CN114420897B - Preparation method of MXene thin film electrode - Google Patents

Preparation method of MXene thin film electrode Download PDF

Info

Publication number
CN114420897B
CN114420897B CN202210223129.3A CN202210223129A CN114420897B CN 114420897 B CN114420897 B CN 114420897B CN 202210223129 A CN202210223129 A CN 202210223129A CN 114420897 B CN114420897 B CN 114420897B
Authority
CN
China
Prior art keywords
mxene
layer
curing
organic dispersion
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210223129.3A
Other languages
Chinese (zh)
Other versions
CN114420897A (en
Inventor
鲁铭
杜明栋
魏超
王丽
李嘉明
王知贺
徐仕翀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Yiyi Technology Co ltd
Jilin Normal University
Original Assignee
Jilin Yiyi Technology Co ltd
Jilin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Yiyi Technology Co ltd, Jilin Normal University filed Critical Jilin Yiyi Technology Co ltd
Priority to CN202210223129.3A priority Critical patent/CN114420897B/en
Publication of CN114420897A publication Critical patent/CN114420897A/en
Application granted granted Critical
Publication of CN114420897B publication Critical patent/CN114420897B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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 of a small-layer MXene, mixing the organic dispersion of the small-layer MXene with a photosensitive resin, performing photo-curing, and curing the obtained MXene-based polymer film on a current collector to obtain the MXene film electrode. The invention takes a few layers of MXene materials as the electrode main body material, adds photosensitive resin, and then ensures that the two-dimensional MXene materials have a three-dimensional structure through photo-curing, thereby preventing the two-dimensional materials from being stacked, providing a foundation for the subsequent curing of electrolyte, effectively improving the interface problem between the electrolyte and the electrode, 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, and is assembled into a solid-state battery with the specific capacity of 0.007mAh/cm 2 。

