CN114420897A - Preparation method of MXene thin film electrode - Google Patents

Preparation method of MXene thin film electrode Download PDF

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CN114420897A
CN114420897A CN202210223129.3A CN202210223129A CN114420897A CN 114420897 A CN114420897 A CN 114420897A CN 202210223129 A CN202210223129 A CN 202210223129A CN 114420897 A CN114420897 A CN 114420897A
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mxene
preparation
organic dispersion
precipitate
thin film
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CN114420897B (en
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鲁铭
杜明栋
魏超
王丽
李嘉明
王知贺
徐仕翀
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Jilin Yiyi Technology Co ltd
Jilin Normal University
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Jilin Yiyi Technology Co ltd
Jilin Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/921—Titanium carbide
    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
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    • 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
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention belongs to the technical field of electrode materials, and provides a preparation method of an MXene thin film electrode, which comprises the following steps: providing an organic dispersion liquid of a small layer of MXene, mixing the organic dispersion liquid of the small layer of MXene with a photosensitive resin, carrying out photocuring, and curing the obtained MXene-based polymer film on a current collector to obtain the MXene film electrode. According to the invention, a few layers of MXene materials are used as electrode main materials, photosensitive resin is added, and then the two-dimensional MXene materials have a three-dimensional configuration through photocuring, so that the stacking of the two-dimensional materials is prevented, a foundation is provided for the subsequent curing of an electrolyte, the problem of an interface between the electrolyte and an electrode is effectively improved, and the electrical property of the battery is improved. The results of the examples show that the MXene thin film electrode prepared by the preparation method provided by the invention is used as the positive electrode to assemble the solid-state battery, and the solid-state batteryThe specific capacity is 0.007mAh/cm2。

Description

Preparation method of MXene thin film electrode
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of an MXene thin film electrode.
Background
With the progress of science and technology, portable devices, power automobiles, intelligent robots and the like gradually enter the lives of people, and then the demand of people on energy sources is higher and higher, wherein fossil energy sources are the most main energy sources consumed globally, but the fossil energy sources have the problems of increasing exhaustion and environmental pollution. Therefore, the search for sustainable clean energy and efficient energy storage technology is of great significance for realizing economic sustainable development. The lithium ion battery has the advantages of no environmental pollution, high energy density, stable output voltage, no memory effect, light weight and the like, and is widely applied to various fields. However, in practical application, certain problems also exist, such as higher battery cost, incapability of high-power charging and discharging, circuit control to be protected, and severely limited performance in extreme environments and certain potential safety hazards, so that the application and development of the lithium ion battery are limited. The solid-state battery has great advantages compared with the traditional lithium ion battery as a battery using a solid electrode and a solid electrolyte, and has the advantages of good safety, light and thin body, higher energy density and good flexibility. However, the electrolyte conductivity of the existing solid-state batteries is too poor and the interface resistance is too large, thereby causing an interface problem between the solid-state electrode and the solid-state electrolyte, which affects the electrical properties of the batteries. The solid electrode material is used as an important component of the solid battery, and the electrode material with excellent preparation performance is expected to solve the problem of an interface between a solid electrode and a solid electrolyte in the existing solid battery.
MXene material is a general name of a two-dimensional layered carbide and nitride material, M represents a transition metal site, X represents nitrogen or a carbon site, and the MXene material is structurally composed of two or more layers of transition metal atoms, is inserted into a honeycomb-shaped 2D grid fence and is intervened by carbon or nitrogen occupying octagonal sites between adjacent transition metal layers. Due to the diversity of properties in the aspects of mechanics, optics, electricity, chemistry, medicine and the like, the nano-porous carbon nano-tube has good application prospects in the aspects of current collectors, conductive ink, electrochromism, photothermal therapy, catalysis, sensors, water purification, dialysis, gas separation, electromagnetic shielding, alternating current, 3D printing and the like. However, MXene, a two-dimensional material, is prone to interlayer stacking during the preparation of solid-state electrodes, and has a reduced specific surface area, so that a solid-state electrode with good electrical properties cannot be obtained. Therefore, how to prepare a solid-state electrode with excellent electrical properties by using the MXene material becomes a problem to be solved in the field.
