CN115403723B - Preparation method and application of lithium anode modified based on covalent organic framework material - Google Patents

Preparation method and application of lithium anode modified based on covalent organic framework material Download PDF

Info

Publication number
CN115403723B
CN115403723B CN202211020520.XA CN202211020520A CN115403723B CN 115403723 B CN115403723 B CN 115403723B CN 202211020520 A CN202211020520 A CN 202211020520A CN 115403723 B CN115403723 B CN 115403723B
Authority
CN
China
Prior art keywords
organic framework
lithium
covalent organic
framework material
cof
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
CN202211020520.XA
Other languages
Chinese (zh)
Other versions
CN115403723A (en
Inventor
翟黎鹏
孙林海
韩点点
杨修贝
米立伟
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.)
Zhongyuan University of Technology
Original Assignee
Zhongyuan University of Technology
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 Zhongyuan University of Technology filed Critical Zhongyuan University of Technology
Priority to CN202211020520.XA priority Critical patent/CN115403723B/en
Publication of CN115403723A publication Critical patent/CN115403723A/en
Application granted granted Critical
Publication of CN115403723B publication Critical patent/CN115403723B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention belongs to the technical field of lithium ion batteries, relates to preparation of lithium cathodes, and in particular relates to a preparation method and application of a lithium cathode modified based on a covalent organic framework material. The method comprises the steps of mixing covalent organic framework materials with coordination groups and rich regular pore structures with a binder, mechanically grinding to form a COF membrane, and placing the COF membrane on the surface of lithium; on one hand, the coordination group has coordination induction effect on lithium ions, so that the aim of inhibiting the growth of lithium dendrites is fulfilled; on the other hand, the special regular pore canal structure can improve the lithium ion conductivity; and finally, the cycling stability of the lithium ion battery taking lithium metal as a negative electrode is improved. At 0.5mA/cm 2 The lithium ion battery can be cycled for more than 200 hours under the current density, the polarization potential has no obvious change, and the discharge capacity of the assembled lithium ion battery can reach 160mAh/g at most after being cycled for 100 circles under the current density of 0.1C, thereby showing higher specific capacity.