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
Along with the progress of science and technology, portable devices, power automobiles, intelligent robots and the like gradually enter the lives of people, and further the demands of people for energy sources are also higher and higher, wherein fossil energy sources are the most main energy sources consumed globally, and however, the fossil energy sources have the problems of exhaustion and environmental pollution. Therefore, searching for sustainable clean energy and efficient energy storage technologies is of great importance for achieving economic sustainable development. The lithium ion battery has the advantages of no pollution to the environment, 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, there are certain problems, such as high battery cost, no high-power charge and discharge, circuit control to be protected, and serious limitation of performance and certain potential safety hazard in extreme environments, so that the application and development of the lithium ion battery are limited. The solid-state battery, which is a battery using a solid electrode and a solid electrolyte, has great advantages over conventional lithium ion batteries in that it is safe, thin and lightweight, has a higher energy density, and has good flexibility. However, the existing solid-state battery has too poor electrolyte conductivity and too large interface resistance, thereby causing interface problems between the solid-state electrode and the solid-state electrolyte, affecting the electrical performance of the battery. 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 interface problem between the solid electrode and the solid electrolyte of the existing solid battery.
The MXene material is a general name of two-dimensional layered carbide and nitride material, M represents a transition state metal site, X represents nitrogen or carbon site, the structure of the MXene material consists of two or more layers of transition state metal atoms, the MXene material is inserted into a honeycomb-shaped 2D grid fence, and carbon or nitrogen occupying an octagonal site between adjacent transition state metal layers is inserted. Because of the diversity of the properties in mechanics, optics, electricity, chemistry, medicine and the like, the dye has good application prospect in the aspects of current collectors, conductive ink, electrochromic, photothermal treatment, catalysis, sensors, water purification, dialysis, gas separation, electromagnetic shielding, communication, 3D printing and the like. However, MXene, which is a two-dimensional material, tends to cause interlayer stacking when preparing a solid electrode, and has a reduced specific surface area, failing to obtain a solid electrode having good electrical properties. Therefore, how to prepare a solid electrode with excellent electrical properties by using an MXene material has become a problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a preparation method of an MXene thin film electrode, which has excellent electrical property and high specific capacity and effectively improves the interface problem between electrolyte and the electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an MXene film electrode, which comprises the following steps:
(1) Providing an organic dispersion of a few layer of MXene;
(2) Mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photo-curing to obtain an MXene-based polymer film;
(3) And (3) curing the MXene-based polymer film obtained in the step (2) on a current collector to obtain the MXene film electrode.
Preferably, the number of layers of the few-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 volume ratio of the mass of the small-layer MXene to 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 few layer MXene in step (1) comprises the steps of:
1) Sequentially adding LiF, HF and Ti to hydrochloric acid 3 AlC 2 Carrying out reaction to obtain Ti-containing alloy 3 C 2 A precipitated reaction solution;
2) The Ti-containing material obtained in the step 1) is subjected to 3 C 2 Performing first centrifugation on the precipitated reaction solution to obtain a first supernatant and Ti 3 C 2 Precipitating;
3) To the Ti obtained in the step 2) 3 C 2 Adding water into the sediment, 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 sediment;
5) Adding ethanol into the MXene precipitate obtained in the step 4), and sequentially performing second ultrasonic treatment and second centrifugation to obtain a second supernatant and a multilayer MXene precipitate;
6) Adding water into the multilayer MXene precipitate obtained in the step 5), and sequentially performing third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few-layer 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 few-layer MXene to the photosensitive resin in the step (2) is 1 (1-3).
Preferably, the light intensity of the photo-curing in the step (2) is 8000-8500 uw/cm 2 The photo-curing time is 30-60 s.
Preferably, the current collector in the step (3) includes a copper sheet or a stainless steel sheet.
Preferably, the light intensity of the curing in the step (3) is 8000-8500 uw/cm 2 The curing time is 30-60 s.
The invention provides a preparation method of an MXene film electrode, which comprises the following steps: (1) providing an organic dispersion of a small layer of MXene; (2) Mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photo-curing to obtain an MXene-based polymer film; (3) And (3) curing the MXene-based polymer film obtained in the step (2) on a current collector to obtain the MXene film electrode. The invention takes a few layers of MXene material as the electrode main body material, is favorable for preventing the stacking of the materials, prepares the MXene material into organic dispersion liquid, adds photosensitive resin, then prepares an MXene-based polymer film by a photocuring method, and finally cures the MXene-based polymer film on a current collector, thereby obtaining a solid electrode, and the photocuring ensures that the two-dimensional MXene material has a three-dimensional configuration, and prevents the two-dimensional materialProvides a basis for the subsequent solidification of the electrolyte, effectively improves the interface problem between the electrolyte and the electrode, and improves the electrical performance 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, and is assembled into a solid-state battery with the specific capacity of 0.007mAh/cm 2 。
