CN115403723A - Preparation method and application of covalent organic framework material modification-based lithium cathode - Google Patents
Preparation method and application of covalent organic framework material modification-based lithium cathode Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, relates to preparation of a lithium cathode, and particularly relates to a preparation method and application of a lithium cathode modified based on a covalent organic framework material. The covalent organic framework material with coordination groups and rich regular pore channel structures is mixed with a binder, mechanically ground to form a COF membrane and placed on the lithium surface; on one hand, the coordination group has coordination induction effect on lithium ions, and the purpose of inhibiting the growth of lithium dendrites is realized; on the other hand, the special regular pore structure can improve the lithium ion conduction performance; finally improve toThe cycling stability of lithium ion batteries with lithium metal as the negative electrode. At 0.5mA/cm 2 The current density of the lithium ion battery can be cycled for more than 200 hours, the polarization potential is not obviously changed, the discharge capacity of the assembled lithium ion battery can reach 160mAh/g after the lithium ion battery is cycled for 100 circles under the current density of 0.1C, and the lithium ion battery shows higher specific capacity.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to preparation of a lithium cathode, and particularly relates to a preparation method and application of a lithium cathode modified based on a covalent organic framework material.
Background
The large use of fossil energy increases the shortage of energy and also causes serious environmental pollution, and the development and utilization of renewable energy such as solar energy, wind energy, and the like are urgently needed. But the problems of instability, discontinuity and the like exist in the use of renewable energy sources and 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 difficulty of research of people. In addition, with the rapid development of various mobile devices and intelligent equipment, various electric vehicles, 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 high specific capacity and good cycling stability, and become mainstream products in the field of secondary batteries at present. However, the lithium ion battery has the problems of high cost, large potential safety hazard and the like due to the problems of limited lithium resources, inflammable electrolyte, dendritic lithium crystal growth and the like. The problems of spontaneous combustion, explosion and the like of the electric automobile and the electric bicycle of the lithium ion battery system are caused, and the attention of people on the safety of the battery is attracted. Therefore, the development of safer and more efficient battery systems has become an important issue in the field of energy storage and conversion.
Most of the anode materials widely researched at present are metal compounds, the synthesis process of the anode materials is complex, and the cost of metal resources is expensive, so that the development and the application of the anode materials are limited. The organic cathode material becomes a research hotspot of the next generation of non-metal cathode materials due to the advantages of wide sources, flexible 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 hindered, and the rate capability is poor; and secondly, the organic material is dissolved in the circulation process due to higher solubility in the electrolyte, so that the organic material has poorer circulation performance. Therefore, the development of an organic negative electrode material with high conductivity and low solubility is very important for a lithium ion battery with high energy and high performance.
Covalent Organic Framework (COF) materials are organic framework materials connected by covalent bonds, have strong structural stability, and also have the advantages of easy modification of functional groups, easy regulation and control of pore channel structures and the like, and are organically compounded with binders through design, experiments and practice to be used as COF films, so that the COF films are expected to develop lithium cathodes capable of conducting lithium ions and inhibiting growth of lithium dendrites. For example, 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 a triazine ring and a carbonyl group, and the lithium battery electrode takes the lithium-philic covalent organic framework with the triazine ring and the carbonyl group 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 literature or patent related to the preparation of covalent organic framework material modified lithium negative electrodes using 2,4,6-trimethyl-1,3,5-triazine and the monomer 2,5-difluoroterephthalaldehyde has been found.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a lithium cathode modified based on a covalent organic framework material. The covalent organic framework material prepared by the invention has a coordination group and a rich and regular pore channel structure, and is modified on a lithium cathode, and the purpose of inhibiting the growth of lithium dendrites is realized by the coordination action of the coordination group and lithium ions; and the special regular pore channel structure can improve the lithium ion conduction performance, and the COF film can effectively prevent the dendritic crystal growth 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 purpose, the technical scheme of the invention is realized as follows:
a preparation method of a 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 performing liquid nitrogen freezing and vacuum pumping processes for 2-5 times;
(2) And (2) heating the substance obtained in the step (1) for reaction, washing and vacuum-drying the substance after the reaction is finished to obtain a covalent organic framework material, and naming the covalent organic framework material 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 to 2).