Description

Preparation method and application of lithium anode modified based on covalent organic framework material
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to preparation of lithium cathodes, and in particular relates to a preparation method and application of a lithium cathode modified based on a covalent organic framework material.
Background
The shortage of energy is exacerbated by the large amount of fossil energy, and serious environmental pollution is also caused, so that the development and utilization of renewable energy sources such as solar energy, wind energy and the like are urgent. But the renewable energy source is unstable, discontinuous and the like in the grid connection process. The safe and efficient energy storage and conversion equipment can effectively realize peak clipping and valley filling of a power grid and storage of renewable energy, so that the equipment becomes a key point and a difficult point of people's research. In addition, along with the rapid development of various mobile devices and intelligent equipment, various electric automobiles, mobile phones, unmanned aerial vehicles and the like in daily life also need to be matched with a safe and environment-friendly high-performance battery system. For example, lithium ion batteries of organic systems have higher specific capacity and good cycle stability, and become the mainstream commodity in the field of secondary batteries at present. However, the problems of limited lithium resources, inflammable electrolyte, growth of lithium dendrites and the like cause the problems of high cost, high potential safety hazard and the like of the lithium ion battery. The electric automobile and the electric bicycle of the lithium ion battery system have the problems of spontaneous combustion, explosion and the like, which attracts attention to the safety of the battery. Therefore, the development of a safer and more efficient battery system has become an important issue in the field of energy storage and conversion.
The anode materials widely studied at present are mostly metal compounds, the synthesis process of the anode materials is complex, and the metal resources are expensive, so that the development and the application of the anode materials are limited. The organic anode material becomes a research hot spot of the next generation of non-metal anode materials due to the advantages of wide sources, smart design and the like. However, the drawbacks of organic materials also limit their development applications: firstly, the conductivity is low, the transmission of lithium ions is blocked, and the rate capability is poor; and secondly, the solubility in the electrolyte is higher, so that the organic material is dissolved in the circulating process, and the circulating performance is poor. Therefore, developing an organic negative electrode material with high conductivity and low solubility is important for high-energy and high-performance lithium ion batteries.
Covalent organic framework materials (COF) are organic framework materials connected through covalent bonds, have strong structural stability, have the advantages of easy modification of functional groups, easy regulation and control of pore channel structures and the like, and are expected to develop lithium cathodes capable of conducting lithium ions and inhibiting growth of lithium dendrites by organically compositing the covalent organic framework materials (COF) with binders through design, experiment and practice. As patent CN114388731a discloses a lithium battery electrode and a preparation method and application thereof, 2-4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 2, 5-dihydroxy-1, 4-phthalaldehyde are used as raw materials to prepare a lithium-philic covalent organic framework with triazine ring and carbonyl, and the lithium battery electrode uses the lithium-philic covalent organic framework with triazine ring and carbonyl as a functional artificial SEI layer of a lithium metal battery, so that smooth deposition of lithium and less lithium dendrites are ensured. However, no related literature or patent has been found for the preparation of covalent organic framework materials for modification of lithium cathodes using 2,4, 6-trimethyl-1, 3, 5-triazine and the monomer 2, 5-difluoroterephthalaldehyde.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a lithium anode modified by covalent organic framework materials. The covalent organic framework material prepared by the invention has coordination groups and a rich and regular pore canal structure, and is modified on a lithium cathode, and the coordination effect of the coordination groups and lithium ions is realized, so that the purpose of inhibiting the growth of lithium dendrites is realized; and the special regular pore canal structure can improve lithium ion conductivity, and the COF film can effectively prevent the growth of dendrites of the lithium cathode, so that the cycle stability of the lithium ion battery taking lithium metal as the cathode is improved.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the preparation method of the covalent organic framework material for lithium negative electrode modification comprises the following steps:
(1) Adding monomer 2,4, 6-trimethyl-1, 3, 5-triazine and monomer 2, 5-difluoro terephthalaldehyde into a mixed solvent, and circularly carrying out liquid nitrogen freezing and vacuum pumping processes for 2-5 times;