Disclosure of Invention
The MXene thin film electrode prepared by the preparation method provided by the invention has excellent electrical properties and high specific capacity, and the problem of an interface between an electrolyte and the electrode is effectively solved.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of an MXene thin film electrode, which comprises the following steps:
(1) providing an organic dispersion of MXene in a small layer;
(2) mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photocuring to obtain an MXene-based polymer film;
(3) and (3) solidifying the MXene-based polymer film obtained in the step (2) on a current collector to obtain an MXene film electrode.
Preferably, the number of the small-layer MXene in the step (1) is 1-10.
Preferably, the organic solvent in the organic dispersion in step (1) comprises N-methylpyrrolidone.
Preferably, the ratio of the mass of the small-layer MXene to the volume of the organic solvent in the organic dispersion liquid of the small-layer MXene in the step (1) is (2.5-3) g: (2-3) mL.
Preferably, the preparation of the organic dispersion of the layered MXene in the step (1) comprises the following steps:
1) adding LiF, HF and Ti to hydrochloric acid in sequence3AlC2Carrying out a reaction to obtain Ti-containing3C2A precipitated reaction solution;
2) the Ti-containing material obtained in the step 1) is3C2Subjecting the precipitated reaction solution to a first centrifugation to obtain a first supernatant and Ti3C2Precipitating;
3) adding Ti obtained in the step 2)3C2Adding water into the precipitate, and performing first ultrasonic treatment;
4) repeating the step 2) and the step 3) until the pH value of the supernatant obtained by centrifugation is more than 6, and obtaining MXene precipitate;
5) adding ethanol into the MXene precipitate obtained in the step 4), and then sequentially performing second ultrasonic treatment and second centrifugation to obtain a second supernatant and multiple layers of MXene precipitate;
6) adding water into the multilayer MXene precipitate obtained in the step 5), and then sequentially performing third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few layers of MXene precipitate;
7) mixing the small-layer MXene precipitate obtained in the step 6) with an organic solvent to obtain an organic dispersion liquid of the small-layer MXene.
Preferably, the power of the first ultrasonic wave in the step 3) is 1200-1500W; the power of the second ultrasonic wave in the step 5) is 1200-1500W; the power of the third ultrasonic wave in the step 6) is 1200-1500W.
Preferably, the mass ratio of the organic dispersion liquid of the MXene with less layers in the step (2) to the photosensitive resin is 1 (1-3).
Preferably, the illumination intensity of photocuring in the step (2) is 8000-8500 uw/cm2The photocuring time is 30-60 s.
Preferably, the current collector in the step (3) comprises a copper sheet or a stainless steel sheet.
Preference is given toThe illumination intensity of the curing in the step (3) is 8000-8500 uw/cm2The curing time is 30-60 s.