Further, the mixed solvent in the step (1) is a mixed solvent of 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile.
Further, the volume ratio of the 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile in the step (1) is (1) - (18): (2) - (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-difluoroterephthalaldehyde dissolved in each 100mL of the mixed solvent is 1) - (5 g.
Further, the temperature of the heating reaction in the step (2) is 100 to 160 ℃, and the time of the heating reaction is 50 to 80h.
Further, in the step (1), the monomer 2,4, 6-trimethyl-1, 3, 5-triazine and the monomer 2, 5-dimethyl terephthalaldehyde are added into a mixed solvent, and the processes of liquid nitrogen freezing and vacuum air suction are circularly carried out for 2-5 times; after the reaction was heated, the covalent organic framework material was obtained by washing and vacuum drying after the reaction was completed, and named COF-0F, and the rest of the procedure was as above, which was used as a comparative example.
A preparation method of a covalent organic framework material modified lithium cathode comprises the following steps:
(1) Mixing the covalent organic framework material prepared by the method of any one of claims 1 to 5 with a binder, adding a solvent, mechanically grinding uniformly, and stamping to form a COF film (the thickness is 50-90 μm);
(2) And (2) 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 cathode to obtain the lithium cathode modified by the covalent organic framework material.
Furthermore, the binder in the step (1) is polytetrafluoroethylene, and 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 the solvent is 5-80mg.
Further, the drying temperature in the step (2) is 60 to 120 ℃, and the drying time is 6 to 24h.
Further, the covalent organic framework material modified lithium cathode prepared by the method is applied to the field of lithium ion batteries.
The invention has the following beneficial effects:
1. the invention applies the COF material with coordination groups (fluorine (-F), carbon-carbon double bonds (-C = C-), and rich regular pore channel structure on the surface of the lithium cathode, and obtains the lithium cathode for the lithium ion battery, which can conduct lithium ions and inhibit lithium dendrites.
2. The lithium cathode modified by the covalent organic framework material prepared by the invention can realize excellent lithium ion conduction function due to rich pore channel structure of COF material, and the electrochemical performance of the lithium cathode 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 at the current density of (a).
3. The covalent organic framework material modified lithium cathode prepared by the invention is rich in fluorine group (-F), carbon-carbon double bond (-C = C-) and other groups due to the COF material, and the functional groups and lithium ions have certain coordination effect, so that the growth of lithium dendrites can be limited in the charging and discharging processes. At 0.5mA/cm 2 Can be circulated for more than 200h under the current density, and the polarization potential has no obvious change.
4. The lithium metal capable of conducting lithium ions and inhibiting lithium dendrites is used as the negative electrode of the lithium ion battery, the positive electrode is lithium iron phosphate, the diaphragm is made of glass fiber, the electrolyte is solid electrolyte, and the discharge capacity can reach more than 160mAh/g after the lithium ion battery assembled under the current density of 0.1C circulates for 100 circles, so that the lithium ion battery shows higher specific capacity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a structural view of comparative example 1 of the present invention.
Fig. 2 is a structural view 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 graph of the specific capacity of the lithium ion battery prepared in example 1 of the present invention.
Fig. 5 is an electron micrograph of a COF material obtained in comparative example 1 of the present invention.
Fig. 6 is an electron micrograph of the COF material obtained in example 1 of the present invention.
FIG. 7 is an impedance diagram of COF-0F obtained in comparative example 1 of the present invention.