(2) And (3) heating the substance obtained in the step (1), washing and drying in vacuum after the reaction is finished to obtain the covalent organic framework material, and the covalent organic framework material is named as COF-49.
Further, in the step (1), the molar ratio of the monomer 2,4, 6-trimethyl-1, 3, 5-triazine to the monomer 2, 5-difluoro terephthalaldehyde is 1 (1-2).
Further, the mixed solvent in the step (1) is a mixed solvent of 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile.
Further, in the step (1), the volume ratio of 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile is (1-18): 2-18): 1-18, and the total mass of the monomer 2,4, 6-trimethyl-1, 3, 5-triazine and the monomer 2, 5-difluoro terephthalaldehyde dissolved in each 100mL of the mixed solvent is 1-5 g.
Further, in the step (2), the temperature of the heating reaction is 100-160 ℃, and the time of the heating reaction is 50-80 h.
Further, in the step (1), monomer 2,4, 6-trimethyl-1, 3, 5-triazine and monomer 2, 5-dimethyl terephthalaldehyde are added into a mixed solvent, and liquid nitrogen freezing and vacuum pumping processes are circularly carried out for 2-5 times; after heating reaction, the reaction was completed, and washed and vacuum-dried to obtain a covalent organic framework material, which was designated as COF-0F, and the remaining steps were the same as above, to be used as a comparative example.
The preparation method of the lithium negative electrode modified by the covalent organic framework material comprises the following steps:
(1) Mixing the covalent organic framework material prepared by the method of any one of claims 1-5 with a binder, adding a solvent, mechanically grinding uniformly, and then stamping to form a COF film sheet (with the thickness of 50-90 μm);
(2) And (3) drying the COF film sheet obtained in the step (1) to obtain a covalent organic framework material film, and then placing the covalent organic framework material film on a lithium negative electrode to obtain the lithium negative electrode modified by the covalent organic framework material.
Further, the binder in the step (1) is polytetrafluoroethylene, wherein the mass ratio of the covalent organic framework material to the binder is 100 (1-30).
Further, the solvent in the step (1) is absolute ethyl alcohol, and the total mass of the covalent organic framework material and the binder dissolved and dispersed in each 4mL of solvent is 5-80 mg.
Further, the drying temperature in the step (2) is 60-120 ℃ and the drying time is 6-24 h.
Furthermore, the covalent organic framework material modified lithium anode prepared by the method is applied to the field of lithium ion batteries.
The invention has the following beneficial effects:
1. the invention uses the COF material with coordination groups (fluorine groups (-F), carbon-carbon double bonds (-C=C-)) and rich regular pore canal structures on the surface of the lithium negative electrode, thereby obtaining the lithium negative electrode capable of conducting lithium ions and inhibiting lithium dendrites for the lithium ion battery.
2. The covalent organic framework material modified lithium negative electrode prepared by the invention can realize excellent lithium ion conduction function due to the rich pore canal structure of the COF material, and the electrochemical performance of the lithium negative electrode is improved. As shown in FIG. 3, at 0.5mA/cm 2 The polarization potential of the lithium ion battery assembled by the modified lithium metal is reduced by 5mV.
3. The covalent organic framework material modified lithium cathode prepared by the invention has a certain coordination function with lithium ions because the COF material is rich in fluorine groups (-F), carbon-carbon double bonds (-C=C-) and other groups, and can limit the growth of lithium dendrites in the charge and discharge processes. At 0.5mA/cm 2 Can be cycled for more than 200 hours under the current density of (2), and has no obvious change in polarization potential.
4. According to the invention, the prepared lithium metal capable of conducting lithium ions and inhibiting lithium dendrites is used as the negative electrode of the lithium ion battery, lithium iron phosphate is selected as the positive electrode, glass fiber is selected as the diaphragm, the electrolyte is solid electrolyte, and the discharge capacity of the assembled lithium ion battery after 100 circles of circulation under the current density of 0.1 ℃ can reach more than 160mAh/g, so that the assembled lithium ion battery has higher specific capacity.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a structural diagram of comparative example 1 of the present invention.
Fig. 2 is a structural diagram of embodiment 1 of the present invention.
Fig. 3 is a polarization potential diagram of a lithium ion battery prepared in example 1 of the present invention.
Fig. 4 is a specific capacity chart of the lithium ion battery prepared in example 1 of the present invention.
Fig. 5 is an electron microscopic view of the COF material obtained in example 1 of the present invention.
FIG. 6 is a graph showing the impedance of COF-0F obtained in comparative example 1 of the present invention.
