into water, carrying out ultrasonic stripping treatment, centrifuging and taking supernate to obtain Mxene dispersion liquid;
(3) and (3) adding the multi-walled carbon nanotube into water, performing ultrasonic dispersion uniformly to obtain a multi-walled carbon nanotube dispersion liquid, then dropwise adding the multi-walled carbon nanotube dispersion liquid into the Mxene dispersion liquid obtained in the step (2), stirring, performing dropwise suction filtration, taking filter residues, and drying to obtain the Mxene flexible composite membrane.
8. A method for preparing a Mxene flexible composite membrane according to claim 7, characterized in that, the MAX phase ceramic material in step (1) is Ti2AlC、Ti2AlN、V2AlC、Nb2AlC、Ta2AlC、Cr2AlC、Ti3AlC2、Ti3SiC2、Ti3AlCN、Mo2Ga2C、Mo2Ti2AlC3、Mo2TiAlC2、Nb4AlC3At least one of; the acidic liquid in the step (1) is hydrofluoric acid or a villaumite-hydrochloric acid mixed solution; the mass percentage concentration of the hydrofluoric acid is 10% -50%; the villiaumite-hydrochloric acid mixed solution is a liquid obtained by uniformly mixing villiaumite and hydrochloric acid, the villiaumite is at least one of lithium fluoride, sodium fluoride and potassium fluoride, and the concentration of the hydrochloric acid is 11-12mol L-1(ii) a In the villaumite-hydrochloric acid mixed solution, the villaumite concentration is 11-12mol L-1(ii) a The etching time in the step (1) is 24-36 h, and the etching temperature is 35-40 ℃.
9. A method for preparing a Mxene flexible composite membrane according to claim 7, characterized in that the time of the ultrasonic peeling treatment in the step (2) is 30-60 min; the mass-volume ratio of the multi-layer Mxene powder material to the water in the step (2) is 0.05-0.1: 1 g/mL; the rotation speed of the centrifugation in the step (2) is 3000-3500rpm, and the centrifugation time is 30-60 min; the mass fraction of the multi-walled carbon nanotube dispersion liquid in the step (3) is 9-10%; the multi-walled carbon nano-tube accounts for 1 to 10 percent of the composite film by mass; the aperture size of the filter membrane used in the step (3) is 0.1-0.45 μm.
10. An Mxene flexible composite film produced by the production method according to any one of claims 7 to 9.
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