The invention provides a preparation method of an MXene thin film electrode, which comprises the following steps: (1) providing an organic dispersion of MXene in a small layer; (2) mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photocuring to obtain an MXene-based polymer film; (3) and (3) solidifying the MXene-based polymer film obtained in the step (2) on a current collector to obtain an MXene film electrode. The invention takes a few layers of MXene materials as electrode main materials, which is beneficial to preventing the stacking of the materials, the MXene-based polymer films are prepared by preparing the electrode main materials into organic dispersion liquid, adding photosensitive resin, then preparing the MXene-based polymer films by a photocuring method, and finally curing the MXene-based polymer films on a current collector to obtain the solid electrode, and the photocuring enables the two-dimensional MXene materials to have three-dimensional configuration, thereby preventing the stacking of the two-dimensional materials, providing a foundation for the curing of subsequent electrolytes, effectively improving the interface problem between the electrolytes and the electrodes, and improving the electrical property of the battery. The results of the examples show that the MXene thin film electrode prepared by the preparation method provided by the invention is used as the positive electrode to assemble the solid-state battery, and the specific capacity of the solid-state battery is 0.007mAh/cm2。
Drawings
FIG. 1 is a schematic representation of MXene-based polymer films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2;
FIG. 2 is a schematic representation of polymer films prepared in comparative examples 3 to 7;
FIG. 3 is a schematic representation of polymer films prepared in comparative examples 10 to 14;
FIG. 4 is a microscope photograph of an MXene-based polymer film prepared in example 1 of the present invention;
FIG. 5 is a microscope photograph of an MXene-based polymer film prepared in example 2 of the present invention;
FIG. 6 is a microscope photograph of an MXene-based polymer film prepared in example 3 of the present invention;
fig. 7 is a microscopic view of an MXene-based polymer film prepared in comparative example 1;
fig. 8 is a microscope image of an MXene-based polymer film prepared in comparative example 2;
fig. 9 is a schematic representation of MXene thin film electrodes prepared in examples 1 and 4 of the present invention;
FIG. 10 is a pictorial view of thin film electrodes prepared in comparative example 3 and comparative example 8;
FIG. 11 is a pictorial view of thin film electrodes prepared in comparative example 4 and comparative example 9;
FIG. 12 is a pictorial view of thin film electrodes prepared in comparative example 11 and comparative example 15;
FIG. 13 is a graph showing the electrical properties of MXene thin film electrode prepared in example 1 of the present invention;
FIG. 14 is a graph of the electrical properties of MXene thin film electrode prepared in example 4 of the present invention;
FIG. 15 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 3;
FIG. 16 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 4;
FIG. 17 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 8;
FIG. 18 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 9;
FIG. 19 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 11;
fig. 20 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 15.
Detailed Description
The invention provides a preparation method of an MXene thin film electrode, which comprises the following steps:
(1) providing an organic dispersion of MXene in a small layer;
(2) mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photocuring to obtain an MXene-based polymer film;
(3) and (3) solidifying the MXene-based polymer film obtained in the step (2) on a current collector to obtain an MXene film electrode.
The invention provides an organic dispersion of MXene in a small amount of layers. The invention takes a few layers of MXene materials as the main materials of the electrode, is beneficial to preventing the stacking of the materials, and is beneficial to ensuring the curing effect of the subsequent photocuring process by preparing the MXene materials into the organic dispersion liquid.
In the invention, the number of the small-layer MXene is preferably 1-10, and more preferably 1-6. The invention preferably uses a small number of MXene layers, which is advantageous in preventing stacking of materials.
In the present invention, the organic solvent in the organic dispersion preferably includes N-methylpyrrolidone. The invention preferably uses N-methyl pyrrolidone as an organic solvent for dispersing the small-layer MXene, which is beneficial to ensuring the curing effect of photocuring and obtaining the electrode material with excellent electrical properties.
In the invention, the ratio of the mass of the small-layer MXene to the volume of the organic solvent in the small-layer MXene organic dispersion liquid is preferably (2.5-3) g: (2-3) mL, more preferably 2.5g:2 mL. The invention preferably controls the ratio of the mass of the small-layer MXene to the volume of the organic solvent in the small-layer MXene organic dispersion liquid to be in the range, and ensures the effective connection of the small-layer MXene in the photocuring process.
In the present invention, the preparation of the organic dispersion of the layered MXene preferably comprises the following steps:
1) adding LiF, HF and Ti to hydrochloric acid in sequence3AlC2Carrying out a reaction to obtain Ti-containing3C2A precipitated reaction solution;
2) the Ti-containing material obtained in the step 1) is3C2Subjecting the precipitated reaction solution to a first centrifugation to obtain a first supernatant and Ti3C2Precipitating;
3) adding Ti obtained in the step 2)3C2Adding water into the precipitate, and performing first ultrasonic treatment;
4) repeating the step 2) and the step 3) until the pH value of the supernatant obtained by centrifugation is more than 6, and obtaining MXene precipitate;
5) adding ethanol into the MXene precipitate obtained in the step 4), and then sequentially performing second ultrasonic treatment and second centrifugation to obtain a second supernatant and multiple layers of MXene precipitate;
6) adding water into the multilayer MXene precipitate obtained in the step 5), and then sequentially performing third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few layers of MXene precipitate;
7) mixing the small-layer MXene precipitate obtained in the step 6) with an organic solvent to obtain an organic dispersion liquid of the small-layer MXene.