FIG. 7 is a graph showing the impedance of COF-49 obtained in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the lithium anode COF-49 based on covalent organic framework material modification (shown in fig. 2) comprises the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 25.5mg of 2, 5-difluoro terephthalaldehyde as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:1.5), and placing the monomer 1 and the monomer 2 into a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.1mL of trifluoroacetic acid and 0.05mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material; an SEM image of this material is shown in fig. 5;
(3) Weighing 90mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 5mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
Comparative example 1
The comparative example is a preparation method (shown in figure 1) of a lithium anode COF-0F based on covalent organic framework material modification, and comprises the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 24.3mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:1.5), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.1mL of trifluoroacetic acid and 0.05mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 90mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 5mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
Example 2
The embodiment is a preparation method of a lithium anode COF-49 based on covalent organic framework material modification, comprising the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 25.5mg of 2, 5-difluoro terephthalaldehyde as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:1.5), and placing the monomer 1 and the monomer 2 into a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.1mL of trifluoroacetic acid and 0.1mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 40mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 5mg of polytetrafluoroethylene is weighed and placed in a mortar as a bonding agent; finally, adding 3mL of absolute ethanol solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
In this example, the acetonitrile in step (1) was 0.1mL, the temperature of the air-drying oven in step (2) was 100℃and the COF material in step (3) was 40mg, the polytetrafluoroethylene was 5mg, and the absolute ethyl alcohol was 3mL, as compared with example 1.
Comparative example 2
The comparative example is a preparation method of a lithium anode COF-0F based on covalent organic framework material modification, and the preparation method comprises the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 24.3mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:1.5), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.1mL of trifluoroacetic acid and 0.1mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 40mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 5mg of polytetrafluoroethylene is weighed and placed in a mortar as a bonding agent; finally, adding 3mL of absolute ethanol solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
In the comparative example, acetonitrile in step (1) was 0.1mL, the temperature of the air-drying oven in step (2) was 100℃and the COF material in step (3) was 40mg, polytetrafluoroethylene was 5mg, and absolute ethyl alcohol was 3mL, as compared with comparative example 1.
Example 3
The embodiment is a preparation method of a lithium anode COF-49 based on covalent organic framework material modification, comprising the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 34mg of 2, 5-difluoro terephthalaldehyde as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:2), and placing the monomer 1 and the monomer 2 into a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.1mL of trifluoroacetic acid and 0.05mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 24 hours to obtain a COF material;
(3) Weighing 100mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 6mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 10min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
Compared with the embodiment 1, 34mg of 2, 5-difluoro terephthalaldehyde in the step (1) is adopted in the embodiment, the vacuum drying time in the step (2) is 24h, the COF material in the step (3) is 100mg, the polytetrafluoroethylene is 10mg, the absolute ethyl alcohol is 6mL, and the grinding time is 10min.
Comparative example 3
The comparative example is a preparation method of a lithium anode COF-0F based on covalent organic framework material modification, and the preparation method comprises the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 32.4mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:2), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.1mL of trifluoroacetic acid and 0.05mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 24 hours to obtain a COF material;
(3) Weighing 100mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 6mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 10min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
Compared with comparative example 1, 32.4mg of 2, 5-dimethyl terephthalaldehyde in the step (1), the vacuum drying time in the step (2) is 24h, the COF material in the step (3) is 100mg, the polytetrafluoroethylene is 10mg, the absolute ethyl alcohol is 6mL, and the grinding time is 10min.
Example 4