Drawings
FIG. 1 is a physical view of the MXene-based polymer films prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention;
FIG. 2 is a physical view of polymer films prepared in comparative examples 3 to 7;
FIG. 3 is a physical view of polymer films prepared in comparative examples 10 to 14;
FIG. 4 is a microscopic view of an MXene-based polymer film prepared in example 1 of the present invention;
FIG. 5 is a microscopic view of an MXene-based polymer film prepared in example 2 of the present invention;
FIG. 6 is a microscopic image of an MXene-based polymer film prepared in example 3 of the present invention;
FIG. 7 is a microscopic image of the MXene-based polymer film prepared in comparative example 1;
FIG. 8 is a microscopic image of an MXene-based polymer film prepared in comparative example 2;
FIG. 9 is a physical view of the MXene thin film electrodes prepared in example 1 and example 4 of the present invention;
FIG. 10 is a physical view of the thin film electrodes prepared in comparative example 3 and comparative example 8;
FIG. 11 is a physical view of the thin film electrodes prepared in comparative example 4 and comparative example 9;
FIG. 12 is a physical view of the thin film electrodes prepared in comparative example 11 and comparative example 15;
FIG. 13 is a graph showing electrical properties of the MXene thin film electrode prepared in example 1 of the present invention;
FIG. 14 is a graph showing the electrical properties of the MXene thin film electrode prepared in example 4 of the present invention;
FIG. 15 is a graph showing electrical properties of the thin film electrode prepared in comparative example 3;
FIG. 16 is a graph showing electrical properties of the thin film electrode prepared in comparative example 4;
FIG. 17 is an electrical property graph of the thin film electrode prepared in comparative example 8;
FIG. 18 is a graph showing electrical properties of the thin film electrode prepared in comparative example 9;
FIG. 19 is a graph showing electrical properties of the thin film electrode prepared in comparative example 11;
FIG. 20 is a graph showing electrical properties of the thin film electrode prepared in comparative example 15.
Detailed Description
The invention provides a preparation method of an MXene film electrode, which comprises the following steps:
(1) Providing an organic dispersion of a few layer of MXene;
(2) Mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photo-curing to obtain an MXene-based polymer film;
(3) And (3) curing the MXene-based polymer film obtained in the step (2) on a current collector to obtain the MXene film electrode.
The present invention provides organic dispersions of low-layer MXene. The invention takes a few layers of MXene material as the electrode main body material, is favorable for preventing the materials from stacking, and is favorable for ensuring the curing effect of the subsequent photocuring process by preparing the material into the organic dispersion liquid.
In the present invention, the number of layers of the small-layer MXene is preferably 1 to 10, more preferably 1 to 6. The invention preferably adopts the small-layer MXene with the number of layers, which is beneficial to preventing the 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 a few layers of MXene, which is beneficial to ensuring the curing effect of photo-curing and obtaining the electrode material with excellent electrical property.
In the present invention, the volume ratio of the mass of the small-layer MXene to the organic solvent in the organic dispersion liquid of the small-layer MXene is preferably (2.5 to 3) g: (2-3) mL, more preferably 2.5g:2mL. The invention preferably controls the volume ratio of the mass of the few-layer MXene and the organic solvent in the organic dispersion liquid of the few-layer MXene within the range, thereby ensuring the effective connection between the few-layer MXene in the photo-curing process.
In the present invention, the preparation of the organic dispersion of the few-layer MXene preferably comprises the steps of:
1) Sequentially adding LiF, HF and Ti to hydrochloric acid 3 AlC 2 Carrying out reaction to obtain Ti-containing alloy 3 C 2 A precipitated reaction solution;
2) The Ti-containing material obtained in the step 1) is subjected to 3 C 2 Performing first centrifugation on the precipitated reaction solution to obtain a first supernatant and Ti 3 C 2 Precipitating;
3) To the Ti obtained in the step 2) 3 C 2 Adding water into the sediment, 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 sediment;
5) Adding ethanol into the MXene precipitate obtained in the step 4), and sequentially performing second ultrasonic treatment and second centrifugation to obtain a second supernatant and a multilayer MXene precipitate;
6) Adding water into the multilayer MXene precipitate obtained in the step 5), and sequentially performing third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few-layer 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 hydrochloric acid in sequence 3 AlC 2 Carrying out reaction to obtain Ti-containing alloy 3 C 2 The reaction solution was precipitated. The present invention preferably uses hydrochloric acid, liF and HF as etchants to prepare the MXene material.
In the invention, the concentration of the hydrochloric acid is preferably 6-8 mol/L; the volume concentration of HF is preferably 40 to 45%. In the present invention, the volume of hydrochloric acid, the mass of LiF, the volume of HF and Ti 3 AlC 2 The mass ratio of (3) is preferably (400-450) mL: (20-25) g: (80-90) mL: (20-25) g, more preferably 400mL:20g:80mL:20g.