The invention preferably adds LiF, HF and Ti to the hydrochloric acid in sequence3AlC2Carrying out a reaction to obtain Ti-containing3C2The reaction solution precipitated. The MXene material is prepared by preferably using hydrochloric acid, LiF and HF as etching agents.
In the invention, the concentration of the hydrochloric acid is preferably 6-8 mol/L; the volume concentration of the HF is preferably 40-45%. In the present invention, the volume of hydrochloric acid, the mass of LiF, the volume of HF and Ti3AlC2The mass ratio of (b) is preferably (400 to 450) mL: (20-25) g: (80-90) mL: (20-25) g, more preferably 400 mL: 20 g: 80mL of: 20 g.
According to the invention, preferably, LiF is added into hydrochloric acid firstly and then reacts, HF is added for continuous reaction, and Ti is added3AlC2Continuing the reaction to obtain Ti-containing3C2The reaction solution precipitated.
In the invention, the reaction time after adding LiF is preferably 30-40 min; the reaction time after the HF is added is preferably 10-20 min; adding Ti3AlC2The preferable reaction time is 24-28 h, and the preferable reaction temperature is 30-35 ℃.
To obtain Ti-containing3C2After the reaction solution is precipitated, the Ti is preferably contained in the solution3C2Subjecting the precipitated reaction solution to a first centrifugation to obtain a first supernatant and Ti3C2And (4) precipitating. In the present invention, Ti is preferably centrifuged3C2The precipitate is separated from the solution.
In the invention, the rotating speed of the first centrifugation is preferably 3500-4000 rpm, and is more preferably 3500 rpm; the time of the first centrifugation is preferably 4-6 min, and more preferably 4 min.
To obtain Ti3C2After precipitation, the present invention preferably adds Ti to the Ti3C2Adding water into the precipitate, and performing first ultrasonic treatment. The invention preferably peels off the MXene material by ultrasound.
In the invention, the power of the first ultrasonic wave is preferably 1200-1500W, and more preferably 1300-1400W; the time of the first ultrasonic is preferably 10-15 min, and more preferably 10 min. In the invention, the dosage of the water is preferably 1100-1200 mL.
After the first ultrasonic treatment is finished, the invention preferably repeats the operation of adding water into the precipitate after the first centrifugal treatment for the first ultrasonic treatment until the pH value of the supernatant obtained by the centrifugal treatment is greater than 6, and MXene precipitate is obtained. The invention preferably realizes the stripping of MXene materials while removing impurities in the precipitate by repeating the first centrifugation and the first ultrasonic treatment.
After obtaining the MXene precipitate, the invention preferably adds ethanol to the MXene precipitate, and then sequentially performs second ultrasonic treatment and second centrifugation to obtain a second supernatant and multiple layers of MXene precipitate. The invention preferably further peels the MXene material by a second ultrasonic wave to obtain a few layers of MXene material.
In the invention, the power of the second ultrasonic wave is preferably 1200-1500W, and more preferably 1300-1400W; the time of the second ultrasound is preferably > 1 h. In the invention, the rotation speed of the second centrifugation is preferably 3500-4000 rpm, and is more preferably 3500 rpm; the time of the second centrifugation is preferably 4-6 min, and more preferably 5 min.
After obtaining the multiple layers of MXene precipitates, the invention preferably adds water to the multiple layers of MXene precipitates, and then sequentially carries out third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few layers of MXene precipitates. The invention preferably prepares the layer-less MXene material by third ultrasonic.