The embodiment is a preparation method of a lithium anode COF-49 based on covalent organic framework material modification, comprising the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 25.5mg of 2, 5-difluoro terephthalaldehyde as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:1.5), and placing the monomer 1 and the monomer 2 into a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.2mL of trifluoroacetic acid and 0.05mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 80 ℃ for 24 hours to obtain a COF material;
(3) Weighing 70mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 4mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 60min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
Compared with the embodiment 1, in the embodiment, the trifluoroacetic acid in the step (1) is 0.2mL, the vacuum drying oven temperature in the step (2) is 80 ℃, the vacuum drying time is 24h, the COF material in the step (3) is 70mg, the polytetrafluoroethylene is 10mg, the absolute ethyl alcohol is 4mL, and the grinding time is 60min.
Comparative example 4
The comparative example is a preparation method of a lithium anode COF-0F based on covalent organic framework material modification, and the preparation method comprises the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 24.3mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:1.5), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.2mL of trifluoroacetic acid and 0.05mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72 hours, terminating the reaction, and then drying in a vacuum oven at 80 ℃ for 24 hours to obtain a COF material;
(3) Weighing 70mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 4mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 60min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
Compared with comparative example 1, in this example, trifluoroacetic acid in step (1) was 0.2mL, the vacuum oven temperature in step (2) was 80 ℃, the vacuum drying time was 24 hours, the COF material in step (3) was 70mg, polytetrafluoroethylene was 10mg, absolute ethyl alcohol was 4mL, and the grinding time was 60 minutes.
Example 5
The embodiment is a preparation method of a lithium anode COF-49 based on covalent organic framework material modification, comprising the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 25.5mg of 2, 5-difluoro terephthalaldehyde as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:1.5), and placing the monomer 1 and the monomer 2 into a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.2mL of trifluoroacetic acid and 0.1mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 24 hours to obtain a COF material;
(3) Weighing 90mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 5mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 60min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
Compared with the embodiment 1, in the embodiment, the trifluoroacetic acid in the step (1) is 0.2mL, the acetonitrile is 0.1mL, the temperature of the blast drying box in the step (2) is 160 ℃, the heating time is 24h, the drying time is 24h, the absolute ethyl alcohol in the step (3) is 5mL, and the grinding time is 60min.
Comparative example 5
The comparative example is a preparation method of a lithium anode COF-0F based on covalent organic framework material modification, and the preparation method comprises the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 24.3mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:1.5), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.9mL of 1, 4-dioxane, 0.9mL of mesitylene, 0.2mL of trifluoroacetic acid and 0.1mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 24 hours to obtain a COF material;
(3) Weighing 90mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 10mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 5mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 60min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 80 ℃ for 12 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
Compared with comparative example 1, in the comparative example, trifluoroacetic acid in the step (1) is 0.2mL, acetonitrile is 0.1mL, the temperature of a blast drying oven in the step (2) is 160 ℃, the heating time is 24h, the drying time is 24h, absolute ethyl alcohol in the step (3) is 5mL, and the grinding time is 60min.
Example 6
The embodiment is a preparation method of a lithium anode COF-49 based on covalent organic framework material modification, comprising the following steps:
(1) Firstly, 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 34.02mg of 2, 5-difluoro terephthalaldehyde is weighed as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:1), and the monomer 1 and the monomer 2 are placed in a glass bottle; adding 0.55mL of 1, 4-dioxane, 0.55mL of mesitylene, 0.06mL of trifluoroacetic acid and 0.03mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 3.7mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 0.037mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 3mL of absolute ethanol solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 60 ℃ for 24 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
Compared with example 1, in the present example, 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine, 34.02mg,0.55mL 1,4-dioxane, 0.55mL of mesitylene, 0.06mL of trifluoroacetic acid and 0.03mL of 2, 6-trimethyl-1, 3, 5-triazine in step (1), 160 ℃ of blast drying oven in step (2) was heated for 50h, 3.7mg of COF material in step (3), 0.037mg of polytetrafluoroethylene, 3mL of absolute ethyl alcohol in step (4) was dried at 60 ℃ for 24h.