The invention preferably adds LiF into hydrochloric acid and then reacts, then HF is added for continuous reaction, and thenInto Ti 3 AlC 2 Continuing the reaction to obtain Ti-containing alloy 3 C 2 The reaction solution was precipitated.
In the invention, the reaction time after LiF is added is preferably 30-40 min; the reaction time after adding HF is preferably 10-20 min; adding Ti 3 AlC 2 The reaction time after the reaction is preferably 24 to 28 hours, and the reaction temperature is preferably 30 to 35 ℃.
Obtaining Ti-containing 3 C 2 After the reaction solution is precipitated, the Ti-containing solution is preferably used in the present invention 3 C 2 Performing first centrifugation on the precipitated reaction solution to obtain a first supernatant and Ti 3 C 2 And (5) precipitation. The invention preferably uses Ti by centrifugation 3 C 2 The precipitate was separated from the solution.
In the present invention, the rotational speed of the first centrifuge is preferably 3500 to 4000rpm, more preferably 3500rpm; the time of the first centrifugation is preferably 4 to 6 minutes, more preferably 4 minutes.
Obtaining Ti 3 C 2 After precipitation, the present invention preferably provides the Ti 3 C 2 The precipitate was added with water and subjected to a first sonication. The present invention preferably peels the MXene material by ultrasound.
In the present invention, the power of the first ultrasound is preferably 1200 to 1500W, more preferably 1300 to 1400W; the time of the first ultrasound is preferably 10 to 15min, more preferably 10min. In the present invention, the amount of water is preferably 1100 to 1200mL.
After the first ultrasound is completed, the invention preferably repeats the operation of adding water into the sediment after the first centrifugation to perform the first ultrasound until the pH of the supernatant obtained by the centrifugation is more than 6, and the MXene sediment is obtained. The present invention preferably further achieves exfoliation of the MXene material while removing impurities in the precipitate by repeating the first centrifugation and the first ultrasound.
After the MXene precipitate is obtained, the present invention preferably adds ethanol to the MXene precipitate, followed by a second sonication and a second centrifugation in sequence to obtain a second supernatant and a multi-layered MXene precipitate. The present invention preferably further strips the MXene material by a second ultrasound to obtain a few layers of MXene material.
In the present invention, the power of the second ultrasound is preferably 1200 to 1500W, more preferably 1300 to 1400W; the time of the second ultrasound is preferably > 1h. In the present invention, the rotation speed of the second centrifuge is preferably 3500 to 4000rpm, more preferably 3500rpm; the time for the second centrifugation is preferably 4 to 6 minutes, more preferably 5 minutes.
After the multi-layer MXene precipitate is obtained, the method preferably adds water to the multi-layer MXene precipitate, and then sequentially carries out third ultrasonic treatment and third centrifugal treatment to obtain a third supernatant and a few-layer MXene precipitate. The invention preferably prepares a few-layer MXene material by third ultrasound.
In the present invention, the power of the third ultrasound is preferably 1200 to 1500W, more preferably 1300 to 1400W; the time of the third ultrasound is preferably > 1h. In the present invention, the rotation speed of the third centrifuge is preferably 3500 to 4000rpm, more preferably 3500rpm; the time for the third centrifugation is preferably 30 to 35 minutes, more preferably 30 minutes.
After obtaining the small-layer MXene precipitate, the present invention preferably mixes the small-layer MXene precipitate with an organic solvent to obtain an organic dispersion of the small-layer MXene.
The operation of mixing the small-layer MXene precipitate with the organic solvent is not particularly limited, and a solid-liquid mixing mode well known to those skilled in the art can be adopted.
After the organic dispersion liquid of the few-layer MXene is obtained, the organic dispersion liquid of the few-layer MXene is mixed with photosensitive resin and then is subjected to photo-curing, so that the MXene-based polymer film is obtained. The invention adds photosensitive resin and adopts a photo-curing method to enable the two-dimensional MXene material to have a three-dimensional configuration, thereby preventing the two-dimensional material from being stacked, providing a foundation for the subsequent curing of electrolyte, effectively improving the interface problem between the electrolyte and the electrode and improving the electrical property of the battery.
In the present invention, the mass ratio of the organic dispersion of the small-layer MXene to the photosensitive resin is preferably 1 (1-3), more preferably 1:1. The invention preferably controls the mass ratio of the organic dispersion liquid of the few-layer MXene and the photosensitive resin within the range, thereby ensuring the effective connection between the few-layer MXene in the photo-curing process.
The source of the photosensitive resin is not particularly limited, 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 wound JX-10 rigid resin.
In the present invention, the light intensity of the photo-curing is preferably 8000 to 8500uw/cm 2 More preferably 8000uw/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time for the photo-curing is preferably 30 to 60 seconds, more preferably 30 to 50 seconds. The invention preferably controls the illumination intensity and time of the photo-curing within the above ranges, thereby ensuring the curing effect of the photo-curing.
After the MXene-based polymer film is obtained, the MXene-based polymer film is solidified on a current collector to obtain the MXene film electrode. The invention realizes the purpose of preparing the solid electrode with excellent electrical property by using the MXene material by solidifying the MXene-based polymer film on the current collector.