In the invention, the power of the third ultrasonic wave is preferably 1200-1500W, and more preferably 1300-1400W; the time of the third ultrasound is preferably > 1 h. In the invention, the rotating speed of the third centrifugation is preferably 3500-4000 rpm, and is more preferably 3500 rpm; the time of the third centrifugation is preferably 30-35 min, and more preferably 30 min.
After obtaining the small-layer MXene precipitate, the invention preferably mixes the small-layer MXene precipitate with an organic solvent to obtain the small-layer MXene organic dispersion liquid.
The operation of mixing the small-layer MXene precipitate and the organic solvent is not particularly limited in the invention, and a solid-liquid mixing mode well known to those skilled in the art can be adopted.
After obtaining the organic dispersion liquid of the small-layer MXene, the invention mixes the organic dispersion liquid of the small-layer MXene with photosensitive resin and then carries out photocuring to obtain the MXene-based polymer film. According to the invention, the photosensitive resin is added, and the photocuring method is adopted, so that the two-dimensional MXene material has a three-dimensional configuration, the two-dimensional material is prevented from being stacked, a foundation is provided for the subsequent curing of the electrolyte, the problem of an interface between the electrolyte and an electrode is effectively improved, and the electrical property of the battery is improved.
In the invention, the mass ratio of the organic dispersion liquid of the small-layer MXene to the photosensitive resin is preferably 1 (1-3), and more preferably 1: 1. The invention preferably controls the mass ratio of the organic dispersion liquid of the few-layer MXene to the photosensitive resin within the range, and ensures the effective connection of the few-layer MXene in the photocuring process.
The source of the photosensitive resin is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the photosensitive resin is preferably a black-cut JX-10 rigid resin.
In the invention, the light intensity of the photocuring is preferably 8000-8500 uw/cm2More preferably 8000uw/cm2(ii) a The time for photocuring is preferably 30-60 s, and more preferably 30-50 s. The invention preferably controls the light intensity and time of the photocuring within the range, thereby ensuring the curing effect of the photocuring.
After obtaining the MXene-based polymer film, the MXene-based polymer film is solidified on a current collector to obtain the MXene film electrode. The MXene-based polymer film is solidified on the current collector, so that the aim of preparing the solid electrode with excellent electrical property by using the MXene material is fulfilled.
In the present invention, the current collector preferably comprises a copper sheet or a stainless steel sheet, and more preferably a copper sheet. The current collector of the present invention is not particularly limited in its origin, and may be a commercially available product known to those skilled in the art.
In the present inventionThe light intensity of the curing is preferably 8000-8500 uw/cm2More preferably 8000uw/cm2(ii) a The curing time is preferably 30 to 60 seconds, and more preferably 30 to 50 seconds.
The invention takes a few layers of MXene materials as electrode main materials, which is beneficial to preventing the stacking of the materials, the MXene-based polymer films are prepared by preparing the electrode main materials into organic dispersion liquid, adding photosensitive resin, then preparing the MXene-based polymer films by a photocuring method, and finally curing the MXene-based polymer films on a current collector to obtain the solid electrode, and the photocuring enables the two-dimensional MXene materials to have three-dimensional configuration, thereby preventing the stacking of the two-dimensional materials, providing a foundation for the curing of subsequent electrolytes, effectively improving the interface problem between the electrolytes and the electrodes, and improving the electrical property of the battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Organic dispersion providing few layers of MXene:
1) adding 20g LiF into 400mL of 6mol/L hydrochloric acid, reacting for 30min, adding 80mL of HF with the volume concentration of 40%, reacting for 10min, and finally adding 20g of Ti3AlC2Reacting at 30 ℃ for 24 hours to obtain Ti-containing3C2A precipitated reaction solution;
2) ti contained in the Ti obtained in the step 1)3C2The precipitated reaction solution was filled into a 100mL centrifugal tube and weighed and leveled, and centrifuged at 3500rpm for 4min to obtain a first clear solution and Ti3C2Precipitating, and pouring the first supernatant into an acidic waste liquid barrel;