Comparative example 6
The comparative example is a preparation method of a lithium anode COF-0F based on covalent organic framework material modification, and the preparation method comprises the following steps:
(1) Firstly, 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 32.4mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:1), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.55mL of 1, 4-dioxane, 0.55mL of mesitylene, 0.06mL of trifluoroacetic acid and 0.03mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 3.7mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 0.037mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 3mL of absolute ethanol solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 60 ℃ for 24 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
Compared with comparative example 1, in this comparative example, 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine, 32.4mg,0.55mL 1,4-dioxane, 0.55mL of mesitylene, 0.06mL of trifluoroacetic acid and 0.03mL of acetonitrile in step (1), 3.7mg of COF material in step (3), 0.037mg of polytetrafluoroethylene, 3mL of absolute ethyl alcohol in step (3) were heated at 160℃for 50 hours, and dried at 60℃for 24 hours in step (4).
Example 7
The embodiment is a preparation method of a lithium anode COF-49 based on covalent organic framework material modification, comprising the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 34.02mg of 2, 5-difluoro terephthalaldehyde is weighed as a monomer 2 (the molar ratio of the monomer 1 to the monomer 2 is 1:2), and the monomer 1 and the monomer 2 are placed in a glass bottle; adding 0.15mL of 1, 4-dioxane, 0.3mL of mesitylene, 2.7mL of trifluoroacetic acid and 2.7mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 80 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 46mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 13.8mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 3mL of absolute ethanol solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 120 ℃ for 6 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-49 modified lithium anode.
Compared with example 1, in this example, in step (1) of 12.3mg,2, 5-difluoro terephthalaldehyde 34.02mg,0.15mL 1,4-dioxane, 0.3mL mesitylene, 2.7mL trifluoroacetic acid and 2.7mL acetonitrile, in step (2) of blast drying 100 ℃ heating 80h, in step (3) of COF material 46mg, polytetrafluoroethylene 13.8mg, absolute ethanol 3mL, in step (4) of 120 ℃ drying 6h.
Comparative example 7
The comparative example is a preparation method of a lithium anode COF-0F based on covalent organic framework material modification, and the preparation method comprises the following steps:
(1) Firstly, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed as a monomer 1, 32.4mg of 2, 5-dimethyl terephthalaldehyde is weighed as a monomer 3 (the mol ratio of the monomer 1 to the monomer 3 is 1:2), and the monomer 1 and the monomer 3 are placed in a glass bottle; adding 0.15mL of 1, 4-dioxane, 0.3mL of mesitylene, 2.7mL of trifluoroacetic acid and 2.7mL of acetonitrile into a glass bottle as a mixed solvent, and finally, carrying out two process cycles of freezing for 5min by liquid nitrogen and vacuum pumping for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 80 hours, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12 hours to obtain a COF material;
(3) Weighing 46mg of the COF material obtained in the step (2) and placing the COF material in a mortar; 13.8mg of polytetrafluoroethylene is weighed as a binder and placed in a mortar; finally, adding 3mL of absolute ethanol solvent into the mortar, and uniformly grinding for 30min;
(4) And (3) punching the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying oven, drying at 120 ℃ for 6 hours, and placing the obtained COF film on the surface of the lithium anode to obtain the COF-0F modified lithium anode.
Compared with comparative example 1, in the comparative example, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine in step (1), 34.02mg,0.15mL 1,4-dioxane of 2, 5-difluoro terephthalaldehyde, 0.3mL of mesitylene, 2.7mL of trifluoroacetic acid and 2.7mL of acetonitrile were heated at 100℃for 80 hours in a blast drying oven in step (2), 46mg of COF material in step (3), 13.8mg of polytetrafluoroethylene and 3mL of absolute ethyl alcohol, and dried at 120℃for 6 hours in step (4).
The following tables are specific example conditions for examples 1-5 and comparative examples 1-5.
Application example
1. Assembly of lithium ion battery
The metal lithium electrode sheet of the above example was punched into a disc with a diameter of 16mm, glass fiber was used as a separator, solid electrolyte was added, and a CR-2032 type button cell was assembled and packaged with a packaging machine, followed by standing for 12 hours or more and then electrochemical performance testing.
2. Assembly of symmetrical batteries
The metal lithium electrode sheet of the above example was punched into a disk with a diameter of 16mm, lithium iron phosphate was selected as a positive electrode, glass fiber was used as a separator, a solid electrolyte was added, and a CR-2032 type button cell was assembled and packaged with a packaging machine, followed by standing for 12 hours or more and then electrochemical performance testing.