In the present invention, the current collector preferably includes a copper sheet or a stainless steel sheet, more preferably a copper sheet. The source of the current collector 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 light intensity of the curing is preferably 8000 to 8500uw/cm 2 More preferably 8000uw/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The curing time is preferably 30 to 60 seconds, more preferably 30 to 50 seconds.
The invention takes a few layers of MXene materials as the electrode main body materials, is favorable for preventing the materials from stacking, and is prepared into organic dispersion liquid, photosensitive resin is added, then a MXene-based polymer film is prepared by a photocuring method, and finally the MXene-based polymer film is solidified on a current collector, so that a solid electrode is obtained, and the photocuring ensures that the two-dimensional MXene materials have a three-dimensional structure, the stacking of the two-dimensional materials is prevented, a foundation is provided for the subsequent solidification of electrolyte, the interface problem between the electrolyte and the electrode is effectively improved, and the electrical property of the battery is improved.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Providing an organic dispersion of a few layers of MXene:
1) 20g LiF was added to 400mL of 6mol/L hydrochloric acid and reacted for 30min, 80mL of HF 40% by volume was added and reacted for 10min, and finally 20g of Ti was added 3 AlC 2 Reacting for 24 hours at 30 ℃ to obtain the Ti-containing alloy 3 C 2 A precipitated reaction solution;
2) Ti-containing material obtained in step 1) 3 C 2 Loading the precipitated reaction solution into a 100mL centrifuge tube, weighing, balancing, and centrifuging at 3500rpm for 4min to obtain a first clear solution and Ti 3 C 2 Precipitating, and pouring the first supernatant into an acid waste liquid barrel;
3) To Ti obtained in step 2) 3 C 2 1100mL of water was added to the precipitate, followed by sonication at 1300W for 10min;
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 at 1300W for 2 hours, and centrifuging at 3500rpm for 5 minutes to obtain a second supernatant and a multilayer 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-layer MXene precipitate;
7) Mixing the few-layer MXene precipitate obtained in the step 6) with N-methyl pyrrolidone to obtain an organic dispersion liquid of the few-layer MXene, wherein the volume ratio of the mass of the few-layer MXene precipitate to the N-methyl pyrrolidone is 2.5 g/2 mL, and the number of layers of the few-layer MXene is 3-6;
(2) Mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin according to the mass ratio of 1:1, and then at 8000uw/cm 2 Curing for 30s under light to obtain an MXene-based polymer film;
(3) Solidifying the MXene-based polymer film obtained in the step (2) on a copper sheet to obtain an MXene film electrode, wherein the solidified illumination intensity is 8000uw/cm 2 The curing time was 30s.
Example 2
The difference from example 1 is that the mass ratio of the organic dispersion of the few 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 few 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 few 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 few layer MXene to the photosensitive resin in step (2) is 1:5.
Comparative example 3
The difference from example 1 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 4
The difference from example 2 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 5
The difference from example 3 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 6
The difference from comparative example 1 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 7
The difference from comparative example 2 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide.
Comparative example 8
The difference from example 1 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide and the copper sheet in step (3) is replaced by a stainless steel sheet.
Comparative example 9
The difference from example 2 is that the N-methylpyrrolidone in step 7) is replaced by N, N-dimethylformamide and the copper sheet in step (3) is replaced by 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 the N-methylpyrrolidone in step 7) is replaced with water and the copper sheet in step (3) is replaced with a stainless steel sheet.
FIG. 1 is a physical view of the MXene-based polymer films prepared in examples 1 to 3 and comparative examples 1 to 2 according to 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 shown in order from left to right. As can be seen from the figure, the MXene is uniformly dispersed in the resin, and the film has high curing degree and high toughness along with the increase of the proportion of the photosensitive resin.
FIG. 2 is a physical view of the polymer films prepared in comparative examples 3 to 7, and the polymer films prepared in comparative examples 3, 4, 5, 6 and 7 are shown in order from left to right. As can be seen from FIG. 2, as the proportion of photosensitive resin increases, the concentration of MXene in the polymer film decreases, and the color of the film becomes lighter, but the degree of curing increases. It can be seen that aqueous films require more photosensitive resin than organic films to achieve full cure.
FIG. 3 is a physical view of the polymer films prepared in comparative examples 10 to 14, and the polymer films prepared in comparative examples 10, 11, 12, 13 and 14 are shown in this order from left to right. As can be seen in FIG. 3, a clear cured layer was present around the film, demonstrating that a uniform dispersion was not formed between the MXene, water and the photosensitive resin.
FIGS. 4 to 8 are microscopic views of the MXene-based polymer films prepared in examples 1 to 3 and comparative examples 1 to 2, respectively, according to the present invention. As can be seen from fig. 4 to 8, as the ratio of the photosensitive resin increases, the MXene content of the polymer film surface decreases, and after the ratio of the organic dispersion of the small layer MXene to the photosensitive resin exceeds 1:3, MXene particles are dispersed independently of each other and cannot form an effective connection.