3) to the Ti obtained in step 2)3C2Adding 1100mL of water into the precipitate, and then performing ultrasonic treatment at 1300W for 10 min;
4) repeating the step 2) and the step 3) until the pH value of the supernatant obtained by centrifugation is more than 6, and obtaining MXene precipitate;
5) adding ethanol into the MXene precipitate obtained in the step 4), performing ultrasonic treatment for 2h at 1300W, and centrifuging at 3500rpm for 5min to obtain a second supernatant and multiple layers of MXene precipitate;
6) adding water into the multilayer MXene precipitate obtained in the step 5), performing ultrasonic treatment at 1300W for 2h, and centrifuging at 3500rpm for 30min to obtain a third supernatant and a few layers of MXene precipitate;
7) mixing the small-layer MXene precipitate obtained in the step 6) with N-methyl pyrrolidone to obtain an organic dispersion liquid of the small-layer MXene, wherein the volume ratio of the mass of the small-layer MXene precipitate to the N-methyl pyrrolidone is 2.5g:2mL, and the number of the small-layer MXene is 3-6;
(2) mixing the organic dispersion liquid of the little-layer MXene obtained in the step (1) with photosensitive resin according to the mass ratio of 1:1, and then mixing at 8000uw/cm2Carrying out photocuring for 30s to obtain an MXene-based polymer film;
(3) curing the MXene-based polymer film obtained in the step (2) on a copper sheet to obtain an MXene film electrode, wherein the cured illumination intensity is 8000uw/cm2The curing time was 30 s.
Example 2
The difference from example 1 is that the mass ratio of the organic dispersion of the small layer MXene to the photosensitive resin in step (2) is 1: 2.
Example 3
The difference from example 1 is that the mass ratio of the organic dispersion of the small layer MXene to the photosensitive resin in step (2) is 1: 3.
Example 4
The difference from example 1 is that the copper sheet in step (3) was replaced with a stainless steel sheet.
Comparative example 1
The difference from example 1 is that the mass ratio of the organic dispersion of the small layer MXene to the photosensitive resin in step (2) is 1: 4.
Comparative example 2
The difference from example 1 is that the mass ratio of the organic dispersion of the small layer MXene to the photosensitive resin in step (2) is 1: 5.
Comparative example 3
The difference from example 1 is that N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 4
The difference from example 2 is that N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 5
The difference from example 3 is that N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 6
The difference from comparative example 1 is that N-methylpyrrolidone in step 7) was replaced with N, N-dimethylformamide.
Comparative example 7
The difference from comparative example 2 is that N-methylpyrrolidone in step 7) was replaced with N, N-dimethylformamide.
Comparative example 8
The difference from example 1 is that N-methylpyrrolidone in step 7) was replaced with N, N-dimethylformamide, and the copper sheet in step (3) was replaced with a stainless steel sheet.
Comparative example 9
The difference from example 2 was that N-methylpyrrolidone in step 7) was replaced with N, N-dimethylformamide, and the copper sheet in step (3) was replaced with a stainless steel sheet.
Comparative example 10
The difference from example 1 is that the N-methylpyrrolidone in step 7) is replaced by water.
Comparative example 11
The difference from example 2 is that the N-methylpyrrolidone in step 7) is replaced by water.
Comparative example 12
The difference from example 3 is that the N-methylpyrrolidone in step 7) is replaced by water.
Comparative example 13
The difference from comparative example 1 is that the N-methylpyrrolidone in step 7) is replaced by water.
Comparative example 14
The difference from comparative example 2 is that the N-methylpyrrolidone in step 7) is replaced by water.
Comparative example 15
The difference from example 2 is that N-methylpyrrolidone in step 7) was replaced with water, and the copper sheet in step (3) was replaced with a stainless steel sheet.
Fig. 1 is a schematic diagram of MXene-based polymer films prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention, and the MXene-based polymer films prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2 are sequentially arranged from left to right. As can be seen from the figure, MXene is uniformly dispersed in the resin, and the film has high curing degree and improved toughness along with the increase of the proportion of the photosensitive resin.
FIG. 2 is a physical diagram of polymer films prepared in comparative examples 3 to 7, which are polymer films prepared in comparative example 3, comparative example 4, comparative example 5, comparative example 6 and comparative example 7 in the order from left to right. As can be seen from fig. 2, as the proportion of the photosensitive resin increases, the concentration of MXene in the polymer film decreases, the color of the film becomes lighter, but the degree of curing increases. It can be seen that the water-based film requires more photosensitive resin than the organic film to achieve complete curing.
FIG. 3 is a physical representation of the polymer films prepared in comparative examples 10 to 14, which are the polymer films prepared in comparative example 10, comparative example 11, comparative example 12, comparative example 13 and comparative example 14 in the order from left to right. As can be seen in fig. 3, there was a ring of clear cured layers around the film, demonstrating that no uniform dispersion could be formed between MXene, water and the photosensitive resin.
FIGS. 4 to 8 are microscope images of MXene-based polymer films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2, respectively. As can be seen from fig. 4 to 8, as the ratio of the photosensitive resin increases, the content of MXene on the surface of the polymer film decreases, and when the ratio of the organic dispersion of small layers of MXene to the photosensitive resin exceeds 1:3 by mass, the MXene particles are dispersed independently of each other, and no effective connection is formed.
Fig. 9 is a physical diagram of the MXene thin film electrodes prepared in examples 1 and 4, wherein the left diagram is the MXene thin film electrode prepared in example 1, and the right diagram is the MXene thin film electrode prepared in example 4. As can be seen from FIG. 9, the MXene thin film electrode prepared by the preparation method provided by the invention has good curing effect.
Fig. 10 is a physical diagram of the thin film electrodes prepared in comparative example 3 and comparative example 8, wherein the left diagram is the thin film electrode prepared in comparative example 3, and the right diagram is the thin film electrode prepared in comparative example 8. As can be seen from fig. 10, the thin film electrode prepared using N, N-dimethylformamide as a solvent was not completely cured, and was lightly wiped with alcohol cotton, and the mixture was stuck to the alcohol cotton to expose the substrate.
Fig. 11 is a physical diagram of the thin film electrodes prepared in comparative example 4 and comparative example 9, wherein the left diagram is the thin film electrode prepared in comparative example 4, and the right diagram is the thin film electrode prepared in comparative example 9. As can be seen from fig. 11, when the thin film electrode is prepared using N, N-dimethylformamide as a solvent, the curing effect is improved by increasing the amount of the photosensitive resin.
Fig. 12 is a physical diagram of the thin film electrodes prepared in comparative example 11 and comparative example 15, wherein the left diagram is the thin film electrode prepared in comparative example 11, and the right diagram is the thin film electrode prepared in comparative example 15. As can be seen from FIG. 12, the film electrode prepared by using water as solvent has better curing effect.
And (3) performance testing:
solid-state batteries were assembled using the thin film electrodes prepared in example 1, example 4, comparative example 3, comparative example 4, comparative example 8, comparative example 9, comparative example 11, and comparative example 15, respectively, as positive electrode materials, and performance tests were performed, and the test results were shown in fig. 13 to 20.
Fig. 13 is a graph showing the electrical properties of an MXene thin film electrode prepared in example 1 of the present invention, fig. 14 is a graph showing the electrical properties of an MXene thin film electrode prepared in example 4 of the present invention, fig. 15 is a graph showing the electrical properties of a thin film electrode prepared in comparative example 3, fig. 16 is a graph showing the electrical properties of a thin film electrode prepared in comparative example 4, fig. 17 is a graph showing the electrical properties of a thin film electrode prepared in comparative example 8, fig. 18 is a graph showing the electrical properties of a thin film electrode prepared in comparative example 9, and fig. 19 is a graph showing the electrical properties of a thin film electrode prepared in comparative example 11And fig. 20 is a graph showing the electrical properties of the thin film electrode prepared in comparative example 15. As can be seen from fig. 13 to 20, the electrical properties of the MXene thin film electrode prepared by using the copper sheet as the current collector and the N-methylpyrrolidone as the solvent are optimal, and can reach 0.007mAh/cm2And is suitable for the preparation and development of solid electrodes.
As can be seen from the above examples, the MXene thin film electrode prepared by the preparation method provided by the invention has excellent electrical properties and high specific capacity which can reach 0.007mAh/cm2The interface problem between the electrolyte and the electrode is effectively improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of an MXene thin film electrode comprises the following steps:
(1) providing an organic dispersion of MXene in a small layer;
(2) mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photocuring to obtain an MXene-based polymer film;
(3) and (3) solidifying the MXene-based polymer film obtained in the step (2) on a current collector to obtain an MXene film electrode.
2. The method according to claim 1, wherein the number of the small layer MXene in the step (1) is 1 to 10.
3. The method according to claim 1, wherein the organic solvent in the organic dispersion in the step (1) comprises N-methylpyrrolidone.
4. The preparation method according to claim 1, wherein the ratio of the mass of the low-layer MXene to the volume of the organic solvent in the organic dispersion liquid of the low-layer MXene in the step (1) is (2.5-3) g: (2-3) mL.
5. The preparation method according to any one of claims 1 to 4, wherein the preparation of the organic dispersion of the layered MXene in the step (1) comprises the following steps:
1) adding LiF, HF and Ti to hydrochloric acid in sequence3AlC2Carrying out a reaction to obtain Ti-containing3C2A precipitated reaction solution;
2) the Ti-containing material obtained in the step 1) is3C2Subjecting the precipitated reaction solution to a first centrifugation to obtain a first supernatant and Ti3C2Precipitating;
3) adding Ti obtained in the step 2)3C2Adding water into the precipitate, and performing first ultrasonic treatment;
4) repeating the step 2) and the step 3) until the pH value of the supernatant obtained by centrifugation is more than 6, and obtaining MXene precipitate;
5) adding ethanol into the MXene precipitate obtained in the step 4), and then sequentially performing second ultrasonic treatment and second centrifugation to obtain a second supernatant and multiple layers of MXene precipitate;
6) adding water into the multilayer MXene precipitate obtained in the step 5), and then sequentially performing third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few layers of MXene precipitate;
7) mixing the small-layer MXene precipitate obtained in the step 6) with an organic solvent to obtain an organic dispersion liquid of the small-layer MXene.
6. The preparation method of claim 5, wherein the power of the first ultrasonic wave in the step 3) is 1200-1500W; the power of the second ultrasonic wave in the step 5) is 1200-1500W; the power of the third ultrasonic wave in the step 6) is 1200-1500W.
7. The preparation method according to claim 1, wherein the mass ratio of the organic dispersion of the MXene with less layers in the step (2) to the photosensitive resin is 1 (1-3).
8. According to claim 1The preparation method is characterized in that the light intensity of the photocuring in the step (2) is 8000-8500 uw/cm2The photocuring time is 30-60 s.
9. The manufacturing method according to claim 1, wherein the current collector in the step (3) comprises a copper sheet or a stainless steel sheet.
10. The method according to claim 1, wherein the curing in step (3) is carried out at an illumination intensity of 8000 to 8500uw/cm2The curing time is 30-60 s.
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CN111977656A (en) * 2020-08-05 2020-11-24 武汉大学 MXene/nitrogen-doped carbon foam composite material with 3D porous neuron structure and preparation method thereof
CN112391087A (en) * 2020-11-25 2021-02-23 广东康烯科技有限公司 Porous molybdenum carbide MXene/reduced graphene oxide-based conductive ink and preparation method thereof

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US20190092641A1 (en) * 2017-09-28 2019-03-28 Murata Manufacturing Co., Ltd. Aligned film and method for producing the same
US20190109358A1 (en) * 2017-10-09 2019-04-11 Nanotek Instruments, Inc. Sodium ion-based internal hybrid electrochemical energy storage cell
CN108511733A (en) * 2018-05-16 2018-09-07 中国科学院金属研究所 A kind of MXene/ bimetallic oxides composite material and preparation method and lithium ion battery negative material
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