3. Electrochemical performance test
Fig. 3 is the polarization potential of a lithium ion battery. From the graph, the polarization potential of COF-49 was 5mV, and the stability was good.
Fig. 4 is a graph showing the high-rate long-cycle performance of the organic composite material of example 1 as a negative electrode material of a lithium ion battery. From the graph, the battery has a charge-discharge capacity of 160mAh/g under the current density of 0.1C, and the organic composite material is proved to have better performance as a negative electrode material of a lithium ion battery.
Fig. 6 is a graph showing the impedance of the organic composite material of comparative example 1 according to the present invention as a negative electrode material for a lithium ion battery. Fig. 7 is a graph showing the impedance of the organic composite material as a negative electrode material of a lithium ion battery in example 1 of the present invention. From the graph, the lithium ion migration number of the COF-49 is larger than that of the COF-0F, and the COF-49 organic composite material is proved to have better performance as a cathode material of a lithium ion battery.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The preparation method of the covalent organic framework material for lithium negative electrode modification is characterized by comprising the following steps of:
(1) Adding monomer 2,4, 6-trimethyl-1, 3, 5-triazine and monomer 2, 5-difluoro terephthalaldehyde into a mixed solvent, and circularly carrying out liquid nitrogen freezing and vacuum pumping processes for 2-5 times;
(2) And (3) heating the substance obtained in the step (1), washing and drying in vacuum after the reaction is finished to obtain the covalent organic framework material, and the covalent organic framework material is named as COF-49.
2. The method for preparing a covalent organic framework material for lithium negative electrode modification according to claim 1, characterized in that: in the step (1), the molar ratio of the monomer 2,4, 6-trimethyl-1, 3, 5-triazine to the monomer 2, 5-difluoro terephthalaldehyde is 1 (1-2).
3. The method for preparing a covalent organic framework material for lithium negative electrode modification according to claim 2, characterized in that: the mixed solvent in the step (1) is a mixed solvent of 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile.
4. A method of preparing a covalent organic framework material for lithium negative electrode modification according to claim 3, characterized in that: in the step (1), the volume ratio of 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile is (1-18): 2-18: (1-18), and the total mass of the monomer 2,4, 6-trimethyl-1, 3, 5-triazine and the monomer 2, 5-difluoro terephthalaldehyde dissolved in each 100mL of mixed solvent is 1-5 g.
5. The method for preparing a covalent organic framework material for lithium negative electrode modification according to claim 4, characterized in that: the temperature of the heating reaction in the step (2) is 100-160 ℃, and the time of the heating reaction is 50-80 h.
6. The preparation method of the lithium anode modified based on the covalent organic framework material is characterized by comprising the following steps:
(1) Mixing the covalent organic framework material prepared by the method of any one of claims 1-5 with a binder, adding a solvent, mechanically grinding uniformly, and then stamping to form a COF film sheet;
(2) And (3) drying the COF film sheet obtained in the step (1) to obtain a covalent organic framework material film, and then placing the covalent organic framework material film on a lithium negative electrode to obtain the lithium negative electrode modified by the covalent organic framework material.
7. The method for preparing a lithium anode modified based on a covalent organic framework material according to claim 6, wherein: the binder in the step (1) is polytetrafluoroethylene, wherein the mass ratio of the covalent organic framework material to the binder is 100 (1-30).
8. The method for preparing a lithium anode modified based on a covalent organic framework material according to claim 7, characterized in that: the solvent in the step (1) is absolute ethyl alcohol, and the total mass of the covalent organic framework material and the binder dispersed in each 4mL of solvent is 5-80 mg.
9. The method for preparing a lithium anode modified based on a covalent organic framework material according to claim 8, wherein: the drying temperature in the step (2) is 60-120 ℃, and the drying time is 6-24 hours.
10. Use of a lithium anode based on covalent organic framework material modification prepared by the method of any one of claims 6-9 in the field of lithium ion batteries.
CN202211020520.XA 2022-08-24 2022-08-24 Preparation method and application of lithium anode modified based on covalent organic framework material Active CN115403723B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211020520.XA CN115403723B (en) 2022-08-24 2022-08-24 Preparation method and application of lithium anode modified based on covalent organic framework material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211020520.XA CN115403723B (en) 2022-08-24 2022-08-24 Preparation method and application of lithium anode modified based on covalent organic framework material