FIG. 9 is a physical view of the MXene thin film electrodes prepared in examples 1 and 4, wherein the left view is the MXene thin film electrode prepared in example 1 and the right view 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 drawing is the thin film electrode prepared in comparative example 3 and the right drawing is the thin film electrode prepared in comparative example 8. As can be seen from fig. 10, the thin film electrode prepared with 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 examples 4 and 9, wherein the left drawing is the thin film electrode prepared in comparative example 4 and the right drawing is the thin film electrode prepared in comparative example 9. As can be seen from fig. 11, the use of N, N-dimethylformamide as a solvent for preparing the thin film electrode increased the amount of photosensitive resin and improved the curing effect.
FIG. 12 is a physical view of the thin film electrodes prepared in comparative examples 11 and 15, wherein the left view is the thin film electrode prepared in comparative example 11 and the right view is the thin film electrode prepared in comparative example 15. As can be seen from fig. 12, the curing effect is better when the thin film electrode is prepared by using water as a solvent.
Performance test:
the solid-state batteries were assembled with 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 as positive electrode materials, respectively, and performance tests were performed, and the test results are shown in fig. 13 to 20.
Fig. 13 is an electrical property graph of the MXene thin film electrode prepared in example 1 of the present invention, fig. 14 is an electrical property graph of the MXene thin film electrode prepared in example 4 of the present invention, fig. 15 is an electrical property graph of the thin film electrode prepared in comparative example 3, fig. 16 is an electrical property graph of the thin film electrode prepared in comparative example 4, fig. 17 is an electrical property graph of the thin film electrode prepared in comparative example 8, fig. 18 is an electrical property graph of the thin film electrode prepared in comparative example 9, fig. 19 is an electrical property graph of the thin film electrode prepared in comparative example 11, and fig. 20 is an electrical property graph of the thin film electrode prepared in comparative example 15. As can be seen from FIGS. 13 to 20, the MXene thin film electrode prepared by using the copper sheet as a current collector and N-methylpyrrolidone as a solvent has optimal electrical properties, which can reach 0.007mAh/cm 2 Is suitable for preparing and developing solid-state 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/cm 2 The interface problem between the electrolyte and the electrode is effectively improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A preparation method of an MXene film electrode comprises the following steps:
(1) Providing an organic dispersion of a few layer of MXene;
(2) Mixing the organic dispersion liquid of the few-layer MXene obtained in the step (1) with photosensitive resin, and then carrying out photo-curing to obtain an MXene-based polymer film;
(3) And (3) curing the MXene-based polymer film obtained in the step (2) on a current collector to obtain the MXene film electrode.
2. The method according to claim 1, wherein the number of layers 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 method according to claim 1, wherein the volume ratio of the mass of the small-layer MXene to the organic solvent in the organic dispersion of the small-layer MXene in the step (1) is (2.5 to 3) g: (2-3) mL.
5. The method according to any one of claims 1 to 4, wherein the preparation of the organic dispersion of the few-layer MXene in the step (1) comprises the steps of:
1) Sequentially adding LiF, HF and Ti to hydrochloric acid 3 AlC 2 Carrying out reaction to obtain Ti-containing alloy 3 C 2 A precipitated reaction solution;
2) The Ti-containing material obtained in the step 1) is subjected to 3 C 2 Performing first centrifugation on the precipitated reaction solution to obtain a first supernatant and Ti 3 C 2 Precipitating;
3) To the Ti obtained in the step 2) 3 C 2 Adding water into the sediment, 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 sediment;
5) Adding ethanol into the MXene precipitate obtained in the step 4), and sequentially performing second ultrasonic treatment and second centrifugation to obtain a second supernatant and a multilayer MXene precipitate;
6) Adding water into the multilayer MXene precipitate obtained in the step 5), and sequentially performing third ultrasonic treatment and third centrifugation to obtain a third supernatant and a few-layer 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 method according to claim 5, wherein the power of the first ultrasound 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 method according to claim 1, wherein the mass ratio of the organic dispersion of the small-layer MXene to the photosensitive resin in the step (2) is 1 (1-3).
8. The method according to claim 1, wherein the light intensity of the photo-curing in the step (2) is 8000 to 8500uw/cm 2 The photo-curing time is 30-60 s.
9. The method of claim 1, wherein the current collector in step (3) comprises a copper sheet or a stainless steel sheet.
10. The method according to claim 1, wherein the light intensity of the curing in the step (3) is 8000 to 8500uw/cm 2 The curing time is 30-60 s.
CN202210223129.3A 2022-03-09 2022-03-09 Preparation method of MXene thin film electrode Active CN114420897B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210223129.3A CN114420897B (en) 2022-03-09 2022-03-09 Preparation method of MXene thin film electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210223129.3A CN114420897B (en) 2022-03-09 2022-03-09 Preparation method of MXene thin film electrode