Fig. 8 is an impedance diagram of the COF-49 obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
This example is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49 (as shown in fig. 2), and includes the following steps:
(1) First, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine was weighed as a monomer 1, 25.5mg of 2, 5-difluoroterephthalaldehyde was weighed as a monomer 2 (molar ratio of monomer 1 to monomer 2 was 1.5), and monomer 1 and monomer 2 were 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 12h to obtain a COF material; the SEM image of the material is shown in figure 6;
(3) Weighing 90mg of the COF material obtained in the step (2) and placing the COF material in a mortar; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 5mL of absolute ethyl alcohol solvent is added into the mortar, and the mixture is uniformly ground for 30min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
Comparative example 1
This comparative example is a preparation method of a covalent organic framework material modified based lithium negative electrode COF-0F (shown in FIG. 1), comprising the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 24.3mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1.5), and placing the monomer 1 and the monomer 3 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72h, terminating the reaction, and drying in a vacuum oven at 120 ℃ for 12h to obtain a COF material; the SEM image of the material is shown in figure 5;
(3) Weighing 90mg of the COF material obtained in the step (2) and placing the COF material in a mortar; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 5mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 30min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-0F.
Example 2
The embodiment is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49, and the preparation method comprises the following steps:
(1) First, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine was weighed as a monomer 1, 25.5mg of 2, 5-difluoroterephthalaldehyde was weighed as a monomer 2 (molar ratio of monomer 1 to monomer 2 was 1.5), and monomer 1 and monomer 2 were 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 to serve as a mixed solvent, and finally, circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 72h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 12h 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; weighing 5mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 3mL of absolute ethyl alcohol solvent is added into the mortar, and the mixture is uniformly ground for 30min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
In this example, acetonitrile was 0.1mL in step (1), the temperature of the forced air oven was 100 ℃ in step (2), 40mg of the COF material, 5mg of polytetrafluoroethylene and 3mL of absolute ethanol were used in step (3), as compared with example 1.
Comparative example 2
The comparative example is a preparation method of a covalent organic framework material modified lithium negative electrode COF-0F, and the preparation method comprises the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 24.3mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1.5), and placing the monomer 1 and the monomer 3 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 to serve as a mixed solvent, and finally, circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 72h, terminating the reaction, and drying in a vacuum oven at 120 ℃ for 12h 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; weighing 5mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 3mL of absolute ethyl alcohol solvent is added into the mortar, and the mixture is uniformly ground for 30min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-0F.
Compared with comparative example 1, in this comparative example, acetonitrile was 0.1mL in step (1), the temperature of the forced air drying oven was 100 ℃ in step (2), the COF material was 40mg in step (3), polytetrafluoroethylene was 5mg, and absolute ethanol was 3mL.
Example 3
The embodiment is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49, and the preparation method comprises the following steps:
(1) First, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine was weighed as a monomer 1, 34mg of 2, 5-difluoroterephthalaldehyde was weighed as a monomer 2 (molar ratio of the monomer 1 to the monomer 2 was 1; 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72h, terminating the reaction, and drying in a vacuum oven at 120 ℃ for 24h 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; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 6mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 10min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
Compared with example 1, in the present example, 34mg of 2, 5-difluoroterephthalaldehyde was used in step (1), vacuum drying time was 24h in step (2), COF material was 100mg in step (3), polytetrafluoroethylene was 10mg, and absolute ethyl alcohol was 6mL, and grinding time was 10min.
Comparative example 3
The comparative example is a preparation method of a covalent organic framework material modified lithium negative electrode COF-0F, and the preparation method comprises the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 32.4mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1; 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 24h 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; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 6mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 10min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-0F.
Compared with the comparative example 1, in the comparative example, 32.4mg of 2, 5-dimethyl terephthalaldehyde is adopted in the step (1), the vacuum drying time is 24 hours in the step (2), 100mg of COF material is adopted in the step (3), 10mg of polytetrafluoroethylene is adopted, 6mL of absolute ethyl alcohol is adopted, and the grinding time is 10min.
Example 4
The embodiment is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49, and the preparation method comprises the following steps:
(1) First, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine was weighed as a monomer 1, 25.5mg of 2, 5-difluoroterephthalaldehyde was weighed as a monomer 2 (molar ratio of monomer 1 to monomer 2 was 1.5), and monomer 1 and monomer 2 were 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 to serve as a mixed solvent, and finally, circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72h, terminating the reaction, and then drying in a vacuum drying oven at 80 ℃ for 24h to obtain a COF material;
(3) Weighing 70mg of the COF material obtained in the step (2) and putting the COF material into a mortar; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, adding 4mL of absolute ethyl alcohol serving as a solvent into the mortar, and uniformly grinding for 60min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
Compared with example 1, in the present example, trifluoroacetic acid in step (1) was 0.2mL, vacuum oven temperature in step (2) was 80 ℃, vacuum drying time was 24h, COF material in step (3) was 70mg, polytetrafluoroethylene was 10mg, absolute ethanol was 4mL, and grinding time was 60min.
Comparative example 4
The comparative example is a preparation method of a covalent organic framework material modified lithium negative electrode COF-0F, and the preparation method comprises the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 24.3mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1.5), and placing the monomer 1 and the monomer 3 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 120 ℃ for 72h, terminating the reaction, and then drying in a vacuum drying oven at 80 ℃ for 24h 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; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, adding 4mL of absolute ethyl alcohol as a solvent into a mortar, and uniformly grinding for 60min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-0F.
Compared with the comparative example 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.
Example 5
The embodiment is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49, which comprises the following steps:
(1) First, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine was weighed as a monomer 1, 25.5mg of 2, 5-difluoroterephthalaldehyde was weighed as a monomer 2 (molar ratio of monomer 1 to monomer 2 was 1.5), and monomer 1 and monomer 2 were 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 24h 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; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 5mL of absolute ethyl alcohol solvent is added into the mortar, and the mixture is uniformly ground for 60min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
Compared with the example 1, in the example, the trifluoroacetic acid in the step (1) is 0.2mL, the acetonitrile is 0.1mL, the temperature of the forced air drying oven 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 covalent organic framework material modified lithium negative electrode COF-0F, and the preparation method comprises the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 24.3mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1.5), and placing the monomer 1 and the monomer 3 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 24h 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; weighing 10mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 5mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 60min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 80 ℃ for 12h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-0F.
Compared with the comparative example 1, in the comparative example, the trifluoroacetic acid is 0.2mL in the step (1), the acetonitrile is 0.1mL, the temperature of the forced air drying oven in the step (2) is 160 ℃, the heating time is 24h, the drying time is 24h, the absolute ethyl alcohol is 5mL in the step (3), and the grinding time is 60min.
Example 6
The embodiment is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49, which comprises 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), and the monomer 1 and the monomer 2 are put 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 12h 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; weighing 0.037mg of polytetrafluoroethylene as a binder and putting the polytetrafluoroethylene in a mortar; finally, 3mL of absolute ethyl alcohol solvent is added into the mortar, and the mixture is uniformly ground for 30min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film sheet, placing the COF film sheet in a drying box, drying at 60 ℃ for 24h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
In this example, in comparison with example 1, 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine, 24.02mg of 2, 5-difluoroterephthalaldehyde, 34.02mg of 0.55mL of 1, 4-dioxane, 0.55mL of mesitylene, 0.06mL of trifluoroacetic acid and 0.03mL were used in step (1), and the mixture was heated at 160 ℃ for 50 hours in an air-blast drying oven in step (2), 3.7mg of COF material in step (3), 0.037mg of polytetrafluoroethylene, 3mL of absolute ethanol and 24 hours in step (4) at 60 ℃.
Comparative example 6
The comparative example is a preparation method of a covalent organic framework material modified lithium negative electrode COF-0F, and the preparation method comprises the following steps:
(1) Firstly, weighing 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 32.4mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1; 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 160 ℃ for 50h, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12h 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; weighing 0.037mg of polytetrafluoroethylene serving as a binder and putting the polytetrafluoroethylene into a mortar; finally, 3mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 30min;
(4) And (4) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 60 ℃ for 24h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-0F.
In comparison with comparative example 1, in this comparative example, 24.6mg of 2,4, 6-trimethyl-1, 3, 5-triazine, 24.4 mg of 2, 5-dimethylterephthalaldehyde, 32.4mg of 0.55mL of 1, 4-dioxane, 0.55mL of mesitylene, 0.06mL of trifluoroacetic acid, and 0.03mL of acetonitrile were used in step (1), the forced air drying oven was heated at 160 ℃ for 50 hours in step (2), 3.7mg of COF material in step (3), 0.037mg of polytetrafluoroethylene, 3mL of absolute ethanol, and dried at 60 ℃ for 24 hours in step (4).
Example 7
The embodiment is a preparation method of a covalent organic framework material modified lithium negative electrode COF-49, which comprises the following steps:
(1) First, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine was weighed as a monomer 1, 34.02mg of 2, 5-difluoroterephthalaldehyde was weighed as a monomer 2 (molar ratio of the monomer 1 to the monomer 2 was 1; 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 80h, terminating the reaction, and then drying in a vacuum oven at 120 ℃ for 12h 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; weighing 13.8mg of polytetrafluoroethylene serving as a binder and putting the polytetrafluoroethylene in a mortar; finally, 3mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 30min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 120 ℃ for 6h, and placing the obtained COF film on the surface of the lithium negative electrode to obtain the COF material modified lithium negative electrode COF-49.
In this example, in comparison with example 1, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine, 34.02mg of 2, 5-difluoroterephthalaldehyde, 0.15ml of 1, 4-dioxane, 0.3mL of mesitylene, 2.7mL of trifluoroacetic acid and 2.7mL of acetonitrile were subjected to forced air drying at 100 ℃ for 80 hours in step (2), 46mg of COF material, 13.8mg of polytetrafluoroethylene, 3mL of absolute ethyl alcohol and 6 hours of drying at 120 ℃ in step (4) in step (3).
Comparative example 7
The comparative example is a preparation method of a covalent organic framework material modified lithium negative electrode COF-0F, and the preparation method comprises the following steps:
(1) Firstly, weighing 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine as a monomer 1, weighing 32.4mg of 2, 5-dimethyl terephthalaldehyde as a monomer 3 (the molar ratio of the monomer 1 to the monomer 3 is 1; 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 to serve as a mixed solvent, and finally circularly performing two processes of freezing for 5min by liquid nitrogen and vacuumizing for 5min for 3 times;
(2) Placing the substance obtained in the step (1) in a forced air drying oven, heating at 100 ℃ for 80h, terminating the reaction, and then drying in a vacuum drying oven at 120 ℃ for 12h to obtain a COF material;
(3) Weighing 46mg of the COF material obtained in the step (2) and placing the COF material into a mortar; weighing 13.8mg of polytetrafluoroethylene serving as a binder and putting the polytetrafluoroethylene in a mortar; finally, 3mL of absolute ethyl alcohol as a solvent is added into a mortar, and the mixture is uniformly ground for 30min;
(4) And (3) stamping the mixture ground in the step (3) to form a COF film, placing the COF film in a drying box, drying at 120 ℃ for 6h, and placing the obtained COF film on the surface of the lithium cathode to obtain the COF material modified lithium cathode COF-0F.
In comparison with comparative example 1, in this comparative example, 12.3mg of 2,4, 6-trimethyl-1, 3, 5-triazine, 34.02mg of 2, 5-difluoroterephthalaldehyde, 0.15mL of 1, 4-dioxane, 0.3mL of mesitylene, 2.7mL of trifluoroacetic acid, and 2.7mL of acetonitrile were used in step (1), the forced air drying oven was heated at 100 ℃ for 80 hours in step (2), 46mg of COF material, 13.8mg of polytetrafluoroethylene, and 3mL of absolute ethanol were used in step (3), and dried at 120 ℃ for 6 hours in step (4).
The following table shows the conditions of the specific examples of examples 1 to 5 and comparative examples 1 to 5.
Application example
1. Lithium ion battery assembly
The metal lithium electrode sheet in the embodiment is punched into a wafer with the diameter of 16mm, glass fiber is used as a diaphragm, solid electrolyte is added, a CR-2032 type button cell is assembled and packaged by a packaging machine, and then the metal lithium electrode sheet is stood for more than 12 hours to carry out electrochemical performance test.
2. Assembly of symmetrical batteries
The metal lithium electrode plate in the embodiment is punched into a wafer with the diameter of 16mm, lithium iron phosphate is selected as a positive electrode, glass fiber is used as a diaphragm, solid electrolyte is added, the CR-2032 type button cell is assembled and packaged by a packaging machine, and then the metal lithium electrode plate is stood for more than 12 hours and then electrochemical performance test is carried out.
3. Electrochemical Performance test
Fig. 3 shows the polarization potential of the lithium ion battery. As can be seen from the figure, the polarization potential of COF-49 was 5mV, and the stability was good.
Fig. 4 is a graph of high-rate long cycle performance of the organic composite material used as a negative electrode material of a lithium ion battery in example 1 of the present invention. As can be seen from the figure, the battery has the charge and discharge capacity of 160mAh/g under the current density of 0.1C, and the organic composite material is proved to have better performance as the negative electrode material of the lithium ion battery.
FIG. 7 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. 8 is an impedance diagram of the organic composite material as the negative electrode material of the lithium ion battery in example 1 of the present invention. From the figure, 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 negative electrode material of a lithium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a covalent organic framework material for lithium negative electrode modification is characterized by comprising the following steps:
(1) Adding the monomer 2,4, 6-trimethyl-1, 3, 5-triazine and the monomer 2, 5-difluoro terephthalaldehyde into a mixed solvent, and circularly performing liquid nitrogen freezing and vacuum pumping for 2-5 times;
(2) And (2) heating the substance obtained in the step (1) for reaction, washing and drying in vacuum after the reaction is finished to obtain a covalent organic framework material, and naming the covalent organic framework material as COF-49.
2. The method of claim 1, wherein the covalent organic framework material for lithium negative electrode modification comprises: 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 of claim 2, wherein the covalent organic framework material for lithium negative electrode modification comprises: the mixed solvent in the step (1) is a mixed solvent of 1, 4-dioxane, mesitylene, trifluoroacetic acid and acetonitrile.
4. The method of claim 3, wherein the covalent organic framework material for lithium negative electrode modification comprises: 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-difluoroterephthalaldehyde dissolved in each 100mL of mixed solvent is 1 to 5g.
5. The method of claim 4, wherein the covalent organic framework material for lithium negative electrode modification comprises: the heating reaction temperature in the step (2) is 100 to 160 ℃, and the heating reaction time is 50 to 80h.
6. A preparation method of a covalent organic framework material modified lithium cathode is characterized by comprising the following steps:
(1) Mixing the covalent organic framework material prepared by the method of any one of claims 1 to 5 with a binder, adding a solvent, mechanically grinding uniformly, and stamping to form a COF film sheet;
(2) And (2) 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 cathode to obtain the lithium cathode modified by the covalent organic framework material.
7. The method for preparing the lithium anode based on the modification of the covalent organic framework material according to claim 6, wherein the method comprises the following steps: 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 based on covalent organic framework material modification according to claim 7, wherein the method comprises the following steps: 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 the solvent is 5-80mg.
9. The method for preparing a lithium anode based on covalent organic framework material modification according to claim 8, wherein the method comprises the following steps: the drying temperature in the step (2) is 60 to 120 ℃, and the drying time is 6 to 24h.
10. The use of a lithium negative electrode based on a covalent organic framework material modification prepared by the method of any one of claims 6 to 9 in the field of lithium ion batteries.
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