Publications (2)

Publication Number Publication Date
CN115403723A CN115403723A (en) 2022-11-29
CN115403723B true CN115403723B (en) 2023-10-13

Family

ID=84161398

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211020520.XA Active CN115403723B (en) 2022-08-24 2022-08-24 Preparation method and application of lithium anode modified based on covalent organic framework material

Country Status (1)

Country Link
CN (1) CN115403723B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101080246A (en) * 2004-04-28 2007-11-28 安希奥设备国际有限责任公司 Compositions and systems for forming crosslinked biomaterials and associated methods of preparation and use
KR20150032138A (en) * 2013-09-16 2015-03-25 솔브레인 주식회사 Electrolyte and lithium secondary battery comprising the same
CN113512033A (en) * 2021-05-19 2021-10-19 南京工业大学 Phenoxazine and phenothiazine covalent triazine framework material and preparation method and application thereof
WO2021247596A1 (en) * 2020-05-30 2021-12-09 Cornell University Functionalized cross-linked polymer networks, methods of making same, and uses thereof
CN114016076A (en) * 2021-10-27 2022-02-08 三峡大学 Nickel-based metal organic framework material and application thereof in electrocatalytic methanol oxidation
CN114784452A (en) * 2022-05-24 2022-07-22 南京工业大学 Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005001979A2 (en) * 2003-06-27 2005-01-06 E.I. Dupont De Nemours And Company Fluorinated sulfonamide compounds and polymer electrolyte membranes pepared therefrom for use in electrochemical cells
CA3069975A1 (en) * 2017-07-17 2019-01-24 NOHMs Technologies, Inc. Modified triazine functional compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101080246A (en) * 2004-04-28 2007-11-28 安希奥设备国际有限责任公司 Compositions and systems for forming crosslinked biomaterials and associated methods of preparation and use
KR20150032138A (en) * 2013-09-16 2015-03-25 솔브레인 주식회사 Electrolyte and lithium secondary battery comprising the same
WO2021247596A1 (en) * 2020-05-30 2021-12-09 Cornell University Functionalized cross-linked polymer networks, methods of making same, and uses thereof
CN113512033A (en) * 2021-05-19 2021-10-19 南京工业大学 Phenoxazine and phenothiazine covalent triazine framework material and preparation method and application thereof
CN114016076A (en) * 2021-10-27 2022-02-08 三峡大学 Nickel-based metal organic framework material and application thereof in electrocatalytic methanol oxidation
CN114784452A (en) * 2022-05-24 2022-07-22 南京工业大学 Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Gao, Y 等.Halogen-functionalized triazine-based organic frameworks towards high performance supercapacitors.《CHEMICAL ENGINEERING JOURNAL》.2020,文献号125967. *
Li, ZP 等.Olefin-Linked Covalent Organic Frameworks with Electronegative Channels as Cationic Highways for Sustainable Lithium Metal Battery Anodes.《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》.2023,第62卷(第37期),文献号e202307459 . *
刘道华.三嗪环共价有机聚合物的制备及其电容去离子应用研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2020,(第2期), B027-1117. *

Also Published As

Publication number Publication date
CN115403723A (en) 2022-11-29

Similar Documents

Publication Publication Date Title
CN103427073B (en) A kind of preparation method of the mesoporous Si/C complex microsphere as lithium cell cathode material
CN102306781A (en) Doped graphene electrode material, macro preparation method and application of doped graphene electrode material
CN108172815B (en) Microspherical zinc vanadate, and preparation method and application thereof
CN111180725A (en) Method for preparing aluminum battery anode material by utilizing MOF (metal organic framework) to induce metal selenide
CN102064319A (en) Negative plate of lead acid super battery, production method and lead acid super battery assembled by negative plate
CN112151787B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN113517426B (en) Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof
CN108807912B (en) C @ SnOx(x=0,1,2)Preparation and application of @ C mesoporous nano hollow sphere structure
CN104966836A (en) Method for improving electrochemical performance of LiFePO4 through polypyrrole/graphene
CN111313111A (en) Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material and application thereof
CN113725421A (en) Preparation method and application of covalent organic framework material modified zinc cathode
CN102842703A (en) Chemical power supply
CN114572956B (en) Nanoscale olivine type sodium iron phosphate and preparation method and application thereof
CN105958027B (en) A kind of manganese base composite positive pole and preparation method thereof
CN113659193A (en) All-solid-state sodium ion battery cell structure, preparation method and battery
CN115403723B (en) Preparation method and application of lithium anode modified based on covalent organic framework material
CN112803018A (en) Silicon-doped graphene composite material and preparation method and application thereof
CN113697787B (en) Method for preparing lithium ion battery anode material by starch modified coated ferric phosphate
CN114171711A (en) Electrode preparation method of water-based zinc ion battery, electrode and battery
CN104882600B (en) The preparation method of lithium ion battery iron oxide microballoon negative material
CN106910895B (en) Organic electrode material and preparation method and application thereof
CN105375013A (en) Method for preparing sodium-doped lithium ferrous silicate/carbon nano-micro structure composite cathode material
CN110589792A (en) Preparation method of anode material ferric pyrophosphate
CN114195115B (en) Modification method of lithium iron phosphate composite material
CN115057862B (en) Pyrazine-quinoxaline organic electrode material and application thereof in lithium ion battery

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