Publications (2)

Publication Number Publication Date
CN114420897A CN114420897A (en) 2022-04-29
CN114420897B true CN114420897B (en) 2024-01-02

Family

ID=81263350

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210223129.3A Active CN114420897B (en) 2022-03-09 2022-03-09 Preparation method of MXene thin film electrode

Country Status (1)

Country Link
CN (1) CN114420897B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11312631B2 (en) * 2017-09-28 2022-04-26 Murata Manufacturing Co., Ltd. Aligned film and method for producing the same
US10566668B2 (en) * 2017-10-09 2020-02-18 Nanotek Instruments Group, Llc Sodium ion-based internal hybrid electrochemical energy storage cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Also Published As

Publication number Publication date
CN114420897A (en) 2022-04-29

Similar Documents

Publication Publication Date Title
CN101630729B (en) Composite electrode materials for high power lithium secondary battery and preparation method thereof
CN107221716A (en) A kind of chargeable water system Zinc ion battery
Zhong et al. Fabrication and activation studies of conducting plastic composite electrodes for redox cells
CN105742635A (en) Stannic oxide/graphene/carbon composite material and preparation method thereof
CN111313089B (en) Preparation method of ion conductor/polyethylene oxide composite solid electrolyte based on ultraviolet crosslinking
CN110993375B (en) Method for preparing compact-structure RGO/MXene-sulfuric acid supercapacitor flexible electrode in one step and application thereof
CN106299275A (en) A kind of preparation method of composite hard carbon anode material of lithium-ion battery
CN110183655A (en) A kind of preparation method of the organic positive electrode of two dimension carbide crystalline base polyimides
CN106558729B (en) A kind of lithium ion battery of graphene as anode sizing agent conductive agent
CN101937994A (en) Graphene/aluminum composite cathode material of lithium ion battery and preparation method thereof
CN110993358A (en) Flexible zinc ion capacitor
CN113451576B (en) Graphite composite material, preparation method thereof and lithium ion battery
CN103632845A (en) Graphene/organic thin film composite current collector, preparation method thereof, electrochemical electrode and electrochemical battery or capacitor
CN1485940A (en) Lithium ion cell, electrode of lithium ion cell and its preparation method
CN116130880A (en) Lithium battery composite diaphragm and production process thereof
CN113012945A (en) Modified Ppy-MXene composite material and preparation method and application thereof
CN105047984A (en) High lithium ion conductivity lithium sulphur battery capable of restraining shuttle of polysulfide ions
CN111081971A (en) Preparation method of electrode of water-based zinc ion battery, electrode and battery
CN114420897B (en) Preparation method of MXene thin film electrode
CN104795244A (en) Cathode material for capacitor battery, capacitor battery and preparation method thereof
CN107579251A (en) Anode sizing agent of lithium ion battery and preparation method thereof on a kind of production line
CN115799622A (en) Composite solid electrolyte particle and preparation method and application thereof
CN104282909A (en) Conductive adhesive for lithium ion battery positive pole, lithium ion battery positive pole and preparation method of conductive adhesive
Jia et al. Aquatic colloidal graphene gel polymer electrolyte for flexible rechargeable zinc air batteries
CN1280940C (en) Lithium/polyparrole secondary button cell and its preparation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant